Formation temperatures of thermogenic and biogenic methane

Science.gov (United States)

Stolper, D.A.; Lawson, M.; Davis, C.L.; Ferreira, A.A.; Santos Neto, E. V.; Ellis, G.S.; Lewan, M.D.; Martini, Anna M.; Tang, Y.; Schoell, M.; Sessions, A.L.; Eiler, J.M.

2014-01-01

Methane is an important greenhouse gas and energy resource generated dominantly by methanogens at low temperatures and through the breakdown of organic molecules at high temperatures. However, methane-formation temperatures in nature are often poorly constrained. We measured formation temperatures of thermogenic and biogenic methane using a “clumped isotope” technique. Thermogenic gases yield formation temperatures between 157° and 221°C, within the nominal gas window, and biogenic gases yield formation temperatures consistent with their comparatively lower-temperature formational environments (<50°C). In systems where gases have migrated and other proxies for gas-generation temperature yield ambiguous results, methane clumped-isotope temperatures distinguish among and allow for independent tests of possible gas-formation models.

Modeling the methane hydrate formation in an aqueous film submitted to steady cooling

Energy Technology Data Exchange (ETDEWEB)

Avendano-Gomez, J.R. [ESIQIE, Laboratorio de Ingenieria Quimica Ambiental, Mexico (Mexico). Inst. Politecnico Nacional; Garcia-Sanchez, F. [Laboratorio de Termodinamica, Mexico (Mexico). Inst. Mexicano del Petroleo; Gurrola, D.V. [UPIBI, Laboratorio de Diseno de Plantas, Mexico (Mexico). Inst. Politecnico Nacional

2008-07-01

Gas hydrates, or clathrate hydrates, are ice-like compounds that results from the kinetic process of crystallization of an aqueous solution supersaturated with a dissolved gas. This paper presented a model that took into account two factors involved in the hydrate crystallization, notably the stochastic nature of crystallization that causes sub-cooling and the heat resulting from the exothermic enthalpy of hydrate formation. The purpose of this study was to model the thermal evolution inside a hydrate forming system which was submitted to an imposed steady cooling. The study system was a cylindrical thin film of aqueous solution at 19 Mpa. The study involved using methane as the hydrate forming molecule. It was assumed that methane was homogeneously dissolved in the aqueous phase. Ethane hydrate was formed through a kinetic process of nucleation and crystallization. In order to predict the onset time of nucleation, the induction time needed to be considered. This paper discussed the probability of nucleation as well as the estimation of the rate of nucleation. It also presented the mathematical model and boundary conditions. These included assumptions and derivation of the model; boundary conditions; initial conditions; and numerical solution of the model equation. It was concluded that the heat source must be considered when investigating crystallization effects. 34 refs., 2 tabs., 2 figs.

Hydrogen storage in double clathrates with tert-butylamine.

Science.gov (United States)

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

2009-06-18

The first proof-of-concept of the formation of a double tert-butylamine (t-BuNH(2)) + hydrogen (H(2)) clathrate hydrate has been demonstrated. Binary clathrate hydrates with different molar concentrations of the large guest t-BuNH(2) (0.98-9.31 mol %) were synthesized at 13.8 MPa and 250 K, and characterized by powder X-ray diffraction and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed under hydrogen pressures. Raman spectroscopic data suggested that the hydrogen molecules occupied the small cages and had similar occupancy to hydrogen in the double tetrahydrofuran (THF) + H(2) clathrate hydrate. The hydrogen storage capacity in this system was approximately 0.7 H(2) wt % at the molar concentration of t-BuNH(2) close to the sII stoichiometry.

Thermodynamic studies on semi-clathrate hydrates of TBAB + gases containing carbon dioxide

International Nuclear Information System (INIS)

Eslamimanesh, Ali

2012-01-01

CO 2 capture has become an important area of research mainly due to its drastic greenhouse effects. Gas hydrate formation as a separation technique shows tremendous potential, both from a physical feasibility as well as an envisaged lower energy utilization criterion. Briefly, gas (clathrate) hydrates are non-stoichiometric, ice-like crystalline compounds formed through a combination of water and suitably sized guest molecule(s) under low-temperatures and elevated pressures. As the pressure required for gas hydrate formation is generally high, therefore, aqueous solution of tetra-n-butyl ammonium bromide (TBAB) is added to the system as a gas hydrate promoter. TBAB generally reduces the required hydrate formation pressure and/or increases the formation temperature as well as modifies the selectivity of hydrate cages to capture CO 2 molecules. TBAB also takes part in the hydrogen-bonded cages. Such hydrates are called 'semi-clathrate' hydrates. Evidently, reliable and accurate phase equilibrium data, acceptable thermodynamic models, and other thermodynamic studies should be provided to design efficient separation processes using the aforementioned technology. For this purpose, phase equilibria of clathrate/semi-clathrate hydrates of various gas mixtures containing CO 2 (CO 2 + CH 4 /N 2 /H 2 ) in the presence of pure water and aqueous solutions of TBAB have been measured in this thesis. In the theoretical section of the thesis, a thermodynamic model on the basis of the van der Waals and Platteeuw (vdW-P) solid solution theory along with the modified equations for determination of the Langmuir constants of the hydrate formers has been successfully developed to represent/predict equilibrium conditions of semi-clathrate hydrates of CO 2 , CH 4 , and N 2 . Later, several thermodynamic consistency tests on the basis of Gibbs-Duhem equation as well as a statistical approach have been applied on the phase equilibrium data of the systems of mixed/simple clathrate hydrates

Pentagonal dodecahedron methane hydrate cage and methanol ...

Indian Academy of Sciences (India)

methane hydrate in sea bed near continental margin and underneath of permafrost ... clathrate structure,6,7 IR spectroscopy analysis of vibra- tional form of guest .... Hydrogen (H71) of the hydroxyl group of methanol is found to have formed ...

An innovative approach to enhance methane hydrate formation kinetics with leucine for energy storage application

International Nuclear Information System (INIS)

Veluswamy, Hari Prakash; Kumar, Asheesh; Kumar, Rajnish; Linga, Praveen

2017-01-01

Highlights: • Innovative combinatorial hybrid approach to reduce nucleation stochasticity and enhance hydrate growth. • Methane hydrate growth curves are similar in UTR and STR configurations in presence of leucine. • Amalgamation of stirred (STR) and unstirred (UTR) configuration is demonstrated. • Reliable method for scale up and commercial production of Solidified Natural Gas (SNG). - Abstract: Natural gas storage in clathrate hydrates or solidified natural gas (SNG) offers the safest, cleanest and the most compact mode of storage aided by the relative ease in natural gas (NG) recovery with minimal cost compared to known conventional methods of NG storage. The stochastic nature of hydrate nucleation and the slow kinetics of hydrate growth are major challenges that needs to be addressed on the SNG production side. A deterministic and fast nucleation coupled with rapid crystallization kinetics would empower this beneficial technology for commercial application. We propose a hybrid combinatorial approach of methane hydrate formation utilizing the beneficial aspect of environmentally benign amino acid (leucine) as a kinetic promoter by combining stirred and unstirred reactor operation. This hybrid approach is simple, can easily be implemented and scaled-up to develop an economical SNG technology for efficient storage of natural gas on a large scale. Added benefits include the minimal energy requirement during hydrate growth resulting in overall cost reduction for SNG technology.

Experimental study and thermodynamic modelling of methane clathrate hydrate dissociation conditions in silica gel porous media in the presence of methanol aqueous solution

International Nuclear Information System (INIS)

Hashemi, Hamed; Javanmardi, Jafar; Zarifi, Mojdeh; Eslamimanesh, Ali; Mohammadi, Amir H.

2012-01-01

Highlights: ► Phase equilibria of hydrates of methane in confined silica gel pores are reported. ► Dissociation data in the presences of methanol aqueous solution are also measured. ► A thermodynamic model is developed for prediction of the obtained data. ► Acceptable agreement is found between the obtained data and the predicted results. - Abstract: In this work, the phase equilibria of clathrate hydrates of methane in the presence of pure water and 0.035 mass fraction of methanol aqueous solution in confined silica gel pores with (10 and 15) nm mean diameters are measured and reported. A thermodynamic model is also developed for prediction of the obtained experimental hydrate dissociation data. The Valderrama–Patel–Teja (VPT-EoS) equation of state (EoS) accompanied with the non-density dependent (NDD) mixing rules coupled with a previously developed activity model are applied to evaluate the fugacity of the species present and the activity coefficient of water in methanol aqueous solution. Acceptable agreement between the reported data and the predicted results using the proposed model and an existing method reported in the literature demonstrates the reliability of the presented model.

Methane storage capacity of the early martian cryosphere

Science.gov (United States)

Lasue, Jeremie; Quesnel, Yoann; Langlais, Benoit; Chassefière, Eric

2015-11-01

Methane is a key molecule to understand the habitability of Mars due to its possible biological origin and short atmospheric lifetime. Recent methane detections on Mars present a large variability that is probably due to relatively localized sources and sink processes yet unknown. In this study, we determine how much methane could have been abiotically produced by early Mars serpentinization processes that could also explain the observed martian remanent magnetic field. Under the assumption of a cold early Mars environment, a cryosphere could trap such methane as clathrates in stable form at depth. The extent and spatial distribution of these methane reservoirs have been calculated with respect to the magnetization distribution and other factors. We calculate that the maximum storage capacity of such a clathrate cryosphere is about 2.1 × 1019-2.2 × 1020 moles of CH4, which can explain sporadic releases of methane that have been observed on the surface of the planet during the past decade (∼1.2 × 109 moles). This amount of trapped methane is sufficient for similar sized releases to have happened yearly during the history of the planet. While the stability of such reservoirs depends on many factors that are poorly constrained, it is possible that they have remained trapped at depth until the present day. Due to the possible implications of methane detection for life and its influence on the atmospheric and climate processes on the planet, confirming the sporadic release of methane on Mars and the global distribution of its sources is one of the major goals of the current and next space missions to Mars.

A statistical method for evaluation of the experimental phase equilibrium data of simple clathrate hydrates

DEFF Research Database (Denmark)

Eslamimanesh, Ali; Gharagheizi, Farhad; Mohammadi, Amir H.

2012-01-01

We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot, and the r......We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot...... in exponential form is used to represent/predict the hydrate dissociation pressures for three-phase equilibrium conditions (liquid water/ice–vapor-hydrate). The investigated hydrate formers are methane, ethane, propane, carbon dioxide, nitrogen, and hydrogen sulfide. It is interpreted from the obtained results...

Marine methane cycle simulations for the period of early global warming

Energy Technology Data Exchange (ETDEWEB)

Elliott, S.; Maltrud, M.; Reagan, M.T.; Moridis, G.J.; Cameron-Smith, P.J.

2011-01-02

Geochemical environments, fates, and effects are modeled for methane released into seawater by the decomposition of climate-sensitive clathrates. A contemporary global background cycle is first constructed, within the framework of the Parallel Ocean Program. Input from organics in the upper thermocline is related to oxygen levels, and microbial consumption is parameterized from available rate measurements. Seepage into bottom layers is then superimposed, representing typical seabed fluid flow. The resulting CH{sub 4} distribution is validated against surface saturation ratios, vertical sections, and slope plume studies. Injections of clathrate-derived methane are explored by distributing a small number of point sources around the Arctic continental shelf, where stocks are extensive and susceptible to instability during the first few decades of global warming. Isolated bottom cells are assigned dissolved gas fluxes from porous-media simulation. Given the present bulk removal pattern, methane does not penetrate far from emission sites. Accumulated effects, however, spread to the regional scale following the modeled current system. Both hypoxification and acidification are documented. Sensitivity studies illustrate a potential for material restrictions to broaden the perturbations, since methanotrophic consumers require nutrients and trace metals. When such factors are considered, methane buildup within the Arctic basin is enhanced. However, freshened polar surface waters act as a barrier to atmospheric transfer, diverting products into the deep return flow. Uncertainties in the logic and calculations are enumerated including those inherent in high-latitude clathrate abundance, buoyant effluent rise through the column, representation of the general circulation, and bacterial growth kinetics.

Marine methane cycle simulations for the period of early global warming

Science.gov (United States)

Elliott, Scott; Maltrud, Mathew; Reagan, Matthew; Moridis, George; Cameron-Smith, Philip

2011-03-01

Geochemical environments, fates, and effects are modeled for methane released into seawater by the decomposition of climate-sensitive clathrates. A contemporary global background cycle is first constructed, within the framework of the Parallel Ocean Program. Input from organics in the upper thermocline is related to oxygen levels, and microbial consumption is parameterized from available rate measurements. Seepage into bottom layers is then superimposed, representing typical seabed fluid flow. The resulting CH4 distribution is validated against surface saturation ratios, vertical sections, and slope plume studies. Injections of clathrate-derived methane are explored by distributing a small number of point sources around the Arctic continental shelf, where stocks are extensive and susceptible to instability during the first few decades of global warming. Isolated bottom cells are assigned dissolved gas fluxes from porous-media simulation. Given the present bulk removal pattern, methane does not penetrate far from emission sites. Accumulated effects, however, spread to the regional scale following the modeled current system. Both hypoxification and acidification are documented. Sensitivity studies illustrate a potential for material restrictions to broaden the perturbations, since methanotrophic consumers require nutrients and trace metals. When such factors are considered, methane buildup within the Arctic basin is enhanced. However, freshened polar surface waters act as a barrier to atmospheric transfer, diverting products into the deep return flow. Uncertainties in the logic and calculations are enumerated including those inherent in high-latitude clathrate abundance, buoyant effluent rise through the column, representation of the general circulation, and bacterial growth kinetics.

Methane bursts as a trigger for intermittent lake-forming climates on post-Noachian Mars

Science.gov (United States)

Kite, Edwin S.; Gao, Peter; Goldblatt, Colin; Mischna, Michael A.; Mayer, David P.; Yung, Yuk L.

2017-10-01

Lakes existed on Mars later than 3.6 billion years ago, according to sedimentary evidence for deltaic deposition. The observed fluviolacustrine deposits suggest that individual lake-forming climates persisted for at least several thousand years (assuming dilute flow). But the lake watersheds’ little-weathered soils indicate a largely dry climate history, with intermittent runoff events. Here we show that these observational constraints, although inconsistent with many previously proposed triggers for lake-forming climates, are consistent with a methane burst scenario. In this scenario, chaotic transitions in mean obliquity drive latitudinal shifts in temperature and ice loading that destabilize methane clathrate. Using numerical simulations, we find that outgassed methane can build up to atmospheric levels sufficient for lake-forming climates, if methane clathrate initially occupies more than 4% of the total volume in which it is thermodynamically stable. Such occupancy fractions are consistent with methane production by water-rock reactions due to hydrothermal circulation on early Mars. We further estimate that photochemical destruction of atmospheric methane curtails the duration of individual lake-forming climates to less than a million years, consistent with observations. We conclude that methane bursts represent a potential pathway for intermittent excursions to a warm, wet climate state on early Mars.

Cyclodextrin-Based Solid-Gas Clathrates

NARCIS (Netherlands)

Pereva, Stiliana; Himitliiska, Tsveta; Spassov, Tony; Stoyanov, S.D.; Arnaudov, L.N.; Dudev, Todor

2015-01-01

"Cyclodextrin-gas" clathrates were obtained by crystallization from water solution of α-, β-, and γ-cyclodextrins (CDs) under pressure of the gas to be entrapped into the CD molecules. When the pressure is released, these clathrates are stable at ambient conditions and dissociate at elevated

Novel nanotechnology for efficient production of binary clathrate hydrates of hydrogen and other compounds

Energy Technology Data Exchange (ETDEWEB)

Di Profio, P.; Arca, S.; Germani, R.; Savelli, G. [Perugia Univ., Perugia (Italy). Dept. of Chemistry, Center of Excellence on Innovative Nanostructured Materials

2008-07-01

The development of a hydrogen-based economy depends on finding ways to store hydrogen, but current hydrogen storage methods have significant disadvantages. One main challenge in storing sufficient amounts of hydrogen (up to 4 weight per cent) into a clathrate matrix is that of a kinetic origin, in that the mass transfer of hydrogen gas into clathrate structures is significantly limited by the macroscopic scale of the gas-liquid or gas-ice interfaces involved. This paper discussed the possibility of storing hydrogen in clathrate hydrates. It presented a newly developed method for preparing binary hydrogen hydrates that is based on the formation of amphiphile-aided nanoemulsions. Nanotechnology is used to reduce the size of hydrate particles to a few nanometers, thereby minimizing the kinetic hindrance to hydrate formation. This process has potential for increasing the amount of hydrogen stored, as it has provided ca. 1 weight per cent of hydrogen. Two new co-formers were also successfully tested, namely cyclopentane and tetrahydrothiophene. 23 refs., 10 figs.

Martian Methane From a Cometary Source: A Hypothesis

Science.gov (United States)

Fries, M.; Christou, A.; Archer, D.; Conrad, P.; Cooke, W.; Eigenbrode, J.; ten Kate, I. L.; Matney, M.; Niles, P.; Sykes, M.;

Methane formation in tritium gas exposed to stainless steel

International Nuclear Information System (INIS)

Morris, G.A.

1977-01-01

Tests were performed to determine the effect cleanliness of a surface exposed to tritium gas had on methane formation. These tests performed on 304 stainless steel vessels, cleaned in various ways, showed that the methane formation was reduced by the use of various cleaning procedures

Silicon clathrates for lithium ion batteries: A perspective

International Nuclear Information System (INIS)

Warrier, Pramod; Koh, Carolyn A.

2016-01-01

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15–20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

Silicon clathrates for lithium ion batteries: A perspective

Science.gov (United States)

Warrier, Pramod; Koh, Carolyn A.

2016-12-01

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15-20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

Silicon clathrates for lithium ion batteries: A perspective

Energy Technology Data Exchange (ETDEWEB)

Warrier, Pramod, E-mail: pramod.warrier@gmail.com; Koh, Carolyn A. [Center for Hydrate Research, Chemical & Biological Engineering Department, Colorado School of Mines, Golden, Colorado 80401 (United States)

2016-12-15

Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15–20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

Volatile inventories in clathrate hydrates formed in the primordial nebula.

Science.gov (United States)

Mousis, Olivier; Lunine, Jonathan I; Picaud, Sylvain; Cordier, Daniel

2010-01-01

The examination of ambient thermodynamic conditions suggests that clathrate hydrates could exist in the Martian permafrost, on the surface and in the interior of Titan, as well as in other icy satellites. Clathrate hydrates are probably formed in a significant fraction of planetesimals in the solar system. Thus, these crystalline solids may have been accreted in comets, in the forming giant planets and in their surrounding satellite systems. In this work, we use a statistical thermodynamic model to investigate the composition of clathrate hydrates that may have formed in the primordial nebula. In our approach, we consider the formation sequence of the different ices occurring during the cooling of the nebula, a reasonable idealization of the process by which volatiles are trapped in planetesimals. We then determine the fractional occupancies of guests in each clathrate hydrate formed at a given temperature. The major ingredient of our model is the description of the guest-clathrate hydrate interaction by a spherically averaged Kihara potential with a nominal set of parameters, most of which are fitted to experimental equilibrium data. Our model allows us to find that Kr, Ar and N2 can be efficiently encaged in clathrate hydrates formed at temperatures higher than approximately 48.5 K in the primitive nebula, instead of forming pure condensates below 30 K. However, we find at the same time that the determination of the relative abundances of guest species incorporated in these clathrate hydrates strongly depends on the choice of the parameters of the Kihara potential and also on the adopted size of cages. Indeed, by testing different potential parameters, we have noted that even minor dispersions between the different existing sets can lead to non-negligible variations in the determination of the volatiles trapped in clathrate hydrates formed in the primordial nebula. However, these variations are not found to be strong enough to reverse the relative abundances

Influence of fluorosurfactants on hydrate formation rates

Energy Technology Data Exchange (ETDEWEB)

Kim, C.U.; Jeong, K.E.; Chae, H.J.; Jeong, S.Y. [Korea Reasearch Inst. of Chemical Technology, Alternative Chemicals/Fuel Research Center, Yuseong-Gu, Daejon (Korea, Republic of)

2008-07-01

Gas hydrates, or clathrates, are ice-like solids that forms when natural gas is in contact with liquid water or ice under high pressure and low temperature. There is significant interest in studying the storage and transportation of gas in the form of hydrates. However, a critical problem impacting the industrial application of gas hydrates for storage and transportation of natural gas is the slow formation rate of natural gas hydrate. Researchers have previously reported on the promotion effect of some additives on gas hydrate formation and hydrate gas content. Fluorosurfactants are significantly superior to nonfluorinated surfactants in wetting action, as well as stability in harsh environments, both thermal and chemical. This paper discussed an experimental investigation into the effects of fluorosurfactants with different ionic types on the formation of methane hydrate. The surfactants used were FSN-100 of DuPont Zonyl as non-ionic surfactant and FC-143 of DuPont as anionic surfactant. The paper discussed the experimental apparatus for methane hydrate formation. It also discussed hydrate formation kinetics and the series of hydrate formation experiments that were conducted in the presence of fluorosurfactants. Last, the paper explored the results of the study. It was concluded that anionic fluorosurfactant of FC-143 had a better promoting effect on methane hydrate formation compared with nonionic surfactant of FSN-100. 8 refs., 2 tabs., 2 figs.

Characteristics of Methane Hydrate Formation in Artificial and Natural Media

Directory of Open Access Journals (Sweden)

Qingbai Wu

2013-03-01

Full Text Available The formation of methane hydrate in two significantly different media was investigated, using silica gel as an artificial medium and loess as a natural medium. The methane hydrate formation was observed through the depletion of water in the matrix, measured via the matrix potential and the relationship between the matrix potential and the water content was determined using established equations. The velocity of methane hydrate nucleation slowed over the course of the reaction, as it relied on water transfer to the hydrate surfaces with lower Gibbs free energy after nucleation. Significant differences in the reactions in the two types of media arose from differences in the water retention capacity and lithology of media due to the internal surface area and pore size distributions. Compared with methane hydrate formation in silica gel, the reaction in loess was much slower and formed far less methane hydrate. The results of this study will advance the understanding of how the properties of the environment affect the formation of gas hydrates in nature.

Energy consumption estimation for greenhouse gas separation processes by clathrate hydrate formation

International Nuclear Information System (INIS)

Tajima, Hideo; Yamasaki, Akihiro; Kiyono, Fumio

2004-01-01

The process energy consumption was estimated for gas separation processes by the formation of clathrate hydrates. The separation process is based on the equilibrium partition of the components between the gaseous phase and the hydrate phase. The separation and capturing processes of greenhouse gases were examined in this study. The target components were hydrofluorocarbon (HFC-134a) from air, sulfur hexafluoride (SF 6 ) from nitrogen, and CO 2 from flue gas. Since these greenhouse gases would form hydrates under much lower pressure and higher temperature conditions than the accompanying components, the effective capturing of the greenhouse gases could be achieved by using hydrate formation. A model separation process for each gaseous mixture was designed from the basis of thermodynamics, and the process energy consumption was estimated. The obtained results were then compared with those for conventional separation processes such as liquefaction separation processes. For the recovery of SF 6 , the hydrate process is preferable to liquefaction process in terms of energy consumption. On the other hand, the liquefaction process consumes less energy than the hydrate process for the recovery of HFC-134a. The capturing of CO 2 by the hydrate process from a flue gas will consume a considerable amount of energy; mainly due to the extremely high pressure conditions required for hydrate formation. The influences of the operation conditions on the heat of hydrate formation were elucidated by sensitivity analysis. The hydrate processes for separating these greenhouse gases were evaluated in terms of reduction of global warming potential (GWP)

Investigation of the Methane Hydrate Formation by Cavitation Jet

Science.gov (United States)

Morita, H.; Nagao, J.

2015-12-01

Methane hydrate (hereafter called "MH") is crystalline solid compound consisting of hydrogen-bonded water molecules forming cages and methane gas molecules enclosed in the cage. When using MH as an energy resource, MH is dissociated to methane gas and water and collect only the methane gas. The optimum MH production method was the "depressurization method". Here, the production of MH means dissociating MH in the geologic layers and collecting the resultant methane gas by production systems. In the production of MH by depressurization method, MH regeneration was consider to important problem for the flow assurance of MH production system. Therefore, it is necessary to clarify the effect of flow phenomena in the pipeline on hydrate regeneration. Cavitation is one of the flow phenomena which was considered a cause of MH regeneration. Large quantity of microbubbles are produced by cavitation in a moment, therefore, it is considered to promote MH formation. In order to verify the possible of MH regeneration by cavitation, it is necessary to detailed understanding the condition of MH formation by cavitation. As a part of a Japanese National hydrate research program (MH21, funded by METI), we performed a study on MH formation using by cavitation. The primary objective of this study is to demonstrate the formation MH by using cavitation in the various temperature and pressure condition, and to clarify the condition of MH formation by using observation results.

Characteristics of Methane Hydrate Formation in Artificial and Natural Media

OpenAIRE

Peng Zhang; Qingbai Wu; Yuzhong Yang

2013-01-01

The formation of methane hydrate in two significantly different media was investigated, using silica gel as an artificial medium and loess as a natural medium. The methane hydrate formation was observed through the depletion of water in the matrix, measured via the matrix potential and the relationship between the matrix potential and the water content was determined using established equations. The velocity of methane hydrate nucleation slowed over the course of the reaction, as it relied on...

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

Science.gov (United States)

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

2006-01-01

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

Observations of CO{sub 2} clathrate hydrate formation and dissolution under deep-ocean disposal conditions

Energy Technology Data Exchange (ETDEWEB)

Warzinski, R.P.; Cugini, A.V. [Department of Energy, Pittsburgh, PA (United States); Holder, G.D. [Univ. of Pittsburgh, Pittsburgh, PA (United States)

1995-11-01

Disposal of anthropogenic emissions of CO{sub 2} may be required to mitigate rises in atmospheric levels of this greenhouse gas if other measures are ineffective and the worst global warming scenarios begin to occur. Long-term storage of large quantities of CO{sub 2} has been proposed, but the feasibility of large land and ocean disposal options remains to be established. Determining the fate of liquid CO{sub 2} injected into the ocean at depths greater than 500 m is complicated by uncertainties associated with the physical behavior of CO{sub 2} under these conditions, in particular the possible formation of the ice-like CO{sub 2} clathrate hydrate. Resolving this issue is key to establishing the technical feasibility of this option. Experimental and theoretical work in this area is reported.

Accurate description of phase diagram of clathrate hydrates on molecular level

Energy Technology Data Exchange (ETDEWEB)

Belosludov, V.; Subbotin, O. [Niklaev Inst. of Inorganic Chemistry, Novosibirsk (Russian Federation). Siberian Branch of Russian Academy of Science; Belosludov, R.; Mizuseki, H.; Kawazoe, Y. [Tohoku Univ., Aoba-ku, Sendai (Japan). Inst. for Materials Research

2008-07-01

A number of experimental and theoretical studies of hydrogen hydrates have been conducted using different methods. In order to accurately estimate the thermodynamic properties of clathrate hydrates that multiply filling the cages, this paper presented a method based on the solid solution theory of van der Waals and Platteeuw with several modifications, including multiple occupancies, host relaxation, and the description of the quantum nature of hydrogen behavior in the cavities. The validity of the proposed approach was verified for argon, methane, and xenon hydrates. The results were in agreement with known experimental data. The model was then used to calculate the curves of monovariant three-phase equilibrium gas-hydrate-ice and the degree of filling of the large and small cavities for pure hydrogen and mixed hydrogen/propane hydrates in a wide range of pressure and at low temperatures. The paper presented the theory, including equations, monovariant equilibria, and computational details. It was concluded that the proposed model accounted for the influence of guest molecules on the host lattice and guest-guest interaction. The model could be used with other inclusion compounds with the same type of composition such as clathrate silicon, zeolites, and inclusion compounds of semiconductor elements. The calculated curves of monovariant equilibrium agree with the experiment. 33 refs., 1 tab., 9 figs.

Titan's Methane Cycle is Closed

Science.gov (United States)

Hofgartner, J. D.; Lunine, J. I.

2013-12-01

Doppler tracking of the Cassini spacecraft determined a polar moment of inertia for Titan of 0.34 (Iess et al., 2010, Science, 327, 1367). Assuming hydrostatic equilibrium, one interpretation is that Titan's silicate core is partially hydrated (Castillo-Rogez and Lunine, 2010, Geophys. Res. Lett., 37, L20205). These authors point out that for the core to have avoided complete thermal dehydration to the present day, at least 30% of the potassium content of Titan must have leached into an overlying water ocean by the end of the core overturn. We calculate that for probable ammonia compositions of Titan's ocean (compositions with greater than 1% ammonia by weight), that this amount of potassium leaching is achievable via the substitution of ammonium for potassium during the hydration epoch. Formation of a hydrous core early in Titan's history by serpentinization results in the loss of one hydrogen molecule for every hydrating water molecule. We calculate that complete serpentinization of Titan's core corresponds to the release of more than enough hydrogen to reconstitute all of the methane atoms photolyzed throughout Titan's history. Insertion of molecular hydrogen by double occupancy into crustal clathrates provides a storage medium and an opportunity for ethane to be converted back to methane slowly over time--potentially completing a cycle that extends the lifetime of methane in Titan's surface atmosphere system by factors of several to an order of magnitude over the photochemically-calculated lifetime.

Mechanism of the thermal conductivity of type-I clathrates

International Nuclear Information System (INIS)

Ikeda, M. S.

2015-01-01

Due to their intrinsically low thermal conductivity, intermetallic type-I clathrates are promising candidates for thermoelectric energy conversion, most notably for waste-heat recovery above room temperature. Combining their low thermal conductivity with the enhanced electrical power factor of strongly correlated materials can be considered as one of the most promising routes to a next generation thermoelectric material. However, although much investigated, the physical origin of the low thermal conductivity of type-I clathrates is still debated. Therefore, the main goal of this thesis was to gain deeper insight into the mechanism of the low thermal conductivity of type-I clathrates. On the basis of recent inelastic neutron and X-ray scattering studies on type-I clathrates and skutterudites, an analytical model for describing the phonon thermal conductivity of such filled cage compounds was developed within this thesis. This model is based on the phononic filter effect and on strongly enhanced Umklapp scattering. Data on several Ge-based single crystalline type-I clathrates are discussed in the context of this model, revealing the influence of host framework vacancies, charge carriers, and large defects such as grain boundaries on the low-temperature thermal conductivity of type-I clathrates. Since for waste heat recovery the thermal conductivity at elevated temperatures is of interest, a sophisticated 3w-experiment for accurate measurements of bulk and thin film materials at elevated temperatures was developed. With the help of this experiment, a universal dependence of the intrinsic phonon thermal conductivity of type-I clathrates on the sound velocity and the lowest-lying guest Einstein mode was demonstrated for the first time. Further investigations on thermoelectric materials including the first Ce-containing type-I clathrate, skutterudites, and thin films complete this doctoral work. (author)

Large methane releases lead to strong aerosol forcing and reduced cloudiness

DEFF Research Database (Denmark)

Kurten, T.; Zhou, L.; Makkonen, R.

2011-01-01

forcing that is comparable in magnitude to the long-wave radiative forcing ("enhanced greenhouse effect") of the added methane. Together, the indirect CH4-O-3 and CH4-OHaerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously......The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller...... contributions from the associated carbon dioxide or ozone increases. Here, we study the effect of strongly elevated methane (CH4) levels on oxidant and aerosol particle concentrations using a combination of chemistry-transport and general circulation models. A 10-fold increase in methane concentrations...

Crystal structure of clathrates of Hofmann dma-type

International Nuclear Information System (INIS)

NIshikiori, Sh.; Ivamoto, T.

1999-01-01

Seven new clathrates Cd(DMA) 2 Ni(CN) 4 ·xG (x=1, G=aniline, 2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,5-xylidine, and x=2, G=2,4,6-trimethylaniline) of Hofmann type are synthesized by amine substitution for dimethylamine (DMA). On the base of x-ray diffraction data it is shown that geometry of guest molecule in cage-like hollow determines the structure of the host and crystal structure of clathrates. Two-dimension metallocomplex of the host of studied clathrates is characterized by elastic folded structure appearing as a result of angular deformation of bond between Cd atoms and host cyanide bridge. Guest molecule orientation is fixed by hydrogen bond. Structural elasticity of the host complex directs to differences in crystal structure of clathrates formed and to considerable variety of incorporated guests [ru

Formation of methane and nitrous oxide in plants

Science.gov (United States)

Keppler, Frank; Lenhart, Katharina

2017-04-01

and mosses, so called cryptogamic covers, were recently identified to release substantial amounts of nitrous oxide (Lenhart et al. 2015). In this presentation we will give a brief overview of recent observations of aerobic methane formation and nitrous oxide emissions from terrestrial vegetation. Furthermore, we will present new results from laboratory incubation experiments that provide further insights into the formation of methane and nitrous oxide from plants. References: Bruhn, D. et al.: Leaf surface wax is a source of plant methane formation under UV radiation and in the presence of oxygen. Plant Biology 16, 512-516, 2014. Chang, C. et al.: Nitrous Oxide Emission through Plants. Soil Science Society of America Journal 62, 35-38, 1998. Dean, J. V., Harper, J. E.: Nitric oxide and nitrous oxide production by soybean and winged bean during the in vivo nitrate reductase assay. Plant Physiology 82, 718-723, 1986. Keppler, F., Boros, M., Frankenberg, C., Lelieveld, J., McLeod, A., Pirttilä, A. M., Röckmann, T., Schnitzler, J.: Methane formation in aerobic environments, Environmental Chemistry, 6, 459-465, 2009. Lenhart, K. et al.: Nitrous oxide and methane emissions from cryptogamic covers. Global Change Biology 21, 3889-3900, 2015. Pihlatie, M., Ambus, P., Rinne, J., Pilegaard, K., Vesala, T.: Plant-mediated nitrous oxide emissions from beech (Fagus sylvatica) leaves. New Phytologist 168, 93-98, 2005. Wang, Z.-P., Chang, S. X., Chen, H., Han, X.-G.: Widespread non-microbial methane production by organic compounds and the impact of environmental stresses, Earth-Science Reviews, 127, 193-202, 2013.

Methane hydrates in quaternary climate change

International Nuclear Information System (INIS)

Kennett, J. P.; Hill, T. M.; Behl, R. J.

2005-01-01

The hydrate reservoir in marine sediments is known to contain a large volume of exchangeable carbon stored as solid methane hydrate and associated free gas. This reservoir has been shown to be potentially unstable in response to changing intermediate water temperature and sea level (pressure). Evidence continues to grow for past episodes of major methane release at times of climatic warming. Yet few studies of late Quaternary climate change include methane hydrates as an integral part of the global climate system, in spite of the largest known oscillations at this time in sea level and upper ocean temperature changes for the Cenozoic or earlier, conditions that favor instability of the methane hydrate reservoir. Abrupt increases in atmospheric methane recorded in polar ice cores are widely believed to have resulted, not from ocean-floor methane degassing, but instead from continental wetland activation, a hypothesis thus far unsupported by geological data. Furthermore, as part of this Wetland Methane Hypothesis, the abrupt methane increases have been seen as a response to climatic warming rather than contributing significantly to the change. An alternative view (formulated as the Clathrate Gun Hypothesis) is that the speed, magnitude and timing of abrupt climate change in the recent geologic past are consistent with the process of major degassing of methane hydrates. We summarize aspects of this hypothesis here and needs to test this hypothesis. (Author)

Large methane releases lead to strong aerosol forcing and reduced cloudiness

DEFF Research Database (Denmark)

Kurten, T.; Zhou, L.; Makkonen, R.

2011-01-01

The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller...... is predicted to significantly decrease hydroxyl radical (OH) concentrations, while moderately increasing ozone (O-3). These changes lead to a 70% increase in the atmospheric lifetime of methane, and an 18% decrease in global mean cloud droplet number concentrations (CDNC). The CDNC change causes a radiative...... forcing that is comparable in magnitude to the long-wave radiative forcing ("enhanced greenhouse effect") of the added methane. Together, the indirect CH4-O-3 and CH4-OHaerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously...

Effect of Gemini-type surfactant on methane hydrate formation

Energy Technology Data Exchange (ETDEWEB)

Jeong, K.E.; Park, J.M.; Kim, C.U.; Chae, H.J.; Jeong, S.Y. [Korea Research Inst. of Chemical Technology, Jang-Dong, Yuseong-Gu, Daejeon (Korea, Republic of)

2008-07-01

Natural gas hydrates are formed from water and natural gas molecules at particular temperatures and pressures that become ice-like inclusion compounds. Gas hydrates offer several benefits such as energy resource potential and high storage capacity of natural gas in the form of hydrates. However, the application of natural gas hydrates has been deterred by its low formation rate and low conversion ratio of water into hydrate resulting in low actual storage capacity. This paper presented an experimental study to determine the effect of adding a novel Gemini-type surfactant on methane hydrate formation. The experimental study was described with reference to the properties of prepared diols and properties of prepared disulfonates. Gemini surfactant is the family of surfactant molecules possessing more than one hydrophobic tail and hydrophilic head group. They generally have better surface-active properties than conventional surfactants of equal chain length. The paper presented the results of the study in terms of the reactions of diols with propane sultone; storage capacity of hydrate formed with and without surfactant; and methane hydrate formation with and without disulfonate. It was concluded that the methane hydrate formation was accelerated by the addition of novel anionic Gemini-type surfactants and that hydrate formation was influenced by the surfactant concentration and alkyl chain length. For a given concentration, the surfactant with the highest chain length demonstrated the highest formation rate and storage capacity. 5 refs., 3 tabs., 4 figs.

Methane Hydrate Formation and Dissociation in the Presence of Silica Sand and Bentonite Clay

Directory of Open Access Journals (Sweden)

Kumar Saw V.

2015-11-01

Full Text Available The formation and dissociation of methane hydrates in a porous media containing silica sand of different sizes and bentonite clay were studied in the presence of synthetic seawater with 3.55 wt% salinity. The phase equilibrium of methane hydrate under different experimental conditions was investigated. The effects of the particle size of silica sand as well as a mixture of bentonite clay and silica sand on methane hydrate formation and its dissociation were studied. The kinetics of hydrate formation was studied under different subcooling conditions to observe its effects on the induction time of hydrate formation. The amount of methane gas encapsulated in hydrate was computed using a real gas equation. The Clausius-Clapeyron equation is used to estimate the enthalpy of hydrate dissociation with measured phase equilibrium data.

Formation and retention of methane in coal

Energy Technology Data Exchange (ETDEWEB)

Hucka, V.J.; Bodily, D.M.; Huang, H.

1992-05-15

The formation and retention of methane in coalbeds was studied for ten Utah coal samples, one Colorado coal sample and eight coal samples from the Argonne Premium Coal Sample Bank.Methane gas content of the Utah and Colorado coals varied from zero to 9 cm{sup 3}/g. The Utah coals were all high volatile bituminous coals. The Colorado coal was a gassy medium volatile bituminous coal. The Argonne coals cover a range or rank from lignite to low volatile bituminous coal and were used to determine the effect of rank in laboratory studies. The methane content of six selected Utah coal seams and the Colorado coal seam was measured in situ using a special sample collection device and a bubble desorbometer. Coal samples were collected at each measurement site for laboratory analysis. The cleat and joint system was evaluated for the coal and surrounding rocks and geological conditions were noted. Permeability measurements were performed on selected samples and all samples were analyzed for proximate and ultimate analysis, petrographic analysis, {sup 13}C NMR dipolar-dephasing spectroscopy, and density analysis. The observed methane adsorption behavior was correlated with the chemical structure and physical properties of the coals.

Raman spectroscopic studies of hydrogen clathrate hydrates.

Science.gov (United States)

Strobel, Timothy A; Sloan, E Dendy; Koh, Carolyn A

2009-01-07

Raman spectroscopic measurements of simple hydrogen and tetrahydrofuran+hydrogen sII clathrate hydrates have been performed. Both the roton and vibron bands illuminate interesting quantum dynamics of enclathrated H(2) molecules. The complex vibron region of the Raman spectrum has been interpreted by observing the change in population of these bands with temperature, measuring the absolute H(2) content as a function of pressure, and with D(2) isotopic substitution. Quadruple occupancy of the large sII clathrate cavity shows the highest H(2) vibrational frequency, followed by triple and double occupancies. Singly occupied small cavities display the lowest vibrational frequency. The vibrational frequencies of H(2) within all cavity environments are redshifted from the free gas phase value. At 76 K, the progression from ortho- to para-H(2) occurs over a relatively slow time period (days). The rotational degeneracy of H(2) molecules within the clathrate cavities is lifted, observed directly in splitting of the para-H(2) roton band. Raman spectra from H(2) and D(2) hydrates suggest that the occupancy patterns between the two hydrates are analogous, increasing confidence that D(2) is a suitable substitute for H(2). The measurements suggest that Raman is an effective and convenient method to determine the relative occupancy of hydrogen molecules in different clathrate cavities.

Surface Assisted Formation of methane Hydrates on Ice and Na Montmorillonite Clay

Energy Technology Data Exchange (ETDEWEB)

Gordon, Margaret Ellen [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Teich-McGoldrick, Stephanie [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Cygan, Randall Timothy [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Meserole, Stephen P. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Rodriguez, Mark A. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2015-07-01

Methane hydrates are extremely important naturally-occurring crystalline materials that impact climate change, energy resources, geological hazards, and other major environmental issues. Whereas significant experimental effort has been completed to understanding the bulk thermodynamics of methane hydrate assemblies, little is understood on heterogeneous nucleation and growth of methane hydrates in clay-rich environments. Controlled synthesis experiments were completed at 265-285 K and 6.89 MPa to examine the impact of montmorillonite surfaces in clay-ice mixtures to nucleate and form methane hydrate. The results suggest that the hydrophilic and methane adsorbing properties of Namontmorillonite reduce the nucleation period of methane hydrate formation in pure ice systems.

Molecular dynamics study of methane hydrate formation at a water/methane interface.

Science.gov (United States)

Zhang, Junfang; Hawtin, R W; Yang, Ye; Nakagava, Edson; Rivero, M; Choi, S K; Rodger, P M

2008-08-28

We present molecular dynamics simulation results of a liquid water/methane interface, with and without an oligomer of poly(methylaminoethylmethacrylate), PMAEMA. PMAEMA is an active component of a commercial low dosage hydrate inhibitor (LDHI). Simulations were performed in the constant NPT ensemble at temperatures of 220, 235, 240, 245, and 250 K and a pressure of 300 bar. The simulations show the onset of methane hydrate growth within 30 ns for temperatures below 245 K in the methane/water systems; at 240 K there is an induction period of ca. 20 ns, but at lower temperatures growth commences immediately. The simulations were analyzed to calculate hydrate content, the propensity for hydrogen bond formation, and how these were affected by both temperature and the presence of the LDHI. As expected, both the hydrogen bond number and hydrate content decreased with increasing temperature, though little difference was observed between the lowest two temperatures considered. In the presence of PMAEMA, the temperature below which sustained hydrate growth occurred was observed to decrease. Some of the implications for the role of PMAEMA in LDHIs are discussed.

UV-visible and resonance Raman spectroscopy of halogen molecules in clathrate hydrates

Energy Technology Data Exchange (ETDEWEB)

Janda, K.C.; Kerenskaya, G.; Goldsheleger, I.U.; Apkarian, V.A.; Fleischer, E.B. [California Univ., Irvine, CA (United States). Dept. of Chemistry

2008-07-01

Resonance Raman spectroscopy was used to study halogen clathrate hydrate solids. In particular, this paper presented an ultraviolet-visible spectra for a polycrystalline sample of chlorine clathrate hydrate and two single crystal samples of bromine clathrate hydrate. UV-visible spectroscopy was used to study the interactions between the halogen guest molecule and the host water lattice. The spectrum for chlorine hydrate had a strong temperature dependence, while the spectra for bromine clathrate hydrate single crystals had a stable cubic type 2 structure as well as a tetragonal structure. A metastable cubic type 1 structure was also observed. Resonance Raman spectroscopy showed how the molecules fit into the host cages. 25 refs., 2 tabs., 7 figs.

Mineral-like clathrate of cadmium cyanide with benzene

International Nuclear Information System (INIS)

Kitazava, T.; Nishimura, A.

1999-01-01

A new mineral-like clathrate of cadmium cyanide with benzene Cd(CN) 2 ·C 6 H 6 is prepared. Data of x-ray diffraction analysis show that benzene molecule is incorporated in cadmium cyanide lattice and a new mineral-like lattice of Cd(CN) 2 belongs to structures of cristobalite type. Clathrate Cd(CN) 2 ·C 6 H 6 crystallizes in trigonal space group R3m, a=8.953(4), c=21929(6) A [ru

Methane formation during deuteron bombardment of carbon in the energy range of 100 to 1500 eV

International Nuclear Information System (INIS)

Sone, K.

1982-01-01

Methane (CD 4 ) formation rates during deuteron bombardment of carbon (Papyex) have been measured in the energy range of 100 to 1500 eV. The temperature dependence of the methane formation rate is well explained by the model proposed by Erents et al. in the temperature range of 600 to 1150 K. The model, however, does not explain the dependence of the methane formation rate on the flux of incident deuterons at a certain temperature near Tsub(m) at which the formation rate has a maximum value. An alternative model is proposed in which the methane formation rate is assumed to be proportional to the product of the following three parameters: the surface concentration of deuterium atoms, the chemical reaction rate for the formation of methane, and the rate of production of vacancies on the surface by the deuteron bombardment. This model predicts an energy dependence of methane formation which has a maximum around 900 eV even at different deuteron fluxes, when the calculated result by Weissman and Sigmund is used for the surface deposited energy responsible for the production of vacancies. (author)

Type I Clathrates as Novel Silicon Anodes: An Electrochemical and Structural Investigation

OpenAIRE

Li, Ying; Raghavan, Rahul; Wagner, Nicholas A.; Davidowski, Stephen K.; Baggetto, Lo?c; Zhao, Ran; Cheng, Qian; Yarger, Jeffery L.; Veith, Gabriel M.; Ellis?Terrell, Carol; Miller, Michael A.; Chan, Kwai S.; Chan, Candace K.

2015-01-01

Silicon clathrates contain cage?like structures that can encapsulate various guest atoms or molecules. An electrochemical evaluation of type I silicon clathrates based on Ba8Al y Si46?y as the anode material for lithium?ion batteries is presented here. Postcycling characterization with nuclear magnetic resonance and X?ray diffraction shows no discernible structural or volume changes even after electrochemical insertion of 44 Li (?1 Li/Si) into the clathrate structure. The observed properties ...

Preservation of carbon dioxide clathrate hydrate in the presence of trehalose under freezer conditions.

Science.gov (United States)

Nagashima, Hironori D; Takeya, Satoshi; Uchida, Tsutomu; Ohmura, Ryo

2016-01-19

To investigate the preservation of CO2 clathrate hydrate in the presence of sugar for the novel frozen dessert, mass fractions of CO2 clathrate hydrate in CO2 clathrate hydrate samples coexisting with trehalose were intermittently measured. The samples were prepared from trehalose aqueous solution with trehalose mass fractions of 0.05 and 0.10 at 3.0 MPa and 276.2 K. The samples having particle sizes of 1.0 mm and 5.6-8.0 mm were stored at 243.2 K and 253.2 K for three weeks under atmospheric pressure. The mass fractions of CO2 clathrate hydrate in the samples were 0.87-0.97 before the preservation, and CO2 clathrate hydrate still remained 0.56-0.76 in the mass fractions for 5.6-8.0 mm samples and 0.37-0.55 for 1.0 mm samples after the preservation. The preservation in the trehalose system was better than in the sucrose system and comparable to that in the pure CO2 clathrate hydrate system. This comparison indicates that trehalose is a more suitable sugar for the novel frozen carbonated dessert using CO2 clathrate hydrate than sucrose in terms of CO2 concentration in the dessert. It is inferred that existence of aqueous solution in the samples is a significant factor of the preservation of CO2 clathrate hydrate in the presence of sugar.

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

Science.gov (United States)

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

2009-10-22

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

Large methane releases lead to strong aerosol forcing and reduced cloudiness

Directory of Open Access Journals (Sweden)

T. Kurtén

2011-07-01

Full Text Available The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller contributions from the associated carbon dioxide or ozone increases. Here, we study the effect of strongly elevated methane (CH₄ levels on oxidant and aerosol particle concentrations using a combination of chemistry-transport and general circulation models. A 10-fold increase in methane concentrations is predicted to significantly decrease hydroxyl radical (OH concentrations, while moderately increasing ozone (O₃. These changes lead to a 70 % increase in the atmospheric lifetime of methane, and an 18 % decrease in global mean cloud droplet number concentrations (CDNC. The CDNC change causes a radiative forcing that is comparable in magnitude to the longwave radiative forcing ("enhanced greenhouse effect" of the added methane. Together, the indirect CH₄-O₃ and CH₄-OH-aerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously large temperature changes associated with historic methane releases.

Thermoelectric properties of low-dimensional clathrates from first principles

Science.gov (United States)

Kasinathan, Deepa; Rosner, Helge

2011-03-01

Type-I inorganic clathrates are host-guest structures with the guest atoms trapped in the framework of the host structure. From a thermoelectric point of view, they are interesting because they are semiconductors with adjustable bandgaps. Investigations in the past decade have shown that type-I clathrates X8 Ga 16 Ge 30 (X = Ba, Sr, Eu) may have the unusual property of ``phonon glass-electron crystal'' for good thermoelectric materials. Among the known clathrates, Ba 8 Ga 16 Ge 30 has the highest figure of merit (ZT~1). To enable a more widespread usage of thermoelectric technology power generation and heating/cooling applications, ZT of at least 2-3 is required. Two different research approaches have been proposed for developing next generation thermoelectric materials: one investigating new families of advanced bulk materials, and the other studying low-dimensional materials. In our work, we concentrate on understanding the thermoelectric properties of the nanostructured Ba-based clathrates. We use semi-classical Boltzmann transport equations to calculate the various thermoelectric properties as a function of reduced dimensions. We observe that there exists a delicate balance between the electrical conductivity and the electronic part of the thermal conductivity in reduced dimensions. Insights from these results can directly be used to control particle size in nanostructuring experiments.

Simulation and Characterization of Methane Hydrate Formation

Science.gov (United States)

Dhakal, S.; Gupta, I.

2017-12-01

The ever rising global energy demand dictates human endeavor to explore and exploit new and innovative energy sources. As conventional oil and gas reserves deplete, we are constantly looking for newer sources for sustainable energy. Gas hydrates have long been discussed as the next big energy resource to the earth. Its global occurrence and vast quantity of natural gas stored is one of the main reasons for such interest in its study and exploration. Gas hydrates are solid crystalline substances with trapped molecules of gas inside cage-like crystals of water molecules. Gases such as methane, ethane, propane and carbon dioxide can form hydrates but in natural state, methane hydrates are the most common. Subsurface geological conditions with high pressure and low temperature favor the formation and stability of gas hydrates. While the occurrence and potential of gas hydrates as energy source has long been studied, there are still gaps in knowledge, especially in the quantitative research of gas hydrate formation and reservoir characterization. This study is focused on exploring and understanding the geological setting in which gas hydrates are formed and the subsequent changes in rock characteristics as they are deposited. It involves the numerical simulation of methane gas flow through fault to form hydrates. The models are representative of the subsurface geologic setting of Gulf of Mexico with a fault through layers of shale and sandstone. Hydrate formation simulated is of thermogenic origin. The simulations are conducted using TOUGH+HYDRATE, a numerical code developed at the Lawrence Berkley National Laboratory for modeling multiphase flow through porous medium. Simulation results predict that as the gas hydrates form in the pores of the model, the porosity, permeability and other rock properties are altered. Preliminary simulation results have shown that hydrates begin to form in the fault zone and gradually in the sandstone layers. The increase in hydrate

Subsurface methane formation in graphite due to exposure to H+ and D+

International Nuclear Information System (INIS)

Chiu, S.; Haasz, A.A.

1994-01-01

The extent of H-D mixing in the form of mixed-isotope methane formation during simultaneous H + /D + bombardment of graphite was measured and found to be a sensitive function of H + -D + ion range separation. The result strongly supports the model that methane molecules are formed at the end of ion range in the bulk of graphite. A long steadily decreasing transient was observed in the methane emission when bombarding a virgin graphite sample with 10 keV D + at 800 K. The effect was less pronounced for low density fine grain isographites (EK98) than for high density pyrolytic graphite (HPG99) and monocrystal carbons. We propose a model which attributes this transient to the creation of new internal ''surfaces'', formed during ion irradiation along with ion-created micropaths. The increase in internal surface area effectively ''dilutes'' the inner surface hydrogen concentration in the region where incident hydrogen ions thermalize. We propose that, initially, methane molecules are formed mainly on inherent internal surfaces (pore and grain/crystallite boundary surfaces) in the region where hydrogen ions thermalize; then as damage builds up, newly produced internal ''surfaces'' also contribute to methane formation. (orig.)

The effects of ice on methane hydrate nucleation: a microcanonical molecular dynamics study.

Science.gov (United States)

Zhang, Zhengcai; Guo, Guang-Jun

2017-07-26

Although ice powders are widely used in gas hydrate formation experiments, the effects of ice on hydrate nucleation and what happens in the quasi-liquid layer of ice are still not well understood. Here, we used high-precision constant energy molecular dynamics simulations to study methane hydrate nucleation from vapor-liquid mixtures exposed to the basal, prismatic, and secondary prismatic planes of hexagonal ice (ice Ih). Although no significant difference is observed in hydrate nucleation processes for these different crystal planes, it is found, more interestingly, that methane hydrate can nucleate either on the ice surface heterogeneously or in the bulk solution phase homogeneously. Several factors are mentioned to be able to promote the heterogeneous nucleation of hydrates, including the adsorption of methane molecules at the solid-liquid interface, hydrogen bonding between hydrate cages and the ice structure, the stronger ability of ice to transfer heat than that of the aqueous solution, and the higher occurrence probability of hydrate cages in the vicinity of the ice surface than in the bulk solution. Meanwhile, however, the other factors including the hydrophilicity of ice and the ice lattice mismatch with clathrate hydrates can inhibit heterogeneous nucleation on the ice surface and virtually promote homogeneous nucleation in the bulk solution. Certainly, the efficiency of ice as a promoter and as an inhibitor for heterogeneous nucleation is different. We estimate that the former is larger than the latter under the working conditions. Additionally, utilizing the benefit of ice to absorb heat, the NVE simulation of hydrate formation with ice can mimic the phenomenon of ice shrinking during the heterogeneous nucleation of hydrates and lower the overly large temperature increase during homogeneous nucleation. These results are helpful in understanding the nucleation mechanism of methane hydrate in the presence of ice.

A Fundamental Study of Inorganic Clathrate and Other Open-Framework Materials

Energy Technology Data Exchange (ETDEWEB)

Nolas, George [Univ. of South Florida, Tampa, FL (United States)

2017-08-15

Due to formidable synthetic challenges, many materials of scientific and technological interest are first obtained as microcrystalline powders. High purity, high yield processing techniques are often lacking and thus care must be taken in interpretation of the observed structural, chemical, and physical properties of powder or polycrystalline materials, which can be strongly influenced by extrinsic properties. Furthermore, the preparation of high-quality single crystals for many materials by traditional techniques can be especially challenging in cases where the elemental constituents have greatly differing melting points and/or vapor pressures, when the desired compound is thermodynamically metastable, or where growth with participation of the melt is generally not possible. New processing techniques are therefore imperative in order to investigate the intrinsic properties of these materials and elucidate their fundamental physical properties. Intermetallic clathrates constitute one such class of materials. The complex crystal structures of intermetallic clathrates are characterized by mainly group 14 host frameworks encapsulating guest-ions in polyhedral cages. The unique features of clathrate structures are intimately related to their physical properties, offering ideal systems for the study of structure-property relationships in crystalline solids. Moreover, intermetallic clathrates are being actively investigated due to their potential for application in thermoelectrics, photovoltaics and opto-electronics, superconductivity, and magnetocaloric technologies. We have developed different processing techniques in order to synthesize phase-pure high yield clathrates reproducibly, as well as grow single crystals for the first time. We also employed these techniques to synthesize new “open-framework” compounds. These advances in materials processing and crystal growth allowed for the investigation of the physical properties of a variety of different clathrate

Type I Clathrates as Novel Silicon Anodes: An Electrochemical and Structural Investigation

Science.gov (United States)

Li, Ying; Raghavan, Rahul; Wagner, Nicholas A.; Davidowski, Stephen K.; Baggetto, Loïc; Zhao, Ran; Cheng, Qian; Yarger, Jeffery L.; Veith, Gabriel M.; Ellis‐Terrell, Carol; Miller, Michael A.; Chan, Kwai S.

2015-01-01

Silicon clathrates contain cage‐like structures that can encapsulate various guest atoms or molecules. An electrochemical evaluation of type I silicon clathrates based on Ba8AlySi46−y as the anode material for lithium‐ion batteries is presented here. Postcycling characterization with nuclear magnetic resonance and X‐ray diffraction shows no discernible structural or volume changes even after electrochemical insertion of 44 Li (≈1 Li/Si) into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from large volume changes. The electrochemical reactions are proposed to occur as single phase reactions at approximately 0.2 and 0.4 V versus Li/Li+ during lithiation and delithiation, respectively, distinct from diamond cubic or amorphous silicon anodes. Reversible capacities as high as 499 mAh g−1 at a 5 mA g−1 rate were observed for silicon clathrate with composition Ba8Al8.54Si37.46, corresponding to ≈1.18 Li/Si. These results show that silicon clathrates could be promising durable anodes for lithium‐ion batteries. PMID:27980951

The potential for methane hydrate formation in deep repositories of spent nuclear fuel in granitic rocks

International Nuclear Information System (INIS)

Tohidi, Bahman; Chapoy, Antonin; Smellie, John; Puigdomenech, Ignasi

2010-12-01

The main aim of this work was to establish whether the pertaining pressure and temperature conditions and dissolved gas concentration in groundwater is conducive to gas hydrate formation using a modelling approach. The hydrate stability pressure-temperature zone of dissolved methane in the presence of salt has been obtained through calculations which show that a decrease in the system pressure and/or an increase in salt concentration favours hydrate formation, as both factors reduce equilibrium gas solubility in the aqueous phase. This behaviour is unlike that of the system including a gas phase, where the water phase is always saturated with methane, and hence the methane solubility in water is not a limiting factor. The main conclusion is that hydrate formation is not possible at the reported methane concentrations and water salinities for the Forsmark and Laxemar sites in Sweden and Olkiluoto in Finland. At the highest salinities and methane concentrations encountered, namely ∼0.00073 mole fraction methane and ∼10 mass % NaCl at a depth of 1,000 m in Olkiluoto, Finland, hydrates could form if the system temperatures and pressures are below 2.5 deg C and 60 bar, respectively, i.e. values that are much lower than those prevailing at that depth (∼20 deg C and ∼100 bar, respectively). Furthermore, the calculated results provide the necessary data to estimate the effect of increase in dissolved methane concentration on potential hydrate formation, as well as two phase flow. The available depth dependency of methane concentration at the sites studied in Sweden and Finland was used in another study to estimate the diffusive flow of methane in the rock volumes. These diffusion rates, which are highest at Olkiluoto, indicate that even if the conditions were to become favourable to methane hydrate formation, then it would take several millions of years before a thin layer of hydrates could be formed, a condition which is outside the required period of satisfactory

The potential for methane hydrate formation in deep repositories of spent nuclear fuel in granitic rocks

Energy Technology Data Exchange (ETDEWEB)

Tohidi, Bahman; Chapoy, Antonin (Hydrafact Ltd, Inst. of Petroleum Engineering, Heriot-Watt Univ., Edinburgh (United Kingdom)); Smellie, John (Conterra AB, Uppsala (Sweden)); Puigdomenech, Ignasi (Swedish Nuclear Fuel and Waste Management Co., Stockholm (Sweden))

2010-12-15

The main aim of this work was to establish whether the pertaining pressure and temperature conditions and dissolved gas concentration in groundwater is conducive to gas hydrate formation using a modelling approach. The hydrate stability pressure-temperature zone of dissolved methane in the presence of salt has been obtained through calculations which show that a decrease in the system pressure and/or an increase in salt concentration favours hydrate formation, as both factors reduce equilibrium gas solubility in the aqueous phase. This behaviour is unlike that of the system including a gas phase, where the water phase is always saturated with methane, and hence the methane solubility in water is not a limiting factor. The main conclusion is that hydrate formation is not possible at the reported methane concentrations and water salinities for the Forsmark and Laxemar sites in Sweden and Olkiluoto in Finland. At the highest salinities and methane concentrations encountered, namely approx0.00073 mole fraction methane and approx10 mass % NaCl at a depth of 1,000 m in Olkiluoto, Finland, hydrates could form if the system temperatures and pressures are below 2.5 deg C and 60 bar, respectively, i.e. values that are much lower than those prevailing at that depth (approx20 deg C and approx100 bar, respectively). Furthermore, the calculated results provide the necessary data to estimate the effect of increase in dissolved methane concentration on potential hydrate formation, as well as two phase flow. The available depth dependency of methane concentration at the sites studied in Sweden and Finland was used in another study to estimate the diffusive flow of methane in the rock volumes. These diffusion rates, which are highest at Olkiluoto, indicate that even if the conditions were to become favourable to methane hydrate formation, then it would take several millions of years before a thin layer of hydrates could be formed, a condition which is outside the required period of

IR reflectance spectroscopy of carbon dioxide clathrate hydrates. Implications for Saturn's icy moons.

Science.gov (United States)

Oancea, A.; Grasset, O.; Le Menn, E.; Bezacier, L.; Bollengier, O.; Le Mouélic, S.; Tobie, G.

2012-04-01

A CO2 spectral band was discovered by VIMS on the Saturn's satellites Dione, Hyperion, Iapetus and Phoebe [1]. The band position on the three first satellites corresponds to CO2 trapped in a complex material, but no indication exists whether this latter is water ice or some mineral or complex organic compound [1]. On Phoebe, the CO2 spectral band is consistent with solid CO2 or CO2 molecules trapped in the small cages of a clathrate hydrate structure [2]. It is thought that clathrate hydrates could play a significant role in the chemistry of the solar nebula [3] and in the physical evolution of astrophysical objects [4]. But so far, no clathrate hydrate structure has been observed in astrophysical environments. Moreover, identification of molecules trapped in a clathrate hydrate structure is extremely difficult because of the strong IR vibration modes of the water ice matrix. In this work, experimental IR reflectance spectra for CO2 clathrate hydrates are studied on grains and films. Clathrates are synthesized in a high pressure autoclave at low temperatures. IR spectral analysis is made with a low pressure and low temperature cryostat. These experimental conditions - 80 spectrum will be presented. A comparison between the absorption bands of CO2 clathrate hydrates obtained in our lab and CO2 absorption bands as detected by VIMS on the icy satellites of Saturn will be shown. This experimental work confirms that VIMS data are not consistent with the presence of structure I CO2 clathrate hydrates on the surface of the icy moons. Possibility of having metastable structure II still remains unsolved and will be discussed. [1] Dalton et al., Space Sci. Rev. 2010, 153 : 113-154. [2] Cruikshank D.P. et al, Icarus, 2010, 206: 561-572. [3] Mousis O. et al , Ap. J. 2009, 691: 1780-1786. [4] Choukroun M. et al, in Solar System Ices, edited by Castillo-Rogez, J. et al., 2011.

[The processes of methane formation and oxidation in the soils of the Russian arctic tundra].

Science.gov (United States)

Berestovskaia, Iu Iu; Rusanov, I I; Vasil'eva, L V; Pimenov, N V

2005-01-01

Methane emission from the following types of tundra soils was studied: coarse humic gleyey loamy cryo soil, peaty gley soil, and peaty gleyey midloamy cryo soil of the arctic tundra. All the soils studied were found to be potential sources of atmospheric methane. The highest values of methane emission were recorded in August at a soil temperature of 8-10 degrees C. Flooded parcels were the sources of atmospheric methane throughout the observation period. The rates of methane production and oxidation in tundra soils of various types at 5 and 15 degrees C were studied by the radioisotope method. Methane oxidation was found to occur in bog water, in the green part of peat moss, and in all the soil horizons studied. Methane formation was recorded in the horizons of peat, in clay with plant roots, and in peaty moss dust of the bogey parcels. At both temperatures, the methane oxidation rate exceeded the rate of methane formation in all the horizons of the mossy-lichen tundra and of the bumpy sinkhole complex. Methanogenesis prevailed only in a sedge-peat moss bog at 15 degrees C. Enrichment bacterial cultures oxidizing methane at 5 and 15 degrees C were obtained. Different types of methanotrophic bacteria were shown to be responsible for methane oxidation under these conditions. A representative of type I methylotrophs oxidized methane at 5 degrees C, and Methylocella tundrae, a psychroactive representative of an acidophilic methanotrophic genus Methylocella, at 15 degrees C.

Increase of methane formation by ethanol addition during continuous fermentation of biogas sludge.

Science.gov (United States)

Refai, Sarah; Wassmann, Kati; van Helmont, Sebastian; Berger, Stefanie; Deppenmeier, Uwe

2014-12-01

Very recently, it was shown that the addition of acetate or ethanol led to enhanced biogas formation rates during an observation period of 24 h. To determine if increased methane production rates due to ethanol addition can be maintained over longer time periods, continuous reactors filled with biogas sludge were developed which were fed with the same substrates as the full-scale reactor from which the sludge was derived. These reactors are well reflected conditions of a full-scale biogas plant during a period of 14 days. When the fermenters were pulsed with 50-100 mM ethanol, biomethanation increased by 50-150 %, depending on the composition of the biogas sludge. It was also possible to increase methane formation significantly when 10-20 mM pure ethanol or ethanolic solutions (e.g. beer) were added daily. In summary, the experiments revealed that "normal" methane production continued to take place, but ethanol led to production of additional methane.

Clathrate Hydrates for Thermal Energy Storage in Buildings: Overview of Proper Hydrate-Forming Compounds

Directory of Open Access Journals (Sweden)

Beatrice Castellani

2014-09-01

Full Text Available Increasing energy costs are at the origin of the great progress in the field of phase change materials (PCMs. The present work aims at studying the application of clathrate hydrates as PCMs in buildings. Clathrate hydrates are crystalline structures in which guest molecules are enclosed in the crystal lattice of water molecules. Clathrate hydrates can form also at ambient pressure and present a high latent heat, and for this reason, they are good candidates for being used as PCMs. The parameter that makes a PCM suitable to be used in buildings is, first of all, a melting temperature at about 25 °C. The paper provides an overview of groups of clathrate hydrates, whose physical and chemical characteristics could meet the requirements needed for their application in buildings. Simulations with a dynamic building simulation tool are carried out to evaluate the performance of clathrate hydrates in enhancing thermal comfort through the moderation of summer temperature swings and, therefore, in reducing energy consumption. Simulations suggest that clathrate hydrates have a potential in terms of improvement of indoor thermal comfort and a reduction of energy consumption for cooling. Cooling effects of 0.5 °C and reduced overheating hours of up to 1.1% are predicted.

Methane Formation by Flame-Generated Hydrogen Atoms in the Flame Ionization Detector

DEFF Research Database (Denmark)

Holm, Torkil; Madsen, Jørgen Øgaard

1996-01-01

, and conceivably all hydrocarbons are quantitatively converted into methane at temperatures below 600 C, that is, before the proper combustion has started. The splitting of the C-C bonds is preceded by hydrogenation of double and triple bonds and aromatic rings. The reactions, no doubt, are caused by hydrogen...... atoms, which are formed in the burning hydrogen and which diffuse into the inner core of the flame. The quantitative formation of methane appears to explain the "equal per carbon" rule for the detector response of hydrocarbons, since all carbons are "exchanged" for methane molecules....

Understanding lattice thermal conductivity in thermoelectric clathrates: A density functional theory study on binary Si-based type-I clathrates

Science.gov (United States)

Euchner, Holger; Pailhès, Stéphane; Giordano, Valentina M.; de Boissieu, Marc

2018-01-01

Despite their crystalline nature, thermoelectric clathrates exhibit a strongly reduced lattice thermal conductivity. While the reason for this unexpected behavior is known to lie in the peculiarities of the complex crystal structure and the interplay of the underlying guest-host framework, their respective roles are still not fully disentangled and understood. Our ab initio study of the most simple type-I clathrate phase, the binary compound Ba8Si46 and its derivatives Ba8 -xSi46 seeks to identify these mechanisms and provides insight into their origin. Indeed, the strongly decreased lattice thermal conductivity in thermoelectric clathrates is a consequence of a reduction of the acoustic phonon bandwidth, a lowering of the acoustic phonon group velocities, and the amplification of three-phonon-scattering processes. While the complexity of the crystal structure is demonstrated not to be the leading factor, the reasons are manifold. A modified Si-Si interaction causes a first decrease of the sound velocity, whereas the presence of flat Ba modes results in an additional lowering. These modes correspond to confined Bloch states that are localized on the Ba atoms and significantly increase the scattering phase space and, together with an increased anharmonicity of the interatomic interactions, strongly affect the phonon lifetimes.

The effect of classical and quantum dynamics on vibrational frequency shifts of H2 in clathrate hydrates

International Nuclear Information System (INIS)

Plattner, Nuria; Meuwly, Markus

2014-01-01

Vibrational frequency shifts of H 2 in clathrate hydrates are important to understand the properties and elucidate details of the clathrate structure. Experimental spectra of H 2 in clathrate hydrates have been measured for different clathrate compositions, temperatures, and pressures. In order to establish reliable relationships between the clathrate structure, dynamics, and observed frequencies, calculations of vibrational frequency shifts in different clathrate environments are required. In this study, a combination of classical molecular dynamics simulations, electronic structure calculations, and quantum dynamical simulation is used to calculate relative vibrational frequencies of H 2 in clathrate hydrates. This approach allows us to assess dynamical effects and simulate the change of vibrational frequencies with temperature and pressure. The frequency distributions of the H 2 vibrations in the different clathrate cage types agree favorably with experiment. Also, the simulations demonstrate that H 2 in the 5 12 cage is more sensitive to the details of the environment and to quantum dynamical effects, in particular when the cage is doubly occupied. We show that for the 5 12 cage quantum effects lead to frequency increases and double occupation is unlikely. This is different for the 5 12 6 4 cages for which higher occupation numbers than one H 2 per cage are likely

Heat-pump cool storage in a clathrate of freon

Science.gov (United States)

Tomlinson, J. J.

Presented are the analytical description and assessment of a unique heat pump/storage system in which the conventional evaporator of the vapor compression cycle is replaced by a highly efficient direct contract crystallizer. The thermal storage technique requires the formation of a refrigerant gas hydrate (a clathrate) and exploits an enthalpy of reaction comparable to the heat of fusion of ice. Additional system operational benefits include cool storage at the favorable temperatures of 4 to 7 C (40 to 45 F), and highly efficient heat transfer ates afforded by he direct contact mechanism. In addition, the experimental approach underway at ORNL to study such a system is discussed.

Formation and retention of methane in coal. Final report

Energy Technology Data Exchange (ETDEWEB)

Hucka, V.J.; Bodily, D.M.; Huang, H.

1992-05-15

The formation and retention of methane in coalbeds was studied for ten Utah coal samples, one Colorado coal sample and eight coal samples from the Argonne Premium Coal Sample Bank.Methane gas content of the Utah and Colorado coals varied from zero to 9 cm{sup 3}/g. The Utah coals were all high volatile bituminous coals. The Colorado coal was a gassy medium volatile bituminous coal. The Argonne coals cover a range or rank from lignite to low volatile bituminous coal and were used to determine the effect of rank in laboratory studies. The methane content of six selected Utah coal seams and the Colorado coal seam was measured in situ using a special sample collection device and a bubble desorbometer. Coal samples were collected at each measurement site for laboratory analysis. The cleat and joint system was evaluated for the coal and surrounding rocks and geological conditions were noted. Permeability measurements were performed on selected samples and all samples were analyzed for proximate and ultimate analysis, petrographic analysis, {sup 13}C NMR dipolar-dephasing spectroscopy, and density analysis. The observed methane adsorption behavior was correlated with the chemical structure and physical properties of the coals.

Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

Energy Technology Data Exchange (ETDEWEB)

Dureckova, Hana, E-mail: houci059@uottawa.ca; Woo, Tom K., E-mail: tom.woo@uottawa.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 5N6 (Canada); Alavi, Saman, E-mail: saman.alavi@nrc-cnrc.gc.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 5N6 (Canada); National Research Council of Canada, 100 Sussex Dr., Ottawa, Ontario K1N 6N5 (Canada); Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia V6T 1Z3 (Canada)

2016-01-28

Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br{sub 2} and Cl{sub 2} in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water–oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formation of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br{sub 2} and Cl{sub 2} clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br{sub 2} and Cl{sub 2} guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br{sub 2} and Cl{sub 2} guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br{sub 2} and Cl{sub 2} guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

Vibrational spectroscopic and quantum theoretical study of host-guest interactions in clathrates: I. Hofmann type clathrates

Directory of Open Access Journals (Sweden)

VLADIMIR M. PETRUSEVSKI

2000-06-01

Full Text Available Hofmann type clatharates are host-guest compounds with the general formula M(NH32M'(CN4·2G, in which M(NH32M'(CN4 is the host lattice and G is benzene, the guest molecule. In previous studies, host-guest interactions have been investigated by analyzing the RT and LNT vibrational (infrared, far infrared and Raman spectra of these clathrates. All the observed changes in the vibrational spectra of these clathrates are referred to a host-guest interaction originating from weak hydrogen bonding between the ammonia hydrogen atoms from the host lattice and the p electron cloud of the guest (benzene molecules. In order to obtain an insight into the relative importance of the local crystalline field vs. the anharmonicity effects on the spectroscopic properties of the guest species upon enclathration, as well as to explain the observed band shifts and splittings, several quantum theoretical approaches are proposed.

Capillary pressure controlled methane hydrate and ice growth-melting patterns in porous media : synthetic silica versus natural sandstone

Energy Technology Data Exchange (ETDEWEB)

Anderson, R.; Tohidi, B.; Webber, B. [Heriot-Watt Univ., Centre for Gas Research, Edinburgh (United Kingdom). Inst. of Petroleum Engineering

2008-07-01

Although naturally-occurring gas hydrates (or clathrate hydrates) in marine sediments can pose a hazard to deepwater hydrocarbon production operations, they represent a potential strategic energy reserve. Gas hydrates can also provide a means for deep ocean carbon dioxide disposal through sequestration/storage. They have long-term importance with respect to ocean margin stability, methane release, and global climate change. However, fundamental knowledge is still lacking regarding the mechanisms of hydrate growth, accumulation and distribution within the subsurface. Marine sediments which host gas hydrates are commonly fine-grained silts, muds, and clays with narrow mean pore diameters, leading to speculation that capillary phenomena could play a significant role in controlling hydrate distribution in the seafloor, and may be partly responsible for discrepancies between observed and predicted hydrate stability zone thicknesses. A close relationship between hydrate inhibition and pore size has been confirmed through previous laboratory studies. Clathrate stability has been significantly reduced in narrow pores. However, the focus of investigations has generally been hydrate dissociation conditions in porous media, with capillary controls on the equally important process of hydrate growth being largely overlooked. This paper presented the results of an experimental investigation into methane hydrate growth and dissociation equilibria in natural medium grained sandstone. The study also compared data with that previously measured for mesoporous silica glasses. The paper discussed solid-liquid phase behaviour in confined geometries including hysteresis in porous media. It also discussed the experimental equipment and method. It was concluded that, as for synthetic silicas, hydrate growth and dissociation in the sandstone were characterised by a measurable hysteresis between opposing transitions, notably hydrate (or ice) formation occurring at temperatures lower than

Confining CO2 inside the nanocavities of the sI clathrate: a quantum dynamics study

International Nuclear Information System (INIS)

Prosmiti, R; Arismendi-Arrieta, D J; Valdés, Á

2015-01-01

Clathrate hydrates have been found to occur naturally, and have been extensively studied due to their important industrial applications, such as the storage of the CO 2 from the atmosphere and control climate change. Thus, quantitative understanding of physical and chemical properties, as well as the factors that control the formation of CO 2 hydrates, on both macroscopic and microscopic levels is essential in several areas of physical science. (paper)

An ir study of M(1-propanethiol)2Ni(CN)4.G (M=Cd,Ni and G=benzene) clathrates

International Nuclear Information System (INIS)

Kartal, Z.; Tuerkoz, D.; Bahceli, S.

2004-01-01

Two Hofmann-propanethiol-type clathrates of the for M(1-propanethiol) 2 Ni(CN) 4 .G (M=Cd or Ni; G = benzene) have been prepared in the powder form. The 1-propanethiol (1-PT) molecules provide the cavities in which the quest benzene molecules in clathrate structure ar accommodated. The infrared investigations of the obtained clathrates indicate that these compounds are similar in structure to the other Hofmann-type clathrates (Authors)

High Pressure Properties of a Ba-Cu-Zn-P Clathrate-I

Directory of Open Access Journals (Sweden)

Juli-Anna Dolyniuk

2016-08-01

Full Text Available The high pressure properties of the novel tetrel-free clathrate, Ba8Cu13.1Zn3.3P29.6, were investigated using synchrotron powder X-ray diffraction. The pressure was applied using a diamond anvil cell. No structural transitions or decomposition were detected in the studied pressure range of 0.1–7 GPa. The calculated bulk modulus for Ba8Cu13.1Zn3.3P29.6 using a third-order Birch-Murnaghan equation of state is 65(6 GPa at 300 K. This bulk modulus is comparable to the bulk moduli of Ge- and Sn-based clathrates, like A8Ga16Ge30 (A = Sr, Ba and Sn19.3Cu4.7P22I8, but lower than those for the transition metal-containing silicon-based clathrates, Ba8TxSi46−x, T = Ni, Cu; 3 ≤ x ≤ 5.

Paraffin molecule mobility in channel clathrates of urea on spectroscopic NMR relaxation data

CERN Document Server

Kriger, Y G; Chekhova, G N

2001-01-01

The temperature dependences of the protons spin-lattice relaxation time (T sub I) in the channel clathrates of urea with paraffins are measured. The data on the T sub I are interpreted within the frames of the model of the paraffins molecules and their fragments orientation in the clathrate channels. The dynamics peculiarities are connected with the disproportion effects of these compounds

Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

Science.gov (United States)

Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

2010-01-14

The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

Hydrogen storage in clathrate hydrates: Current state of the art and future directions

International Nuclear Information System (INIS)

Veluswamy, Hari Prakash; Kumar, Rajnish; Linga, Praveen

2014-01-01

Hydrogen is looked upon as the next generation clean energy carrier, search for an efficient material and method for storing hydrogen has been pursued relentlessly. Improving hydrogen storage capacity to meet DOE targets has been challenging and research efforts are continuously put forth to achieve the set targets and to make hydrogen storage a commercially realizable process. This review comprehensively summarizes the state of the art experimental work conducted on the storage of hydrogen as hydrogen clathrates both at the molecular level and macroscopic level. It identifies future directions and challenges for this exciting area of research. Hydrogen storage capacities of different clathrate structures – sI, sII, sH, sVI and semi clathrates have been compiled and presented. In addition, promising new approaches for increasing hydrogen storage capacity have been described. Future directions for achieving increased hydrogen storage and process scale up have been outlined. Despite few limitations in storing hydrogen in the form of clathrates, this domain receives prominent attention due to more environmental-friendly method of synthesis, easy recovery of molecular hydrogen with minimum energy requirement, and improved safety of the process

Thermodynamic and structural signatures of water-driven methane-methane attraction in coarse-grained mW water.

Science.gov (United States)

Song, Bin; Molinero, Valeria

2013-08-07

Hydrophobic interactions are responsible for water-driven processes such as protein folding and self-assembly of biomolecules. Microscopic theories and molecular simulations have been used to study association of a pair of methanes in water, the paradigmatic example of hydrophobic attraction, and determined that entropy is the driving force for the association of the methane pair, while the enthalpy disfavors it. An open question is to which extent coarse-grained water models can still produce correct thermodynamic and structural signatures of hydrophobic interaction. In this work, we investigate the hydrophobic interaction between a methane pair in water at temperatures from 260 to 340 K through molecular dynamics simulations with the coarse-grained monatomic water model mW. We find that the coarse-grained model correctly represents the free energy of association of the methane pair, the temperature dependence of free energy, and the positive change in entropy and enthalpy upon association. We investigate the relationship between thermodynamic signatures and structural order of water through the analysis of the spatial distribution of the density, energy, and tetrahedral order parameter Qt of water. The simulations reveal an enhancement of tetrahedral order in the region between the first and second hydration shells of the methane molecules. The increase in tetrahedral order, however, is far from what would be expected for a clathrate-like or ice-like shell around the solutes. This work shows that the mW water model reproduces the key signatures of hydrophobic interaction without long ranged electrostatics or the need to be re-parameterized for different thermodynamic states. These characteristics, and its hundred-fold increase in efficiency with respect to atomistic models, make mW a promising water model for studying water-driven hydrophobic processes in more complex systems.

Water Transfer Characteristics during Methane Hydrate Formation Processes in Layered Media

Directory of Open Access Journals (Sweden)

Yousheng Deng

2011-08-01

Full Text Available Gas hydrate formation processes in porous media are always accompanied by water transfer. To study the transfer characteristics comprehensively, two kinds of layered media consisting of coarse sand and loess were used to form methane hydrate in them. An apparatus with three PF-meter sensors detecting water content and temperature changes in media during the formation processes was applied to study the water transfer characteristics. It was experimentally observed that the hydrate formation configurations in different layered media were similar; however, the water transfer characteristics and water conversion ratios were different.

Measurement of Clathrate Hydrate Thermodynamic Stability in the Presence of Ammonia

Science.gov (United States)

Dunham, Marc

2012-01-01

There is a lack of data available for the stability of clathrate hydrates in the presence of ammonia for low-to-moderate pressures in the 0-10 MPa range. Providing such data will allow for a better understanding of natural mass transfer processes on celestial bodies like Titan and Enceladus, on which destabilization of clathrates may be responsible for replenishment of gases in the atmosphere. The experimental process utilizes a custom-built gas handling system (GHS) and a cryogenic calorimeter to allow for the efficient testing of samples under varying pressures and gas species.

Methane Seepage on Mars: Where to Look and Why.

Science.gov (United States)

Oehler, Dorothy Z; Etiope, Giuseppe

2017-12-01

Words: Mars-Methane-Seepage-Clathrate-Fischer-Tropsch-Serpentinization. Astrobiology 17, 1233-1264.

Methane cycling. Nonequilibrium clumped isotope signals in microbial methane.

Science.gov (United States)

Wang, David T; Gruen, Danielle S; Lollar, Barbara Sherwood; Hinrichs, Kai-Uwe; Stewart, Lucy C; Holden, James F; Hristov, Alexander N; Pohlman, John W; Morrill, Penny L; Könneke, Martin; Delwiche, Kyle B; Reeves, Eoghan P; Sutcliffe, Chelsea N; Ritter, Daniel J; Seewald, Jeffrey S; McIntosh, Jennifer C; Hemond, Harold F; Kubo, Michael D; Cardace, Dawn; Hoehler, Tori M; Ono, Shuhei

2015-04-24

Methane is a key component in the global carbon cycle, with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply substituted "clumped" isotopologues (for example, (13)CH3D) has recently emerged as a proxy for determining methane-formation temperatures. However, the effect of biological processes on methane's clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on (13)CH3D abundances and results in anomalously elevated formation-temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters. Copyright © 2015, American Association for the Advancement of Science.

Methane hydrate synthesis from ice: Influence of pressurization and ethanol on optimizing formation rates and hydrate yield

Science.gov (United States)

Chen, Po-Chun.; Huang, Wuu-Liang; Stern, Laura A.

2010-01-01

Polycrystalline methane gas hydrate (MGH) was synthesized using an ice-seeding method to investigate the influence of pressurization and ethanol on the hydrate formation rate and gas yield of the resulting samples. When the reactor is pressurized with CH4 gas without external heating, methane hydrate can be formed from ice grains with yields up to 25% under otherwise static conditions. The rapid temperature rise caused by pressurization partially melts the granular ice, which reacts with methane to form hydrate rinds around the ice grains. The heat generated by the exothermic reaction of methane hydrate formation buffers the sample temperature near the melting point of ice for enough time to allow for continuous hydrate growth at high rates. Surprisingly, faster rates and higher yields of methane hydrate were found in runs with lower initial temperatures, slower rates of pressurization, higher porosity of the granular ice samples, or mixtures with sediments. The addition of ethanol also dramatically enhanced the formation of polycrystalline MGH. This study demonstrates that polycrystalline MGH with varied physical properties suitable for different laboratory tests can be manufactured by controlling synthesis procedures or parameters. Subsequent dissociation experiments using a gas collection apparatus and flowmeter confirmed high methane saturation (CH 4·2O, with n = 5.82 ± 0.03) in the MGH. Dissociation rates of the various samples synthesized at diverse conditions may be fitted to different rate laws, including zero and first order.

Structure and physical properties of type-I clathrate solid-solution Ba8PtxGe46-x-y□y (□=vacancy)

International Nuclear Information System (INIS)

Melnychenko-Koblyuk, N.; Grytsiv, A.; Rogl, P.; Rotter, M.; Lackner, R.; Bauer, E.; Fornasari, L.; Marabelli, F.; Giester, G.

2007-01-01

Formation, crystal chemistry, and physical properties were investigated for the solid-solution Ba 8 Pt x Ge 46-x-y □ y (□ is a vacancy) deriving from binary clathrate Ba 8 Ge 43 □ 3 with a solubility limit of ∼3.5 Pt atoms/f.u. at T=800 deg. C. Structural investigations throughout the homogeneity region confirm isotypism with the cubic primitive clathrate type-I structure (space group type Pm3n) and lattice parameters ranging from a=1.0657(2) nm for Ba 8 Ge 43 □ 3 to a=1.0752(2) nm for Ba 8 Pt 3.5 Ge 41.5 □ 1.0 . Phase relations for the region concerning the clathrate solution were derived at subsolidus temperatures as well as at 800 deg. C. Transport properties evidence electrons as the majority charge carriers in the system with a slight dependency on the Pt content. The system is located close to a semiconducting regime with a gap in the electronic density of states of a few thousand K. No low temperature maximum is obvious from thermal conductivity which is dominated by the lattice contribution. Thermal conductivity furthermore documents a high efficiency of phonon scattering on vacancies

Methane production from formate, acetate and H2/CO2; focusing on kinetics and microbial characterization

DEFF Research Database (Denmark)

Pan, Xiaofang; Angelidaki, Irini; Alvarado-Morales, Merlin

2016-01-01

For evaluating the methanogenesis from typical methanogenic precursors (formate, acetate and H-2/CO2), CH4 production kinetics were investigated at 37 +/- 1 degrees C in batch anaerobic digestion tests and stimulated by modified Gompertz model. The results showed that maximum methanation rate from...... formate, acetate and H-2/CO2 were 19.58 +/- 0.49, 42.65 +/- 1.17 and 314.64 +/- 3.58 N mL/gVS/d in digested manure system and 6.53 +/- 0.31, 132.04 +/- 3.96 and 640.16 +/- 19.92 N mL/gVS/d in sewage sludge system during second generation incubation. Meanwhile the model could not fit well in granular...... sludge system, while the rate of formate methanation was faster than from H-2/CO2 and acetate. Considering both the kinetic results and microbial assay we could conclude that H-2/CO2 methanation was the fastest methanogenic step in digested manure and sewage sludge system with Methanomicrobiales...

Concentrations and carbon isotope compositions of methane in the cored sediments from offshore SW Taiwan

Energy Technology Data Exchange (ETDEWEB)

Chuang, P.C.; Yang, T.F.; Hong, W.L. [National Taiwan Univ., Taipei, Taiwan (China). Dept. of Geosciences; Lin, S.; Chen, J.C. [National Taiwan Univ., Taipei, Taiwan (China). Inst. of Oceanography; Sun, C.H. [CPC Corp., Wen Shan, Miaoli, Taiwan (China). Exploration and Development Research Inst.; Wang, Y. [Central Geological Survey, MOEA, Taipei, Taiwan (China)

2008-07-01

Gas hydrates are natural occurring solids that contain natural gases, mainly methane, within a rigid lattice of water molecules. They are a type of non-stoichiometric clathrates and metastable crystal products in low temperature and high pressure conditions and are widely distributed in oceans and in permafrost regions around the world. Gas hydrates have been considered as potential energy resources for the future since methane is the major gas inside gas hydrates. Methane is also a greenhouse gas that might affect the global climates from the dissociations of gas hydrates. Bottom simulating reflections (BSRs) have been found to be widely distributed in offshore southwestern Taiwan therefore, inferring the existence of potential gas hydrates underneath the seafloor sediments. This paper presented a study that involved the systematic collection of sea waters and cored sediments as well as the analysis of the gas composition of pore-space of sediments through ten cruises from 2003 to 2006. The paper discussed the results in terms of the distribution of methane concentrations in bottom waters and cored sediments; methane fluxes in offshore southwestern Taiwan; and isotopic compositions of methane in pore spaces of cored sediments. It was concluded that the carbon isotopic compositions of methane demonstrated that biogenic gas source was dominated at shallower depth. However, some thermogenic gases might be introduced from deeper source in this region. 15 refs., 5 figs.

Roles of Clathrate Hydrates in Crustal Heating and Volatile Storage/Release on Earth, Mars, and Beyond

Science.gov (United States)

Kargel, J. S.; Beget, J.; Furfaro, R.; Prieto-Ballesteros, O.; Palmero-Rodriguez, J. A.

2007-12-01

Clathrate hydrates are stable through much of the Solar System. These materials and hydrate-like amorphous associations of water with N2, CO, CH4, CO2, O2 and other molecules could, in fact, constitute the bulk of the non-rock components of some icy satellites, comets, and Kuiper Belt Objects. CO2 clathrate is thermodynamically stable at the Martian South Pole surface and could form a significant fraction of both Martian polar caps and icy permafrost distributed across one-third of the Martian surface. CH4 clathrate is the largest clathrate material in Earth's permafrost and cold seafloor regions, and it may be a major volatile reservoir on Mars, too. CO2 clathrate is less abundant on Earth but it might store most of Mars' CO2 inventory and thus may be one of the critical components in the climate system of that planet, just as CH4 clathrate is for Earth. These ice-like phases not only store biologically, geologically, and climatologically important gases, but they also are natural thermal insulators. Thus, they retard the conductive flow of geothermal heat, and thick accumulations of them can modify geotherms, cause brines to exist where otherwise they would not, and induce low-grade metamorphism of upper crustal rocks underlying the insulating bodies. This mechanism of crustal heating may be especially important in assisting hydrogeologic activity on Mars, gas-rich carbonaceous asteroids, icy satellites, and Kuiper Belt Objects. These worlds, compared to Earth, are comparatively energy starved and frozen but may partly make up for their deficit of joules by having large accumulations of joule-conserving hydrates. Thick, continuous layers of clathrate may seal in gases and produce high gas fugacities in aquifers underlying the clathrates, thus producing gas-rich reservoirs capable of erupting violently. This may have happened repeatedly in Earth history, with global climatic consequences for abrupt climate change. We have hypothesized that such eruptions may have

Methane Recycling During Burial of Methane Hydrate-Bearing Sediments

Science.gov (United States)

You, K.; Flemings, P. B.

2017-12-01

We quantitatively investigate the integral processes of methane hydrate formation from local microbial methane generation, burial of methane hydrate with sedimentation, and methane recycling at the base of the hydrate stability zone (BHSZ) with a multiphase multicomponent numerical model. Methane recycling happens in cycles, and there is not a steady state. Each cycle starts with free gas accumulation from hydrate dissociation below the BHSZ. This free gas flows upward under buoyancy, elevates the hydrate saturation and capillary entry pressure at the BHSZ, and this prevents more free gas flowing in. Later as this layer with elevated hydrate saturation is buried and dissociated, the large amount of free gas newly released and accumulated below rapidly intrudes into the hydrate stability zone, drives rapid hydrate formation and creates three-phase (gas, liquid and hydrate) equilibrium above the BHSZ. The gas front retreats to below the BHSZ until all the free gas is depleted. The shallowest depth that the free gas reaches in one cycle moves toward seafloor as more and more methane is accumulated to the BHSZ with time. More methane is stored above the BHSZ in the form of concentrated hydrate in sediments with relatively uniform pore throat, and/or with greater compressibility. It is more difficult to initiate methane recycling in passive continental margins where the sedimentation rate is low, and in sediments with low organic matter content and/or methanogenesis reaction rate. The presence of a permeable layer can store methane for significant periods of time without recycling. In a 2D system where the seafloor dips rapidly, the updip gas flow along the BHSZ transports more methane toward topographic highs where methane gas and elevated hydrate saturation intrude deeper into the hydrate stability zone within one cycle. This could lead to intermittent gas venting at seafloor at the topographic highs. This study provides insights on many phenomenon associated with

Short-term effect of acetate and ethanol on methane formation in biogas sludge.

Science.gov (United States)

Refai, Sarah; Wassmann, Kati; Deppenmeier, Uwe

2014-08-01

Biochemical processes in biogas plants are still not fully understood. Especially, the identification of possible bottlenecks in the complex fermentation processes during biogas production might provide potential to increase the performance of biogas plants. To shed light on the question which group of organism constitutes the limiting factor in the anaerobic breakdown of organic material, biogas sludge from different mesophilic biogas plants was examined under various conditions. Therefore, biogas sludge was incubated and analyzed in anaerobic serum flasks under an atmosphere of N2/CO2. The batch reactors mirrored the conditions and the performance of the full-scale biogas plants and were suitable test systems for a period of 24 h. Methane production rates were compared after supplementation with substrates for syntrophic bacteria, such as butyrate, propionate, or ethanol, as well as with acetate and H2+CO2 as substrates for methanogenic archaea. Methane formation rates increased significantly by 35 to 126 % when sludge from different biogas plants was supplemented with acetate or ethanol. The stability of important process parameters such as concentration of volatile fatty acids and pH indicate that ethanol and acetate increase biogas formation without affecting normally occurring fermentation processes. In contrast to ethanol or acetate, other fermentation products such as propionate, butyrate, or H2 did not result in increased methane formation rates. These results provide evidence that aceticlastic methanogenesis and ethanol-oxidizing syntrophic bacteria are not the limiting factor during biogas formation, respectively, and that biogas plant optimization is possible with special focus on methanogenesis from acetate.

Synthesis and thermoelectric properties of rare earth Yb-doped Ba8−xYbxSi30Ga16 clathrates

International Nuclear Information System (INIS)

Liu, Lihua; Li, Feng; Wei, Yuping; Chen, Ning; Bi, Shanli; Qiu, Hongmei; Cao, Guohui; Li, Yang

2014-01-01

Highlights: • Samples with the chemical formula Ba8− x Yb x Si 30 Ga 16 (x = 0, 0.5, 0.7, 1 and 1.5) were prepared. • Some Yb atoms enter the clathrate lattice to replace Ba, while other Yb atoms are oxidized as Yb 2 O 3 . • The thermal conductivity decreases with Yb-doping. • Thermoelectric figure of merit ZT significantly increased. -- Abstract: The potential thermoelectric and magnetic application of clathrate materials with rare-earth doping is the focus of much of the recent research activity in the synthetic material physics and chemistry. A series of clathrate samples with the chemical formula Ba 8−x Yb x Si 30 Ga 16 (x = 0, 0.5, 0.7, 1 and 1.5) were prepared by combining arc melting, ball milling and spark plasma sintering (SPS) techniques. X-ray diffraction and scanning electronic microscopy combined with energy-dispersive X-ray spectroscopy (EDS) analysis showed the dominant phase to be the type-I clathrate. Whereas, X-ray structural refinement and EDS analysis indicated that some Yb atoms enter the clathrate lattice to replace Ba at 2a sites, while other Yb atoms are oxidized as Yb 2 O 3 precipitated around grain boundaries. The solid solubility of Yb into clathrate lattice yielded x ∼ 0.3. Comparative analysis between Yb-doped and Yb-free clathrates showed that the thermal conductivity decreases with Yb-doping. Consequently, thermoelectric figure of merit ZT significantly increased

Synthesis and thermal conductivity of type II silicon clathrates

Science.gov (United States)

Beekman, M.; Nolas, G. S.

2006-08-01

We have synthesized and characterized polycrystalline Na 1Si 136 and Na 8Si 136, compounds possessing the type II clathrate hydrate crystal structure. Resistivity measurements from 10 to 300 K indicate very large resistivities in this temperature range, with activated temperature dependences indicative of relatively large band gap semiconductors. The thermal conductivity is very low; two orders-of-magnitude lower than that of diamond-structure silicon at room temperature. The thermal conductivity of Na 8Si 136 displays a temperature dependence that is atypical of crystalline solids and more indicative of amorphous materials. This work is part of a continuing effort to explore the many different compositions and structure types of clathrates, a class of materials that continues to be of interest for scientific and technological applications.

Electrochemical stability of ionic clathrate hydrates and their structural consideration

International Nuclear Information System (INIS)

Lee, Wonhee; Lim, Dongwook; Lee, Huen

2013-01-01

Although electrochemical stability is an essential factor in relation to the potential applications of ionic clathrate hydrates to solid electrolytes, most studies regarding the proton conductors have focused on their ionic conductivity and thermal stability. Solid electrolytes in various electrochemical devices have to endure the applied potentials; thus, we examined the linear sweep voltammograms of various tetraalkylammonium hydroxide hydrates in order to shed light on the trend of electrochemical stability depending on the hydrate structure. We revealed that the electrochemical stability of Me 4 NOH hydrates is mainly affected by both their ionic concentration and cage occupancy. In particular, the true clathrate structures of β-Me 4 NOH hydrates are more electrochemically stable than their α-forms that possess partially broken hydrogen bonds. We also observed that the binary THF–Pr 4 NOH and pure Bu 4 NOH clathrate hydrates exhibit greater electrochemical stability than those of pure Me 4 NOH hydrates having lower or similar ionic concentrations. These results are considered to arise from the fact that each of the Pr 4 N + and Bu 4 N + ions occupies an extended space comprising four cages, which leads to stabilization of the larger unit, whereas a Me 4 N + ion is completely included only in one cage

Methane emissions from oceans, coasts, and freshwater habitats: New perspectives and feedbacks on climate

Science.gov (United States)

Hamdan, Leila J.; Wickland, Kimberly P.

2016-01-01

Methane is a powerful greenhouse gas, and atmospheric concentrations have risen 2.5 times since the beginning of the Industrial age. While much of this increase is attributed to anthropogenic sources, natural sources, which contribute between 35% and 50% of global methane emissions, are thought to have a role in the atmospheric methane increase, in part due to human influences. Methane emissions from many natural sources are sensitive to climate, and positive feedbacks from climate change and cultural eutrophication may promote increased emissions to the atmosphere. These natural sources include aquatic environments such as wetlands, freshwater lakes, streams and rivers, and estuarine, coastal, and marine systems. Furthermore, there are significant marine sediment stores of methane in the form of clathrates that are vulnerable to mobilization and release to the atmosphere from climate feedbacks, and subsurface thermogenic gas which in exceptional cases may be released following accidents and disasters (North Sea blowout and Deepwater Horizon Spill respectively). Understanding of natural sources, key processes, and controls on emission is continually evolving as new measurement and modeling capabilities develop, and different sources and processes are revealed. This special issue of Limnology and Oceanography gathers together diverse studies on methane production, consumption, and emissions from freshwater, estuarine, and marine systems, and provides a broad view of the current science on methane dynamics of aquatic ecosystems. Here, we provide a general overview of aquatic methane sources, their contribution to the global methane budget, and key uncertainties. We then briefly summarize the contributions to and highlights of this special issue.

Observation of interstitial molecular hydrogen in clathrate hydrates.

Science.gov (United States)

Grim, R Gary; Barnes, Brian C; Lafond, Patrick G; Kockelmann, Winfred A; Keen, David A; Soper, Alan K; Hiratsuka, Masaki; Yasuoka, Kenji; Koh, Carolyn A; Sum, Amadeu K

2014-09-26

The current knowledge and description of guest molecules within clathrate hydrates only accounts for occupancy within regular polyhedral water cages. Experimental measurements and simulations, examining the tert-butylamine + H2 + H2O hydrate system, now suggest that H2 can also be incorporated within hydrate crystal structures by occupying interstitial sites, that is, locations other than the interior of regular polyhedral water cages. Specifically, H2 is found within the shared heptagonal faces of the large (4(3)5(9)6(2)7(3)) cage and in cavities formed from the disruption of smaller (4(4)5(4)) water cages. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 in solids and reveals new insight into guest-guest and guest-host interactions in clathrate hydrates, with potential implications in increasing overall energy storage properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Global Assessment of Methane Gas Hydrates: Outreach for the public and policy makers

Science.gov (United States)

Beaudoin, Yannick

2010-05-01

The United Nations Environment Programme (UNEP), via its official collaborating center in Norway, GRID-Arendal, is in the process of implementing a Global Assessment of Methane Gas Hydrates. Global reservoirs of methane gas have long been the topic of scientific discussion both in the realm of environmental issues such as natural forces of climate change and as a potential energy resource for economic development. Of particular interest are the volumes of methane locked away in frozen molecules known as clathrates or hydrates. Our rapidly evolving scientific knowledge and technological development related to methane hydrates makes these formations increasingly prospective to economic development. In addition, global demand for energy continues, and will continue to outpace supply for the foreseeable future, resulting in pressure to expand development activities, with associated concerns about environmental and social impacts. Understanding the intricate links between methane hydrates and 1) natural and anthropogenic contributions to climate change, 2) their role in the carbon cycle (e.g. ocean chemistry) and 3) the environmental and socio-economic impacts of extraction, are key factors in making good decisions that promote sustainable development. As policy makers, environmental organizations and private sector interests seek to forward their respective agendas which tend to be weighted towards applied research, there is a clear and imminent need for a an authoritative source of accessible information on various topics related to methane gas hydrates. The 2008 United Nations Environment Programme Annual Report highlighted methane from the Arctic as an emerging challenge with respect to climate change and other environmental issues. Building upon this foundation, UNEP/GRID-Arendal, in conjunction with experts from national hydrates research groups from Canada, the US, Japan, Germany, Norway, India and Korea, aims to provide a multi-thematic overview of the key

Growth mode transition of tetrahydrofuran clathrate hydrates in the guest/host concentration boundary layer.

Science.gov (United States)

Sabase, Yuichiro; Nagashima, Kazushige

2009-11-19

Clathrate hydrates are known to form a thin film along a guest/host boundary. We present here the first report of tetrahydrofuran (THF) clathrate hydrate formation in a THF/water concentration boundary layer. We found that the THF-water system also forms a hydrate film separating the guest/host phases. The lateral growth rate of the film increases as supercooling increases. The thickness of the film at the growth tip decreases as supercooling and the lateral growth rate increase. These tendencies are consistent with reports of experiments for other hydrates and predictions of heat-transfer models. After film formation and slight melting, two types of growth modes are observed, depending on temperature T. At T = 3.0 degrees C, the film slowly thickens. The thickening rate is much lower than the lateral growth rate, as reported for other hydrates. At T agglomerate of small polycrystalline hydrates forms in each phase. Grain boundaries in the film and pore spaces in the agglomerate act as paths for permeation of each liquid. Timing when continuous nucleation starts is dominantly controlled by the time of initiation of liquid permeation through the film. Digital particle image velocimetry analysis of the agglomerate shows that it expands not by growth at the advancing front but rather by continuous nucleation in the interior. Expansion rates of the agglomerate tend to be higher for the cases of multipermeation paths in the film and the thinner film. We suppose that the growth mode transition to continuous nucleation is caused by the memory effect due to slight melting of the hydrate film.

Synergistic methane formation on pyrolytic graphite due to combined H+ ion and H0 atom impact

International Nuclear Information System (INIS)

Haasz, A.A.; Davis, J.W.; Auciello, O.; Strangeby, P.C.; Vietzke, E.; Flaskamp, K.; Philipps, V.

1986-06-01

Exposure of graphite to multispecies hydrogenic impact, as is the case in tokamaks, could lead to synergistic mechanisms resulting in an enhancement of methane formation, and consequently in increased carbon erosion. We present results obtained in controlled experiments in our laboratories in Toronto and Juelich for the synergistic methane production due to combined sub-eV H 0 atoms and energetic H + ion impact on pyrolytic graphite. Flux densities were 10 14 -2x10 16 H 0 /cm 2 s for the sub-eV H 0 atoms and 6x10 12 -5x10 15 H + /cm 2 for H + ions of 300 eV to 2.5 keV energy. Synergistic factors (defined as the ratio of methane formation rate due to combined H 0 and H + fluxes to the sum of the formation rates due to separate species impact) ranged from about 1.5-15 for the experimental parameters used. In addition, a spectrum of formed hydrocarbons in the synergistic reaction of H + and H 0 on graphite is presented

Thermodynamic promotion of carbon dioxide-clathrate hydrate formation by tetrahydrofuran, cyclopentane and their mixtures

DEFF Research Database (Denmark)

Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

2013-01-01

Gas clathrate hydrate dissociation pressures are reported for mixtures of carbon dioxide, water and thermodynamic promoters forming structure II hydrates.Hydrate (H)-aqueous liquid (Lw)-vapour (V) equilibrium pressures for the ternary system composed of water, tetrahydrofuran (THF), and carbon....... It is shown that upon adding THF to the pure aqueous phase to form a 4mass percent solution, the equilibrium pressure of the formed hydrates may be lowered compared to the ternary system of water, cyclopentane and carbon dioxide. © 2013 Elsevier Ltd....... dioxide (CO2), with 5.0mole percent THF in the initial aqueous phase, are presented in the temperature range from 283.3K to 285.2K. At 283.3K, the three-phase equilibrium pressure is determined to be 0.61MPa (absolute pressure).Four-phase hydrate (H)-aqueous liquid (Lw)-organic liquid (La)-vapour (V...

The inhibition of methane hydrate formation by water alignment underneath surface adsorption of surfactants

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Ngoc N.; Nguyen, Anh V.; Dang, Liem X.

2017-06-01

Sodium dodecyl sulfate (SDS) has been widely shown to strongly promote the formation of methane hydrate. Here we show that SDS displays an extraordinary inhibition effect on methane hydrate formation when the surfactant is used in sub-millimolar concentration (around 0.3 mM). We have also employed Sum Frequency Generation vibrational spectroscopy (SFG) and molecular dynamics simulation (MDS) to elucidate the molecular mechanism of this inhibition. The SFG and MDS results revealed a strong alignment of water molecules underneath surface adsorption of SDS in its sub-millimolar solution. Interestingly, both the alignment of water and the inhibition effect (in 0.3 mM SDS solution) went vanishing when an oppositely-charged surfactant (tetra-n-butylammonium bromide, TBAB) was suitably added to produce a mixed solution of 0.3 mM SDS and 3.6 mM TBAB. Combining structural and kinetic results, we pointed out that the alignment of water underneath surface adsorption of dodecyl sulfate (DS-) anions gave rise to the unexpected inhibition of methane hydration formation in sub-millimolar solution of SDS. The adoption of TBAB mitigated the SDS-induced electrostatic field at the solution’s surface and, therefore, weakened the alignment of interfacial water which, in turn, erased the inhibition effect. We discussed this finding using the concept of activation energy of the interfacial formation of gas hydrate. The main finding of this work is to reveal the interplay of interfacial water in governing gas hydrate formation which sheds light on a universal molecular-scale understanding of the influence of surfactants on gas hydrate formation. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.

Observation of ice sheet formation on methane and ethane gas hydrates using a scanning confocal microscopy

Energy Technology Data Exchange (ETDEWEB)

Nagao, J.; Shimomura, N.; Ebinuma, T.; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohira, Sapporo (Japan). Methane Hydrate Research Lab.

2008-07-01

Interest in gas hydrates has increased in recent years due to the discovery of large deposits under the ocean floor and in permafrost regions. Natural gas hydrates, including methane, is expected to become a new energy source and a medium for energy storage and transportation. Gas hydrates consist of an open network of water molecules that are hydrogen-bonded in a similar manner to ice. Gas molecules are interstitially engaged under high pressures and low temperatures. Although the dissociation temperature of methane hydrate under atmospheric pressure is about 193 K, studies have shown that methane hydrate can be stored at atmospheric pressure and 267 K for 2 years. Because of this phenomenon, known as self-preservation, transportation and storage of methane hydrate can occur at temperature conditions milder than those for liquefied methane gas at atmospheric pressure. This study examined the surface changes of methane and ethane hydrates during dissociation using an optical microscope and confocal scanning microscope (CSM). This paper reported on the results when the atmospheric gas pressure was decreased. Ice sheets formed on the surfaces of methane and ethane gas hydrates due to depressurizing dissociation of methane and ethane hydrates when the methane and ethane gas pressures were decreased at designated temperatures. The dissociation of methane gas hydrate below below 237 K resulted in the generation of small ice particles on the hydrate surface. A transparent ice sheet formed on the hydrate surface above 242 K. The thickness of the ice sheet on the methane hydrate surface showed the maximum of ca. 30 {mu}m at 253 K. In the case of ethane hydrates, ice particles and ice sheets formed below 262 and 267 respectively. Since the ice particles and ice sheets were formed by water molecules generated during the gas hydrate dissociation, the mechanism of ice sheet formation depends on the dissociation rate of hydrate, ice particle sintering rate, and water molecule

Clathrates - An Exploration of the Chemistry of Caged Compounds

Indian Academy of Sciences (India)

also found on the icy moons of our solar system, at Saturn and .... This mineral loses water rapidly on heating and seemed ... The prototype of clathrate-I structure for gas hydrate has a .... Useful for studies of air pollution, process control and.

Early Mars serpentinization-derived CH4 reservoirs, H2 induced warming and paleopressure evolution

Science.gov (United States)

Lasue, J.; Chassefiere, E.; Langlais, B.; Quesnel, Y.

2016-12-01

CH4 has been observed on Mars both by remote sensing and in situ during the past 15 years. Early Mars serpentinization is one possible abiotic mechanism that could not only produce methane, but also explain the observed Martian remanent magnetic field. Assuming a cold early Mars, a cryosphere could trap such CH4 as clathrates in stable form at depth. We recently estimated the maximum storage capacity of such clathrate layer to be about 2x1019 to 2x1020 moles of methane. Such reservoirs may be stable or unstable, depending on many factors that are poorly constrained: major and sudden geological events such as the Tharsis bulge formation, the Hellas impact or the martian polar wander, could have destabilized the clathrates early in the history of the planet and released large quantities of gas in the atmosphere. Here we estimate the associated amounts of serpentinization-derived CH4 stored in the cryosphere that have been released to the atmosphere at the end of the Noachian and the beginning of the Hesperian. Due to rapid clathrate dissociation and photochemical conversion of CH4 to H2, these episodes of massive CH4 release may have resulted in transient H2-rich atmospheres, at typical levels of 10-20% in a background 1-2 bar CO2 atmosphere. We propose that the early Mars cryosphere had a sufficient CH4 storage capacity to have maintained H2-rich transient atmospheres during a total time period up to several Myr or tens of Myr, having potentially contributed - by collision-induced heating effect of atmospheric H2 - to the formation of valley networks during the late Noachian and early Hesperian.

A spectroscopic study of the structure and occupancies of clathrate hydrates incorporating hydrogen

Science.gov (United States)

Grim, R. Gary

With the ability to store and concentrate gases inside a clean and abundant water framework, clathrate hydrates are considered to be a promising material for many applications related to gas storage, separation, and sequestration. Hydrates of hydrogen are particularly interesting, for in addition to these potential applications, the small molecular size provides an opportunity for use as a model guest in many fundamental studies such as guest diffusion, multiple guest occupancy, and quantum mechanical effects upon confinement. In attempt to study these effects and the viability of H 2 hydrates as an energy storage material, a combined experimental and theoretical approach incorporating Raman spectroscopy, X-ray and neutron diffraction, nuclear magnetic resonance, ab-initio calculations, and molecular dynamic simulations was performed. One of the most significant challenges in the application of H2 clathrate hydrates is the demanding thermodynamic requirements needed for stability. In recent years, a mechanism known as the `tuning' effect had reportedly solved this issue where thermodynamic requirements could be reduced while simultaneously maintaining high storage capacities. In this work, the viability and validity of this technique is explored and alternative explanations in the form of epitaxial hydrate growth under high driving force conditions are discussed. A second, and equally important challenge facing clathrate hydrates as a future storage material is the overall storage capacity of H2. In previous work, H2 has only been experimentally verified to occupy the small 512 and 43566 3 cages and also in the large 51264 cages of the type II clathrate, often with an energy deficient promoter. In order to achieve more robust energy densities, other hydrate cages must be accessible. Herein a new method for increasing overall hydrate energy densities is presented involving the incorporation of H2 in the large cages of the type I clathrate with CH4 as a co

Hydration of krypton and consideration of clathrate models of hydrophobic effects from the perspective of quasi-chemical theory.

Science.gov (United States)

Ashbaugh, Henry S; Asthagiri, D; Pratt, Lawrence R; Rempe, Susan B

2003-09-01

Ab initio molecular dynamics (AIMD) results on a krypton-water liquid solution are presented and compared to recent XAFS results for the radial hydration structure for a Kr atom in liquid water solution. Though these AIMD calculations have important limitations of scale, the comparisons with the liquid solution results are satisfactory and significantly different from the radial distributions extracted from the data on the solid Kr/H(2)O clathrate hydrate phase. The calculations also produce the coordination number distribution that can be examined for metastable coordination structures suggesting possibilities for clathrate-like organization; none are seen in these results. Clathrate pictures of hydrophobic hydration are discussed, as is the quasi-chemical theory that should provide a basis for clathrate pictures. Outer shell contributions are discussed and estimated; they are positive and larger than the positive experimental hydration free energy of Kr(aq), implying that inner shell contributions must be negative and of comparable size. Clathrate-like inner shell hydration structures on a Kr atom solute are obtained for some, but not all, of the coordination number cases observed in the simulation. The structures found have a delicate stability. Inner shell coordination structures extracted from the simulation of the liquid, and then subjected to quantum chemical optimization, always decomposed. Interactions with the outer shell material are decisive in stabilizing coordination structures observed in liquid solution and in clathrate phases. The primitive quasi-chemical estimate that uses a dielectric model for the influence of the outer shell material on the inner shell equilibria gives a contribution to hydration free energy that is positive and larger than the experimental hydration free energy. The 'what are we to tell students' question about hydrophobic hydration, often answered with structural clathrate pictures, is then considered; we propose an

Overview: Nucleation of clathrate hydrates.

Science.gov (United States)

Warrier, Pramod; Khan, M Naveed; Srivastava, Vishal; Maupin, C Mark; Koh, Carolyn A

2016-12-07

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

Overview: Nucleation of clathrate hydrates

Science.gov (United States)

Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

2016-12-01

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

chemical kinetic study of nitrogen oxides formation in methane flameless combustion

International Nuclear Information System (INIS)

Alvarado T, Pedro N; Cadavid S, Francisco; Mondragon, P Fanor; Ruiz, Wilson

2009-01-01

The present paper deals with the nitrogen oxides formation in a flameless combustion process characterized for using air highly diluted and preheated at high temperatures. The combustion model used in this study was the one dimensional counterflow methane air diffusion flame. The NOx production rate analysis showed that the thermal and prompt mechanisms are the most important for the formation and consumption of NO under dilution conditions for the oxidant in N 2 and combustion products. These mechanisms are related since the starting reaction for NO formation (N2 molecular dissociation) belongs to the prompt mechanism while the NO formation is reported mainly for the thermal mechanism reactions. On the other hand, the NO - NO 2 equilibrium showed that the reaction rates are comparable to that obtained by the thermal and prompt mechanisms, but its global contribution to NO formation are almost insignificant due to the oxidation reaction with radicals HO 2 .

Inelastic neutron scattering and spectral measurements of advanced cold moderator materials

International Nuclear Information System (INIS)

Conrad, H.; Prager, M.; Nuenighoff, K.; Pohl, C.; Kuhs, W.F.

2004-01-01

Inelastic neutron scattering with emphasis on energetically low lying modes as well as cold neutron leakage measurements have been performed on four prospective advanced cold moderator materials. Employing the time-of-flight instrument SV29 at the Juelich FRJ-2 reactor, spectra have been obtained from synthetic methane clathrate, tetrahydro-furane (THF) clathrate, 1,3,5-trimethyl-benzene (mesitylene) and light water ice at several temperatures between 2 K and 70 K. Clearly separated excitations at energy transfers of ±1 meV, +2 meV and +3 meV have been observed with synthetic methane clathrate. In mesitylene a wealth of low lying excitations have been observed. In the quenched phase we found lines at 4.7, 7.2, 9.6, 13.6, 15.4, 18.4, 19.0, 23.0, 29.5 and 34.3 meV, respectively. In the annealed phase, we observed significant shifts with the majority of lines. The lowest lying lines now are located at 7.0, 8.5 and 10.5 meV, respectively. In hexagonal ice at T=2 K up to now unreported low lying energy levels were found at energy transfers of 1.8 meV and 2.8 meV. An additional line at about 10 meV could be detected in THF clathrate. Mesitylene, synthetic methane clathrate and water ice, all at T=20 K, have been tested as moderators at the Juelich spallation mock-up JESSICA. The expected gain in neutron leakage current at energies around 2 meV as compared to conventional liquid hydrogen moderators has been observed for methane clathrate and mesitylene. (orig.)

Polymorphism in Br2 clathrate hydrates.

Science.gov (United States)

Goldschleger, I U; Kerenskaya, G; Janda, K C; Apkarian, V A

2008-02-07

The structure and composition of bromine clathrate hydrate has been controversial for more than 170 years due to the large variation of its observed stoichiometries. Several different crystal structures were proposed before 1997 when Udachin et al. (Udachin, K. A.; Enright, G. D.; Ratcliffe, C. I.; Ripmeester, J. A. J. Am. Chem. Soc. 1997, 119, 11481) concluded that Br2 forms only the tetragonal structure (TS-I). We show polymorphism in Br2 clathrate hydrates by identifying two distinct crystal structures through optical microscopy and resonant Raman spectroscopy on single crystals. After growing TS-I crystals from a liquid bromine-water solution, upon dropping the temperature slightly below -7 degrees C, new crystals of cubic morphology form. The new crystals, which have a limited thermal stability range, are assigned to the CS-II structure. The two structures are clearly distinguished by the resonant Raman spectra of the enclathrated Br2, which show long overtone progressions and allow the extraction of accurate vibrational parameters: omega(e) = 321.2 +/- 0.1 cm(-1) and omega(e)x(e) = 0.82 +/- 0.05 cm(-1) in TS-I and omega(e) = 317.5 +/- 0.1 cm(-1) and omega(e)x(e) = 0.70 +/- 0.1 cm(-1) in CS-II. On the basis of structural analysis, the discovery of the CS-II crystals implies stability of a large class of bromine hydrate structures and, therefore, polymorphism.

Numerical and experimental investigation of NO{sub x} formation in lean premixed combustion of methane

Energy Technology Data Exchange (ETDEWEB)

Bengtsson, K; Benz, P; Marti, T; Schaeren, R; Schlegel, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

A high pressure jet-stirred reactor has been built and employed to investigate NO{sub x} formation in lean premixed combustion of methane/air. Experimental results are compared with numerical predictions using the model of a perfectly stirred reactor and elementary reaction mechanisms. Four reaction mechanisms are considered with respect to NO{sub x} formation. (author) 3 figs., 6 refs.

Superconductivity of Ba8Si46-xGax clathrates

Science.gov (United States)

Li, Yang; Zhang, Ruihong; Chen, Ning; Ma, Xingqiao; Cao, Guohui; Luo, Z. P.; Hu, C. R.; Ross, Joseph H., Jr.

2007-03-01

We have presented a combined experimental and theoretical study of the effect of Gallium substitution on the superconductivity of the type I clathrate Ba8Si46-xGax. In Ga-doped clathrates, the Ga state is found to be strongly hybridized with the cage conduction-band state. Ga substitution results in a shift toward to a lower energy, a decrease of density of states at Fermi level, a lowering of the carrier concentration and a breakage of integrity of the sp3 hybridized networks. These play key roles in the suppression of superconductivity. For Ba8Si40Ga6, the onset of the superconducting transition occurs at Tc=3.3 K. The investigation of the magnetic superconducting state shows that Ba8Si40Ga6 is a type II superconductor. The critical magnetic fields were measured to be Hc1=35 Oe and Hc2=8.5 kOe. Our estimate of the lectron-phonon coupling reveals that Ba8Si40Ga6 is a moderate phonon-mediated BCS superconductor.

Coloration and darkening of methane clathrate and other ices by charged particle irradiation - Applications to the outer solar system

Science.gov (United States)

Thompson, W. Reid; Murray, B. G. J. P. T.; Khare, B. N.; Sagan, Carl

1987-01-01

The results of laboratory experiments simulating the irradiation of hydrocarbon-H2O or hydrocarbon-H2O/NH3 clathrates by charged particles in the outer solar system are reported. Ices produced by condensing and boiling liquid CH4 on an H2O frost surface at 100 K or by cocondensing frosts from gaseous mixtures were exposed to coronal-discharge electron irradiation at 77 K, and the spectral properties of the irradiated surfaces were determined. Significant darkening of the initially white ices was observed at doses of 1 Gerg/sq cm, corresponding to 8-500 yrs of irradiation by Uranian magnetospheric electrons on the surfaces of the principal Uranian satellites, or to total destruction of CH4 in the upper 1 mm of the satellite surfaces after 0.05-3.0 Myr. It is estimated that 10 m or more of icy satellite or comet surfaces would be radiation-hardened to a CH4-free ice-tholin mixture over 4 Gyr.

Catalytic aromatization of methane.

Science.gov (United States)

Spivey, James J; Hutchings, Graham

2014-02-07

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) ΔG°(r) = +433 kJ mol(-1) ΔH°(r) = +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.

The synthesis and the spectroscopic, thermal, and structural properties of the M2[(fumarate)Ni(CN)4]·2(1,4-Dioxane) clathrate (M = Co, Ni, Cd and Hg)

Science.gov (United States)

Kartal, Zeki; Yavuz, Abdülkerim

2018-03-01

In this study, the clathrates of fumarate-tetracyanonickel-dioxane, given by the formula M2[(fumarate)Ni(CN)4]·2(1,4-Dioxane) (M = Co, Ni, Cd and Hg), have been obtained for the first time through chemical methods. These clathrates have been characterized by elemental, thermal, FT-IR, and FT-Raman spectroscopies. The parameters of structures of clathrates have been determined by X-ray powder diffraction. The thermal behaviors of these clathrates have been also investigated by thermo-gravimetric analysis (TGA), differential thermal analysis (DTA), and derivative thermal gravimetric analysis (DTG) in the range of 20-900 °C. X-ray powder diffraction data have been recorded at ambient temperature in the 2θ range 5-50°. The FT-IR and FT-Raman spectra of clathrates have been recorded in the region of 4000-400 cm-1 and 4000-100 cm-1, respectively. The results of the spectral and thermal analyses of the newly synthesized clathrates of fumarate-tetracyanonickel-dioxane suggest that these clathrates are new examples of the Hofmann-type dioxane clathrates. In our study, the Hofmann-type dioxane clathrates, which are formed by bounding electrons of oxygen-donor atoms of fumarate ion ligand molecule to transition metal atoms, consist of the corrugated |M-Ni(CN)4|∞ polymeric layers, which are held in parallel through the chain of (-M-fumarate-M-).

Application of gas hydrate formation in separation processes: A review of experimental studies

International Nuclear Information System (INIS)

Eslamimanesh, Ali; Mohammadi, Amir H.; Richon, Dominique; Naidoo, Paramespri; Ramjugernath, Deresh

2012-01-01

Highlights: ► Review of gas hydrate technology applied to separation processes. ► Gas hydrates have potential to be a future sustainable separation technology. ► More theoretical, simulation, and economic studies needed. - Abstract: There has been a dramatic increase in gas hydrate research over the last decade. Interestingly, the research has not focussed on only the inhibition of gas hydrate formation, which is of particular relevance to the petroleum industry, but has evolved into investigations on the promotion of hydrate formation as a potential novel separation technology. Gas hydrate formation as a separation technology shows tremendous potential, both from a physical feasibility (in terms of effecting difficult separations) as well as an envisaged lower energy utilization criterion. It is therefore a technology that should be considered as a future sustainable technology and will find wide application, possibly replacing a number of current commercial separation processes. In this article, we focus on presenting a brief description of the positive applications of clathrate hydrates and a comprehensive survey of experimental studies performed on separation processes using gas hydrate formation technology. Although many investigations have been undertaken on the positive application of gas hydrates to date, there is a need to perform more theoretical, experimental, and economic studies to clarify various aspects of separation processes using clathrate/semi-clathrate hydrate formation phenomena, and to conclusively prove its sustainability.

The rates measurement of methane hydrate formation and dissociation using micro-drilling system application for gas hydrate exploration

Energy Technology Data Exchange (ETDEWEB)

Bin Dou [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)]|[Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Reinicke, K.M. [Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Guosheng Jiang; Xiang Wu; Fulong Ning [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)

2006-07-01

When drilling through gas hydrate bearing formations, the energy supplied by virtue of the drilling process may lead to a destabilization of the hydrates surrounding the wellbore. Therefore, as the number of oil and gas fields being development in deepwater and onshore arctic environments increases, greater emphasis should be placed on quantifying the risks, gas hydrates pose to drilling operations. The qualification of these risks requires a comprehensive understanding of gas hydrate-formation and dissociation as a result of drilling induced processes. To develop the required understanding of gas hydrat formation and dissociation, the authors conducted laboratory experiments by using a micro-drilling system, to study the dissociation rates of methane hydrates contained in a tank reactor. The test facility used is a development of China University of Geosciences. The rates of methane hydrate formation and dissociation in the tank reactor were measured at steady-state conditions at pressures ranging from 0.1 to 25 MPa and temperatures ranging from -5 to 20 C. The experimental results show that the rate of hydrate formation is strongly influenced by the fluid system used to form the hydrates, pressure and temperature, with the influence of the temperature on methane hydrate dissociation being stronger than that of the pressure. Drilling speed, drilling fluids and hydrate dissociation inhibitors were also shown to influence hydrate dissociation rate. The derived results have been used to predict hydrate drilling stability for several drilling fluid systems.

NO{sub x} formation in lean premixed combustion of methane at high pressures

Energy Technology Data Exchange (ETDEWEB)

Bengtsson, K U.M.; Griebel, P; Schaeren, R [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

High pressure experiments in a jet-stirred reactor have been performed to study the NO{sub x} formation in lean premixed combustion of methane/air mixtures. The experimental results are compared with numerical predictions using four well known reaction mechanisms and a model which consists of a series of two perfectly stirred reactors and a plug flow reactor. (author) 2 figs., 7 refs.

A study of the methane hydrate formation by in situ turbidimetry

Energy Technology Data Exchange (ETDEWEB)

Herri, J M

1996-02-02

The study of the Particle Size Distribution (PSD) during the processes of crystallization is a subject of considerable interest, notably in the offshore exploitation of liquid fuels where the gas hydrate crystallization can plug production, treatment and transport facilities. The classical remedy to this problem is mainly thermodynamic additives such as alcohols or salts, but a new way of research is the use of dispersant additives which avoid crystals formation. In this paper, we show an original apparatus that is able to measure in situ the polychromatic UV-Visible turbidity spectrum in a pressurised reactor. We apply this technology to the calculation of the PSD during the crystallization of methane hydrate particles in a stirred semi-batch tank reactor. We discuss the mathematics treatment of the turbidity spectrum in order to determine the PSD and especially the method of matrix inversion with constraint. Moreover, we give a method to calculate theoretically the refractive index of the hydrate particles and we validate it experimentally with the methane hydrate particles. We apply this technology to the study of the crystallization of methane hydrate from pure liquid water and methane gas into the range of temperature [0-2 deg. C], into the range of pressure [30-100 bars] and into the range of stirring rate [0-600 rpm]. We produce a set of experiments concerning these parameters. Then we realize a model of the crystallization taking into account the processes of nucleation, of growth, of agglomeration and flotation. We compare this model with the experimental results concerning the complex influence of stirring rate at 1 deg. C and 30 bars. Then, we investigate the influence of additives such as Fontainebleau Sand, Potassium Chloride and a surfactant such as Poly-Vinyl-Pyrrolydone. (authors). 133 refs., 210 figs., 54 tabs.

Methane oxidation and formation of EPS in compost: effect of oxygen concentration

International Nuclear Information System (INIS)

Wilshusen, J.H.; Hettiaratchi, J.P.A.; Visscher, A. de; Saint-Fort, R.

2004-01-01

Oxygen concentration plays an important role in the regulation of methane oxidation and the microbial ecology of methanotrophs. However, this effect is still poorly quantified in soil and compost ecosystems. The effect of oxygen on the formation of exopolymeric substances (EPS) is as yet unknown. We studied the effect of oxygen on the evolution of methanotrophic activity. At both high and low oxygen concentrations, peak activity was observed twice within a period of 6 months. Phospholipid fatty acid analysis showed that there was a shift from type I to type II methanotrophs during this period. At high oxygen concentration, EPS production was about 250% of the amount at low oxygen concentration. It is hypothesized that EPS serves as a carbon cycling mechanism for type I methanotrophs when inorganic nitrogen is limiting. Simultaneously, EPS stimulates nitrogenase activity in type II methanotrophs by creating oxygen-depleted zones. The kinetic results were incorporated in a simulation model for gas transport and methane oxidation in a passively aerated biofilter. Comparison between the model and experimental data showed that, besides acting as a micro-scale diffusion barrier, EPS can act as a barrier to macro-scale diffusion, reducing the performance of such biofilters. - 1.5% oxygen resulted in a slightly higher and more stable methane oxidation activity

FY1995 molecular control technology for mining of methane-gas-hydrate; 1995 nendo methane hydrate no bunshi seigyo mining

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

The objectives of the investigation are as follows: 1) developing a method to control formation/dissociation of methane-gas-hydrate, 2) developing a technology to displace methane gas by CO{sub 2} in methane-gas-hydrate deposit, 3) developing a technology to produce methane gas from the deposit efficiently. The final purpose of the project is to create new mining industry that solves both the problems of energy and global environment. 1) Clustering of water molecules is found to play the key role in the methane gas hydrate formation. 2) Equilibrium properties and kinetics of gas hydrates formation and dissociation in bulk-scale gas-hydrate are clarified in the practical environmental conditions. 3) Particle size of hydrate deposit influences the formation and dissociation of bulk-scale gas-hydrate crystal. 4) Mass transfer between gas and liquid phase in turbulent bubbly flow is a function of bubble diameter. The mass transfer depends on interfacial dynamics. (NEDO)

Natural gas: A bridge to the future?

International Nuclear Information System (INIS)

Andriesse, C.D.

1991-01-01

Natural gas is the cleanest fossil fuel, but never got the chance to develop its use. The reason for that is the notion that the natural gas supplies would last for only some decennia. That is only right for the conventional gas supplies. In ice crystals, some hundreds of meters deep in the oceans, enormous methane reserves, many times larger than the conventional supplies, are enclosed in so-called clathrates. From the literature it appears that other sources of natural gas or methane and new options to use these energy sources are considered or to be developed. Attention is paid to the methane reserves in geologic formations, methane produced by microbes, and methane in clathrates. It is estimated that the methane reserve is 8 x 10 2 3 Joule. By using natural gas as a fuel CO 2 emission will be reduced considerably. Methane emission however must be limited, because of the reducing effect of methane on the oxygen production in the troposphere. The large reserves of methane also offer good prospects for the production of hydrogen, large-scale applications to generate electric power or the use of CH 4 as a fuel in the transportation sector. New techniques and economic, social and institutional factors determine how fast the use of natural gas will increase. It is expected that 0.54 Tm 3 of natural gas will be needed for the twelve countries of the European Community. Main users in the year 2030 will be the electric power industry (39%), industry (26%), households and trade (18%), and transportation sector and supply (15%). In 2030 63% of natural gas has to be imported. 3 refs

Experimental and detailed kinetic modeling study of PAH formation in laminar co-flow methane diffusion flames

DEFF Research Database (Denmark)

Cuoci, Alberto; Frassoldati, Alessio; Faravelli, Tiziano

2013-01-01

In the present paper, synchrotron VUV photoionization mass spectrometry is used to study the detailed chemistry of co-flow methane diffusion flames with different dilution ratios. The experimental results constitute a comprehensive characterization of species important for PAH and soot formation...

Raman scattering of type-I clathrate compounds

International Nuclear Information System (INIS)

Takasu, Y.; Hasegawa, T.; Ogita, N.; Udagawa, M.; Avila, M.A.; Takabatake, T.

2006-01-01

Lattice dynamical properties of the type-I clathrate compounds of A 8 Ga 16 Ge 30 (A=Eu, Sr, Ba) have been investigated by Raman scattering. We are successful in the assignment of the observed Raman active phonons to proper symmetry and are able to separate the guest atom origin modes from framework origin modes for the first time experimentally. From the measurements of temperature dependence of the guest origin peaks, we also demonstrate the difference of the behavior of the guest atom at high temperature and low temperature

Enhanced Selectivity of the Separation of CO2 from N2 during Crystallization of Semi-Clathrates from Quaternary Ammonium Solutions

International Nuclear Information System (INIS)

Herri, J.M.; Bouchemoua, A.; Kwaterski, M.; Brantuas, P.; Galfre, A.; Bouillot, B.; Douzet, J.; Ouabbas, Y.; Cameirao, A.

2014-01-01

CO 2 mitigation is crucial environmental problem and a societal challenge for this century. CO 2 capture and sequestration is a route to solve a part of the problem, especially for the industries in which the gases to be treated are well localized. CO 2 capture by using hydrate is a process in which the cost of the separation is due to compression of gases to reach the gas hydrate formation conditions. Under pressure, the water and gas forms a solid that encapsulates preferentially CO 2 . The gas hydrate formation requires high pressures and low temperatures, which explains the use of thermodynamic promoters to decrease the operative pressure. Quaternary ammonium salts represent an interesting family of components because of their thermodynamic effect, but also because they can generate crystals that are easily handled. In this work, we have made experiments concerning the equilibrium of (CO 2 , N 2 ) in presence of Tetra-n-Butyl Ammonium Bromide (TBAB) which form a semi-clathrate hydrate. We propose equilibrium data (pressure, temperature) in presence of TBAB at different concentrations and we compare them to the literature. We have also measured the composition of the hydrate phase in equilibrium with the gas phase at different CO 2 concentrations. We observe that the selectivity of the separation is dramatically increased in comparison to the selectivity of the pure water gas clathrate hydrate. We observe also a benefice on the operative pressure which can be dropped down to the atmospheric pressure. (authors)

Pressure-induced phase transformations in the Ba8Si46 clathrate

DEFF Research Database (Denmark)

Yang, Lirong; Ma, Y.M.; Iitaka, T.

2006-01-01

The nature of isostructural transformations of a type-I Ba8Si46 clathrate has been studied by in situ high-pressure angle-dispersive x-ray powder diffraction using liquid He as pressure transmitting medium. The good quality of the diffraction data permitted refinement of structural and thermal...

Adsorbed Carbon Formation and Carbon Hydrogenation for CO_2 Methanation on the Ni(111) Surface: ASED-MO Study

International Nuclear Information System (INIS)

Choe, Sang Joon; Kang, Hae Jin; Kim, Su Jin; Park, Sung Bae; Park, Dong Ho; Huh, Do Sung

2005-01-01

Using the ASED-MO (Atom Superposition and Electron Delocalization-Molecular Orbital) theory, we investigated carbon formation and carbon hydrogenation for CO_2 methanation on the Ni (111) surface. For carbon formation mechanism, we calculated the following activation energies, 1.27 eV for CO_2 dissociation, 2.97 eV for the CO, 1.93 eV for 2CO dissociation, respectively. For carbon methanation mechanism, we also calculated the following activation energies, 0.72 eV for methylidyne, 0.52 eV for methylene and 0.50 eV for methane, respectively. We found that the calculated activation energy of CO dissociation is higher than that of 2CO dissociation on the clean surface and base on these results that the CO dissociation step are the ratedetermining of the process. The C-H bond lengths of CH_4 the intermediate complex are 1.21 A, 1.31 A for the C···H_(_1_), and 2.82 A for the height, with angles of 105 .deg. for H_(_1_)CH and 98 .deg. for H_(_1_)CH_(_1_)

Phase equilibria of carbon dioxide and methane gas-hydrates predicted with the modified analytical S-L-V equation of state

Directory of Open Access Journals (Sweden)

Span Roland

2012-04-01

Full Text Available Gas-hydrates (clathrates are non-stoichiometric crystallized solutions of gas molecules in the metastable water lattice. Two or more components are associated without ordinary chemical union but through complete enclosure of gas molecules in a framework of water molecules linked together by hydrogen bonds. The clathrates are important in the following applications: the pipeline blockage in natural gas industry, potential energy source in the form of natural hydrates present in ocean bottom, and the CO2 separation and storage. In this study, we have modified an analytical solid-liquid-vapor equation of state (EoS [A. Yokozeki, Fluid Phase Equil. 222–223 (2004] to improve its ability for modeling the phase equilibria of clathrates. The EoS can predict the formation conditions for CO2- and CH4-hydrates. It will be used as an initial estimate for a more complicated hydrate model based on the fundamental EoSs for fluid phases.

Motion of Br2 molecules in clathrate cages. A computational study of the dynamic effects on its spectroscopic behavior.

Science.gov (United States)

Bernal-Uruchurtu, M I; Janda, Kenneth C; Hernández-Lamoneda, R

2015-01-22

This work looks into the spectroscopic behavior of bromine molecules trapped in clathrate cages combining different methodologies. We developed a semiempirical quantum mechanical model to incorporate through molecular dynamics trajectories, the effect movement of bromine molecules in clathrate cages has on its absorption spectra. A simple electrostatic model simulating the cage environment around bromine predicts a blue shift in the spectra, in good agreement with the experimental evidence.

FTIR spectroscopic study on the Hofmann -Td- type clathrates: Ni(benzoic acid)2M(CN)4.aniline (M=Zn, Cd, Hg)

International Nuclear Information System (INIS)

Kesan, G.; Kartal, Z.

2010-01-01

The Hofmann-Td-type clathrates formulated as Ni(L) 2 M(CN) 4 .nG where L is a bidentate or a pair of unidentate ligand molecule, M is Zn, Cd or Hg, G is a guest molecule and n is the number of guest molecule. The host lattice of the Hofmann-Td-type clathrates is formed from endless chains of -Ni-L-L-Ni-L-L-Ni- and M(CN) 4 ions arranged between the consecutive crossing -Ni-L-L-Ni-L-L-Ni- chains with the O-ends bound to the Ni metal atoms. These polymeric layers are held in parallel by Van der Walls interaction between ligand molecules. This structure provides α-type cavity. In this study, Ni(Benzoic Acid ) 2M(CN) 4 .Aniline (M = Zn, Cd, Hg) is obtained for the first time by means of chemical methods in powder form and their infrared spectra are reported in range of (4000-400) cm - 1. The spectral data suggest that the new clathrates are similar in structure to the Hofmann-type clathrates.

Formation of polycyclic aromatic hydrocarbons and soot in fuel-rich oxidation of methane in a laminar flow reactor

DEFF Research Database (Denmark)

Skjøth-Rasmussen, Martin Skov; Glarborg, Peter; Østberg, M.

2004-01-01

Conversion of methane to higher hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), and soot was investigated under fuel-rich conditions in a laminar flow reactor. The effects of stoichiometry, dilution, and water vapor addition were studied at temperatures between 1073 and 1823 K. A chemical...... kinetic mechanism was established for methane oxidation, with emphasis on formation of higher hydrocarbons and PAH. A submodel for soot formation was adopted from the work of Frenklach and co-workers without changes. Modeling predictions showed good agreement with experimental results. Reactants, stable...... decrease with increasing addition of water vapor. The effect is described qualitatively by the reaction mechanism. The enhanced oxidation of acetylene is attributed to higher levels of hydroxyl radicals, formed from the reaction between the water vapor and hydrogen atoms....

Study on gas hydrate as a new energy resource in the twenty first century

Energy Technology Data Exchange (ETDEWEB)

Ryu, Byung Jae; Kim, Won Sik; Oh, Jae Ho [Korea Institute of Geology Mining and Materials, Taejon (Korea)] [and others

1998-12-01

Methane hydrate, a special type of clathrate hydrates, is a metastable solid compound mainly consisted of methane and water and generally called as gas hydrate. It is stable in the specific low- temperature/high-pressure conditions. Very large amount of methane that is the main component of natural gas, is accumulated in the form of methane hydrate subaquatic areas. Methane hydrate are the major reservoir of methane on the earth. On the other hand, the development and transmission through pipeline of oil and natural gas in the permafrost and deep subaquatic regions are significantly complicated by formation and dissociation of methane hydrate. The dissociation of natural methane hydrates caused by increasing temperature and decreasing pressure could cause the atmospheric pollution and geohazard. The formation, stable existence and dissociation of natural methane hydrates depend on the temperature, pressure, and composition of gas and characteristics of the interstitial waters. For the study on geophysical and geological conditions for the methane hydrate accumulation and to find BSR in the East Sea, Korea, the geophysical surveys using air-gun system, multibeam echo sounder, SBP were implemented in last September. The water temperature data vs. depth were obtained to determine the methane hydrate stability zone in the study area. The experimental equilibrium condition of methane hydrate was also measured in 3 wt.% sodium chloride solution. The relationship between Methane hydrate formation time and overpressure was analyzed through the laboratory work. (author). 49 refs., 6 tabs., 26 figs.

Structural and thermoelectric properties of the type-I Sn clathrates Cs8Sn46−n(n=0,2) from Density Functional Theory (DFT)

KAUST Repository

Egbele, Peter O.; Shoko, Elvis; Joubert, Daniel P.

2018-01-01

Sn clathrates are promising phonon glass, electron crystal materials (PGEC), in which the phonon free paths are short and the electron free paths are long. We analysed the relaxed structure of Sn clathrates using four different Density Funtional

Methane hydrate distribution from prolonged and repeated formation in natural and compacted sand samples: X-ray CT observations

Energy Technology Data Exchange (ETDEWEB)

Rees, E.V.L.; Kneafsey, T.J.; Seol, Y.

2010-07-01

To study physical properties of methane gas hydrate-bearing sediments, it is necessary to synthesize laboratory samples due to the limited availability of cores from natural deposits. X-ray computed tomography (CT) and other observations have shown gas hydrate to occur in a number of morphologies over a variety of sediment types. To aid in understanding formation and growth patterns of hydrate in sediments, methane hydrate was repeatedly formed in laboratory-packed sand samples and in a natural sediment core from the Mount Elbert Stratigraphic Test Well. CT scanning was performed during hydrate formation and decomposition steps, and periodically while the hydrate samples remained under stable conditions for up to 60 days. The investigation revealed the impact of water saturation on location and morphology of hydrate in both laboratory and natural sediments during repeated hydrate formations. Significant redistribution of hydrate and water in the samples was observed over both the short and long term.

Adsorption of methane and CO2 onto olivine surfaces in Martian dust conditions

Science.gov (United States)

Escamilla-Roa, Elizabeth; Martin-Torres, Javier; Sainz-Díaz, C. Ignacio

2018-04-01

Methane has been detected on all planets of our Solar System, and most of the larger moons, as well as in dwarf-planets like Pluto and Eric. The presence of this molecule in rocky planets is very interesting because its presence in the Earth's atmosphere is mainly related to biotic processes. Space instrumentation in orbiters around Mars has detected olivine on the Martian soil and dust. On the other hand the measurements of methane from the Curiosity rover report detection of background levels of atmospheric methane with abundance that is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, elevated levels of methane about this background have been observed implying that Mars is episodically producing methane from an additional unknown source, making the reasons of these temporal fluctuations of methane a hot topic in planetary research. The goal of this study is to investigate at atomic level the interactions during the adsorption processes of methane and other Mars atmospheric species (CO2, H2O) on forsterite surfaces, through electronic structure calculations based on the Density Functional Theory (DFT). We propose two models to simulate the interaction of adsorbates with the surface of dust mineral, such as binary mixtures (5CH4+5H2O/5CH4+5CO2) and as a semi-clathrate adsorption. We have obtained interesting results of the adsorption process in the mixture 5CH4+5CO2. Associative and dissociative adsorptions were observed for water and CO2 molecules. The methane molecules were only trapped and held by water or CO2 molecules. In the dipolar surface, the adsorption of CO2 molecules produced new species: one CO from a CO2 dissociation, and, two CO2 molecules chemisorbed to mineral surface forming in one case a carbonate group. Our results suggest that CO2 has a strong interaction with the mineral surface when methane is present. These results could be confirmed after the

Physics of coal methane: decisive role of iron compounds

Energy Technology Data Exchange (ETDEWEB)

Gavriljuk, V. G., E-mail: gavr@imp.kiev.ua; Skoblik, A. P. [G.V. Kurdyumov Institute for Metal Physics (Ukraine); Shanina, B. D.; Konchits, A. A. [V. Ye. Lashkarev Institute for Semiconductor Physics (Ukraine)

2016-12-15

The role of iron in formation of the coal methane is clarified based on the studies performed on the coal samples taken from different mines in Donetsk coal basin. Using Mössbauer spectroscopy, a correlation is found between the iron content and methane capacity of coal seams. By means of electron paramagnetic resonance, it is found that iron increases the concentration of non-compensated electron spins, i.e. dangled bonds at the carbon atoms. These bonds can be occupied by hydrogen atoms as a prerequisite of methane formation. The two-valence iron is shown to be the most effective in the increase of spin concentration. By using the ion mass spectrometry, the modelling of methane formation is carried out on the mechanical mixture of the iron-free reactor graphite, iron compounds and diluted sulphuric acid as a source of hydrogen atoms. The proposed mechanism is also confirmed by methane formation in the mixture of iron compounds and the coal from the mine where the iron and methane are practically absent.

A polyether glycol derived from cashew nutshell as a kinetic inhibitor for methane hydrate formation

Energy Technology Data Exchange (ETDEWEB)

Ferreira, Jorge Cesar; Esteves, Pierre M., E-mail: pesteves@iq.ufrj.br [Instituto de Quimica, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ (Brazil); Teixeira, Adriana [Centro de Pesquisa e Desenvolvimento Leopoldo Americo Miguez de Mello, PETROBRAS, Rio de Janeiro, RJ (Brazil)

2012-07-01

The polyether glycol derived from cashew nutshell liquid inhibited the formation of methane hydrate. The polymer proved to be more efficient than the polyvinyl pyrrolidone-poly(N-vinyl) caprolactam (PVP-PVCap) co-polymer under tested conditions (CH{sub 4}, 1470 psi and 4 degree C), being the latter one of the best commercially available hydrate inhibitors. (author)

Hysteresis of methane hydrate formation/decomposition at subsea geological conditions

International Nuclear Information System (INIS)

Klapproth, Alice; Piltz, Ross; Peterson, Vanessa K.; Kennedy, Shane J.; Kozielski, Karen A.; Hartley, Patrick G.

2009-01-01

Full text: Gas hydrates are a major risk when transporting oil and gas in offshore subsea pipelines. Under typical conditions in these pipelines (at high pressure and low temperature) the formation of gas hydrates is favourable. The hydrates form large solid plugs that can block pipelines and can even cause them to burst. This represents a major problem for the gas mining industry, which currently goes to extreme measures to reduce the risk of hydrate formation because there is no reliable experimental data on hydrate processes. The mechanisms of gas hydrate formation, growth and inhibition are poorly understood. A clear understanding of the fundamental processes will allow development of cost effective technologies to avoid production losses in gas pipelines. We are studying the nucleation of the methane hydrates by measuring the hysteresis of hydrate formation/decomposition by neutron diffraction. When a gas hydrate is decomposed (melted) the resulting water has a 'supposed memory effect' raising the probability of rapid hydrate reformation. This rapid reformation does not occur for pure water where nucleation can be delayed by several hours (induction time) due to metastability [1]. The memory effect can only be destroyed by extreme heating of the effected area. Possible causes of this effect include residual water structure, persistent hydrate crystal lites remaining in solution and remaining dissolved gas. We will compare the kinetics of formation and the stability region of hydrate formation of 'memory' water for comparison with pure water. This information has important implications for the oil and gas industry because it should provide a better understanding of the role of multiple dissociation and reformation of gas hydrates in plug formation.

Computational characterization of 13C NMR lineshapes of carbon dioxide in structure 1 clathrate hydrates

Energy Technology Data Exchange (ETDEWEB)

Dornan, P.; Woo, T.K. [Ottawa Univ., ON (Canada). Dept. of Chemistry

2008-07-01

Nonspherical large cages in structure one clathrates impose non-uniform motion of nonspherical guest molecules and anisotropic lineshapes in nuclear magnetic resonance (NMR) spectra of the guest. This paper presented a general method for calculating the chemical shift lineshape anisotropy of guest molecules in clathrate hydrate compounds from molecular dynamics simulations for the case of weak host, guest dipolar coupling. In order to calculate the cage chemical shielding tensors and the NMR lineshape produced by each guest molecule, the study involved the use of orientational distributions from molecular dynamics simulation along with time and powder angle averaging. The total predicted lineshape anisotropy was calculated from the superposition of the lineshapes of all guests. The approach was applied to calculate the temperature dependent 13C NMR lineshape anisotropy of carbon dioxide in structure 1 clathrates. The paper presented the computational methodology and results and discussion. It was concluded that the resulting lineshapes were in good agreement with the experimental 13C NMR spectrum at each temperature. The method provided a uniform procedure to calculate the lineshapes at different temperatures and no prior assumptions about the nature of the motion of the guest in cages was required. 37 refs., 2 tabs., 3 figs.

Formaldehyde formation in coupled oxidation of methane and methanol over V2O5 and MoO3 silica supported catalysts

International Nuclear Information System (INIS)

Lojewska, J.; Makowski, W.; Fajardo Farre, A.; Dziembaj, R.

2003-01-01

The effect of methanol on partial oxidation of methane has been studied on standard molybdena and vanadia catalysts supported on silica. Prior to catalytic tests the catalysts were characterized by BET, SEM/EDAX and TPR/O methods. Three types of catalytic tests were performed giving temperature and contact time dependence on the catalyst activity and selectivity: partial oxidations of methane, methanol and methane/methanol mixtures. The methanol showed an activating impact on the partial oxidation of methane over all used catalysts samples, but the strongest one over Mo 3 /SiO 2 . In the absence of CH 3 OH the only catalyst, which exhibited HCHO selectivity, was low loaded vanadia catalyst. It has been put forward that methanol may enhance formation of oxygen active species, prerequisites for activating methane molecules, through reducing vanadia cations and causing breakage of vanadium oxygen bonds. (author)

Structural and thermoelectric properties of the type-I Sn clathrates Cs8Sn46−n(n=0,2) from Density Functional Theory (DFT)

KAUST Repository

Egbele, Peter O.

2018-02-08

Sn clathrates are promising phonon glass, electron crystal materials (PGEC), in which the phonon free paths are short and the electron free paths are long. We analysed the relaxed structure of Sn clathrates using four different Density Funtional Exchange-Correlation functionals. The phonon structures were investigated as a first step in order to determine the phonon contribution to the thermal conductivity. We determined the Seebeck coefficient and electrical conductivity of the clathrate compound and the thermoelectric figure of merit. A glimpse into the dynamics of the system for the evaluation of the thermoelectric and electronic properties is presented.

Carbon and hydrogen isotope ratios of bacterial methane and its formation mechanism

International Nuclear Information System (INIS)

Sugimoto, A.; Wada, E.

1993-01-01

Anaerobic incubations of paddy soil collected from Konosu, Japan, were carried out for 10 weeks to clarify the general principles that govern the variation of carbon isotopic composition of bacterial methane from freshwater areas. The δ 13 C value of produced CH 4 was highly variable ranging from -60 to -33%, corresponding to change in its formation pathways: acetate fermentation and CO 2 /H 2 reduction. The δ 13 C value of CH 4 from CO 2 /H 2 was estimated as -77 to -60%, adopting 45% of δ 13 C difference between the CH 4 and its source CO 2 . The δ 13 C value of methyl carbon of acetate accumulated with addition of inhibitor for methanogenesis ranged from -43 to -30%, which was considered with the δ 13 C value of CH 4 from acetate. Variability of CH 4 δ 13 C resulted from the difference in contribution of each biological process. It was demonstrated that δ 13 C value of methane was a useful indicator for assessing the contribution of each process in wetlands and paddy fields. (author)

Study on molecular controlled mining system of methane hydrate; Methane hydrate no bunshi seigyo mining ni kansuru kenkyu

Energy Technology Data Exchange (ETDEWEB)

Kuriyagawa, M; Saito, T; Kobayashi, H; Karasawa, H; Kiyono, F; Nagaoki, R; Yamamoto, Y; Komai, T; Haneda, H; Takahashi, Y [National Institute for Resources and Environment, Tsukuba (Japan); Nada, H [Science and Technology Agency, Tokyo (Japan)

1997-02-01

Basic studies are conducted for the collection of methane from the methane hydrate that exists at levels deeper than 500m in the sea. The relationship between the hydrate generation mechanism and water cluster structure is examined by use of mass spectronomy. It is found that, among the stable liquid phase clusters, the (H2O)21H{sup +} cluster is the most stable. Stable hydrate clusters are in presence in quantities, and participate in the formation of hydrate crystal nuclei. For the elucidation of the nucleus formation mechanism, a kinetic simulation is conducted of molecules in the cohesion system consisting of water and methane molecules. Water molecules that array near methane molecules at the normal pressure is disarrayed under a higher pressure for rearray into a hydrate structure. Hydrate formation and breakdown in the three-phase equilibrium state of H2O, CH4, and CO2 at a low temperature and high pressure are tested, which discloses that supercooling is required for formation, that it is possible to extract CH4 first for replacement by guest molecule CO2 since CO2 is stabler than CH4 at a lower pressure or higher temperature, and that formation is easier to take place when the grain diameter is larger at the formation point since larger grain diameters result in a higher formation temperature. 3 figs.

Cultivation-independent analysis of archaeal and bacterial communities of the formation water in an Indian coal bed to enhance biotransformation of coal into methane

Energy Technology Data Exchange (ETDEWEB)

Singh, Durgesh Narain; Kumar, Ashok; Tripathi, Anil Kumar [Banaras Hindu Univ., Varanasi (India). School of Biotechnolgy; Sarbhai, Munish Prasad [Oil and Natural Gas Commission, Ahmedabad (India). Inst. of Reservoir Studies

2012-02-15

Biogenic origin of the significant proportion of coal bed methane has indicated the role of microbial communities in methanogenesis. By using cultivation-independent approach, we have analysed the archaeal and bacterial community present in the formation water of an Indian coal bed at 600-700 m depth to understand their role in methanogenesis. Presence of methanogens in the formation water was inferred by epifluorescence microscopy and PCR amplification of mcrA gene. Archaeal 16S rRNA gene clone library from the formation water metagenome was dominated by methanogens showing similarity to Methanobacterium, Methanothermobacter and Methanolinea whereas the clones of bacterial 16S rRNA gene library were closely related to Azonexus, Azospira, Dechloromonas and Thauera. Thus, microbial community of the formation water consisted of predominantly hydrogenotrophic methanogens and the proteobacteria capable of nitrogen fixation, nitrate reduction and polyaromatic compound degradation. Methanogenic potential of the microbial community present in the formation water was elucidated by the production of methane in the enrichment culture, which contained 16S rRNA gene sequences showing close relatedness to the genus Methanobacterium. Microcosm using formation water as medium as well as a source of inoculum and coal as carbon source produced significant amount of methane which increased considerably by the addition of nitrite. The dominance of Diaphorobacter sp. in nitrite amended microcosm indicated their important role in supporting methanogenesis in the coal bed. This is the first study indicating existence of methanogenic and bacterial community in an Indian coal bed that is capable of in situ biotransformation of coal into methane. (orig.)

Nonequilibrium clumped isotope signals in microbial methane

Science.gov (United States)

Wang, David T.; Gruen, Danielle S.; Lollar, Barbara Sherwood; Hinrichs, Kai-Uwe; Stewart, Lucy C.; Holden, James F.; Hristov, Alexander N.; Pohlman, John W.; Morrill, Penny L.; Könneke, Martin; Delwiche, Kyle B.; Reeves, Eoghan P.; Sutcliffe, Chelsea N.; Ritter, Daniel J.; Seewald, Jeffrey S.; McIntosh, Jennifer C.; Hemond, Harold F.; Kubo, Michael D.; Cardace, Dawn; Hoehler, Tori M.; Ono, Shuhei

2015-01-01

Methane is a key component in the global carbon cycle with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply-substituted “clumped” isotopologues, e.g., 13CH3D, has recently emerged as a proxy for determining methane-formation temperatures; however, the impact of biological processes on methane’s clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on 13CH3D abundances and results in anomalously elevated formation temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters.

Phase Behaviour of Methane Hydrate Under Conditions Relevant to Titan's Interior

Science.gov (United States)

Sclater, G.; Fortes, A. D.; Crawford, I. A.

2018-06-01

The high-pressure behaviour Clathrate hydrates, thought to be abundant in the outer solar system, underpins planetary modelling efforts of the interior of Titan, where clathrates are hypothesised to be the source of the dense N2, CH4 atmosphere.

Abiotic methane formation during experimental serpentinization of olivine.

Science.gov (United States)

McCollom, Thomas M

2016-12-06

Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH 4 ). In many cases, the CH 4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH 4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH 4 synthesis have been observed. Here, the potential for abiotic formation of CH 4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13 C-labeled inorganic carbon source was used to unambiguously determine the origin of CH 4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH 4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH 4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH 4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH 4 was observed in one experiment performed under conditions that allowed an H 2 -rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH 4 .

Ductile flow of methane hydrate

Science.gov (United States)

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

2003-01-01

Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.

Structure and dynamics of cold water super-Earths: the case of occluded CH4 and its outgassing

International Nuclear Information System (INIS)

Levi, A.; Podolak, M.; Sasselov, D.

2014-01-01

In this work, we study the transport of methane in the external water envelopes surrounding water-rich super-Earths. We investigate the influence of methane on the thermodynamics and mechanics of the water mantle. We find that including methane in the water matrix introduces a new phase (filled ice), resulting in hotter planetary interiors. This effect renders the super-ionic and reticulating phases accessible to the lower ice mantle of relatively low-mass planets (∼5 M E ) lacking a H/He atmosphere. We model the thermal and structural profile of the planetary crust and discuss five possible crustal regimes which depend on the surface temperature and heat flux. We demonstrate that the planetary crust can be conductive throughout or partly confined to the dissociation curve of methane clathrate hydrate. The formation of methane clathrate in the subsurface is shown to inhibit the formation of a subterranean ocean. This effect results in increased stresses on the lithosphere, making modes of ice plate tectonics possible. The dynamic character of the tectonic plates is analyzed and the ability of this tectonic mode to cool the planet is estimated. The icy tectonic plates are found to be faster than those on a silicate super-Earth. A mid-layer of low viscosity is found to exist between the lithosphere and the lower mantle. Its existence results in a large difference between ice mantle overturn timescales and resurfacing timescales. Resurfacing timescales are found to be 1 Ma for fast plates and 100 Ma for sluggish plates, depending on the viscosity profile and ice mass fraction. Melting beneath spreading centers is required in order to account for the planetary radiogenic heating. The melt fraction is quantified for the various tectonic solutions explored, ranging from a few percent for the fast and thin plates to total melting of the upwelled material for the thick and sluggish plates. Ice mantle dynamics is found to be important for assessing the composition of the

Synthesis of polyphenylacetylene by radiation-induced polymerization in deoxycholic acid clathrate

International Nuclear Information System (INIS)

Cataldo, Franco; Strazzulla, Giovanni; Iglesias-Groth, Susana

2009-01-01

Phenylacetylene was polymerized as inclusion compound (clathrate) inside deoxycholic acid (DOCA) crystals. The polymerization was initiated by γ radiation and a total dose of 320 kGy was employed. The resulting polyphenylacetylene (PPA) was isolated by dissolution of deoxycholic acid in boiling ethanol. PPA high polymer was accompanied by a series of phenylacetylene oligomers, which were detected by liquid chromatographic analysis (HPLC). PPA was characterized by electronic absorption spectroscopy and by FT-IR spectroscopy in comparison to a reference PPA prepared by a stereospecific catalyst. The microstructure of PPA from inclusion polymerization was highly trans type, similar to that observed on PPA prepared by bulk radiolysis. No optical activity was detected by polarimetry on PPA prepared by inclusion polymerization. The host-guest complex PPA/DOCA was studied by differential thermal analysis (DTA) and by thermogravimetry (TGA). DTA provided evidences of the host-guest complex formation from the shift of the melting point of DOCA while the TGA confirmed the identity - in terms of thermal behaviour - of the PPA from inclusion polymerization with that from stereospecific polymerization

Technical Note: Methionine, a precursor of methane in living plants

Science.gov (United States)

Lenhart, K.; Althoff, F.; Greule, M.; Keppler, F.

2015-03-01

When terrestrial plants were identified as producers of the greenhouse gas methane, much discussion and debate ensued not only about their contribution to the global methane budget but also with regard to the validity of the observation itself. Although the phenomenon has now become more accepted for both living and dead plants, the mechanism of methane formation in living plants remains to be elucidated and its precursor compounds to be identified. We made use of stable isotope techniques to verify the in vivo formation of methane, and, in order to identify the carbon precursor, 13C positionally labeled organic compounds were employed. Here we show that the amino acid L-methionine acts as a methane precursor in living plants. Employing 13C-labeled methionine clearly identified the sulfur-bound methyl group of methionine as a carbon precursor of methane released from lavender (Lavandula angustifolia). Furthermore, when lavender plants were stressed physically, methane release rates and the stable carbon isotope values of the emitted methane greatly increased. Our results provide additional support that plants possess a mechanism for methane production and suggest that methionine might play an important role in the formation of methane in living plants, particularly under stress conditions.

Electric double-layer capacitor based on an ionic clathrate hydrate.

Science.gov (United States)

Lee, Wonhee; Kwon, Minchul; Park, Seongmin; Lim, Dongwook; Cha, Jong-Ho; Lee, Huen

2013-07-01

Herein, we suggest a new approach to an electric double-layer capacitor (EDLC) that is based on a proton-conducting ionic clathrate hydrate (ICH). The ice-like structures of clathrate hydrates, which are comprised of host water molecules and guest ions, make them suitable for applications in EDLC electrolytes, owing to their high proton conductivities and thermal stabilities. The carbon materials in the ICH Me4NOH⋅5 H2O show a high specific capacitance, reversible charge-discharge behavior, and a long cycle life. The ionic-hydrate complex provides the following advantages in comparison with conventional aqueous and polymer electrolytes: 1) The ICH does not cause leakage problems under normal EDLC operating conditions. 2) The hydrate material can be utilized itself, without requiring any pre-treatments or activation for proton conduction, thus shortening the preparation procedure of the EDLC. 3) The crystallization of the ICH makes it possible to tailor practical EDLC dimensions because of its fluidity as a liquid hydrate. 4) The hydrate solid electrolyte exhibits more-favorable electrochemical stability than aqueous and polymer electrolytes. Therefore, ICH materials are expected to find practical applications in versatile energy devices that incorporate electrochemical systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A possible reason behind the initial formation of pentagonal dodecahedron cavities in sI-methane hydrate nucleation: A DFT study

Science.gov (United States)

Mondal, Sukanta; Goswami, Tamal; Jana, Gourhari; Misra, Anirban; Chattaraj, Pratim Kumar

2018-01-01

In this letter, a possible reason behind selective host-guest organization in the initial stage of sI methane hydrate nucleation is provided, through density functional theory based calculations. In doing so, we have connected earlier experimental and theoretical observations on the structure and energetics of sI methane hydrate to our findings. Geometry and relative stability of small (H2O)5 and (H2O)6 clusters, presence of CH4 guest, integrity and cavity radius of (H2O)20 and (H2O)24, as well as the weak van der Waals type of forces, particularly dispersion interaction, are major factors responsible for initial formation of methane encapsulated dodecahedron cavity over tetrakaidecahedron.

Phase equilibrium measurements of structure II clathrate hydrates of hydrogen with various promoters

NARCIS (Netherlands)

Torres Trueba, A.; Rovetto, L.J.; Florusse, L.J.; Kroon, M.C.; Peters, C.J.

2011-01-01

Phase equilibrium measurements of single and mixed organic clathrate hydrates with hydrogen were determined within a pressure range of 2.0–14.0 MPa. The organic compounds studied were furan, 2,5-dihydrofuran, tetrahydropyran, 1,3-dioxolane and cyclopentane. These organic compounds are known to form

Methane Hydrate in Confined Spaces: An Alternative Storage System.

Science.gov (United States)

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

2018-03-14

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

Exploring the possibility to store the mixed oxygen-hydrogen cluster in clathrate hydrate in molar ratio 1:2 (O2+2H2).

Science.gov (United States)

Qin, Yan; Du, Qi-Shi; Xie, Neng-Zhong; Li, Jian-Xiu; Huang, Ri-Bo

2017-05-01

An interesting possibility is explored: storing the mixture of oxygen and hydrogen in clathrate hydrate in molar ratio 1:2. The interaction energies between oxygen, hydrogen, and clathrate hydrate are calculated using high level quantum chemical methods. The useful conclusion points from this study are summarized as follows. (1) The interaction energies of oxygen-hydrogen mixed cluster are larger than the energies of pure hydrogen molecular cluster. (2) The affinity of oxygen molecules with water molecules is larger than that of the hydrogen molecules with water molecules. (3) The dimension of O 2 -2H 2 interaction structure is smaller than the dimension of CO 2 -2H 2 interaction structure. (4) The escaping energy of oxygen molecules from the hydrate cell is larger than that of the hydrogen molecules. (5) The high affinity of the oxygen molecules with both the water molecules and the hydrogen molecules may promote the stability of oxygen-hydrogen mixture in the clathrate hydrate. Therefore it is possible to store the mixed (O 2 +2H 2 ) cluster in clathrate hydrate. Copyright © 2017 Elsevier Inc. All rights reserved.

Methane Storage in Biosilica-Supported Semiclathrates at Ambient Temperature and Pressure

Science.gov (United States)

Li, Liang; Wang, Suying; Wang, Weixing

2018-01-01

Two key issues regarding the use of clathrates and semiclathrates for practical gas storage and transport is the pressure-temperature stability of the material and very low formation kinetics. For many practical applications, the avoidance of cooling, gas overpressure, and mechanical mixing would be very desirable. Here, we show that biosilica supports from rice husks greatly enhance gases uptake kinetics in tetra-iso-amyl ammonium bromide semiclathrates without introducing complex mixing technologies. These systems show excellent thermal stability and good recyclability.

Collagen tissue treated with chitosan solution in H2O/CO2 mixtures: Influence of clathrates hydrates on the structure and mechanical properties.

Science.gov (United States)

Chaschin, Ivan S; Bakuleva, Natalia P; Grigoriev, Timofei E; Krasheninnikov, Sergey V; Nikitin, Lev N

2017-03-01

A mixture of water/carbon dioxide is a "green" perspective solvent from the viewpoint of biomedical applications. Clathrate hydrates are formed this solvent under certain conditions and a very interesting question is the impact of clathrates hydrates on the structure and properties of bovine pericardium, which is used in biomedicine, in particular as a main part of biological heart valve prostheses. The aim of the present work is to investigate the influence of clathrates on the structure and mechanical properties of the collagen tissue treated with chitosan in H 2 O/CO 2 mixtures under pressure 3.0-3.5MPa and temperatures 2-4°C. It was first found that the clathrate hydrates in this media due to the strong fluctuations "bomb" collagen tissue of bovine pericardium, which is manifested in the appearance of numerous small gaps (pores) with mean size of 225±25nm and large pores with size of 1-3μ on the surface and within collagen matrices. High porosity leads to averaging characteristics of the organization structure in tissues with different orientation of the collagen fibers. As a result, the mechanical properties of the collagen tissue with a different orientation of the collagen fibrils become similar, which is quite different from their original properties. The structural changes caused by the influence of the environment clathrate hydrates led to a significant decrease of the tensile strength (30-47% in total, p<0.05) and initial elastic moduli (74-83%, p<0.05). However, the final elastic moduli and the maximum tensile virtually unchanged compared to the control. Nevertheless, it was found that the direct deposition of chitosan from the H 2 O/CO 2 mixtures with clathrate improve the mechanical-strength properties of the porous matrices. We believe that these improved mechanical properties are achieved due to particularly deep and uniform impregnation of the collagen matrix with chitosan from its pressurized solutions in H 2 O/CO 2 mixtures. Copyright © 2016

Experimental study of methanic fermentation of straw

Energy Technology Data Exchange (ETDEWEB)

Dopter, P; Beerens, H

1952-12-03

The amount of liquid manure obtainable was a limiting factor in methanic fermentation of wheat straw. An equal volume of 0.2% aqueous solution of Na formate could be substituted for 90% of the normal requirements of liquid manure. This shortened the preliminary stages of cellulosic fermentation when no methane was produced and slightly increased the subsequent yield of methane.

Systematic Studies on Anharmonicity of Rattling Phonons in Type I Clathrates by Low Temperature Heat Capacity Measurements

Science.gov (United States)

Tanigaki, Katsumi; Wu, Jiazhen; Tanabe, Yoichi; Heguri, Satoshi; Shiimotani, Hidekazu; Tohoku University Collaboration

2014-03-01

Clathrates are featured by cage-like polyhedral hosts mainly composed of the IVth group elements of Si, Ge, or Sn and alkali metal or alkaline-earth metal elements can be accommodated inside as a guest atom. One of the most intriguing issues in clathrates is their outstanding high thermoelectric performances thanks to the low thermal conductivity. Being irrespective of good electric conductivity σ, the guest atom motions provide a low-energy lying less-dispersive phonons and can greatly suppress thermal conductivity κ. This makes clathrates close to the concept of ``phonon glass electron crystal: PGEC'' and useful in thermoelectric materials from the viewpoint of the figure of merit. In the present study, we show that the local phonon anharmonicity indicated by the tunneling-term of the endohedral atoms (αT) and the itinerant-electron term (γeT), both of which show T-linear dependences in specific heat Cp, can successfully be separated by employing single crystals with various carrier concentrations in a wide range of temperture experimennts. The factors affecting on the phonon anharmonicity as well as the strength of electron-phonon interactions will be discussed based on our recent experiments. The research was financially supported by Ministry of Education, Science, Sports and Culture, Grant in Aid for Science, and Technology of Japan.

A Possible Sink for Methane on Mars

NARCIS (Netherlands)

Nørnberg, P.; Jensen, S. J. K.; Skibsted, J.; Jakobsen, H. J.; ten Kate, I. L.; Gunnlaugsson, H. P.; Merrison, J. P.; Finster, K.; Bak, E.; Iversen, J. J.; Kondrup, J. C.

2014-01-01

Mechanical simulated wind activation of mineral surfaces act as a trap for Methane through formation of covalent Si-C bonds stable up to temperatures above 250 C. This mechanism is proposed as a Methane sink on Mars.

Experimental determination of methane hydrate formation in the presence of ammonia

Energy Technology Data Exchange (ETDEWEB)

Dong, T.B.; Wang, L.Y.; Liu, A.X.; Guo, X.Q.; Chen, G.J.; Ma, Q.L.; Li, G.W. [China Univ. of Petroleum, Beijng (China). State Key Laboratory of Heavy Oil Processing

2008-07-01

Gas hydrates are non-stoichiometric inclusion compounds that are created by a lattice of water molecules. The host molecule has a strong hydrogen bond and encages low molecular weight gases or volatile liquids. The guest molecules favor hydrate formation. Historically, gas hydrates have been thought to be problematic during natural gas transportation because the formed solid hydrate can block pipelines and cause tubing and casing collapse. However, the discovery of huge deposits of gas hydrates in deep-sea sediments and in permafrost has renewed interest in gas hydrates as a new energy resource. This paper discussed a study that is a part of an ongoing experimental and computational program dealing with the thermodynamics of gas hydrate formation in ammonia-water systems. The purpose of the study was to develop a new method to separate and recycle the vent gas of ammonia synthesis by forming or dissociating hydrate. The hydrate-forming conditions of methane in ammonia and water system were studied and reported in this paper with reference to the experimental apparatus and procedure. The materials and preparation of samples were also explained. The experimental results showed that the ammonia had an inhibitive effect on the hydrate formation. 26 refs., 2 tabs., 3 figs.

Hydrothermal waste package interactions with methane-containing basalt groundwater

International Nuclear Information System (INIS)

McGrail, B.P.

1984-01-01

Hydrothermal waste package interaction tests were conducted with a mixture of crushed glass, basalt, and steel in methane-containing synthetic basalt groundwater. In the absence of gamma radiolysis, methane was found to have little influence on the corrosion behavior of the waste package constituents. Under gamma radiolysis, methane was found to significantly lower the solution oxidation potential when compared to identical tests without methane. In addition, colloidal hydrocarbon polymers that have been produced under the irradiation conditions of these experiments were not formed. The presence of the waste package constituents apparently inhibited the formation of the polymers. However, the mechanism which prevented their formation was not determined

Gas hydrates and clathrates. Flow assurance, environmental and economic perspectives and the Nigerian liquefied natural gas project

International Nuclear Information System (INIS)

Gbaruko, B.C.; Igwe, J.C.; Nwokeoma, R.C.; Gbaruko, P.N.

2007-01-01

Gas hydrates are nonstoichiometric crystalline compounds that belong to the inclusion group known as clathrates. They occur when water molecules attach themselves together through hydrogen bonding and form cavities which can be occupied by a single gas or volatile liquid molecule. Gas hydrates, asphaltenes and waxes are three major threats to flow assurance that must be well assessed by design team uptime. Gas hydrates are also looked upon as a future energy source and as a potential climate hazard. The purpose of this review is to show the chemistry and mechanism of gas hydrate formation, the problems they pose, especially to flow assurance, their system implications, their environmental and economic perspectives with respect to their prospects as storage and transport alternative to the liquefied natural gas technology. (author)

The anomalous halogen bonding interactions between chlorine and bromine with water in clathrate hydrates.

Science.gov (United States)

Dureckova, Hana; Woo, Tom K; Udachin, Konstantin A; Ripmeester, John A; Alavi, Saman

2017-10-13

Clathrate hydrate phases of Cl 2 and Br 2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen-halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen-halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme-substrate compounds. The nature of the halogen-water interactions for the Cl 2 and Br 2 molecules in two isolated clathrate hydrate cages has recently been studied with ab initio calculations and Natural Bond Order analysis (Ochoa-Resendiz et al. J. Chem. Phys. 2016, 145, 161104). Here we present the results of ab initio calculations and natural localized molecular orbital analysis for Cl 2 and Br 2 guests in all cage types observed in the cubic structure I and tetragonal structure I clathrate hydrates to characterize the orbital interactions between the dihalogen guests and water. Calculations with isolated cages and cages with one shell of coordinating molecules are considered. The computational analysis is used to understand the nature of the halogen bonding in these materials and to interpret the guest positions in the hydrate cages obtained from the X-ray crystal structures.

Effects of ensiling treatments on lactic acid production and supplementary methane formation of maize and amaranth--an advanced green biorefining approach.

Science.gov (United States)

Haag, Nicola Leonard; Nägele, Hans-Joachim; Fritz, Thomas; Oechsner, Hans

2015-02-01

A green biorefinery enables the material and energetic use of biomass via lactic acid and methane production. Different ensiling techniques were applied to maize and amaranth with the aim to increase the amount of lactic acid in the silage. In addition the methane formation potential of the ensiled samples and the remaining solid residues after separating the organic juice were assessed. Treating maize with homofermentative lactic acid bacteria in combination with carbonated lime increased the amount of lactic acid about 91.9%. For amaranth no additional lactic acid production was obtained by treating the raw material. Specific methane yields for the solid residues of amaranth were significantly lower in comparison to the corresponding silages. The most promising treatment resulted in a production of 127.9±4.1 g kg(-1) DM lactic acid and a specific methane yield for the solid residue of 349.5±6.6 lN kg(-1) ODM. Copyright © 2014 Elsevier Ltd. All rights reserved.

Distribution of Al atoms in the clathrate-I phase Ba8AlxSi46-x at x = 6.9.

Science.gov (United States)

Bobnar, Matej; Böhme, Bodo; Wedel, Michael; Burkhardt, Ulrich; Ormeci, Alim; Prots, Yurii; Drathen, Christina; Liang, Ying; Nguyen, Hong Duong; Baitinger, Michael; Grin, Yuri

2015-07-28

The clathrate-I phase Ba8AlxSi46-x has been structurally characterized at the composition x = 6.9 (space group Pm3[combining macron]n, no. 223, a = 10.4645(2) Å). A crystal structure model comprising the distribution of aluminium and silicon atoms in the clathrate framework was established: 5.7 Al atoms and 0.3 Si atoms occupy the crystallographic site 6c, while 1.2 Al atoms and 22.8 Si atoms occupy site 24k. The atomic distribution was established based on a combination of (27)Al and (29)Si NMR experiments, X-ray single-crystal diffraction and wavelength-dispersive X-ray spectroscopy.

Methane recovery from coal mine gas using hydrate formation in water-in-oil emulsions

International Nuclear Information System (INIS)

Zhong, Dong-Liang; Ding, Kun; Lu, Yi-Yu; Yan, Jin; Zhao, Wei-Long

2016-01-01

Highlights: • A water-in-oil emulsion was developed for CH_4 separation from coal mine methane gas. • Stable W/O emulsions were obtained with water cut in the range of (10–70%). • Gas hydrates nucleated faster with the reduction of water–oil volume ratio. • Gas uptake increased with the decrease of water–oil volume ratio. • CH_4 recovery was greatly enhanced by hydrate formation in W/O emulsions. - Abstract: In this work, a water-in-oil (W/O) emulsion was developed using liquid water, mineral oil, Sorbitan monooleate (Span 80), and cyclopentane. It was employed to enhance gas hydrate formation for CH_4 separation from a simulated coal mine methane (CMM) gas (30 mol% CH_4, 60 mol% N_2, and 10 mol% O_2). The stability test at atmospheric pressure and at a high pressure of 3.5 MPa showed that stable W/O emulsions were obtained when the water–oil volume ratio (WOR) was below 80%. The emulsified droplets size was measured with WOR ranging from 10% to 70%. Then kinetic experiments of CH_4 separation by hydrate formation in W/O emulsions were carried out at 273.6 K and (3.5–5.0) MPa in batch operation. The results indicated that water–oil volume ratio is a key factor that affects the kinetics of gas hydrate formation from the CMM gas mixture. Hydrate nucleation was observed to occur faster while WOR was decreased, and gas uptake increased significantly with the decrease of WOR. CH_4 concentration in the recovered gas mixture was increased to 52 mol% as compared to 30 mol% in the original gas mixture through one-stage hydrate formation in the W/O emulsions. It was found that the experimental conditions of 273.6 K, 3.5 MPa and WOR = 30% were favorable for CH_4 recovery from the CMM gas. The CH_4 recovery obtained under these conditions was 43%. It was higher than those obtained at WOR = 10% and 70%, and was greatly increased as compared with those obtained in the same reactor with the presence of TBAB (26%) and CP (33%).

Reaction of methane with coal

Energy Technology Data Exchange (ETDEWEB)

Yang, K.; Batts, B.D.; Wilson, M.A.; Gorbaty, M.L.; Maa, P.S.; Long, M.A.; He, S.J.X.; Attala, M.I. [Macquarie University, Macquarie, NSW (Australia). School of Chemistry

1997-10-01

A study of the reactivities of Australian coals and one American coal with methane or methane-hydrogen mixtures, in the range 350-400{degree}C and a range of pressures (6.0-8.3 MPa, cold) is reported. The effects of aluminophosphates (AIPO) or zeolite catalysts, with and without exchanged metals, on reactivity have also been examined. Yields of dichloromethane extractable material are increased by using a methane rather than a nitrogen atmosphere and different catalysts assist dissolution to various extends. It appears that surface exchanged catalysts are effective, but incorporating metals during AIPO lattice formation is detrimental. Aluminium phosphate catalysts are unstable to water produced during coal conversion, but are still able to increase extraction yields. For the American coal, under methane-hydrogen and a copper exchanged zeolite, 51.5% conversion was obtained, with a product selectivity close to that obtained under hydrogen alone, and with only 2% hydrogen consumption. The conversion under methane-hydrogen was also to that obtained under hydrogen alone, while a linear dependence of conversion on proportion of methane would predict a 43% conversion under methane-hydrogen. This illustrates a synergistic effect of the methane-hydrogen atmosphere for coal liquefaction using this catalyst systems. 31 refs., 5 figs., 7 tabs.

An effect of surface properties on detachment of adhered solid to cooling surface for formation of clathrate hydrate slurry

Science.gov (United States)

Daitoku, Tadafumi; Utaka, Yoshio

In air-conditioning systems, it is desirable that the liquid-solid phase change temperature of a cool energy storage material is approximately 10 °C from the perspective of improving coefficient of performance (COP). Moreover, a thermal storage material that forms slurry can realize large heat capacity of working fluids. Since the solid that adheres to the heat transfer surface forms a thermal resistance layer and remarkably reduces the rate of cold storage, it is important to avoid the adhesion of a thick solid layer on the surface so as to realize efficient energy storage. Considering a harvest type cooling unit, the force required for removing the solid phase from the heat transfer surface was studied. Tetra-n-butylammonium Bromide (TBAB) clathrate hydrate was used as a cold storage material. The effect of the heat transfer surface properties on the scraping force for detachment of adhered solid of TBAB hydrate to the heat transfer surface was examined experimentally.

Synergistic methane formation kinetics for hydrogen impact on carbon

International Nuclear Information System (INIS)

Haasz, A.A.; Davis, J.W.

1986-06-01

A physical/chemical model is presented for the reaction kinetics for methane formation from carbon, due to bombardment by energetic (∼ 100's eV) H + ions and thermal (∼ 1 eV) H 0 atoms. While the model was developed for H + and H 0 , it can be readily applied to non-hydrogenic energetic particles (ions or atoms, e.g., Ar + , He + , He) in combination with thermal (∼ 1 eV) hydrogen (again ions or atoms) impacting on carbon. Both collisional (in the case of the energetic particles) and chemical reaction processes are included. Special cases of sub-eV H 0 alone, energetic H + alone and combined H 0 plus H + were considered and fitted to experimental data. Generally good agreement was found between theoretical predictions and experimental results over the experimental flux and H + energy ranges studied (H 0 flux: 6x10 14 - 7x10 15 H 0 /cm 2 s, H + flux: 6x10 12 - 5x10 15 H + /cm 2 s, H + energy: 300 eV/H + and 1 keV/H + )

Iodine capture by Hofmann-type clathrate Ni(II)(pz)[Ni(II)(CN)_4

International Nuclear Information System (INIS)

Massasso, Giovanni; Long, Jerome; Haines, Julien; Devautour-Vinot, Sabine; Maurin, Guillaume; Larionova, Joulia; Guerin, Christian; Guari, Yannick; Grandjean, Agnes; Onida, Barbara; Donnadieu, Bruno

2014-01-01

The thermally stable Hofmann-type clathrate framework Ni(II)(pz)[Ni(II)(CN)_4] (pz = pyrazine) was investigated for the efficient and reversible sorption of iodine (I_2) in the gaseous phase and in solution with a maximum adsorption capacity of 1 mol of I_2 per 1 mol of Ni(II)pz)[Ni(II)(CN)_4] in solution. (authors)

Hydrothermal waste package interactions with methane-containing basalt groundwater

International Nuclear Information System (INIS)

McGrail, B.P.

1984-11-01

Hydrothermal waste package interaction tests with methane-containing synthetic basalt groundwater have shown that in the absence of gamma radiolysis, methane has little influence on the glass dissolution rate. Gamma radiolysis tests at fluxes of 5.5 x 10 5 and 4.4 x 10 4 R/hr showed that methane-saturated groundwater was more reducing than identical experiments where Ar was substituted for CH 4 . Dissolved methane, therefore, may be beneficial to the waste package in limiting the solubility of redox sensitive radionuclides such a 99 Tc. Hydrocarbon polymers known to form under the irradiation conditions of these tests were not produced. The presence of the waste package constituents apparently inhibited the formation of the polymers, however, the mechanism which prevented their formation was not determined

Detection of Abiotic Methane in Terrestrial Continental Hydrothermal Systems: Implications for Methane on Mars

Science.gov (United States)

Socki, Richard A.; Niles, Paul B.; Gibson, Everett K., Jr.; Romanek, Christopher S.; Zhang, Chuanlun L.; Bissada, Kadry K.

2008-01-01

The recent detection of methane in the Martian atmosphere and the possibility that its origin could be attributed to biological activity, have highlighted the importance of understanding the mechanisms of methane formation and its usefulness as a biomarker. Much debate has centered on the source of the methane in hydrothermal fluids, whether it is formed biologically by microorganisms, diagenetically through the decomposition of sedimentary organic matter, or inorganically via reduction of CO2 at high temperatures. Ongoing research has now shown that much of the methane present in sea-floor hydrothermal systems is probably formed through inorganic CO2 reduction processes at very high temperatures (greater than 400 C). Experimental results have indicated that methane might form inorganically at temperatures lower still, however these results remain controversial. Currently, methane in continental hydrothermal systems is thought to be formed mainly through the breakdown of sedimentary organic matter and carbon isotope equilibrium between CO2 and CH4 is thought to be rarely present if at all. Based on isotopic measurements of CO2 and CH4 in two continental hydrothermal systems, we suggest that carbon isotope equilibration exists at temperatures as low as 155 C. This would indicate that methane is forming through abiotic CO2 reduction at lower temperatures than previously thought and could bolster arguments for an abiotic origin of the methane detected in the martian atmosphere.

The formation of gas hydrates and the effect of inhibitiors on their ...

African Journals Online (AJOL)

Natural gas hydrate is a solid crystalline compound produced by combining water and gas and it is considered as the clathrates. Guest gas molecules are stuck insider the pores of water networks produced by hydrogen bonds between molecules of water. There are different ways to analyze the hydrate formation operating ...

NH3 quantum rotators in Hofmann clathrates: intensity and width of rotational transition lines

International Nuclear Information System (INIS)

Vorderwisch, Peter; Sobolev, Oleg; Desmedt, Arnaud

2004-01-01

Inelastic structure factors for rotational transitions of uniaxial NH 3 quantum rotators, measured in a Hofmann clathrate with biphenyl as guest molecule, agree with those calculated for free rotators. A finite intrinsic line width, found for rotational transitions involving the rotational level j=3 at low temperature, supports a recently suggested model based on resonant rotor-rotor coupling

Methane excess in Arctic surface water-triggered by sea ice formation and melting.

Science.gov (United States)

Damm, E; Rudels, B; Schauer, U; Mau, S; Dieckmann, G

2015-11-10

Arctic amplification of global warming has led to increased summer sea ice retreat, which influences gas exchange between the Arctic Ocean and the atmosphere where sea ice previously acted as a physical barrier. Indeed, recently observed enhanced atmospheric methane concentrations in Arctic regions with fractional sea-ice cover point to unexpected feedbacks in cycling of methane. We report on methane excess in sea ice-influenced water masses in the interior Arctic Ocean and provide evidence that sea ice is a potential source. We show that methane release from sea ice into the ocean occurs via brine drainage during freezing and melting i.e. in winter and spring. In summer under a fractional sea ice cover, reduced turbulence restricts gas transfer, then seawater acts as buffer in which methane remains entrained. However, in autumn and winter surface convection initiates pronounced efflux of methane from the ice covered ocean to the atmosphere. Our results demonstrate that sea ice-sourced methane cycles seasonally between sea ice, sea-ice-influenced seawater and the atmosphere, while the deeper ocean remains decoupled. Freshening due to summer sea ice retreat will enhance this decoupling, which restricts the capacity of the deeper Arctic Ocean to act as a sink for this greenhouse gas.

Anaerobic digestion of glucose with separated acid production and methane formation

Energy Technology Data Exchange (ETDEWEB)

Cohen, R J; Zoetemeyer, R J; Van Deursen, A; Van Andel, J G

1979-01-01

In a two-phase anaerobic-digestion system, with separate reactors for the acidification and methane fermentation phases, the glucose of a 1% glucose solution was almost completely converted into biomass and gases. The acid reactor was operated at 30/sup 0/C and a pH of 6.0, with a retention time of 10 h. The main products of the acid-forming phase were hydrogen, carbon dioxide, butyrate and acetate. On a molar base, these products represented over 96% of all products formed. On average, 12% of the COD content of the influent was evolved as hydrogen. The effluent of the first reactor was pumped to the methane reactor after passing through a storage vessel. The methane reactor was operated at 30/sup 0/C, pH 7.8 and a retention time of 100 h. Approximately 98% of the organic substances fed to this reactor were converted to methane, carbon dioxide and biomass. About 11% of the glucose fed to the digesting system was converted to bacterial mass.

Heterogeneous Nucleation of Methane Hydrate in a Water-Decane-Methane Emulsion

Science.gov (United States)

Shestakov, V. A.; Kosyakov, V. I.; Manakov, A. Yu.; Stoporev, A. S.; Grachev, E. V.

2018-07-01

Heterogeneous nucleation in disperse systems with metastable disperse phases plays an important role in the mechanisms of environmental and technological processes. The effect the concentration and activity of particles that initiate the formation of a new phase have on nucleation processes in such systems is considered. An approach is proposed that allows construction of a spectrum of particle activity characterizing the features of nucleation in a sample, based on the fraction of crystallized droplets depending on the level of supercooling and the use of Weibull's distribution. The proposed method is used to describe experimental data on the heterogeneous nucleation of methane hydrate in an emulsion in a water-decane-methane system.

Anaerobic digestion of gucose with separated acid production and methane formation

Energy Technology Data Exchange (ETDEWEB)

Cohen, A; Zoetemeyer, R J; van Deursen, A; van Andel, J G

1979-01-01

In a two-phase anaerobic-digestion system, with separate reactors for the acidification phase and the methane fermentation phase, the Universiteit van Amsterdam found the glucose of a 1% glucose solution (sucrose/starch-containing wastewater from agricultural industries) to be almost completely converted into biomass and gases. The acid reactor was operated at 86/sup 0/F (30/sup 0/C) and pH 6.0, with a retention time of 10 hr. The main products of the acid-forming phase were hydrogen, carbon dioxide, butyrate, and acetate. On a molar base, these products represented over 96% of all products formed. On the average, 12% of the chemical-oxygen-demand content of the influent was evolved as hydrogen. The effluent of the first reactor went to the methane reactor after passing through a storage vessel. The methane reactor operated at 86/sup 0/F (30/sup 0/C), pH 7.8, and a retention time of 100 hr. Approximately 98% of the organic substances fed to this reactor was converted to methane, carbon dioxide, and biomass. About 11% of the glucose fed to the digesting system was converted to bacterial mass.

Geodetic data support trapping of ethane in Titan's polar crust

Science.gov (United States)

Sotin, Christophe; Rambaux, Nicolas

2016-04-01

Titan's surface is characterized by polar depressions that strongly influence interpretations of the gravity data. This study investigates several geodynamical models that can explain these depressions. For each model, the values of the three moments of inertia are computed numerically by discretizing the interior in spherical coordinates. The study shows that a Pratt model where the polar subsurface is made of ethane clathrates can explain the polar depression, the abrupt jump in altitude at about 60 degrees latitude, and the values of the degree 2 gravity coefficients. This model, proposed by Choukroun and Sotin [1], is based on the stability of ethane clathrate hydrates relative to methane clathrate hydrates. In addition to fitting the geodetic data, it explains the absence of ethane in Titan's atmosphere although ethane is the main product of the photolysis of methane. Other geophysical models based on latitudinal variations in the tidal heating production or in the heat flux at the base of the icy crust do not provide such a good match to the gravity and topographic observations. The ethane-clathrate model predicts that all the ethane produced by photolysis of methane at the present rate during the last billion years could be stored in the polar subsurface. It is consistent with the age of Titan's surface and that of Titan's atmospheric methane inferred from geological and geochemical observations by the Cassini/Huygens mission. The present study also emphasizes the role of mass anomalies on the interpretation of the degree 2 gravity coefficients. It shows that for Titan, a slow rotator, the values of the two equatorial moments of inertia (MoI) are largely affected by the polar depressions whereas the value of polar MoI is not. Therefore, as pointed out by previous calculations [2], calculating the moment of inertia (MoI) factor from the value of J2 could lead to major errors. This is not the case for our preferred Titan's model for which the negative polar

Hydrate phase equilibrium and structure for (methane + ethane + tetrahydrofuran + water) system

International Nuclear Information System (INIS)

Sun Changyu; Chen Guangjin; Zhang Lingwei

2010-01-01

The separation of methane and ethane through forming hydrate is a possible choice in natural gas, oil processing, or ethylene producing. The hydrate formation conditions of five groups of (methane + ethane) binary gas mixtures in the presence of 0.06 mole fraction tetrahydrofuran (THF) in water were obtained at temperatures ranging from (277.7 to 288.2) K. In most cases, the presence of THF in water can lower the hydrate formation pressure of (methane + ethane) remarkably. However, when the composition of ethane is as high as 0.832, it is more difficult to form hydrate than without THF system. Phase equilibrium model for hydrates containing THF was developed based on a two-step hydrate formation mechanism. The structure of hydrates formed from (methane + ethane + THF + water) system was also determined by Raman spectroscopy. When THF concentration in initial aqueous solution was only 0.06 mole fraction, the coexistence of structure I hydrate dominated by ethane and structure II hydrate dominated by THF in the hydrate sample was clearly demonstrated by Raman spectroscopic data. On the contrary, only structure II hydrate existed in the hydrate sample formed from (methane + ethane + THF + water) system when THF concentration in initial aqueous solution was increased to 0.10 mole fraction. It indicated that higher THF concentration inhibited the formation of structure I hydrate dominated by ethane and therefore lowered the trapping of ethane in hydrate. It implies a very promising method to increase the separation efficiency of methane and ethane.

Experimental investigation of methane release from hydrate formation in sandstone through both hydrate dissociation and CO{sub 2} sequestration

Energy Technology Data Exchange (ETDEWEB)

Husebo, J.; Graue, A.; Kvamme, B. [Bergen Univ., Bergen (Norway). Dept. of Physics and Technology; Stevens, J.; Howard, J.J. [ConocoPhillips, Ponca City, OK (United States); Baldwin, B.A. [Green Country Petrophysics LLC, Dewey, OK (United States)

2008-07-01

Large amounts of natural gas trapped in hydrate reservoirs are found in Arctic regions and in deep offshore locations around the world. Natural gas production from hydrate deposits offer significant potential for future energy needs. However, research is needed in order to propose potential production schemes for natural gas hydrates. Natural gas molecules can be freed from hydrate structured cages by depressurization, by heating and by exposing the hydrate to a substance that will form a thermodynamically more stable hydrate structure. This paper provided a comparison of two approaches for releasing methane from methane hydrate in porous sandstone. The study scope covered the dissociation rate of methane hydrate in porous media through depressurization, and also referred to previous work done on producing methane from hydrates in sandstone while sequestering carbon dioxide (CO{sub 2}). The study was conducted in a laboratory setting. The paper discussed the experimental design which included the placing of a pressure- and temperature-controlled sample holder inside the bore of a magnetic resonance imager. The experimental procedures were then outlined, with reference to hydrate formation; carbon dioxide sequestration; hydrate dissociation experiments with constant volume; and hydrate dissociation experiments at constant pressure. The constant volume experiments demonstrated that in order to dissociate a large amount of hydrate, the initial depressurization had to be significantly lower than the hydrate stability pressure. 9 refs., 9 figs.

Direct Aromaization of Methane

Energy Technology Data Exchange (ETDEWEB)

George Marcelin

1997-01-15

The thermal decomposition of methane offers significant potential as a means of producing higher unsaturated and aromatic hydrocarbons when the extent of reaction is limited. Work in the literature previous to this project had shown that cooling the product and reacting gases as the reaction proceeds would significantly reduce or eliminate the formation of solid carbon or heavier (Clo+) materials. This project studied the effect and optimization of the quenching process as a means of increasing the amount of value added products during the pyrolysis of methane. A reactor was designed to rapidly quench the free-radical combustion reaction so as to maximize the yield of aromatics. The use of free-radical generators and catalysts were studied as a means of lowering the reaction temperature. A lower reaction temperature would have the benefits of more rapid quenching as well as a more feasible commercial process due to savings realized in energy and material of construction costs. It was the goal of the project to identify promising routes from methane to higher hydrocarbons based on the pyrolysis of methane.

Phase equilibria, crystal chemistry, electronic structure and physical properties of Ag-Ba-Ge clathrates

Energy Technology Data Exchange (ETDEWEB)

Zeiringer, I.; Chen Mingxing [Institute of Physical Chemistry, University of Vienna, Waehringerstr. 42, 1090 Wien (Austria); Bednar, I.; Royanian, E.; Bauer, E. [Institute of Solid State Physics, Vienna University of Technology, Wiedner Hauptstr. 8-10, 1040 Wien (Austria); Podloucky, R.; Grytsiv, A. [Institute of Physical Chemistry, University of Vienna, Waehringerstr. 42, 1090 Wien (Austria); Rogl, P., E-mail: peter.franz.rogl@univie.ac.at [Institute of Physical Chemistry, University of Vienna, Waehringerstr. 42, 1090 Wien (Austria); Effenberger, H. [Institute of Mineralogy and Crystallography, University of Vienna, A-1090 Wien (Austria)

2011-04-15

In the Ag-Ba-Ge system the clathrate type-{Iota} solid solution, Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y}, extends at 800 deg. C from binary Ba{sub 8}Ge{sub 43{open_square}3} ({open_square} is a vacancy) to Ba{sub 8}Ag{sub 5.3}Ge{sub 40.7}. For the clathrate phase (1 {<=} x {<=} 5.3) the cubic space group Pm3-bar n was established by X-ray powder diffraction and confirmed by X-ray single-crystal analyses of the samples Ba{sub 8}Ag{sub 2.3}Ge{sub 41.9{open_square}1.8} and Ba{sub 8}Ag{sub 4.4}Ge{sub 41.3{open_square}0.3}. Increasing the concentration of Ag causes the lattice parameters of the solid solution to increase linearly from a value of a = 1.0656 (x = 0, y = 3) to a = 1.0842 (x = 4.8, y = 0) nm. Site preference determination using X-ray refinement reveals that Ag atoms preferentially occupy the 6d site randomly mixed with Ge and vacancies, which become filled in the compound Ba{sub 8}Ag{sub 4.8}Ge{sub 41.2} when the Ag content increases. At 600 {sup o}C the phase region of the clathrate solution Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y} becomes separated from the Ba-Ge boundary and extends from 6.6 to 9.8 at.% Ag. The compound Ba{sub 6}Ge{sub 25} (clathrate type-{Iota}X) dissolves at 800 {sup o}C a maximum of 1.5 at.% Ag. The homogeneity regions of the two ternary compounds BaAg{sub 2-x}Ge{sub 2+x} (ThCr{sub 2}Si{sub 2}-type, 0.2 {<=} x {<=} 0.7) and Ba(Ag{sub 1-x}Ge{sub x}){sub 2} (AlB{sub 2}-type, 0.65 {<=} x {<=} 0.75) were established at 800 deg. C. Studies of transport properties for the series of Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y} compounds evidenced that electrons are the predominant charge carriers with the Fermi energy close to a gap. Its position can be fine-tuned by the substitution of Ge by Ag atoms and by mechanical processing of the starting material, Ba{sub 8}Ge{sub 43}. The proximity of the electronic structure at Fermi energy of Ba{sub 8}Ag{sub x}Ge{sub 46-x-y{open_square}y} to a gap is also corroborated by density

An assessment of coalbed methane exploration projects in Canada

Energy Technology Data Exchange (ETDEWEB)

Dawson, F.M.; Marchioni, D.L.; Anderson, T.C.; McDougall, W.J. [Suncor Energy Inc., Calgary, AB (Canada)

2000-07-01

A critical assessment of coalbed methane exploration opportunities is presented. Geological and production data from 59 well bores drilled in Canada's major coal basins are evaluated to assess the coalbed methane potential of the deposits. Data acquisition, geology, gas content, coal quality, adsorption isotherms, formation testing, and a technical assessment are presented for each area. Areas with the best potential for economic coalbed methane accumulations are indicated. 6 refs., 153 figs., 99 tabs.

Template-Assisted Wet-Combustion Synthesis of Fibrous Nickel-Based Catalyst for Carbon Dioxide Methanation and Methane Steam Reforming.

Science.gov (United States)

Aghayan, M; Potemkin, D I; Rubio-Marcos, F; Uskov, S I; Snytnikov, P V; Hussainova, I

2017-12-20

Efficient capture and recycling of CO 2 enable not only prevention of global warming but also the supply of useful low-carbon fuels. The catalytic conversion of CO 2 into an organic compound is a promising recycling approach which opens new concepts and opportunities for catalytic and industrial development. Here we report about template-assisted wet-combustion synthesis of a one-dimensional nickel-based catalyst for carbon dioxide methanation and methane steam reforming. Because of a high temperature achieved in a short time during reaction and a large amount of evolved gases, the wet-combustion synthesis yields homogeneously precipitated nanoparticles of NiO with average particle size of 4 nm on alumina nanofibers covered with a NiAl 2 O 4 nanolayer. The as-synthesized core-shell structured fibers exhibit outstanding activity in steam reforming of methane and sufficient activity in carbon dioxide methanation with 100% selectivity toward methane formation. The as-synthesized catalyst shows stable operation under the reaction conditions for at least 50 h.

Radiation effects on methane in the presence of molecular sieves

International Nuclear Information System (INIS)

Shimizu, Y.; Nagai, S.; Hatada, M.

1983-01-01

Product analysis has been carried out for the radiation-induced reaction of methane in the presence of molecular sieves (MS) 3A, 4A, 5A and 13X. Irradiation of methane over MS 4A selectively produces C 2 hydrocarbons, while the use of MS 5A leads to C 2 and C 3 hydrocarbons. The selectivity and yields of these hydrocarbons, however, decrease with irradiation time, owing to deposition of carbonaceous solid produced from methane on the surface of the molecular sieves. The carbonaceous solid is decomposed to low-molecular-weight hydrocarbons when irradiated in an H 2 atmosphere. Material balance estimated for the radiation-chemical reaction of argon containing 2 mol% methane over MS 5A reveals that the carbonaceous solid is highly abundant in carbon atoms. On the other hand the formation of carbonaceous solids plays a less important role in the radiation-chemical reaction of methane in the presence of silica gel, which is found to exhibit greater activity for the formation of hydrocarbons than the molecular sieves. (author)

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

Science.gov (United States)

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

2018-03-01

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

Modeling dissociation behaviour of methane hydrate in porous soil media

Energy Technology Data Exchange (ETDEWEB)

Jayasinghe, A.G.; Grozic, J.L.H. [Calgary Univ., AB (Canada). Dept. of Civil Engineering

2008-07-01

Gas hydrates, or clathrates, exist in the form of crystalline solid structures of hydrogen bonded water molecules where the lattice cages are occupied by guest gas molecules. Methane gas hydrates are the most common. As such, hydrate bearing sediments are considered to be a potential future energy resource. Gas hydrates also function as a source or sink for atmospheric methane, which may influence global warming. The authors emphasized that an understanding of the behaviour of soils containing gas hydrates is necessary in order to develop ways of recovering the vast gas resources that exist in the form of hydrates, particularly since hydrates are also suspected to be a potential factor in the initiation and propagation of submarine slope failures. Gas hydrate dissociation occurs when water and gas are released, resulting in an increase in pore fluid pressure, thereby causing significant reductions in effective stress leading to sediment failure. Dissociation may occur as a result of pressure reductions or increases in temperature. This study focused on the strength and deformation behaviour of hydrate bearing soils associated with temperature induced dissociation. Modeling the dissociation behavior of hydrates in porous soil media involves an understanding of the geomechanics of hydrate dissociation. This paper addressed the issue of coupling the hydrate dissociation problem with the soil deformation problem. A mathematical framework was constructed in which the thermally stimulated hydrate dissociation process in porous soil media under undrained conditions was considered with conduction heat transfer. It was concluded that a knowledge of geomechanical response of hydrate bearing sediments will enable better estimates of benefits and risks associated with the recovery process, thereby ensuring safe and economical exploration. 20 refs., 1 fig., 1 appendix.

Methane-induced Activation Mechanism of Fused Ferric Oxide-Alumina Catalysts during Methane Decomposition

KAUST Repository

Reddy Enakonda, Linga

2016-06-27

Activation of Fe2O3-Al2O3 with CH4 (instead of H2) is a meaningful method to achieve catalytic methane decomposition (CMD). This reaction of CMD is more economic and simple against commercial methane steam reforming (MSR) as it produces COx-free H2. In this study, for the first time, structure changes of the catalyst were screened during CH4 reduction with time on stream. The aim was to optimize the pretreatment conditions through understanding the activation mechanism. Based on results from various characterization techniques, reduction of Fe2O3 by CH4 proceeds in three steps: Fe2O3→Fe3O4→FeO→Fe0. Once Fe0 is formed, it decomposes CH4 with formation of Fe3C, which is the crucial initiation step in the CMD process to initiate formation of multiwall carbon nanotubes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical trends of the band gaps of idealized crystal of semiconducting silicon clathrates, M8Si38A8 (M = Na, K, Rb, Cs; A = Ga, Al, In), predicted by first-principle pseudopotential calculations

International Nuclear Information System (INIS)

Imai, Yoji; Imai, Motoharu

2011-01-01

Research highlights: → This paper reports the results of electronic structural calculations of Si clathrate, M 8 Si 38 Ga 8 (M: the encapsulated guest alkali atom; Na, K, Rb, and Cs). → All of them are found to be indirect semiconductors with the calculated gaps (E g ) from 0.45 to 0.89 eV, which should be compared to the calculated gap of 0.65 eV of crystalline Si with the diamond structure. The gaps become wider with the promotion to the heavier guest alkali atoms and the reasons of gap widening are discussed using the calculated dependence of E g on the cell-volume of guest-free silicon clathrate (Si 46 ). Effect of the substitutional elements in the clathrate framework (Al and In in place of Ga) was also discussed. - Abstract: We have calculated the band structures of Si clathrate, M 8 Si 38 Ga 8 (M = Na, K, Rb, and Cs), using the density-functional theory under the generalized gradient corrected local density approximation, where M is the encapsulated guest alkali atom. They are found to be indirect semiconductors with the calculated gaps (E g ) from 0.45 to 0.89 eV, which should be compared to the calculated gap of 0.65 eV of crystalline Si with the diamond structure. The gaps become wider with the promotion to the heavier guest alkali atoms and the reasons of gap widening are discussed using the calculated dependence of E g on the cell-volume of guest-free silicon clathrate (Si 46 ). Effect of the substitutional elements in the clathrate framework (Al and In in place of Ga) was also discussed.

Methane clumped isotopes in the Songliao Basin (China): New insights into abiotic vs. biotic hydrocarbon formation

Science.gov (United States)

Shuai, Yanhua; Etiope, Giuseppe; Zhang, Shuichang; Douglas, Peter M. J.; Huang, Ling; Eiler, John M.

2018-01-01

Abiotic hydrocarbon gas, typically generated in serpentinized ultramafic rocks and crystalline shields, has important implications for the deep biosphere, petroleum systems, the carbon cycle and astrobiology. Distinguishing abiotic gas (produced by chemical reactions like Sabatier synthesis) from biotic gas (produced from degradation of organic matter or microbial activity) is sometimes challenging because their isotopic and molecular composition may overlap. Abiotic gas has been recognized in numerous locations on the Earth, although there are no confirmed instances where it is the dominant source of commercially valuable quantities in reservoir rocks. The deep hydrocarbon reservoirs of the Xujiaweizi Depression in the Songliao Basin (China) have been considered to host significant amounts of abiotic methane. Here we report methane clumped-isotope values (Δ18) and the isotopic composition of C1-C3 alkanes, CO2 and helium of five gas samples collected from those Xujiaweizi deep reservoirs. Some geochemical features of these samples resemble previously suggested identifiers of abiotic gas (13C-enriched CH4; decrease in 13C/12C ratio with increasing carbon number for the C1-C4 alkanes; abundant, apparently non-biogenic CO2; and mantle-derived helium). However, combining these constraints with new measurements of the clumped-isotope composition of methane and careful consideration of the geological context, suggests that the Xujiaweizi depression gas is dominantly, if not exclusively, thermogenic and derived from over-mature source rocks, i.e., from catagenesis of buried organic matter at high temperatures. Methane formation temperatures suggested by clumped-isotopes (167-213 °C) are lower than magmatic gas generation processes and consistent with the maturity of local source rocks. Also, there are no geological conditions (e.g., serpentinized ultramafic rocks) that may lead to high production of H2 and thus abiotic production of CH4 via CO2 reduction. We propose

Leaf surface wax is a source of plant methane formation under UV radiation and in the presence of oxygen

DEFF Research Database (Denmark)

Bruhn, Dan; Mikkelsen, Teis Nørgaard; Rolsted, M. M. M.

2014-01-01

to this, we demonstrated that the UV radiation-induced CH4 emission is independent of leaf area index above unity. Further, we observed that the presence of O2 in the atmosphere was necessary for achieving the highest rates of CH4 emission. Methane formation from leaf surface wax is supposedly a two...... investigated the potential of the leaf surface wax itself as a source of UV radiationinduced leaf aerobic CH4 formation. Isolated leaf surface wax emitted CH4 at substantial rates in response to UV radiation. This discovery has implications for how the phenomenon should be scaled to global levels. In relation...

Competition between intermolecular interaction and configuration entropy as the structure-determining factor for inclusion compounds

Energy Technology Data Exchange (ETDEWEB)

Subbotin, O.; Belosludov, V.; Adamova, T. [Russian Academy of Science, Novosibirsk (Russian Federation). Nikolaev Inst. of Inorganic Chemistry; Belosludov, R.; Kawazoe, Y. [Tohoku Univ., Aoba-ku, Sendai (Japan). Inst. for Materials Research; Kudoh, J.I. [Tohoku Univ., Aoba-ku, Sendai (Japan). Center for Northeast Asia Studies

2008-07-01

This paper presented a newly developed method to accurately predict the thermodynamic properties of clathrate hydrates, particularly their structural phase transitions under pressure. The method is based on the theory of Van-der-Waals and Platteeuw with some modifications that include the influence of guest molecules on the host lattice. The model was used to explain the exception from the established rule that small guest molecules form structure s1 and large molecules form structure s2 hydrates. In this study, the thermodynamic properties of argon (Ar) hydrate and methane hydrate, each in both cubic structure s1 and s2 were modelled. The model showed that two competing factors play a role in the formation of inclusions, notably the intermolecular interaction of guest molecules with water molecules, and the configuration entropy. Competition of these 2 factors determines the structure of hydrate formed at different pressures. The model provides an accurate description of the thermodynamic properties of gas hydrates and how they behave under pressure. For the argon hydrates, the structural phase transition from structure s2 to s1 at high pressure was predicted, while methane hydrates were predicted to be metastable in the s2 structure. The model can be used for other inclusion compounds with the same type of composition such as clathrate silicon, zeolites, and inclusion compounds of semiconductor elements. 17 refs., 5 figs.

Methane Hydrate Formation from Enhanced Organic Carbon Burial During Glacial Lowstands: Examples from the Gulf of Mexico

Science.gov (United States)

Malinverno, A.; Cook, A.; Daigle, H.; Oryan, B.

2017-12-01

Methane hydrates in fine-grained marine sediments are often found within veins and fractures occupying discrete depth intervals that are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the methane hydrate stability zone (MHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. We investigate here the hypothesis that these hydrate deposits form in sediments that were deposited during glacial lowstands and contain higher amounts of labile particulate organic carbon (POC), leading to enhanced microbial methanogenesis. During Pleistocene lowstands, river loads are deposited near the steep top of the continental slope and turbidity currents transport organic-rich, fine-grained sediments to deep waters. Faster sedimentation rates during glacial periods result in better preservation of POC because of decreased exposure times to oxic conditions. The net result is that more labile POC enters the methanogenic zone and more methane is generated in these sediments. To test this hypothesis, we apply an advection-diffusion-reaction model with a time-dependent deposition of labile POC at the seafloor controlled by glacioeustatic sea level variations in the last 250 kyr. The model is run for parameters estimated at three sites drilled by the 2009 Gulf of Mexico Joint Industry Project: Walker Ridge in the Terrebonne Basin (WR313-G and WR313-H) and Green Canyon near the canyon embayment into the Sigsbee Escarpment (GC955-H). In the model, gas hydrate forms in sediments with higher labile POC content deposited during the glacial cycle between 230 and 130 kyr (marine isotope stages 6 and 7). The corresponding depth intervals in the three sites contain hydrates, as shown by high bulk electrical resistivities and resistive subvertical fracture fills. This match supports the hypothesis that enhanced POC burial during glacial lowstands can result in hydrate formation from in situ

Methane Hydrate Formation from Enhanced Organic Carbon Burial During Glacial Lowstands: Examples from the Gulf of Mexico

Energy Technology Data Exchange (ETDEWEB)

Malinverno, Alberto; Cook, Ann; Daigle, Hugh; Oryan, Bar

2017-12-15

Methane hydrates in fine-grained marine sediments are often found within veins and fractures occupying discrete depth intervals that are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the methane hydrate stability zone (MHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. We investigate here the hypothesis that these hydrate deposits form in sediments that were deposited during glacial lowstands and contain higher amounts of labile particulate organic carbon (POC), leading to enhanced microbial methanogenesis. During Pleistocene lowstands, river loads are deposited near the steep top of the continental slope and turbidity currents transport organic-rich, fine-grained sediments to deep waters. Faster sedimentation rates during glacial periods result in better preservation of POC because of decreased exposure times to oxic conditions. The net result is that more labile POC enters the methanogenic zone and more methane is generated in these sediments. To test this hypothesis, we apply an advection-diffusion-reaction model with a time-dependent deposition of labile POC at the seafloor controlled by glacioeustatic sea level variations in the last 250 kyr. The model is run for parameters estimated at three sites drilled by the 2009 Gulf of Mexico Joint Industry Project: Walker Ridge in the Terrebonne Basin (WR313-G and WR313-H) and Green Canyon near the canyon embayment into the Sigsbee Escarpment (GC955-H). In the model, gas hydrate forms in sediments with higher labile POC content deposited during the glacial cycle between 230 and 130 kyr (marine isotope stages 6 and 7). The corresponding depth intervals in the three sites contain hydrates, as shown by high bulk electrical resistivities and resistive subvertical fracture fills. This match supports the hypothesis that enhanced POC burial during glacial lowstands can result in hydrate formation from in situ

Methane eddy covariance flux measurements from a low flying aircraft: Bridging the scale gap between local and regional emissions estimates

Science.gov (United States)

Sayres, D. S.; Dobosy, R.; Dumas, E. J.; Kochendorfer, J.; Wilkerson, J.; Anderson, J. G.

2017-12-01

The Arctic contains a large reservoir of organic matter stored in permafrost and clathrates. Varying geology and hydrology across the Arctic, even on small scales, can cause large variability in surface carbon fluxes and partitioning between methane and carbon dioxide. This makes upscaling from point source measurements such as small flux towers or chambers difficult. Ground based measurements can yield high temporal resolution and detailed information about a specific location, but due to the inaccessibility of most of the Arctic to date have only made measurements at very few sites. In August 2013, a small aircraft, flying low over the surface (5-30 m), and carrying an air turbulence probe and spectroscopic instruments to measure methane, carbon dioxide, nitrous oxide, water vapor and their isotopologues, flew over the North Slope of Alaska. During the six flights multiple comparisons were made with a ground based Eddy Covariance tower as well as three region surveys flights of fluxes over three areas each approximately 2500 km2. We present analysis using the Flux Fragment Method and surface landscape classification maps to relate the fluxes to different surface land types. We show examples of how we use the aircraft data to upscale from a eddy covariance tower and map spatial variability across different ecotopes.

Photofragment imaging of methane

International Nuclear Information System (INIS)

Heck, A.J.; Zare, R.N.; Chandler, D.W.

1996-01-01

The photolysis of methane is studied using photofragment imaging techniques. Our study reveals that the photolysis of methane proceeds via many different pathways. The photofragment imaging technique is used to resolve and characterize these various pathways and provides therefore unique insight into the dynamical processes that govern this photodissociation. The formation of H-atom photofragments following absorption of a Lyman-α photon, and H 2 photofragments following absorption of two ultraviolet photons (λ=210 endash 230 nm) are studied. The measured H-atom photofragment images reveal that a channel that produces fast H atoms concomitant with methyl fragments is dominant in the Lyman-α photolysis of methane. This channel leads to an anisotropic recoil of the fragments. A secondary channel is observed leading to the formation of somewhat slower H atoms, but an unique identification of this second channel is not possible from the data. At least part of these slower H atoms are formed via a channel that produces H atoms concomitant with CH and H 2 photofragments. The recoil of these slower H atoms appears to be isotropic. The measured, state-resolved H 2 (v,J), photofragment images reveal that two channels lead to H 2 photofragments from the two-photon photolysis of methane: a channel that leads to H 2 products concomitant with methylene fragments; and a channel that leads to H 2 products concomitant with CH and H fragments. H 2 (v,J) rotational and vibrational distributions are measured for each of these two channels separately. The H 2 products formed via the H 2 +CH 2 channel are rotationally and vibrationally highly excited, whereas those formed via the H 2 +CH+H channel are rotationally and vibrationally cooler. Rotational distributions of H 2 formed via the H 2 +CH+H channel are well reproduced by Boltzmann distributions. (Abstract Truncated)

Pressure-induced amorphization and collapse of magnetic order in the type-I clathrate Eu8Ga16Ge30

Science.gov (United States)

Mardegan, J. R. L.; Fabbris, G.; Veiga, L. S. I.; Adriano, C.; Avila, M. A.; Haskel, D.; Giles, C.

2013-10-01

We investigate the low temperature structural and electronic properties of the type-I clathrate Eu8Ga16Ge30 under pressure using x-ray powder diffraction (XRD), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD) techniques. The XRD measurements reveal a transition to an amorphous phase above 18 GPa. Unlike previous reports on other clathrate compounds, no volume collapse is observed prior to the crystalline-amorphous phase transition which takes place when the unit cell volume is reduced to 81% of its ambient pressure value. Fits of the pressure-dependent relative volume to a Murnaghan equation of state yield a bulk modulus B0=65±3 GPa and a pressure derivative B0'=3.3±0.5. The Eu L2-edge XMCD data shows quenching of the magnetic order at a pressure coincident with the crystalline-amorphous phase transition. This information along with the persistence of an Eu2+ valence state observed in the XANES spectra up to the highest pressure point (22 GPa) indicates that the suppression of XMCD intensity is due to the loss of long range magnetic order. When compared with other clathrates, the results point to the importance of guest ion-cage interactions in determining the mechanical stability of the framework structure and the critical pressure for amorphization. Finally, the crystalline structure is not found to recover after pressure release, resulting in an amorphous material that is at least metastable at ambient pressure and temperature.

Inhibition of Methane Hydrate Formation by Ice-Structuring Proteins

DEFF Research Database (Denmark)

Jensen, Lars; Ramløv, Hans; Thomsen, Kaj

2010-01-01

, assumed biodegradable, are capable of inhibiting the growth of methane hydrate (a structure I hydrate). The ISPs investigated were type III HPLC12 (originally identified in ocean pout) and ISP type III found in meal worm (Tenebrio molitor). These were compared to polyvinylpyrrolidone (PVP) a well...... of inhibitors. The profile of the nonlinear growth was concentration-dependent but also dependent on the stirring rate. ISP type III HPLC12 decreased the growth rate of methane hydrate during the linear growth period by 17−75% at concentrations of 0.01−0.1 wt % (0.014−0.14 mM) while ISP from Tenebrio molitor...... and PVP decreased the growth rate by 30% and 39% at concentrations of 0.004 wt % (0.005 mM) and 0.1 wt % (0.1 mM), respectively. Considering the low concentration of Tenebrio molitor ISP used, these results indicate that ISP from Tenebrio molitor is the most effective hydrate inhibitor among those...

Dissolved methane in New York groundwater, 1999-2011

Science.gov (United States)

Kappel, William M.; Nystrom, Elizabeth A.

2012-01-01

New York State is underlain by numerous bedrock formations of Cambrian to Devonian age that produce natural gas and to a lesser extent oil. The first commercial gas well in the United States was dug in the early 1820s in Fredonia, south of Buffalo, New York, and produced methane from Devonian-age black shale. Methane naturally discharges to the land surface at some locations in New York. At Chestnut Ridge County Park in Erie County, just south of Buffalo, N.Y., several surface seeps of natural gas occur from Devonian black shale, including one behind a waterfall. Methane occurs locally in the groundwater of New York; as a result, it may be present in drinking-water wells, in the water produced from those wells, and in the associated water-supply systems (Eltschlager and others, 2001). The natural gas in low-permeability bedrock formations has not been accessible by traditional extraction techniques, which have been used to tap more permeable sandstone and carbonate bedrock reservoirs. However, newly developed techniques involving horizontal drilling and high-volume hydraulic fracturing have made it possible to extract previously inaccessible natural gas from low-permeability bedrock such as the Marcellus and Utica Shales. The use of hydraulic fracturing to release natural gas from these shale formations has raised concerns with water-well owners and water-resource managers across the Marcellus and Utica Shale region (West Virginia, Pennsylvania, New York and parts of several other adjoining States). Molofsky and others (2011) documented the widespread natural occurrence of methane in drinking-water wells in Susquehanna County, Pennsylvania. In the same county, Osborn and others (2011) identified elevated methane concentrations in selected drinking-water wells in the vicinity of Marcellus gas-development activities, although pre-development samples were not available for comparison. In order to manage water resources in areas of gas-well drilling and hydraulic

Lattice dynamics study of low energy guest–host coupling in clathrate hydrate

International Nuclear Information System (INIS)

Yang Yuehai; Dong Shunle; Wang Lin

2008-01-01

Our lattice dynamics simulation of Xe-hydrate with four-site TIP4P oxygen-shell model can accurately reproduce each peak position in the inelastic incoherent neutron scattering spectrum at the acoustic band (below 15meV) and yield correct relative intensity. Based on the results, the uncertain profile at ∼6 meV is assigned to anharmonic guest modes coupled strongly to small cages. Blue shift is proposed in phonon dispersion sheet in the case of anticrossing and found to be an evident signal for guest-host coupling that explains the anomalous thermal conductivity of clathrate hydrate

Methane in the Northern West Siberian Basin. Generation, dynamics of the reservoirs and exchange with the atmosphere

International Nuclear Information System (INIS)

Cramer, B.

1997-07-01

Based on compositional data and isotope geochemistry natural gas in northern West Siberia can be divided into three groups. These are: natural gas in Jurassic rocks, natural gas in Neocomian rocks and natural gas from the Aptian to Cenomanian Pokur Formation. Natural gas in Jurassic rocks was generated thermogenically from rocks of the Jurassic Tyumen Formation. Natural gas in Neocomian rocks is also of thermogenic origin, possibly being generated from the organic matter of Lower Cretaceous sediments. The largest accumulation of natural gas occurs in sandstone reservoirs in the Pokur Formation. This gas can be described as a mixture between thermogenic gas from deeper strata and isotopically light almost pure methane. 98.6% of this gas consists of methane with an unusual isotope signature of -51.2 permille. It is not possible to explain the existence of this methane with established concepts of gas generation. A new model was developed to examine the possibility of a thermogenic origin of the isotopically light methane in early mature rocks of the Pokur Formation. Based on pyrolysis experiments and reaction kinetic calculations the model enables the simulation of stable carbon isotope ratios of hydrocarbon components in natural gas. The temperature dependent kinetic isotope fractionation is defined by a difference in the activation energies of 12 C-and 13 C-methane generation. The application of the new method to two coaly sandstones of the Pokur Formation results in a good correspondence between modelled carbon isotope ratios of δ 13 C values of methane in the reservoirs. The mass of methane thermogenically generated within the Pokur Formation under the gas field structures, however, is not sufficient to explain the mass of accumulated methane. (orig./SR) [de

Pre-combustion capture of carbon dioxide in a fixed bed reactor using the clathrate hydrate process

International Nuclear Information System (INIS)

Babu, Ponnivalavan; Kumar, Rajnish; Linga, Praveen

2013-01-01

Hydrate based gas separation (HBGS) process with silica sand and silica gel as contact medium was employed to capture CO 2 from fuel gas mixture. Gas uptake measurement at three different pressures (7.5, 8.5 and 9.0 MPa) and 274.15 K were conducted for hydrate formation kinetics and overall conversion of water to hydrate, rate of hydrate formation were determined. Water conversion of up to 36% was achieved with silica sand bed compared to 13% conversion in the silica gel bed. Effect of driving force on the rate of hydrate formation and gas consumption was significant in silica sand bed whereas it was found to be insignificant in silica gel bed. Hydrate dissociation experiments by thermal stimulation (at constant pressure) alone and a combination of depressurization and thermal stimulation were carried out for complete recovery of the hydrated gas. A driving force of 23 K was found to be sufficient to recover all the hydrated gas within 1 h. This study indicates that silica sand can be an effective porous media for separation of CO 2 from fuel gas when compared to silica gel. - Highlights: ► The clathrate process for pre-combustion capture of carbon dioxide in a novel fixed bed reactor is presented. ► Performance of two contact media (silica gel and silica sand) was investigated. ► Water to hydrate conversion was higher in a silica sand column. ► A pressure reduction and thermal stimulation approach is presented for a complete recovery of the hydrated gas

Lattice Dynamics Study of Phonon Instability and Thermal Properties of Type-I Clathrate K₈Si46 under High Pressure.

Science.gov (United States)

Zhang, Wei; Zeng, Zhao Yi; Ge, Ni Na; Li, Zhi Guo

2016-07-25

For a further understanding of the phase transitions mechanism in type-I silicon clathrates K₈Si 46 , ab initio self-consistent electronic calculations combined with linear-response method have been performed to investigate the vibrational properties of alkali metal K atoms encapsulated type-I silicon-clathrate under pressure within the framework of density functional perturbation theory. Our lattice dynamics simulation results showed that the pressure induced phase transition of K₈Si 46 was believed to be driven by the phonon instability of the calthrate lattice. Analysis of the evolution of the partial phonon density of state with pressure, a legible dynamic picture for both guest K atoms and host lattice, was given. In addition, based on phonon calculations and combined with quasi-harmonic approximation, the specific heat of K₈Si 46 was derived, which agreed very well with experimental results. Also, other important thermal properties including the thermal expansion coefficients and Grüneisen parameters of K₈Si 46 under different temperature and pressure were also predicted.

Abiotic production of methane in terrestrial planets.

Science.gov (United States)

Guzmán-Marmolejo, Andrés; Segura, Antígona; Escobar-Briones, Elva

2013-06-01

On Earth, methane is produced mainly by life, and it has been proposed that, under certain conditions, methane detected in an exoplanetary spectrum may be considered a biosignature. Here, we estimate how much methane may be produced in hydrothermal vent systems by serpentinization, its main geological source, using the kinetic properties of the main reactions involved in methane production by serpentinization. Hydrogen production by serpentinization was calculated as a function of the available FeO in the crust, given the current spreading rates. Carbon dioxide is the limiting reactant for methane formation because it is highly depleted in aqueous form in hydrothermal vent systems. We estimated maximum CH4 surface fluxes of 6.8×10(8) and 1.3×10(9) molecules cm(-2) s(-1) for rocky planets with 1 and 5 M⊕, respectively. Using a 1-D photochemical model, we simulated atmospheres with volume mixing ratios of 0.03 and 0.1 CO2 to calculate atmospheric methane concentrations for the maximum production of this compound by serpentinization. The resulting abundances were 2.5 and 2.1 ppmv for 1 M⊕ planets and 4.1 and 3.7 ppmv for 5 M⊕ planets. Therefore, low atmospheric concentrations of methane may be produced by serpentinization. For habitable planets around Sun-like stars with N2-CO2 atmospheres, methane concentrations larger than 10 ppmv may indicate the presence of life.

Global Methane Biogeochemistry

Science.gov (United States)

Reeburgh, W. S.

2003-12-01

. Methane absorbs infrared radiation in the troposphere, as do CO2 and H2O, and is an important greenhouse gas (Lacis et al., 1981; Ramanathan et al., 1985).A number of review articles on atmospheric CH4 have appeared during the last 15 years. Cicerone and Oremland (1988) reviewed evidence for the temporal atmospheric increase, updated source estimates in the global CH4 budget, and placed constraints on the global budget, emphasizing that the total is well constrained, but that the constituent sources may be uncertain by a factor of 2 or more. This paper was part of a special section in Global Biogeochemical Cycles that resulted from a 1987 American Chemical Society Symposium, "Atmospheric Methane: Formation and Fluxes form the Biosphere and Geosphere." Tyler (1991) and Wahlen (1993) emphasized new information on stable isotopes of CH4 and 14CH4, respectively. Several reviews deal with the microbially mediated CH4 oxidation. King (1992) reviewed the ecology of microbial CH4 oxidation, emphasizing the important role of this process in global CH4 dynamics. R. S. Hanson and T. E. Hanson (1996) reviewed the physiology and taxonomy of methylotrophic bacteria, their role in the global carbon cycle, and the ecology of methanotrophic bacteria. Conrad (1996) reviewed the role of soils and soil microbial communities as controllers of CH4 fluxes, as well as those of H2, CO, OCS, N2O, and NO. Two meetings focusing on CH4 biogeochemistry were held in 1991: an NATO Advanced Science Workshop held at Mt. Hood, OR, and the Tenth International Symposium on Environmental Biogeochemistry (ISEB). A dedicated issue of Chemosphere (26(1-4), 1993) contains contributions from the NATO workshop; two additional volumes (Khalil, 1993 and Khalil, 2000) contain a report of the workshop and updates of important topics. Contributions to the ISEB meeting are presented in Oremland (1993). Wuebbles and Hayhoe (2002) reviewed the effects of CH4 on atmospheric chemistry and examined the direct and indirect

Methane production from coal by a single methanogen

Science.gov (United States)

Sakata, S.; Mayumi, D.; Mochimaru, H.; Tamaki, H.; Yamamoto, K.; Yoshioka, H.; Suzuki, Y.; Kamagata, Y.

2017-12-01

Previous geochemical studies indicate that biogenic methane greatly contributes to the formation of coalbed methane (CBM). It is unclear, however, what part of coal is used for the methane production and what types of microbes mediate the process. Here we hypothesized that methylotrophic methanogens use methoxylated aromatic compounds (MACs) derived from lignin. We incubated 11 species of methanogens belonging to order Methanosarcinales with 7 types of MACs. Two strains of methanogens, i.e., Methermicoccus shengliensis AmaM and ZC-1, produced methane from the MACs. In fact, these methanogens used over 30 types of commercially available MACs in addition to methanol and methylamines. To date, it is widely believed that methanogens use very limited number of small compounds such as hydrogen plus carbon dioxide, acetate, and methanol, and only three methanogenic pathways are recognized accordingly. Here, in contrast, two Methermicoccus strains used many types of MACs. We therefore propose this "methoxydotrophic" process as the fourth methanogenic pathway. Incubation of AmaM with 2-methoxybenzoate resulted in methanogenesis associated with the stoichiometric production of 2-hydroxybenzoate. Incubation with 2-methoxy-[7-13C] benzoate and with [13C] bicarbonate indicated that two thirds of methane carbon derived from the methoxy group and one third from CO2. Furthermore, incubation with [2-13C] acetate resulted in significant increases of 13C in both methane and CO2. These results suggest the occurrence of O-demethylation, CO2 reduction and acetyl-CoA metabolism in the methoxydotrophic methanogenesis. Furthermore, incubation of AmaM with lignite, subbituminous or bituminous coals in the bicarbonate-buffered media revealed that AmaM produced methane directly from coals via the methoxydotrophic pathway. Although 4 types of MACs were detected in the coal media in addition to methanol and methylamines, their total concentrations were too low to account for the methane

Raton basin assessment of coalbed methane resources. [USA - Colorado and New Mexico

Energy Technology Data Exchange (ETDEWEB)

Stevens, S H; Kelso, B S; Lombardi, T E; Coates, J -M [Advanced Research International, Arlington, VA (USA)

1993-02-01

Coalbed methane resources of the Raton basin were assessed through an analysis of public and proprietary sources encompassing stratigraphic, structural, hydrologic, coal rank, and gas-content data. Mapping of coal seams within the Vermejo Formation and Raton Formation revealed several net-coal thickness maxima of 80 ft along the synclinal axis of the basin. However, this sizable coal resource is distributed among multiple, thin, laterally discontinuous coal seams; approximately 60 percent of the total coal in the Raton Formation and 50 percent in the Vermejo Formation occur in seams thinner than 4 ft. Coal rank of the basal Vermejo Formation ranges from high-volatile C to low-volatile bituminous, indicating adequate thermal maturity for methane-generation. Coal seam gas contents show considerable scatter, ranging from 4 to 810 CF/T (ash free), and vary more closely with depth below the hydrologic potentiometric surface than with depth below ground level. Exclusive of shallow and intruded coal seams, in-place coalbed methane resources are estimated at 8.4 to 12.1 TCF, with a mean average of 10.2 TCF. The apparent highest concentration of coalbed methane (24 BCF/mi[sup 2]) occurs along the La Veta trough in Colorado in an area that is geologically less well studied. A second maximum of 8 BCF/mi[sup 2] occurs southeast of Vermejo Park in New Mexico. Successful coalbed methane development in the Raton basin will require favourable coal seam geometry, depth, and reservoir properties in addition to sufficient in-place resources. Local fracturing and enhanced permeability may occur along folds, such as the Vermejo anticline, that splay off the Sangre de Cristo thrust belt. 16 refs., 9 figs.

Crystal structure and thermoelectric properties of clathrate, Ba{sub 8}Ni{sub 3.5}Si{sub 42.0}: Small cage volume and large disorder of the guest atom

Energy Technology Data Exchange (ETDEWEB)

Roudebush, John H., E-mail: jhr@princeton.edu [Department of Chemistry, University of California, One Shields Ave., Davis, CA 95616 (United States); Orellana, Mike [Department of Chemistry, University of California, One Shields Ave., Davis, CA 95616 (United States); Bux, Sabah [Thermal Energy Conversion Technologies Group, Jet Propulsion Laboratory/California Institute of Technology, Pasadena, CA 91109 (United States); Yi Tanghong; Kauzlarich, Susan M. [Department of Chemistry, University of California, One Shields Ave., Davis, CA 95616 (United States)

2012-08-15

Samples with the type-I clathrate composition Ba{sub 8}Ni{sub x}Si{sub 46-x} have been synthesized and their structure and thermoelectric properties characterized. Microprobe analysis indicates the Ni incorporation to be 2.62{<=}x{<=}3.53. The x=3.5 phase crystallizes in the type-I clathrate structure (space group: Pm-3n) with a lattice parameter of 10.2813(3) A. The refined composition was Ba{sub 8}Ni{sub 3.5}Si{sub 42.0}, with small vacancies, 0.4 and 0.5 atoms per formula unit, at the 2a and 6c sites, respectively. The position of the Ba2 atom in the large cage was modeled using a 4-fold split position (24j site), displaced 0.18 A from the cage center (6d site). The volume of the large cage is calculated to be 146 A{sup 3}, smaller than other clathrates with similar cation displacement. The sample shows n-type behavior with a maximum of -50 {mu}V/K at 823 K above which the Seebeck coefficient decreases, suggesting mixed carriers. Lattice thermal conductivity, {kappa}{sub l}, is 55 mW/K above 600 K. - Graphical abstract: Seebeck coefficient and resistivity of the type-I clathrate Ba{sub 8}Ni{sub 3.5}Si{sub 41.0}. Structure show's large displacement of the Ba cation in the large cage (6c site). Highlights: Black-Right-Pointing-Pointer Crystal structure of the Ba{sub 8}Ni{sub 3.5}Si{sub 41.0} reported. Black-Right-Pointing-Pointer Vacancies at the 2a and 6c sites. Black-Right-Pointing-Pointer Large disorder of Ba guest atom, 0.18 A from cage center. Black-Right-Pointing-Pointer Structure is compared to Ba{sub 8}Si{sub 46} and other type-I clathrates. Black-Right-Pointing-Pointer Max Seebeck of -50.7 {mu}V/C at 798.4 K, thermal conductivity {approx}55 mW/K.

Anaerobic oxidation of methane and sulfate reduction along the Chilean continental margin

DEFF Research Database (Denmark)

Treude, T.; Niggemann, J.; Kallmeyer, J.

2005-01-01

of AOM and SR activity, methane, sulfate, sulfide, pH, total chlorins, and a variety of other geochemical parameters. Depth-integrated rates of AOM within the SMT were between 7 and 1124 mmol m(-2) a(-1), effectively removing methane below the sediment-water interface. Single measurements revealed AOM...... with high organic input, to analyze the impact of AOM on the methane budget, and to determine the contribution of AOM to SR within the sulfate-methane transition zone (SMT). Furthermore, we investigated the formation of authigenic carbonates correlated with AOM. We determined the vertical distribution...

Abiotic Production of Methane in Terrestrial Planets

Science.gov (United States)

Guzmán-Marmolejo, Andrés; Escobar-Briones, Elva

2013-01-01

Abstract On Earth, methane is produced mainly by life, and it has been proposed that, under certain conditions, methane detected in an exoplanetary spectrum may be considered a biosignature. Here, we estimate how much methane may be produced in hydrothermal vent systems by serpentinization, its main geological source, using the kinetic properties of the main reactions involved in methane production by serpentinization. Hydrogen production by serpentinization was calculated as a function of the available FeO in the crust, given the current spreading rates. Carbon dioxide is the limiting reactant for methane formation because it is highly depleted in aqueous form in hydrothermal vent systems. We estimated maximum CH4 surface fluxes of 6.8×108 and 1.3×109 molecules cm−2 s−1 for rocky planets with 1 and 5 M⊕, respectively. Using a 1-D photochemical model, we simulated atmospheres with volume mixing ratios of 0.03 and 0.1 CO2 to calculate atmospheric methane concentrations for the maximum production of this compound by serpentinization. The resulting abundances were 2.5 and 2.1 ppmv for 1 M⊕ planets and 4.1 and 3.7 ppmv for 5 M⊕ planets. Therefore, low atmospheric concentrations of methane may be produced by serpentinization. For habitable planets around Sun-like stars with N2-CO2 atmospheres, methane concentrations larger than 10 ppmv may indicate the presence of life. Key Words: Serpentinization—Exoplanets—Biosignatures—Planetary atmospheres. Astrobiology 13, 550–559. PMID:23742231

Effect of hemicellulolytic enzymes on mesophilic methane fermentation

Energy Technology Data Exchange (ETDEWEB)

Oi, S; Matsui, Y; Iizuka, M; Yamamoto, T

1977-01-01

Mesophilic methane fermentation was examined using soybean seed coat, a waste from soybean processing for oil manufacture, with or without treatment with hemicellulolytic enzymes of Aspergillus niger, and the following results were obtained: (1) The methane fermentation bacteria acclimated to soybean seed coat medium were shown to consume monosaccharides and evolve methane in the following decreasing order: glucose, fructose, mannose > xylose, galactose, glucosamine, galacturonic acid > arabinose. The bacteria were also shown to form methane from a gas mixture of hydrogen and carbon dioxide. (2) In fermentation of soybean seed coat treated with the fungal enzyme, about 70% of the total sugar content as consumed in four weeks, and the gas evolution was about twice that without the fungal enzyme. The gas evolved was composed of 60% methane and 36% carbon dioxide. In general, vigorous evolution of hydrogen and carbon dioxide occurred at a very early stage of fermentation, and was followed by formation of methane. The maximum gas evolution of the enzyme-treated mash took place in 6 days while that of untreated mash occurred one week later. Chemical oxygen demand of the supernatant of the former mash was decreased by fermentation to 7.0% of the initial level.

Titan's Tropopause Temperatures from CIRS: Implications for Stratospheric Methane Cloud Formation

Science.gov (United States)

Anderson, C. M.; Samuelson, R. E.; Achterberg, R. K.; Barnes, J. W.; Flasar, F. M.

2012-01-01

Analysis of Cassini Composite Infrared Spectrometer (CIRS) far-IR spectra enable the construction of Titan's temperature profile in the altitude region containing the tropopause. Whereas the methane V4 band at 1306/cm (7.7 microns) is the primary opacity source for deducing thermal structure between 100 km and 500 km, N2-N2 collision-induced absorption between 70 and 140/cm (143 microns and 71 microns) is utilized to determine temperatures at Titan's tropopause. Additional opacity due to aerosol and nitrile ices must also be taken into account in this part of the far-IR spectral region. The spectral characteristics of these particulate opacities have been deduced from CIRS limb data at 58degS, 15degS, 15degN, and 85degN. Empirically, the spectral shapes of these opacities appear to be independent of both latitude and altitude below 300 km (Anderson and Samuelson, 2011, Icarus 212, 762-778), justifying the extension of these spectral properties to all latitudes. We find that Titan's tropopause temperature is cooler than the HAS! value of 70.5K by approx. 6K. This leads to the possibility that subsidence at high northern latitudes can cause methane condensation in the winter polar stratosphere. A search for methane clouds in this region is in progress.

Synthesis and Characterization of Novel Copper(II 2D Coordination Polymers from a Fluorinated Flexible Ligand with Remarkable Clathration Ability

Directory of Open Access Journals (Sweden)

Kayoko Kasai

2011-11-01

Full Text Available Two-dimensional (2D grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyltetrafluorobenzene (bpf with Cu(NO32 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf2(NO32]·(biphenyl2}n (1, {[Cu(bpf2(NO32]·(m-C6H4(OMe22}n (2, {[Cu(bpf2(NO32]·PhtBu}n (3 and {[Cu(bpf2(NO3(H2O]NO3·(bpf0.5}n (4 were determined. The grid networks were held together by C–H···O and C–H···F hydrogen bonds via the NO3− anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds.

CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane.

Science.gov (United States)

Khadka, Nimesh; Dean, Dennis R; Smith, Dayle; Hoffman, Brian M; Raugei, Simone; Seefeldt, Lance C

2016-09-06

The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild-type nitrogenase and a nitrogenase with amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by two or eight electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it is demonstrated that nitrogenase preferentially reduces CO2 by two electrons/protons to formate (HCOO(-)) at rates >10 times higher than rates of CO2 reduction to CO and CH4. Quantum mechanical calculations on the doubly reduced FeMo-cofactor with a Fe-bound hydride and S-bound proton (E2(2H) state) favor a direct reaction of CO2 with the hydride ("direct hydride transfer" reaction pathway), with facile hydride transfer to CO2 yielding formate. In contrast, a significant barrier is observed for reaction of Fe-bound CO2 with the hydride ("associative" reaction pathway), which leads to CO and CH4. Remarkably, in the direct hydride transfer pathway, the Fe-H behaves as a hydridic hydrogen, whereas in the associative pathway it acts as a protic hydrogen. MoFe proteins with amino acid substitutions near FeMo-cofactor (α-70(Val→Ala), α-195(His→Gln)) are found to significantly alter the distribution of products between formate and CO/CH4.

Study of hydrogen-molecule guests in type II clathrate hydrates using a force-matched potential model parameterised from ab initio molecular dynamics

Science.gov (United States)

Burnham, Christian J.; Futera, Zdenek; English, Niall J.

2018-03-01

The force-matching method has been applied to parameterise an empirical potential model for water-water and water-hydrogen intermolecular interactions for use in clathrate-hydrate simulations containing hydrogen guest molecules. The underlying reference simulations constituted ab initio molecular dynamics (AIMD) of clathrate hydrates with various occupations of hydrogen-molecule guests. It is shown that the resultant model is able to reproduce AIMD-derived free-energy curves for the movement of a tagged hydrogen molecule between the water cages that make up the clathrate, thus giving us confidence in the model. Furthermore, with the aid of an umbrella-sampling algorithm, we calculate barrier heights for the force-matched model, yielding the free-energy barrier for a tagged molecule to move between cages. The barrier heights are reasonably large, being on the order of 30 kJ/mol, and are consistent with our previous studies with empirical models [C. J. Burnham and N. J. English, J. Phys. Chem. C 120, 16561 (2016) and C. J. Burnham et al., Phys. Chem. Chem. Phys. 19, 717 (2017)]. Our results are in opposition to the literature, which claims that this system may have very low barrier heights. We also compare results to that using the more ad hoc empirical model of Alavi et al. [J. Chem. Phys. 123, 024507 (2005)] and find that this model does very well when judged against the force-matched and ab initio simulation data.

Methane clumped isotopes: Progress and potential for a new isotopic tracer

Energy Technology Data Exchange (ETDEWEB)

Douglas, Peter M. J.; Stolper, Daniel A.; Eiler, John M.; Sessions, Alex L.; Lawson, Michael; Shuai, Yanhua; Bishop, Andrew; Podlaha, Olaf G.; Ferreira, Alexandre A.; Santos Neto, Eugenio V.; Niemann, Martin; Steen, Arne S.; Huang, Ling; Chimiak, Laura; Valentine, David L.; Fiebig, Jens; Luhmann, Andrew J.; Seyfried, William E.; Etiope, Giuseppe; Schoell, Martin; Inskeep, William P.; Moran, James J.; Kitchen, Nami

2017-11-01

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding hydrocarbon systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a potentially valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. We review different processes affecting methane clumped isotope compositions, describe the relationships between conventional isotope and clumped isotope data, and summarize the types of information that this measurement can provide in different Earth and planetary environments.

A computational study of radiation and gravity effect on temperature and soot formation in a methane air co-flow diffusion flame

Energy Technology Data Exchange (ETDEWEB)

Bhowal, Arup Jyoti, E-mail: arupjyoti.bhowal@heritageit.edu [Department of Mechanical Engineering, Heritage Institute of Technology, Chowbaga Road, Anandapur, Kolkata-700 107, West Bengal (India); Mandal, Bijan Kumar, E-mail: bkm375@yahoo.co.in [Department of Mechanical Engineering, Indian Institute of Engineering Science and Technology, Shibpur, Howrah – 711103, West Bengal (India)

2016-07-12

An effort has been made for a quantitative assessment of the soot formed under steady state in a methane air co flow diffusion flame by a numerical simulation at normal gravity and at lower gravity levels of 0.5 G, 0.1 G and 0.0001 G (microgravity). The peak temperature at microgravity is reduced by about 50 K than that at normal gravity level. There is an augmentation of soot formation at lower gravity levels. Peak value at microgravity multiplies by a factor of ∼7 of that at normal gravity. However, if radiation is not considered, soot formation is found to be much more.

The distribution of methane in groundwater in Alberta (Canada) and associated aqueous geochemistry conditions

Science.gov (United States)

Humez, Pauline; Mayer, Bernhard; Nightingale, Michael; Becker, Veith; Kingston, Andrew; Taylor, Stephen; Millot, Romain; Kloppmann, Wolfram

2016-04-01

Development of unconventional energy resources such as shale gas and coalbed methane has generated some public concern with regard to the protection of groundwater and surface water resources from leakage of stray gas from the deep subsurface. In terms of environmental impact to and risk assessment of shallow groundwater resources, the ultimate challenge is to distinguish: (a) natural in-situ production of biogenic methane, (b) biogenic or thermogenic methane migration into shallow aquifers due to natural causes, and (c) thermogenic methane migration from deep sources due to human activities associated with the exploitation of conventional or unconventional oil and gas resources. We have conducted a NSERC-ANR co-funded baseline study investigating the occurrence of methane in shallow groundwater of Alberta (Canada), a province with a long record of conventional and unconventional hydrocarbon exploration. Our objective was to assess the occurrence and sources of methane in shallow groundwaters and to also characterize the hydrochemical environment in which the methane was formed or transformed through redox processes. Ultimately our aim was to determine whether methane was formed in-situ or whether it migrated from deeper formations into shallow aquifers. Combining hydrochemical and dissolved and free geochemical gas data from 372 groundwater samples obtained from 186 monitoring wells of the provincial groundwater observation well network (GOWN) in Alberta, it was found that methane is ubiquitous in groundwater in Alberta and is predominantly of biogenic origin. The highest concentrations of dissolved biogenic methane (> 0.01 mM or > 0.2 mg/L), characterized by δ13CCH4 values deep thermogenic gas that had migrated in significant amounts into shallow aquifers either naturally or via anthropogenically induced pathways. This study shows that the combined interpretation of aqueous geochemistry data in concert with the chemical and isotopic composition of dissolved and

Methane emissions from MBT landfills

Energy Technology Data Exchange (ETDEWEB)

Heyer, K.-U., E-mail: heyer@ifas-hamburg.de; Hupe, K.; Stegmann, R.

2013-09-15

Highlights: • Compilation of methane generation potential of mechanical biological treated (MBT) municipal solid waste. • Impacts and kinetics of landfill gas production of MBT landfills, approach with differentiated half-lives. • Methane oxidation in the waste itself and in soil covers. • Estimation of methane emissions from MBT landfills in Germany. - Abstract: Within the scope of an investigation for the German Federal Environment Agency (“Umweltbundesamt”), the basics for the estimation of the methane emissions from the landfilling of mechanically and biologically treated waste (MBT) were developed. For this purpose, topical research including monitoring results regarding the gas balance at MBT landfills was evaluated. For waste treated to the required German standards, a methane formation potential of approximately 18–24 m{sup 3} CH{sub 4}/t of total dry solids may be expected. Monitoring results from MBT landfills show that a three-phase model with differentiated half-lives describes the degradation kinetics in the best way. This is due to the fact that during the first years of disposal, the anaerobic degradation processes still proceed relatively intensively. In addition in the long term (decades), a residual gas production at a low level is still to be expected. Most of the soils used in recultivation layer systems at German landfills show a relatively high methane oxidation capacity up to 5 l CH{sub 4}/(m{sup 2} h). However, measurements at MBT disposal sites indicate that the majority of the landfill gas (in particular at non-covered areas), leaves the landfill body via preferred gas emission zones (hot spots) without significant methane oxidation. Therefore, rather low methane oxidation factors are recommended for open and temporarily covered MBT landfills. Higher methane oxidation rates can be achieved when the soil/recultivation layer is adequately designed and operated. Based on the elaborated default values, the First Order Decay (FOD

Dry Reforming of Methane Using a Nickel Membrane Reactor

Directory of Open Access Journals (Sweden)

Jonas M. Leimert

2017-12-01

Full Text Available Dry reforming is a very interesting process for synthesis gas generation from CH 4 and CO 2 but suffers from low hydrogen yields due to the reverse water–gas shift reaction (WGS. For this reason, membranes are often used for hydrogen separation, which in turn leads to coke formation at the process temperatures suitable for the membranes. To avoid these problems, this work shows the possibility of using nickel self-supported membranes for hydrogen separation at a temperature of 800 ∘ C. The higher temperature effectively suppresses coke formation. The paper features the analysis of the dry reforming reaction in a nickel membrane reactor without additional catalyst. The measurement campaign targeted coke formation and conversion of the methane feedstock. The nickel approximately 50% without hydrogen separation. The hydrogen removal led to an increase in methane conversion to 60–90%.

Diverse origins of Arctic and Subarctic methane point source emissions identified with multiply-substituted isotopologues

Science.gov (United States)

Douglas, P. M. J.; Stolper, D. A.; Smith, D. A.; Walter Anthony, K. M.; Paull, C. K.; Dallimore, S.; Wik, M.; Crill, P. M.; Winterdahl, M.; Eiler, J. M.; Sessions, A. L.

2016-09-01

Methane is a potent greenhouse gas, and there are concerns that its natural emissions from the Arctic could act as a substantial positive feedback to anthropogenic global warming. Determining the sources of methane emissions and the biogeochemical processes controlling them is important for understanding present and future Arctic contributions to atmospheric methane budgets. Here we apply measurements of multiply-substituted isotopologues, or clumped isotopes, of methane as a new tool to identify the origins of ebullitive fluxes in Alaska, Sweden and the Arctic Ocean. When methane forms in isotopic equilibrium, clumped isotope measurements indicate the formation temperature. In some microbial methane, however, non-equilibrium isotope effects, probably related to the kinetics of methanogenesis, lead to low clumped isotope values. We identify four categories of emissions in the studied samples: thermogenic methane, deep subsurface or marine microbial methane formed in isotopic equilibrium, freshwater microbial methane with non-equilibrium clumped isotope values, and mixtures of deep and shallow methane (i.e., combinations of the first three end members). Mixing between deep and shallow methane sources produces a non-linear variation in clumped isotope values with mixing proportion that provides new constraints for the formation environment of the mixing end-members. Analyses of microbial methane emitted from lakes, as well as a methanol-consuming methanogen pure culture, support the hypothesis that non-equilibrium clumped isotope values are controlled, in part, by kinetic isotope effects induced during enzymatic reactions involved in methanogenesis. Our results indicate that these kinetic isotope effects vary widely in microbial methane produced in Arctic lake sediments, with non-equilibrium Δ18 values spanning a range of more than 5‰.

A study of the process of joint formation of methane gas-hydrate and authigenic carbonates in bottom sediments in the Sea of Okhotsk

Energy Technology Data Exchange (ETDEWEB)

Esikov, A D [AN SSSR, Moscow (USSR). Water Problems Inst.; Pashkina, V I [AN SSSR, Moscow (USSR). Inst. Okeanologii

1990-01-01

The discovery of gas-hydrates in bottom sediments in the Sea of Okhotsk has allowed isotope fractionation of oxygen and hydrogen to be determined in the formation of the crystal lattice. It was established that the structure of gas-hydrate selectively included the heavier isotopes of oxygen and hydrogen, so that the gas-hydrate water had values of {delta}{sup 18}O = +1.9 per mille and {delta}D = +23 per mille, whereas the interstitial water was ''lighter'' in isotopes, with the values of {delta}{sup 18}O = -0.5 per mille and {delta}D = -5 per mille (relative to SMOW (standard mean ocean water)). The formation of gas-hydrates under the conditions of underwater discharge of methane alters the chemical composition of interstitial water, so that the carbonate equilibrium is shifted, and carbonates of authigenic origin are formed. The isotope composition of the carbonates is characterized by a low content of {sup 13}C({delta}{sup 13}C from -39.3 to -51.8 per mille PDB) and a high content of {sup 18}O({delta}{sup 18}O from + 2.7 to +6.3 per mille PDB) in comparison with carbonates of sea origin. These characteristics of the isotope composition suggest the participation of methane in the formation of authigenic carbonates, due to its anaerobic oxidation and the involvement of sulfate in the silt water. (author).

Quantitative evaluation of ruminal methane and carbon dioxide formation from formate through C-13 stable isotope analysis in a batch culture system.

Science.gov (United States)

He, Z X; Qiao, J Y; Yan, Q X; Tan, Z L; Wang, M

2018-04-12

Methane produced from formate is one of the important methanogensis pathways in the rumen. However, quantitative information of CH4 production from formate has been rarely reported. The aim of this study was to characterize the conversion rate (CR) of formic acid into CH4 and CO2 by rumen microorganisms. Ground lucerne hay was incubated with buffered ruminal fluid for 6, 12, 24 and 48 h. Before the incubation, 13C-labeled H13COOH was also supplied into the incubation bottle at a dose of 0, 1.5, 2.2 or 2.9 mg/g of DM substrate. There were no interactions (P>0.05) between dose and incubation time for all variables evaluated. When expressed as an absolute amount (ml in gas sample) or a relative CR (%), both 13CH4 and 13CO2 production quadratically increased (P<0.01) with the addition of H13COOH. The total 13C (13CH4 and 13CO2) CR was also quadratically increased (P<0.01) when H13COOH was added. Moreover, formate addition linearly decreased (P<0.031) the concentrations of NH3-N, total and individual volatile fatty acids (acetate, propionate and butyrate), and quadratically decreased (P<0.014) the populations of protozoa, total methanogens, Methanosphaera stadtmanae, Methanobrevibacter ruminantium M1, Methanobrevibacter smithii and Methanosarcina barkeri. In summary, formate affects ruminal fermentation and methanogenesis, as well as the rumen microbiome, in particular microorganisms which are directly or indirectly involved in ruminal methanogenesis. This study provides quantitative verification for the rapid dissimilation of formate into CH4 and CO2 by rumen microorganisms.

Evidence for a hydrogen-sink mechanism of (+)catechin-mediated emission reduction of the ruminant greenhouse gas methane

NARCIS (Netherlands)

Becker, P.M.; Wikselaar, van P.G.; Franssen, M.C.R.; Vos, de C.H.; Hall, R.D.; Beekwilder, M.J.

2014-01-01

Methane formation in the rumen is a major cause of greenhouse gas emission. Plant secondary compounds in ruminant diets, such as essential oils, saponins and tannins, are known to affect methane production. However, their methane-lowering properties have generally been associated with undesired side

First experience with the new solid methane moderator at the IBR-2 reactor

International Nuclear Information System (INIS)

Beliakov, A.A.; Shabalin, E.P.; Tretyakov, I.T.

2001-01-01

In the 1999 Fall the solid methane moderator (CM) has been installed and tested at full power at the IBR-2 pulsed reactor. Its main features are a beryllium reflector and a light water premoderator. Radiation load on the methane was three times as much as that of IPNS facility, namely, 0.1 W/g. Effects of temperature, operation time, concentration of a hydrogen scavenger, and annealing procedure on both neutron and service performances were studied. Maximum operation time of a newly loaded portion of methane was 4 days. In this time around 30% of methane is transformed into hydrogen, ethane, and high molecular hydrocarbons, and yet no deterioration in cold neutron intensity was detected. Among new knowledge, the most important are two facts observed: two-fold decrease in hydrogen formation rate when methane is poisoned with 2.5% to 5% of ethylene, and low formation rate of solid, inremovable products of radiolysis - (1.5/3)10 -7 g/J, which means that after 10 years of operation the methane chamber will be filled with only 100 g of residue. Gain of factor 20 in cold neutron flux was obtained as compared to the routine grooved light water moderator. Presently, it is the highest among the intense pulsed neutron sources. (author)

Platinum single crystal electrodes for the electrocatalysis of methane oxidation

Directory of Open Access Journals (Sweden)

Mayara Munaretto

2011-03-01

Full Text Available The main objective of this paper is to characterize the voltammetric profiles of platinum single crystals of low Miller indexes Pt(100 and Pt(110 and study their catalytic activities on the oxidation of methane. In this way, it was developed a metallic surface modified by presence of other metal oxide, which presents catalytic activity for this reaction. It is well known that the electrooxidation of methane (CH4 leads mainly to the formation of CO2 and H2O, however, the oxidation can also lead to the formation of CO, a reaction intermediate that has strong interaction with metal surfaces, such as platinum. This molecule tends to accumulate on the platinum surface and to passive it, due to the self-poisoning, decreasing its catalytic activity. Therefore, the main aim of this work was the development of a platinum electrode modified by deposition of titanium oxide, which presented electrocatalytic properties for the oxidation of methane.

Bioelectrochemical enhancement of methane production in low temperature anaerobic digestion at 10 °C

NARCIS (Netherlands)

Liu, Dandan; Zhang, Lei; Chen, Si; Buisman, Cees; Heijne, ter Annemiek

2016-01-01

Anaerobic digestion at low temperature is an attractive technology especially in moderate climates, however, low temperature results in low microbial activity and low rates of methane formation. This study investigated if bioelectrochemical systems (BESs) can enhance methane production from

Influence of operating pressure on the biological hydrogen methanation in trickle-bed reactors.

Science.gov (United States)

Ullrich, Timo; Lindner, Jonas; Bär, Katharina; Mörs, Friedemann; Graf, Frank; Lemmer, Andreas

2018-01-01

In order to investigate the influence of pressures up to 9bar absolute on the productivity of trickle-bed reactors for biological methanation of hydrogen and carbon dioxide, experiments were carried out in a continuously operated experimental plant with three identical reactors. The pressure increase promises a longer residence time and improved mass transfer of H 2 due to higher gas partial pressures. The study covers effects of different pressures on important parameters like gas hourly space velocity, methane formation rate, conversion rates and product gas quality. The methane content of 64.13±3.81vol-% at 1.5bar could be increased up to 86.51±0.49vol-% by raising the pressure to 9bar. Methane formation rates of up to 4.28±0.26m 3 m -3 d -1 were achieved. Thus, pressure increase could significantly improve reactor performance. Copyright © 2017 Elsevier Ltd. All rights reserved.

MethaneSat: Detecting Methane Emissions in the Barnett Shale Region

Science.gov (United States)

Propp, A. M.; Benmergui, J. S.; Turner, A. J.; Wofsy, S. C.

2017-12-01

In this study, we investigate the new information that will be provided by MethaneSat, a proposed satellite that will measure the total column dry-air mole fraction of methane at 1x1 km or 2x2 km spatial resolution with 0.1-0.2% random error. We run an atmospheric model to simulate MethaneSat's ability to characterize methane emissions from the Barnett Shale, a natural gas province in Texas. For comparison, we perform observation system simulation experiments (OSSEs) for MethaneSat, the National Oceanic and Atmospheric administration (NOAA) surface and aircraft network, and Greenhouse Gases Observing Satellite (GOSAT). The results demonstrate the added benefit that MethaneSat would provide in our efforts to monitor and report methane emissions. We find that MethaneSat successfully quantifies total methane emissions in the region, as well as their spatial distribution and steep gradients. Under the same test conditions, both the NOAA network and GOSAT fail to capture this information. Furthermore, we find that the results for MethaneSat depend far less on the prior emission estimate than do those for the other observing systems, demonstrating the benefit of high sampling density. The results suggest that MethaneSat would be an incredibly useful tool for obtaining detailed methane emission information from oil and gas provinces around the world.

Lattice Dynamics Study of Phonon Instability and Thermal Properties of Type-I Clathrate K8Si46 under High Pressure

Directory of Open Access Journals (Sweden)

Wei Zhang

2016-07-01

Full Text Available For a further understanding of the phase transitions mechanism in type-I silicon clathrates K8Si46, ab initio self-consistent electronic calculations combined with linear-response method have been performed to investigate the vibrational properties of alkali metal K atoms encapsulated type-I silicon-clathrate under pressure within the framework of density functional perturbation theory. Our lattice dynamics simulation results showed that the pressure induced phase transition of K8Si46 was believed to be driven by the phonon instability of the calthrate lattice. Analysis of the evolution of the partial phonon density of state with pressure, a legible dynamic picture for both guest K atoms and host lattice, was given. In addition, based on phonon calculations and combined with quasi-harmonic approximation, the specific heat of K8Si46 was derived, which agreed very well with experimental results. Also, other important thermal properties including the thermal expansion coefficients and Grüneisen parameters of K8Si46 under different temperature and pressure were also predicted.

Detection of Occupancy Differences in Methane Gas Hydrates by Raman Spectroscopy

DEFF Research Database (Denmark)

Hansen, Susanne Brunsgaard; Berg, Rolf W.; Stenby, Erling Halfdan

2004-01-01

of reservoir fluids due to plugging. Methods to prevent hydrate formation are in use, e.g. by injection of inhibitors. From environmental and security points of view an easy way to detect hydrate formation is of interest. We have tried to detect methane hydrate formation by use of Raman spectroscopy....

A transient kinetic study of nickel-catalyzed methanation: Final report

International Nuclear Information System (INIS)

Hoost, T.E.; Goodwin, J.G. Jr.

1988-11-01

The results of this study are in two major parts. In Part I the use of steady-state isotopic transients of multiple elements (C, H, and O) under actual methanation reaction conditions has permitted an assessment of the reactivity of water on a Ni powder catalyst. It was concluded based on the addition of isotopic water that oxygen, once reacted to form water, is able to readsorb even where the surface coverage of CO remains high. At the low relative partial pressures of water used, however, there was no effect of added water on the formation of methane. The surface residence time of water determined from isotopic transients contains the residence time on the surface during the primary formation reaction as well as the time spent during readsorption(s). Part II addressed how a catalyst modifier (in this case Cl) affects methanation in CO hydrogenation using steady-state isotopic transient kinetic analysis (SSITKA) of methanation. The results obtained using silica-supported Ru suggest the structural rearrangements induced by the presence of chlorine, rather than selective site blocking or electronic interactions, may be the primary mechanism of chlorine modification of the catalytic properties of supported metals for CO hydrogenation. SSITKA indicated that the decrease in methanation activity with increasing initial Cl concentration was a function of a decrease in the number of reactive surface intermediates (or sites) and not of a change in site activity. 36 refs., 10 figs., 5 tabs

The origin of methane and biomolecules from a CO2 cycle on terrestrial planets

Science.gov (United States)

Civiš, Svatopluk; Knížek, Antonín; Ivanek, Ondřej; Kubelík, Petr; Zukalová, Markéta; Kavan, Ladislav; Ferus, Martin

2017-10-01

Understanding the chemical evolution of newly formed terrestrial planets involves uncertainties in atmospheric chemical composition and assessing the plausibility of biomolecule synthesis. In this study, an original scenario for the origin of methane on Mars and terrestrial planets is suggested. Carbon dioxide in Martian and other planetary atmospheres can be abiotically converted into a mixture of methane and carbon monoxide by `methanogenesis' on porous mineral photoactive surfaces under soft ultraviolet irradiation. On young planets exposed to heavy bombardment by interplanetary matter, this process can be followed by biomolecule synthesis through the reprocessing of reactive reducing atmospheres by impact-induced shock waves. The proposed mechanism of methanogenesis may help to answer the question concerning the formation of methane and carbon monoxide by photochemical processes, the formation of biomolecules on early Earth and other terrestrial planets, and the source and seasonal variation of methane concentrations on Mars.

The direct aromatization of methane

Energy Technology Data Exchange (ETDEWEB)

Marcelin, G.; Oukaci, R.; Migone, R.A.; Kazi, A.M. [Altamira Instruments, Pittsburgh, PA (United States)

1995-12-31

The thermal decomposition of methane shows significant potential as a process for the production of higher unsaturated and aromatic hydrocarbons when the extent of the reaction is limited. Thermodynamic calculations have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that cooling the product and reacting gases as the reaction proceeds can significantly reduce or eliminate the formation of solid carbon and heavier (C{sub 10+}) materials. Much work remains to be done in optimizing the quenching process and this is one of the goals of this program. Means to lower the temperature of the reaction are being studied as this result in a more feasible commercial process due to savings realized in energy and material of construction costs. The use of free-radical generators and catalysts will be investigated as a means of lowering the reaction temperature thus allowing faster quenching. It is highly likely that such studies will lead to a successful direct methane to higher hydrocarbon process.

Coke Formation During Hydrocarbons Pyrolysis. Part Two: Methane Thermal Cracking Formation de coke pendant la pyrolyse des hydrocarbures. Deuxième partie : pyrolyse du méthane

Directory of Open Access Journals (Sweden)

Billaud F.

2006-11-01

Full Text Available Part one of this article dealt with coking in a steam cracking furnace. In this process, coke deposition is a very complex phenomenon due to the number of parameters involved. Nevertheless, for this process, coke deposition is a secondary reaction which does not affect steam cracking yields. It is completely different for methane thermal cracking. Coke is one of the main products of this reaction. Part two of this article deals with coke deposition on the walls of the reactors used for methane thermal cracking. After a brief description of the different set-ups used to study coke deposition, the main parameters involved are listed. The importance of temperature, conversion, type of diluent, and hydrocarbon partial pressure will be enhanced. To conclude, two approaches to the mechanism are proposed to explain coke formation during methane thermal cracking. La première partie de cet article faisait le point sur les réactions indésirables de cokage dans les réacteurs de vapocraquage : dans le cadre de ce procédé, la formation de coke est un phénomène complexe du fait du nombre important de paramètres mis en jeu. Toutefois, pour ce procédé, la réaction de formation du coke à la paroi des réacteurs est une réaction secondaire qui n'affecte pas les rendements de vapocraquage. Ceci est complètement différent dans le cas de la pyrolyse thermique du méthane, procédé pour lequel le coke est un produit principal et indésirable de la réaction. La seconde partie de cet article est consacrée plus particulièrement à la formation du coke, lors de la pyrolyse du méthane et présente les principaux résultats expérimentaux décrits dans la littérature. Parmi les différents montages expérimentaux utilisés pour mesurer le dépôt de coke, il est mentionné, à partir des travaux de la littérature, les 2 techniques suivantes : - la technique de la paroi chaude, - la technique du fil chaud. Pour la première technique, les montages exp

Characterization of Methane Degradation and Methane-Degrading Microbes in Alaska Coastal Water

Energy Technology Data Exchange (ETDEWEB)

Kirchman, David L. [Univ. of Delaware, Lewes, DE (United States)

2012-03-29

The net flux of methane from methane hydrates and other sources to the atmosphere depends on methane degradation as well as methane production and release from geological sources. The goal of this project was to examine methane-degrading archaea and organic carbon oxidizing bacteria in methane-rich and methane-poor sediments of the Beaufort Sea, Alaska. The Beaufort Sea system was sampled as part of a multi-disciplinary expedition (Methane in the Arctic Shelf or MIDAS) in September 2009. Microbial communities were examined by quantitative PCR analyses of 16S rRNA genes and key methane degradation genes (pmoA and mcrA involved in aerobic and anaerobic methane degradation, respectively), tag pyrosequencing of 16S rRNA genes to determine the taxonomic make up of microbes in these sediments, and sequencing of all microbial genes (metagenomes ). The taxonomic and functional make-up of the microbial communities varied with methane concentrations, with some data suggesting higher abundances of potential methane-oxidizing archaea in methane-rich sediments. Sequence analysis of PCR amplicons revealed that most of the mcrA genes were from the ANME-2 group of methane oxidizers. According to metagenomic data, genes involved in methane degradation and other degradation pathways changed with sediment depth along with sulfate and methane concentrations. Most importantly, sulfate reduction genes decreased with depth while the anaerobic methane degradation gene (mcrA) increased along with methane concentrations. The number of potential methane degradation genes (mcrA) was low and inconsistent with other data indicating the large impact of methane on these sediments. The data can be reconciled if a small number of potential methane-oxidizing archaea mediates a large flux of carbon in these sediments. Our study is the first to report metagenomic data from sediments dominated by ANME-2 archaea and is one of the few to examine the entire microbial assemblage potentially involved in

Methane hydrates in marine sediments - Untapped source of energy

Digital Repository Service at National Institute of Oceanography (India)

Jauhari, P.

(Egorov et al 1999). Many known gas seep areas and mud volcanoes are characterised by the formation of authigenic carbonates. In the Gulf of Mexico, which is the best studied area, the association of bacterial mats, gas hydrates and authigenic carbonates... of methane hydrates offshore southern Mexico. In : Watkins, J.S., Moore J.R. et al. (Eds). Initial Reports deep Sea Drilling Project Leg 66. Washington, D.C., US Government Printing Office, pp. 547-556. Singh, A., & Singh, B.D. 1999. Methane Gas...

Alcoholic fermentation process and methane formation unit with biomass in fixed bed; Processo de fermentacao alcoolica e fermentador de metanizacao com biomassa em leito fixo

Energy Technology Data Exchange (ETDEWEB)

Camilleri, Claude [Societe Generale de Techniques Nouvelles (France)

1986-01-01

The pollution, measured from Biochemical Oxygen Demand, is constituted primary of organic carbon. The pollution abatement is made traditionally by thr reduction of this carbon by an aerobic way. Were made some tries in order to recover this carbon as an energy source and the methane formation process arises like the most attractive alternative 2 figs.

Effect of conditioners upon the thermodynamics and kinetics of methane hydrate formation. A preliminary structure-properties relationship study

Energy Technology Data Exchange (ETDEWEB)

Di Profio, Pietro; Arca, Simone; Germani, Raimondo; Savelli, Gianfranco

2005-07-01

The synthesis and stability of gas hydrates was found to be heavily affected by the presence of small quantities of additives, or conditioners, particularly surfactants. In a recent work, we showed that the enhancement of hydrate formation, both from previously described and newly synthesized surfactants, is probably due to surfactant monomers, rather than micelles, and that the features of hydrate induction time should not be used as a measure of critical micelle concentration. In the present paper, we discuss the results of a structure-properties relationship study in which a preliminary attempt to relate the structural features of several amphiphilic additives to some kinetic and thermodynamic parameters of methane hydrate formation - e.g., induction times, rate of formation, occupancy, etc. - is conducted. According to the present study, it is found that, for a particular conditioner, a reduction of induction time does not correlate to an increase of the formation rate and occupancy, and vice versa. This may be related to the nature of chemical moieties forming a particular amphiphile (e.g., the hydrophobic tail, head group, counterion, etc.). The understanding of the mechanisms by which those moieties play their differential role may be the key tool to the design and synthesis of tailored conditioners. (Author)

Competing quantum effects in the free energy profiles and diffusion rates of hydrogen and deuterium molecules through clathrate hydrates.

Science.gov (United States)

Cendagorta, Joseph R; Powers, Anna; Hele, Timothy J H; Marsalek, Ondrej; Bačić, Zlatko; Tuckerman, Mark E

2016-11-30

Clathrate hydrates hold considerable promise as safe and economical materials for hydrogen storage. Here we present a quantum mechanical study of H 2 and D 2 diffusion through a hexagonal face shared by two large cages of clathrate hydrates over a wide range of temperatures. Path integral molecular dynamics simulations are used to compute the free-energy profiles for the diffusion of H 2 and D 2 as a function of temperature. Ring polymer molecular dynamics rate theory, incorporating both exact quantum statistics and approximate quantum dynamical effects, is utilized in the calculations of the H 2 and D 2 diffusion rates in a broad temperature interval. We find that the shape of the quantum free-energy profiles and their height relative to the classical free energy barriers at a given temperature, as well as the rate of diffusion, are strongly affected by competing quantum effects: above 25 K, zero-point energy (ZPE) perpendicular to the reaction path for diffusion between cavities decreases the quantum rate compared to the classical rate, whereas at lower temperatures tunneling outcompetes the ZPE and as a result the quantum rate is greater than the classical rate.

Effect of Different Operating Temperatures on the Biological Hydrogen Methanation in Trickle Bed Reactors

Directory of Open Access Journals (Sweden)

Andreas Lemmer

2018-05-01

Full Text Available To improve the reactor efficiency, this study investigated the influence of temperature on the biological hydrogen methanation (BHM in trickle-bed reactors (TBR. Rising temperatures increase the metabolic activity of methanogenic microorganisms, thus leading to higher reactor specific methane formation rates (MFR. In order to quantify the potential for improved performance, experiments with four different operating temperatures ranging from 40 to 55 °C were carried out. Methane content increased from 88.29 ± 2.12 vol % at 40 °C to 94.99 ± 0.81 vol % at 55 °C with a stable biological process. Furthermore, a reactor specific methane formation rate (MFR of up to 8.85 ± 0.45 m3 m−3 d−1 was achieved. It could be shown that the microorganisms were able to adapt to higher temperatures within hours. The tests showed that TBR performance with regard to BHM can be significantly increased by increasing the operating temperature.

The influence of methane/argon plasma composition on the formation of the hydrogenated amorphous carbon films

International Nuclear Information System (INIS)

Chen, Hsin-Hung; Liao, Jiunn-Der; Weng, Chih-Chiang; Hsieh, Jui-Fu; Chang, Chia-Wei; Lin, Chao-Hsien; Cho, Ting-Pin

2011-01-01

The quality of the a-C:H films was particularly correlated with the mixed ratio of methane/argon plasma. For a constant supply of energy and flowing rate, the optical emission from H α intensity linearly increased with the addition of methane in argon plasma, while that from intensities of radiation of diatmoic radicals (CH*and C 2 *) exponentially decreased. For the a-C:H films, the added methane in argon plasma tended to raise the quantity of hydrogenated carbon or sp 3 C-H structure, which exponentially decreased the nano-hardness and friction coefficient of the films. In contrast, the electric resistance of the films enlarged dramatically with the increase of the methane content in argon plasma. It is therefore advantageous to balance the mechanical properties and electrical resistance of the a-C:H film by adjusting plasma composition in the course of the film-growing process.

The effect of the condensed-phase environment on the vibrational frequency shift of a hydrogen molecule inside clathrate hydrates.

Science.gov (United States)

Powers, Anna; Scribano, Yohann; Lauvergnat, David; Mebe, Elsy; Benoit, David M; Bačić, Zlatko

2018-04-14

We report a theoretical study of the frequency shift (redshift) of the stretching fundamental transition of an H 2 molecule confined inside the small dodecahedral cage of the structure II clathrate hydrate and its dependence on the condensed-phase environment. In order to determine how much the hydrate water molecules beyond the confining small cage contribute to the vibrational frequency shift, quantum five-dimensional (5D) calculations of the coupled translation-rotation eigenstates are performed for H 2 in the v=0 and v=1 vibrational states inside spherical clathrate hydrate domains of increasing radius and a growing number of water molecules, ranging from 20 for the isolated small cage to over 1900. In these calculations, both H 2 and the water domains are treated as rigid. The 5D intermolecular potential energy surface (PES) of H 2 inside a hydrate domain is assumed to be pairwise additive. The H 2 -H 2 O pair interaction, represented by the 5D (rigid monomer) PES that depends on the vibrational state of H 2 , v=0 or v=1, is derived from the high-quality ab initio full-dimensional (9D) PES of the H 2 -H 2 O complex [P. Valiron et al., J. Chem. Phys. 129, 134306 (2008)]. The H 2 vibrational frequency shift calculated for the largest clathrate domain considered, which mimics the condensed-phase environment, is about 10% larger in magnitude than that obtained by taking into account only the small cage. The calculated splittings of the translational fundamental of H 2 change very little with the domain size, unlike the H 2 j = 1 rotational splittings that decrease significantly as the domain size increases. The changes in both the vibrational frequency shift and the j = 1 rotational splitting due to the condensed-phase effects arise predominantly from the H 2 O molecules in the first three complete hydration shells around H 2 .

The effect of the condensed-phase environment on the vibrational frequency shift of a hydrogen molecule inside clathrate hydrates

Science.gov (United States)

Powers, Anna; Scribano, Yohann; Lauvergnat, David; Mebe, Elsy; Benoit, David M.; Bačić, Zlatko

2018-04-01

We report a theoretical study of the frequency shift (redshift) of the stretching fundamental transition of an H2 molecule confined inside the small dodecahedral cage of the structure II clathrate hydrate and its dependence on the condensed-phase environment. In order to determine how much the hydrate water molecules beyond the confining small cage contribute to the vibrational frequency shift, quantum five-dimensional (5D) calculations of the coupled translation-rotation eigenstates are performed for H2 in the v =0 and v =1 vibrational states inside spherical clathrate hydrate domains of increasing radius and a growing number of water molecules, ranging from 20 for the isolated small cage to over 1900. In these calculations, both H2 and the water domains are treated as rigid. The 5D intermolecular potential energy surface (PES) of H2 inside a hydrate domain is assumed to be pairwise additive. The H2-H2O pair interaction, represented by the 5D (rigid monomer) PES that depends on the vibrational state of H2, v =0 or v =1 , is derived from the high-quality ab initio full-dimensional (9D) PES of the H2-H2O complex [P. Valiron et al., J. Chem. Phys. 129, 134306 (2008)]. The H2 vibrational frequency shift calculated for the largest clathrate domain considered, which mimics the condensed-phase environment, is about 10% larger in magnitude than that obtained by taking into account only the small cage. The calculated splittings of the translational fundamental of H2 change very little with the domain size, unlike the H2 j = 1 rotational splittings that decrease significantly as the domain size increases. The changes in both the vibrational frequency shift and the j = 1 rotational splitting due to the condensed-phase effects arise predominantly from the H2O molecules in the first three complete hydration shells around H2.

Squeezing clathrate cages to host trivalent rare-earth guests

Energy Technology Data Exchange (ETDEWEB)

Wang, Jian [Iowa State Univ., Ames, IA (United States). Department of Chemistry; Ames Lab., Ames, IA (United States); He, Yuping [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Mordvinova, Natalia E. [Laboratoire CRISMAT, ENSICAEN, CNRS UMR (France); Lebedev, Oleg [Laboratoire CRISMAT, ENSICAEN, CNRS UMR (France); Kovnir, Kirill [Iowa State Univ., Ames, IA (United States). Department of Chemistry; Ames Lab., Ames, IA (United States)

2017-11-01

Strike difference of the trivalent rare-earth cations from their alkali and alkaline-earth peers is in the presence of localized 4f-electrons and strong spin-orbit coupling. Placing trivalent rare-earth cations inside the fullerene molecules or in between the blocks of itinerant magnetic intermetallics gave rise to plethora of fascinating properties and materials. A long-time missing but hardly desired piece is the semiconducting or metallic compound where rare-earth cations are situated inside the oversized polyhedral cages of three-dimensional framework. In this work we present a synthesis of such compounds, rare-earth containing clathrates Ba_8-xR_xCu₁₆P₃₀. The unambiguous proofs of their composition and crystal structure were achieved by a combination of synchrotron powder diffraction, time-of-flight neutron powder diffraction, scanning-transmission electron microscopy, and electron energy-loss spectroscopy. Our quantum-mechanical calculations and experimental characterizations show that the incorporation of the rare-earth cations significantly enhances the hole mobility and concentration which results in the drastic increase in the thermoelectric performance.

Methane Provenance Determined by CH2D2 and 13CH3D Abundances

Science.gov (United States)

Kohl, I. E.; Giunta, T.; Warr, O.; Ash, J. L.; Ruffine, L.; Sherwood Lollar, B.; Young, E. D.

2017-12-01

Determining the provenance of naturally occurring methane gases is of major interest to energy companies and atmospheric climate modelers, among others. Bulk isotopic compositions and other geochemical tracers sometimes fail to provide definitive determinations of sources of methane due to complications from mixing and complicated chemical pathways of origin. Recent measurements of doubly-substituted isotopologues of methane, CH2D2 (UCLA) and 13CH3D (UCLA, CalTech, and MIT) have allowed for major improvements in sourcing natural methane gases. Early work has focused on formation temperatures obtained when the relative abundances of both doubly-substituted mass-18 species are consistent with internal equilibrium. When methane gases do not plot on the thermodynamic equilibrium curve in D12CH2D2 vs D13CH3D space, temperatures determined from D13CH3D values alone are usually spurious, even when appearing reasonable. We find that the equilibrium case is actually rare and almost exclusive to thermogenic gases produced at temperatures exceeding 100°C. All other relevant methane production processes appear to generate gases that are not in isotopologue-temperature equilibrium. When gases show departures from equilibrium as determined by the relationship between CH2D2 and 13CH3D abundances, data fall within empirically defined fields representing formation pathways. These fields are thus far consistent between different geological settings and and between lab experiments and natural samples. We have now defined fields for thermogenic gas production, microbial methanogenesis, low temperature abiotic (Sabatier) synthesis and higher temperature FTT synthesis. The majority of our natural methane data can be explained by mixing between end members originating within these production fields. Mixing can appear complex, resulting in both hyper-clumped and anti-clumped isotopologue abundances. In systems where mixtures dominate and end-members are difficult to sample, mixing models

Temperature dependence of bioelectrochemical CO2 conversion and methane production with a mixed-culture biocathode.

Science.gov (United States)

Yang, Hou-Yun; Bao, Bai-Ling; Liu, Jing; Qin, Yuan; Wang, Yi-Ran; Su, Kui-Zu; Han, Jun-Cheng; Mu, Yang

2018-02-01

This study evaluated the effect of temperature on methane production by CO 2 reduction during microbial electrosynthesis (MES) with a mixed-culture biocathode. Reactor performance, in terms of the amount and rate of methane production, current density, and coulombic efficiency, was compared at different temperatures. The microbial properties of the biocathode at each temperature were also analyzed by 16S rRNA gene sequencing. The results showed that the optimum temperature for methane production from CO 2 reduction in MES with a mixed-culture cathode was 50°C, with the highest amount and rate of methane production of 2.06±0.13mmol and 0.094±0.01mmolh -1 , respectively. In the mixed-culture biocathode MES, the coulombic efficiency of methane formation was within a range of 19.15±2.31% to 73.94±2.18% due to by-product formation at the cathode, including volatile fatty acids and hydrogen. Microbial analysis demonstrated that temperature had an impact on the diversity of microbial communities in the biofilm that formed on the MES cathode. Specifically, the hydrogenotrophic methanogen Methanobacterium became the predominant archaea for methane production from CO 2 reduction, while the abundance of the aceticlastic methanogen Methanosaeta decreased with increased temperature. Copyright © 2017. Published by Elsevier B.V.

Biogenic methane potential of marine sediments. Application of chemical thermodynamics

Energy Technology Data Exchange (ETDEWEB)

Arning, E.T.; Schulz, H.M. [Helmholtz Centre Potsdam GFZ, Potsdam (Germany); Berk, W. van [Technical Univ. of Clausthal (Germany). Dept. of Hydrogeology

2013-08-01

Accumulations of biogenic methane-dominated gas are widespread and occur in a variety of depositional settings and rock types. However, the potential of biogenic methane remains underexplored. This is mainly due to the fact that quantitative assessments applying numerical modeling techniques for exploration purposes are generally lacking to date. Biogenic methane formation starts in relatively shallow marine sediments below the sulfate reduction zone. When sulfate is exhausted, methanogenesis via the CO{sub 2} reduction pathway is often the dominant biogenic methane formation process in marine sediments (Claypool and Kaplan, 1974). The process can be simplified by the reaction: 2CH{sub 2}O + Ca{sup 2+} + H{sub 2}O {yields} CH{sub 4} + CaCO{sub 3} + 2H{sup +}. The products of early diagenetic reactions initiate coupled equilibrium reactions that induce a new state of chemical equilibrium among minerals, pore water and gas. The driving force of the complex biogeochemical reactions in sedimentary environments during early diagenesis is the irreversible redox-conversion of organic matter. Early diagenetic formation of biogenic methane shortly after deposition ('early diagenesis') was retraced using PHREEQC computer code that is applied to calculate homogenous and heterogeneous mass-action equations in combination with one-dimensional diffusion driven transport (Parkhurst and Appelo, 1999). Our modeling approach incorporates interdependent diagenetic reactions evolving into a diffusive multi-component and multiphase system by means of thermodynamic equilibrium calculations of species distribution (Arning et al., 2011, 2012, 2013). Reaction kinetics of organic carbon conversion is integrated into the set of equilibrium reactions by defining type and amount of converted organic matter in a certain time step. It is the aim (1) to calculate quantitatively thermodynamic equilibrium conditions (composition of pore water, mineral phase and gas phase assemblage) in

How to oxidize atmospheric CH4? - A challenge for the future

International Nuclear Information System (INIS)

Chazelas, Bruno; Leger, Alain; Ollivier, Marc

2006-01-01

Methane is an active Greenhouse effect gas whose concentration will likely increase in the future. The possible destabilisation of CH 4 clathrates (hydrates) due to anthropogenic climate warming, and the resulting outgasing of methane, could lead to a major increase of the global Greenhouse effect, with dramatic consequences for Humanity. For these reasons, the study of possible countermeasures should be actively considered. Here, we suggest taking advantage of the thermodynamic instability of CH 4 in air, and search for ways to oxidize it

Microbial Formation of Ethane in Anoxic Estuarine Sediments

OpenAIRE

Oremland, Ronald S.

1981-01-01

Estuarine sediment slurries produced methane and traces of ethane when incubated under hydrogen. Formation of methane occurred over a broad temperature range with an optimum above 65°C. Ethane formation had a temperature optimum at 40°C. Formation of these two gases was inhibited by air, autoclaving, incubation at 4 and 80°C, and by the methanogenic inhibitor, 2-bromoethanesulfonic acid. Ethane production was stimulated by addition of ethylthioethanesulfonic acid, and production from ethylthi...

Biogenic Methane Generation Potential in the Eastern Nankai Trough, Japan: Effect of Reaction Temperature and Total Organic Carbon

Science.gov (United States)

Aung, T. T.; Fujii, T.; Amo, M.; Suzuki, K.

2017-12-01

Understanding potential of methane flux from the Pleistocene fore-arc basin filled turbiditic sedimentary formation along the eastern Nankai Trough is important in the quantitative assessment of gas hydrate resources. We considered generated methane could exist in sedimentary basin in the forms of three major components, and those are methane in methane hydrate, free gas and methane dissolved in water. Generation of biomethane strongly depends on microbe activity and microbes in turn survive in diverse range of temperature, salinity and pH. This study aims to understand effect of reaction temperature and total organic carbon on generation of biomethane and its components. Biomarker analysis and cultural experiment results of the core samples from the eastern Nankai Trough reveal that methane generation rate gets peak at various temperature ranging12.5°to 35°. Simulation study of biomethane generation was made using commercial basin scale simulator, PetroMod, with different reaction temperature and total organic carbon to predict how these effect on generation of biomethane. Reaction model is set by Gaussian distribution with constant hydrogen index and standard deviation of 1. Series of simulation cases with peak reaction temperature ranging 12.5°to 35° and total organic carbon of 0.6% to 3% were conducted and analyzed. Simulation results show that linear decrease in generation potential while increasing reaction temperature. But decreasing amount becomes larger in the model with higher total organic carbon. At higher reaction temperatures, >30°, extremely low generation potential was found. This is due to the fact that the source formation modeled is less than 1 km in thickness and most of formation do not reach temperature more than 30°. In terms of the components, methane in methane hydrate and free methane increase with increasing TOC. Drastic increase in free methane was observed in the model with 3% of TOC. Methane amount dissolved in water shows almost

Biogas crops grown in energy crop rotations: Linking chemical composition and methane production characteristics.

Science.gov (United States)

Herrmann, Christiane; Idler, Christine; Heiermann, Monika

2016-04-01

Methane production characteristics and chemical composition of 405 silages from 43 different crop species were examined using uniform laboratory methods, with the aim to characterise a wide range of crop feedstocks from energy crop rotations and to identify main parameters that influence biomass quality for biogas production. Methane formation was analysed from chopped and over 90 days ensiled crop biomass in batch anaerobic digestion tests without further pre-treatment. Lignin content of crop biomass was found to be the most significant explanatory variable for specific methane yields while the methane content and methane production rates were mainly affected by the content of nitrogen-free extracts and neutral detergent fibre, respectively. The accumulation of butyric acid and alcohols during the ensiling process had significant impact on specific methane yields and methane contents of crop silages. It is proposed that products of silage fermentation should be considered when evaluating crop silages for biogas production. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Combined gas-phase oxidation of methane and ethylene

International Nuclear Information System (INIS)

Pogosyan, N.M.; Pogosyan, M.D.

2009-01-01

It is established that depending on the reaction conditions combined oxidation of methane and ethylene may result in ethylene and propylene oxides with high selectivity with respect to the process, where in the initial reaction mixture methane is replaced by the same quantity of nitrogen. The formed additional methyl radicals increase the yield of all reaction products except CO. At low temperatures methyl radicals react with oxygen resulting in methyl peroxide radicals, which in turn, reacting with ethylene provide its epoxidation and formation of other oxygen-containing products. At high temperatures as a result of addition reaction between methyl radicals and ethylene, propyl radicals are formed that, in turn yield propylene. Alongside with positive influence on the yield of reaction products, methane exerts negative influence upon the conversion, that is it decreases the rate of ethylene and oxygen conversion, simultaneously decreasing significantly the yield of CO

Thermodynamic analysis of carbon formation in solid oxide fuel cells with a direct internal reformer fueled by ethanol, methanol, and methane

International Nuclear Information System (INIS)

Laosiripojana, N.; Assabumrungrat, S.; Pavarajarn, V.; Sangtongkitcharoen, W.; Tangjitmatee, A.; Praserthdam, P.

2004-01-01

'Full text:' This paper concerns a detailed thermodynamic analysis of carbon formation for a Direct Internal Reformer (DIR) Solid Oxide Fuel Cells (SOFC). The modeling of DIR-SOFC fueled by ethanol, methanol, and methane were compared. Two types of fuel cell electrolytes, i.e. oxygen-conducting and hydrogen-conducting, are considered. Equilibrium calculations were performed to find the ranges of inlet steam/fuel ratio where carbon formation is thermodynamically unfavorable in the temperature range of 500-1200 K. It was found that the key parameters determining the boundary of carbon formation are temperature, type of solid electrolyte and extent of the electrochemical reaction of hydrogen. The minimum requirements of H2O/fuel ratio for each type of fuel in which the carbon formation is thermodynamically unfavored were compared. At the same operating conditions, DIR-SOFC fueled by ethanol required the lowest inlet H2O/fuel ratio in which the carbon formation is thermodynamically unfavored. The requirement decreased with increasing temperature for all three fuels. Comparison between two types of the electrolytes reveals that the hydrogen-conducting electrolyte is impractical for use, regarding to the tendency of carbon formation. This is due mainly to the water formed by the electrochemical reaction at the electrodes. (author)

Do Pleistocene Glacial-Interglacial Cycles Control Methane Hydrate Formation? An Example from Green Canyon, Gulf of Mexico

Science.gov (United States)

Oryan, B.; Malinverno, A.; Goldberg, D.; Fortin, W.

2017-12-01

Well GC955-H was drilled in the Green Canyon region under the Gulf of Mexico Gas Hydrates Joint Industry Project in 2009. Logging-while-drilling resistivity logs obtained at the well indicate that the saturation of gas hydrate varies between high and low values in an alternating fashion. This trend is observed from 180 to 360mbsf, depths that correspond to the Late Pleistocene. Similar gas hydrate saturation patterns have been observed in other Gulf of Mexico locations (Walker Ridge sites WR313-G and 313-H) in Late Pleistocene sediments. Our hypothesis is that these variations in saturation can be explained by sea level changes through time during glacial-interglacial cycles. A higher amount of organic matter is deposited and buried in the sediment column during glacial intervals when sea level is low. Microbes in the sediment column degrade organic matter and produce methane gas as a byproduct. Higher availability of organic matter in the sediment column can increase the concentration of methane in the sediment pore water and in turn lead to the formation of gas hydrate. We use a time-dependent numerical model of the formation of gas hydrate to test this hypothesis. The model predicts the volume and distribution of gas hydrates using mass balance equations. Model inputs include in situ porosity determined from bulk density logs; local thermal gradient estimated from the depth of the bottom of the gas hydrate stability zone in proximity to the well; and sedimentation rate determined using the biostratigraphy of an industry well in the vicinity of GC955-H. Initial results show a good match between gas hydrate saturation predicted by the model and resistivity logs obtained in the well. We anticipate that this correlation will establish whether a causal link exists between the saturation of gas hydrate in this reservoir and glacioeustatic sea level changes in the Late Pleistocene.

Experimental Equipment Validation for Methane (CH4) and Carbon Dioxide (CO2) Hydrates

Science.gov (United States)

Saad Khan, Muhammad; Yaqub, Sana; Manner, Naathiya; Ani Karthwathi, Nur; Qasim, Ali; Mellon, Nurhayati Binti; Lal, Bhajan

2018-04-01

Clathrate hydrates are eminent structures regard as a threat to the gas and oil industry in light of their irritating propensity to subsea pipelines. For natural gas transmission and processing, the formation of gas hydrate is one of the main flow assurance delinquent has led researchers toward conducting fresh and meticulous studies on various aspects of gas hydrates. This paper highlighted the thermodynamic analysis on pure CH4 and CO2 gas hydrates on the custom fabricated equipment (Sapphire cell hydrate reactor) for experimental validation. CO2 gas hydrate formed at lower pressure (41 bar) as compared to CH4 gas hydrate (70 bar) while comparison of thermodynamic properties between CH4 and CO2 also presented in this study. This preliminary study could provide pathways for the quest of potent hydrate inhibitors.

Comparison of Nonprecious Metal Cathode Materials for Methane Production by Electromethanogenesis.

KAUST Repository

Siegert, Michael

2014-02-18

In methanogenic microbial electrolysis cells (MMCs), CO2 is reduced to methane using a methanogenic biofilm on the cathode by either direct electron transfer or evolved hydrogen. To optimize methane generation, we examined several cathode materials: plain graphite blocks, graphite blocks coated with carbon black or carbon black containing metals (platinum, stainless steel or nickel) or insoluble minerals (ferrihydrite, magnetite, iron sulfide, or molybdenum disulfide), and carbon fiber brushes. Assuming a stoichiometric ratio of hydrogen (abiotic):methane (biotic) of 4:1, methane production with platinum could be explained solely by hydrogen production. For most other materials, however, abiotic hydrogen production rates were insufficient to explain methane production. At -600 mV, platinum on carbon black had the highest abiotic hydrogen gas formation rate (1600 ± 200 nmol cm(-3) d(-1)) and the highest biotic methane production rate (250 ± 90 nmol cm(-3) d(-1)). At -550 mV, plain graphite (76 nmol cm(-3) d(-1)) performed similarly to platinum (73 nmol cm(-3) d(-1)). Coulombic recoveries, based on the measured current and evolved gas, were initially greater than 100% for all materials except platinum, suggesting that cathodic corrosion also contributed to electromethanogenic gas production.

TITAN'S TRANSPORT-DRIVEN METHANE CYCLE

International Nuclear Information System (INIS)

Mitchell, Jonathan L.

2012-01-01

The mechanisms behind the occurrence of large cloud outbursts and precipitation on Titan have been disputed. A global- and annual-mean estimate of surface fluxes indicated only 1% of the insolation, or ∼0.04 W m –2 , is exchanged as sensible and/or latent fluxes. Since these fluxes are responsible for driving atmospheric convection, it has been argued that moist convection should be quite rare and precipitation even rarer, even if evaporation globally dominates the surface-atmosphere energy exchange. In contrast, climate simulations indicate substantial cloud formation and/or precipitation. We argue that the top-of-atmosphere (TOA) radiative imbalance is diagnostic of horizontal heat transport by Titan's atmosphere, and thus constrains the strength of the methane cycle. Simple calculations show the TOA radiative imbalance is ∼0.5-1 W m –2 in Titan's equatorial region, which implies 2-3 MW of latitudinal heat transport by the atmosphere. Our simulation of Titan's climate suggests this transport may occur primarily as latent heat, with net evaporation at the equator and net accumulation at higher latitudes. Thus, the methane cycle could be 10-20 times previous estimates. Opposing seasonal transport at solstices, compensation by sensible heat transport, and focusing of precipitation by large-scale dynamics could further enhance the local, instantaneous strength of Titan's methane cycle by a factor of several. A limited supply of surface liquids in regions of large surface radiative imbalance may throttle the methane cycle, and if so, we predict more frequent large storms over the lakes district during Titan's northern summer.

The effect of stirring on the heterogeneous nucleation of water and of clathrates of tetrahydrofuran/water mixtures

Directory of Open Access Journals (Sweden)

P.W. Wilson

2016-03-01

Full Text Available The statistics of liquid-to-crystal nucleation are measured for both water and for clathrate-forming mixtures of tetrahydrofuran (THF and water using an automatic lag time apparatus (ALTA. We measure the nucleation temperature using this apparatus in which a single sample is repeatedly cooled, nucleated and thawed. The effect of stirring on nucleation has been evaluated numerically and is discussed. We find that stirring of the solution makes no difference to the nucleation temperature of a given solution in a given tube.

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

Science.gov (United States)

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

2015-01-01

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

An advanced cold moderator using solid methane pellets

International Nuclear Information System (INIS)

Foster, C.A.; Carpenter, J.M.

2001-01-01

This paper reports developments of the pellet formation and transport technologies required for producing a liquid helium or hydrogen cooled methane pellet moderator. The Phase I US DOE SBIR project, already completed, demonstrated the production of 3 mm transparent pellets of frozen methane and ammonia and transport of the pellets into a 40 cc observation cell cooled with liquid helium. The methane pellets, formed at 72 K, stuck together during the loading of the cell. Ammonia pellets did not stick and fell readily under vibration into a packed bed with a 60% fill fraction. A 60% fill fraction should produce a very significant increase in long-wavelength neutron production and advantages in shorter pulse widths as compared to a liquid hydrogen moderator. The work also demonstrated a method of rapidly changing the pellets in the moderator cell. The Phase II project, just now underway, will develop a full-scale pellet source and transport system with a 1.5 L 'moderator' cell. The Phase II effort will also produce an apparatus to sub-cool the methane pellets to below 20 K, which should prevent the methane pellets from sticking together. In addition to results of the phase I experiments, the presentation includes a short video of the pellets, and a description of plans for the Phase II project. (author)

Generalized hypothesis of the origin of the living-matter simplest elements, transformation of the Archean atmosphere, and the formation of methane-hydrate deposits

International Nuclear Information System (INIS)

Ostrovskii, Viktor E; Kadyshevich, Elena A

2007-01-01

The original hydrate hypothesis of the origin of living-matter simplest elements (LMSEs), i.e., the 'Life Origination Hydrate hypothesis,' abbreviated as the LOH hypothesis, is discussed. It includes notions of the interdependence and interconditionality of processes leading to the life origin, to the transformation of the primary atmosphere, and to the underground methane-hydrate formation. Saturation of the young earth's crust with nebular hydrogen is taken into consideration for the first time. The origin of LMSEs is regarded as a result of regular and thermodynamically caused inevitable chemical transformations and of the universal physical and chemical laws. According to the LOH hypothesis, LMSEs originated repeatedly and, maybe, are now originating from methane (or other simple hydrocarbons), niter, and phosphate within boundary layers of the solid phases of the hydrates of the simplest hydrocarbons. It is assumed that the phenomenon of monochirality of nucleic acids is caused by geometric features of the structure matrix. (reviews of topical problems)

Generalized hypothesis of the origin of the living-matter simplest elements, transformation of the Archean atmosphere, and the formation of methane-hydrate deposits

Energy Technology Data Exchange (ETDEWEB)

Ostrovskii, Viktor E [L. Ya. Karpov Institute of Physical Chemistry, Moscow (Russian Federation); Kadyshevich, Elena A [A.M. Obukhov Institute of Atmospheric Physics, Russian Academy of Sciences, Moscow (Russian Federation)

2007-02-28

The original hydrate hypothesis of the origin of living-matter simplest elements (LMSEs), i.e., the 'Life Origination Hydrate hypothesis,' abbreviated as the LOH hypothesis, is discussed. It includes notions of the interdependence and interconditionality of processes leading to the life origin, to the transformation of the primary atmosphere, and to the underground methane-hydrate formation. Saturation of the young earth's crust with nebular hydrogen is taken into consideration for the first time. The origin of LMSEs is regarded as a result of regular and thermodynamically caused inevitable chemical transformations and of the universal physical and chemical laws. According to the LOH hypothesis, LMSEs originated repeatedly and, maybe, are now originating from methane (or other simple hydrocarbons), niter, and phosphate within boundary layers of the solid phases of the hydrates of the simplest hydrocarbons. It is assumed that the phenomenon of monochirality of nucleic acids is caused by geometric features of the structure matrix. (reviews of topical problems)

Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

International Nuclear Information System (INIS)

Li, Lin; Borry, Richard W.; Iglesia, Enrique

2000-01-01

Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

In situ NMR studies of hydrogen storage kinetics and molecular diffusion in clathrate hydrate at elevated hydrogen pressures

Energy Technology Data Exchange (ETDEWEB)

Okuchi, T. [Okayama Univ., Misasa, Tottori (Japan); Moudrakovski, I.L.; Ripmeester, J.A. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences

2008-07-01

The challenge of storing high-density hydrogen into compact host media was investigated. The conventional storage scheme where an aqueous solution is frozen with hydrogen gas is too slow for practical use in a hydrogen-based society. Therefore, the authors developed a faster method whereby hydrogen was stored into gas hydrates. The hydrogen gas was directly charged into hydrogen-free, crystalline hydrate powders with partly empty lattices. The storage kinetics and hydrogen diffusion into the hydrate was observed in situ by nuclear magnetic resonance (NMR) in a pressurized tube cell. At pressures up to 20 MPa, the storage was complete within 80 minutes, as observed by growth of stored-hydrogen peak into the hydrate. Hydrogen diffusion within the crystalline hydrate media is the rate-determining step of current storage scheme. Therefore, the authors measured the diffusion coefficient of hydrogen molecules using the pulsed field gradient NMR method. The results show that the stored hydrogen is very mobile at temperatures down to 250 K. As such, the powdered hydrate media should work well even in cold environments. Compared with more prevailing hydrogen storage media such as metal hydrides, clathrate hydrates have the advantage of being free from hydrogen embrittlement, more chemically durable, more environmentally sound, and economically affordable. It was concluded that the powdered clathrate hydrate is suitable as a hydrogen storage media. 22 refs., 4 figs.

Dynamics of Permafrost Associated Methane Hydrate in Response to Climate Change

Science.gov (United States)

You, K.; Flemings, P. B.

2014-12-01

The formation and melting of methane hydrate and ice are intertwined in permafrost regions. A shortage of methane supply leads to formation of hydrate only at depth, below the base of permafrost. We consider a system with the ground surface initially at 0 oC with neither ice nor hydrate present. We abruptly decrease the temperature from 0 to -10 oC to simulate the effect of marine regression/ global cooling. A low methane supply rate of 0.005 kg m-2 yr-1 from depth leads to distinct ice and hydrate layers: a 100 m continuous hydrate layer is present beneath 850 m at 80 k.y.. However, a high methane supply rate of 0.1 kg m-2 yr-1 leads to 50 m ice-bonded methane hydrate at the base of permafrost, and the hydrate layer distributes between the depth of 350 and 700 m at 80 k.y.. We apply our model to illuminate future melting of hydrate at Mallik, a known Arctic hydrate accumulation. We assume a 600 m thick ice saturated (average 90%) layer extending downward from the ground surface. We increase the surface temperature linearly from -6 to 0 oC for 300 yr and then keep the surface temperature at 0 oC to reflect future climate warming caused by doubling of CO2. Hydrate melting is initiated at the base of the hydrate layer after 15 k.y.. Methane gas starts to vent to the atmosphere at 38 k.y. with an average flux of ~ 0.35 g m-2 yr-1. If the 600 m thick average ice saturation is decreased to half (45%) (or to zero), methane gas starts to vent to the atmosphere at 29 k.y. (or at 20 k.y.) with the same average flux. These results are found by a newly-developed fully-coupled multiphase multicomponent fluid flow and heat transport model. Our thermodynamic equilibrium-based model emphasizes the role of salinity in both ice and hydrate dynamics.

Megafauna and frozen soil: the drivers of atmospheric CH4 dynamics

Science.gov (United States)

Zimov, N.; Zimov, S. A.

2010-12-01

During the last deglaciation (LD) a strong increase in atmospheric methane (CH4) concentrations occurred simultaneously with a rise in Greenland temperatures indicating that in the north, during this time period, strong CH4 sources “awakened”, as additionally documented by the appearance of a strong gradient between northern (Greenland) and southern (Antarctica) hemisphere atmospheric CH4 concentrations. This rise could not be caused by wetland expansion. A reconstruction of peatland formation dynamics has indicated that wetlands on Earth were few in LD and only actively expanded 10,000 yr BP, after atmospheric CH4 concentrations began to decline. Destabilization of methane clathrates also could not be the source for atmospheric CH4 increase. Geological CH4 (including methane clathrates) has the highest deuterium content (δD) among all of the known sources of CH4 while atmospheric CH4 δD values determined for the LD were record low. To explain recorded atmospheric CH4 and its isotopic dynamics required a strong northern source, which was active only during the LD and that provided very low δD CH4 values. Such a source is permafrost thawing under anaerobic conditions (or better stated soils of mammoth steppe-tundra ecosystems). Permafrost thawing is the strongest, among known, wetland sources (usually over 100g CH4/m2yr) and has a unique isotopic signature (δD = -400 per mil (-338 to -479 per mil), δ13C = -73 per mil (-58 to -99 per mil)). The main sources of atmospheric CH4 have different isotopic signatures (δ13C, δD). The isotopic content of atmospheric CH4 is a simple function of the weight average for all of the sources. Inclusion of permafrost source into a budget model of the atmospheric methane and its isotopes allowed us to reconstruct the dynamics of methane’s main sources. Model indicated geological source to be negligible as in LGM so and in LD and Holocene. During the glaciation, the largest methane source was megafauna, whose 1

Hydrogen storage and carbon dioxide sequestration in TBAF semi-clathrate hydrates: Kinetics and evolution of hydrate-phase composition by in situ raman spectroscopy - Abstract -

NARCIS (Netherlands)

Torres Trueba, A.; Radoviæ, I.R.; Zevenbergen, J.F.; Kroon, M.C.; Peters, C.J.

2012-01-01

Carbon dioxide (CO2) represents almost one third of the emissions from the combustion of fossil fuels additionally, CO2 has been identified as the mayor contributor of global warming. Hydrogen (H2), on the other hand, due to its properties is considered a promising energy carrier. Clathrate hydrates

Conversion of methane to methanol in an ac dielectric barrier discharge

International Nuclear Information System (INIS)

Aghamir, F M; Matin, N S; Jalili, A H; Esfarayeni, M H; Khodagholi, M A; Ahmadi, R

2004-01-01

A dielectric barrier discharge (DBD) has been used to investigate the conversion of methane to methanol and higher hydrocarbons in ac non-equilibrium plasmas. Experiments were carried out at atmospheric pressure and ambient temperature. A non-equilibrium plasma was generated in a DBD reactor by applying a high voltage to the reactor electrodes. Activation of methane molecules led to the production of C 2 hydrocarbons and methanol. The effect of the applied voltage, residence time and feed mixture such as helium and oxygen on the methane conversion and product selectivity was studied. Helium appears to have no effect on the conversion and selectivity at our applied voltages. The methane conversion increases significantly on introduction of oxygen in the feed stream. Inclusion of oxygen leads to the formation of methanol. Our results show that production of methanol is initiated around an applied voltage of 12 kV and the conversion of methane increases with increasing voltage and residence time, while the product selectivity is independent of the applied voltage

Isotopic studies on oxidative methane coupling over samarium oxide

International Nuclear Information System (INIS)

Otsuka, Kiyoshi; Inaida, Masakatsu; Wada, Yuji; Komatsu, Takayuki; Morikawa, Akira

1989-01-01

The evident kinetic isotope effect was observed for the formations of ethylene and ethane through the oxidative coupling of methane on Sm 2 O 3 , when CH 4 and CD 4 were used as the reactants. Ethanes formed in the reaction of a mixture of CH 4 , CD 4 , and O 2 were C 2 H 6 , C 2 H 3 D 3 , and C 2 D 6 as major products. These results indicate that the rate-determining step of the reaction is abstraction of hydrogen from methane and that ethane is formed through the coupling of methyl intermediate. (author)

Methane production and methane consumption: a review of processes underlying wetland methane fluxes.

NARCIS (Netherlands)

Segers, R.

1998-01-01

Potential rates of both methane production and methane consumption vary over three orders of magnitude and their distribution is skew. These rates are weakly correlated with ecosystem type, incubation temperature, in situ aeration, latitude, depth and distance to oxic/anoxic interface. Anaerobic

Intense methane ebullition from open water area of a shallow peatland lake on the eastern Tibetan Plateau.

Science.gov (United States)

Zhu, Dan; Wu, Yan; Chen, Huai; He, Yixin; Wu, Ning

2016-01-15

Methane fluxes from a shallow peatland lake (3450 m a.s.l., 1.6 km(2) in area, maximum depth peatlands to the lake. The shallowness of the water column could be another important favorable factor for methane-containing bubble formation in the sediment and their transportation to the atmosphere. The methane ebullition must have been enhanced by the low atmospheric pressure (ca. 672 hPa) in the high-altitude environment. For a better understanding on the mechanism of methane emission from alpine lakes, more lakes on the Tibetan Plateau should be studied in the future for their methane ebullition. Copyright © 2015 Elsevier B.V. All rights reserved.

Observation of Binding and Rotation of Methane and Hydrogen within a Functional Metal–Organic Framework

KAUST Repository

Savage, Mathew; da Silva, Ivan; Johnson, Mark; Carter, Joseph H.; Newby, Ruth; Suetin, Mikhail; Besley, Elena; Manuel, Pascal; Rudić, Svemir; Fitch, Andrew N.; Murray, Claire; David, William I. F.; Yang, Sihai; Schrö der, Martin

2016-01-01

The key requirement for a portable store of natural gas is to maximize the amount of gas within the smallest possible space. The packing of methane (CH4) in a given storage medium at the highest possible density is, therefore, a highly desirable but challenging target. We report a microporous hydroxyl-decorated material, MFM-300(In) (MFM = Manchester Framework Material, replacing the NOTT designation), which displays a high volumetric uptake of 202 v/v at 298 K and 35 bar for CH4 and 488 v/v at 77 K and 20 bar for H2. Direct observation and quantification of the location, binding, and rotational modes of adsorbed CH4 and H2 molecules within this host have been achieved, using neutron diffraction and inelastic neutron scattering experiments, coupled with density functional theory (DFT) modeling. These complementary techniques reveal a very efficient packing of H2 and CH4 molecules within MFM-300(In), reminiscent of the condensed gas in pure component crystalline solids. We also report here, for the first time, the experimental observation of a direct binding interaction between adsorbed CH4 molecules and the hydroxyl groups within the pore of a material. This is different from the arrangement found in CH4/water clathrates, the CH4 store of nature.

Observation of Binding and Rotation of Methane and Hydrogen within a Functional Metal–Organic Framework

KAUST Repository

Savage, Mathew

2016-07-27

The key requirement for a portable store of natural gas is to maximize the amount of gas within the smallest possible space. The packing of methane (CH4) in a given storage medium at the highest possible density is, therefore, a highly desirable but challenging target. We report a microporous hydroxyl-decorated material, MFM-300(In) (MFM = Manchester Framework Material, replacing the NOTT designation), which displays a high volumetric uptake of 202 v/v at 298 K and 35 bar for CH4 and 488 v/v at 77 K and 20 bar for H2. Direct observation and quantification of the location, binding, and rotational modes of adsorbed CH4 and H2 molecules within this host have been achieved, using neutron diffraction and inelastic neutron scattering experiments, coupled with density functional theory (DFT) modeling. These complementary techniques reveal a very efficient packing of H2 and CH4 molecules within MFM-300(In), reminiscent of the condensed gas in pure component crystalline solids. We also report here, for the first time, the experimental observation of a direct binding interaction between adsorbed CH4 molecules and the hydroxyl groups within the pore of a material. This is different from the arrangement found in CH4/water clathrates, the CH4 store of nature.

Predicting hydrocarbon potential of an earth formation underlying a body of water

International Nuclear Information System (INIS)

Kaplan, I.R.; Demaison, G.J.

1983-01-01

A method for the on-site collection and examination of small concentrations of methane dissolved in water so as to predict hydrocarbon potential of an earth formation underlying a body of water, said formation being a source of said methane, comprises: (i) sampling the water; (ii) continuously vacuum separating said water into liquid and gas phases; (iii) quantitatively separating interfering gas species from methane; (iv) quantitatively oxidising said methane; (v) cryogenically trapping the resulting gaseous carbon dioxide and water vapor at a trapping station, and (vi) isotopically examining said trapped carbon dioxide and water vapour for carbon and deuterium distribution. (author)

Origin of methane and sources of high concentrations in Los Angeles groundwater

Science.gov (United States)

Kulongoski, Justin; McMahon, Peter B.; Land, Michael; Wright, Michael; Johnson, Theodore; Landon, Matthew K.

2018-01-01

In 2014, samples from 37 monitoring wells at 17 locations, within or near oil fields, and one site >5 km from oil fields, in the Los Angeles Basin, California, were analyzed for dissolved hydrocarbon gas isotopes and abundances. The wells sample a variety of depths of an aquifer system composed of unconsolidated and semiconsolidated sediments under various conditions of confinement. Concentrations of methane in groundwater samples ranged from 0.002 to 150 mg/L—some of the highest concentrations reported in a densely populated urban area. The δ13C and δ2H of the methane ranged from −80.8 to −45.5 per mil (‰) and −249.8 to −134.9‰, respectively, and, along with oxidation‐reduction processes, helped to identify the origin of methane as microbial methanogenesis and CO2 reduction as its main formation pathway. The distribution of methane concentrations and isotopes is consistent with the high concentrations of methane in Los Angeles Basin groundwater originating from relatively shallow microbial production in anoxic or suboxic conditions. Source of the methane is the aquifer sediments rather than the upward migration or leakage of thermogenic methane associated with oil fields in the basin.

Methylotrophic methanogenesis governs the biogenic coal bed methane formation in Eastern Ordos Basin, China

Energy Technology Data Exchange (ETDEWEB)

Guo, Hongguang; Yu, Zhisheng; Liu, Ruyin [Graduate Univ. of Chinese Academy of Sciences, Beijing (China). College of Resources and Environment; Zhang, Hongxun [Graduate Univ. of Chinese Academy of Sciences, Beijing (China). College of Resources and Environment; Chinese Academy of Sciences, Beijing (China). Research Center for Eco-Environmental Sciences; Zhong, Qiding; Xiong, Zhenghe [China National Research Institute of Food and Fermentation Industries, Beijing (China). Food Analysis using Isotope Technology Lab

2012-12-15

To identify the methanogenic pathways present in a deep coal bed methane (CBM) reservoir associated with Eastern Ordos Basin in China, a series of geochemical and microbiological studies was performed using gas and water samples produced from the Liulin CBM reservoir. The composition and stable isotopic ratios of CBM implied a mixed biogenic and thermogenic origin of the methane. Archaeal 16S rRNA gene analysis revealed the dominance of the methylotrophic methanogen Methanolobus in the water produced. The high potential of methane production by methylotrophic methanogens was found in the enrichments using the water samples amended with methanol and incubated at 25 and 35 C. Methylotrophic methanogens were the dominant archaea in both enrichments as shown by polymerase chain reaction (PCR)-denaturing gradient gel electrophoresis (DGGE). Bacterial 16S rRNA gene analysis revealed that fermentative, sulfate-reducing, and nitrate-reducing bacteria inhabiting the water produced were a factor in coal biodegradation to fuel methanogens. These results suggested that past and ongoing biodegradation of coal by methylotrophic methanogens and syntrophic bacteria, as well as thermogenic CBM production, contributed to the Liulin CBM reserves associated with the Eastern Ordos Basin. (orig.)

High-temperature conversion of methane on a composite gadolinia-doped ceria-gold electrode

DEFF Research Database (Denmark)

Marina, O.A.; Mogensen, Mogens Bjerg

1999-01-01

Direct electrochemical oxidation of methane was attempted on a gadolinia-doped ceria Ce(0.6)Gd(0.4)O(1.8) (CG4) electrode in a solid oxide fuel cell using a porous gold-CG4 mixture as current collector Gold is relatively inert to methane in contrast to other popular SOFC anode materials such as n......Direct electrochemical oxidation of methane was attempted on a gadolinia-doped ceria Ce(0.6)Gd(0.4)O(1.8) (CG4) electrode in a solid oxide fuel cell using a porous gold-CG4 mixture as current collector Gold is relatively inert to methane in contrast to other popular SOFC anode materials...... such as nickel and platinum. CG4 was found to exhibit a low electrocatalytic activity for methane oxidation as well as no significant reforming activity implying that the addition of an electrocatalyst or cracking catalyst to the CG4 anode is required for SOFC operating on methane. The methane conversion...... observed at the open-circuit potential and low anodic overpotentials seems to be due to thermal methane cracking in the gas phase and on the alumina surfaces in the cell housing. At high anodic overpotentials, at electrode potentials where oxygen evolution was expected to take place, the formation of CO(2...

[Microbial Processes and Genesis of Methane Gas Jets in the Coastal Areas of the Crimea Peninsula].

Science.gov (United States)

Malakhova, T V; Kanapatskii, T A; Egorov, V N; Malakhova, L V; Artemov, Yu G; Evtushenko, D B; Gulin, S B; Pimenov, N V

2015-01-01

Hydroasoustic techniques were used for detection and mapping of gas jet areas in the coastal regions of the Crimean peninsula. Gas seep areas in the bays Laspi, Khersones, and Kazach'ya were chosen for detailed microbiological investigation. The first type of gas jets, observed in the Laspi Bay, was probably associated with discarge of deep thermogenic methane along the faults. Methane isotopic composition was char- acterized by Δ13C of -35.3 degrees. While elevated rates of aerobic methane oxidation were revealed in the sandy sediments adjacent to the methane release site, no evidence of bacterial mats was found. The second type of gas emission, observed in the Khersones Bay, was accompanied by formation of bacterial biofilms of the "Thiodendron" microbial community type, predominated by filamentous, spirochete-like organisms, in the areas of gas seepage. The isotopic composition of methane was there considerably lower (-60.4 degrees), indicating a considerable contribution of modern microbial methane to the gas bubbles discharged in this bay. Activity of the third type of gas emission, the seeps of the Kazach'ya Bay, probably depended directly on modern microbial processes of organic matter degradation in the upper sediment layers. The rates of sulfate reduction and methanogenesis were 260 and 34 μmol dm(-3) day(-1), respectively. Our results indicate different mechanisms responsible for formation of methane jets in the Laspi Bay and in the coastal areas of the Heracles Peninsula, where the bays Kazach'ya and Khersones are located.

Thermoelectric properties of In-substituted Ge-based clathrates prepared by HPHT

Directory of Open Access Journals (Sweden)

Binwu Liu

2018-03-01

Full Text Available Bulk materials Ba8Ga16InxGe30-x (x = 0.5, 1.0, 1.5 were prepared by High-Pressure and High-Temperature (HPHT method and the crystal structure has been confirmed by X-ray diffraction and cell refinement. The actual In composition was much lower than the starting composition, and lattice constants increased with the increase of substitution. As the temperature increased, the Seebeck coefficient and electrical resistivity increased first and then decreased, while the thermal conductivity was the opposite, which leads to significant enhancement on thermoelectric properties of the clathrates. The substitution of indium elements decreased the seebeck coefficient and electrical resistivity, and also changed the microstructure of the compounds. A minimum thermal conductivity of 0.84 Wm−1K−1 was obtained, and a good ZT value of 0.52 was achieved. The grain boundaries and lattice defects generated by high pressure can effectively scatter phonons of different frequencies, which reduce the lattice thermal conductivity.

Gas hydrate phase equilibria measurement techniques and phase rule considerations

International Nuclear Information System (INIS)

Beltran, Juan G.; Bruusgaard, Hallvard; Servio, Phillip

2012-01-01

Highlights: → Inconsistencies found in hydrate literature. → Clarification to the number of variables needed to satisfy and justify equilibrium data. → Application of phase rule to mixed hydrate systems. → Thermodynamically consistent format to present data. - Abstract: A brief review of the Gibbs phase rule for non-reacting systems and its correct application to clathrate hydrates is presented. Clarification is provided for a common mistake found in hydrate phase-equilibria literature, whereby initial compositions are used as intensive variables to satisfy the Gibbs phase rule instead of the equilibrium values. The system of (methane + carbon dioxide + water) under (hydrate + liquid + vapor) equilibrium is used as a case study to illustrate key points and suggestions to improve experimental techniques are proposed.

A two component model for thermal emission from organic grains in Comet Halley

Science.gov (United States)

Chyba, Christopher; Sagan, Carl

1988-01-01

Observations of Comet Halley in the near infrared reveal a triple-peaked emission feature near 3.4 micrometer, characteristic of C-H stretching in hydrocarbons. A variety of plausible cometary materials exhibit these features, including the organic residue of irradiated candidate cometary ices (such as the residue of irradiated methane ice clathrate, and polycyclic aromatic hydrocarbons. Indeed, any molecule containing -CH3 and -CH2 alkanes will emit at 3.4 micrometer under suitable conditions. Therefore tentative identifications must rest on additional evidence, including a plausible account of the origins of the organic material, a plausible model for the infrared emission of this material, and a demonstration that this conjunction of material and model not only matches the 3 to 4 micrometer spectrum, but also does not yield additional emission features where none is observed. In the case of the residue of irradiated low occupancy methane ice clathrate, it is argued that the lab synthesis of the organic residue well simulates the radiation processing experienced by Comet Halley.

Microbial methane in the shallow Paleozoic sediments and glacial deposits of Illinois, U.S.A.

Science.gov (United States)

Coleman, D.D.; Liu, Chao-Li; Riley, K.M.

1988-01-01

Methane formed by the microbial decomposition of buried organic matter is virtually ubiquitous in the groundwaters of Illinois. Chemical and carbon isotopic compositions are reported for gas samples collected from over 200 private and municipal water wells and from 39 small gas wells completed in glacial deposits (drift-gas wells). Carbon and hydrogen isotopic data for methane, carbon dioxide and water show that these gases were formed by the carbon dioxide reduction pathway, the same mechanism which has been previously shown to be responsible for microbial methane formation in the marine environment. The isotopic composition of methane in these samples can be closely correlated with the chemical composition of the gas and with water chemistry. The data are interpreted as indicating that isotopically very light methane is found in waters where the residence time of groundwater in the methanogenesis zone was very short relative to the methane production rate. ?? 1988.

Atmospheric methane removal by methane-oxidizing bacteria immobilized on porous building materials.

Science.gov (United States)

Ganendra, Giovanni; De Muynck, Willem; Ho, Adrian; Hoefman, Sven; De Vos, Paul; Boeckx, Pascal; Boon, Nico

2014-04-01

Biological treatment using methane-oxidizing bacteria (MOB) immobilized on six porous carrier materials have been used to mitigate methane emission. Experiments were performed with different MOB inoculated in building materials at high (~20 % (v/v)) and low (~100 ppmv) methane mixing ratios. Methylocystis parvus in autoclaved aerated concrete (AAC) exhibited the highest methane removal rate at high (28.5 ± 3.8 μg CH₄ g⁻¹ building material h⁻¹) and low (1.7 ± 0.4 μg CH₄ g⁻¹ building material h⁻¹) methane mixing ratio. Due to the higher volume of pores with diameter >5 μm compared to other materials tested, AAC was able to adsorb more bacteria which might explain for the higher methane removal observed. The total methane and carbon dioxide-carbon in the headspace was decreased for 65.2 ± 10.9 % when M. parvus in Ytong was incubated for 100 h. This study showed that immobilized MOB on building materials could be used to remove methane from the air and also act as carbon sink.

Rain increases methane production and methane oxidation in a boreal thermokarst bog

Science.gov (United States)

Neumann, R. B.; Moorberg, C.; Turner, J.; Wong, A.; Waldrop, M. P.; Euskirchen, E. S.; Edgar, C.; Turetsky, M. R.

2017-12-01

Bottom-up biogeochemical models of wetland methane emissions simulate the response of methane production, oxidation and transport to wetland conditions and environmental forcings. One reason for mismatches between bottom-up and top-down estimates of emissions is incomplete knowledge of factors and processes that control microbial rates and methane transport. To advance mechanistic understanding of wetland methane emissions, we conducted a multi-year field investigation and plant manipulation experiment in a thermokarst bog located near Fairbanks, Alaska. The edge of the bog is experiencing active permafrost thaw, while the center of the bog thawed 50 to 100 years ago. Our study, which captured both an average year and two of the wettest years on record, revealed how rain interacts with vascular vegetation and recently thawed permafrost to affect methane emissions. In the floating bog, rain water warmed and oxygenated the subsurface, but did not alter soil saturation. The warmer peat temperatures increased both microbial methane production and plant productivity at the edge of the bog near the actively thawing margin, but minimally altered microbial and plant activity in the center of the bog. These responses indicate processes at the edge of the bog were temperature limited while those in the center were not. The compounding effect of increased microbial activity and plant productivity at the edge of the bog doubled methane emissions from treatments with vascular vegetation during rainy years. In contrast, methane emissions from vegetated treatments in the center of the bog did not change with rain. The oxygenating influence of rain facilitated greater methane oxidation in treatments without vascular vegetation, which offset warming-induced increases in methane production at the edge of the bog and decreased methane emissions in the center of the bog. These results elucidate the complex and spatially variable response of methane production and oxidation in

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

Science.gov (United States)

Shuai, Yanhua; Douglas, Peter M. J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael D.; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-02-01

Multiply isotopically substituted molecules ('clumped' isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature-time conditions corresponding to 'low,' 'mature,' and 'over-mature' stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions ('high' to 'over-mature' stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where 'secondary' cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl

Historical methane hydrate project review

Science.gov (United States)

Collett, Timothy; Bahk, Jang-Jun; Frye, Matt; Goldberg, Dave; Husebo, Jarle; Koh, Carolyn; Malone, Mitch; Shipp, Craig; Torres, Marta

2013-01-01

Blake Ridge in the Atlantic Ocean in 1995, have also contributed greatly to our understanding of the geologic controls on the formation, occurrence, and stability of gas hydrates in marine environments. For the most part methane hydrate research expeditions carried out by the ODP and IODP provided the foundation for our scientific understanding of gas hydrates. The methane hydrate research efforts under ODP-­‐IODP have mostly dealt with the assessment of the geologic controls on the occurrence of gas hydrate, with a specific goal to study the role methane hydrates may play in the global carbon cycle.Over the last 10 years, national led methane hydrate research programs, along with industry interest have led to the development and execution of major methane hydrate production field test programs. Two of the most important production field testing programs have been conducted at the Mallik site in the Mackenzie River Delta of Canada and in the Eileen methane hydrate accumulation on the North Slope of Alaska. Most recently we have also seen the completion of the world’s first marine methane hydrate production test in the Nankai Trough in the offshore of Japan. Industry interest in gas hydrates has also included important projects that have dealt with the assessment of geologic hazards associated with the presence of hydrates.The scientific drilling and associated coring, logging, and borehole monitoring technologies developed in the long list of methane hydrate related field studies are one of the most important developments and contributions associated with methane hydrate research and development activities. Methane hydrate drilling has been conducted from advanced scientific drilling platforms like the JOIDES Resolution and the D/V Chikyu, which feature highly advanced integrated core laboratories and borehole logging capabilities. Hydrate research drilling has also included the use of a wide array of industry, geotechnical and multi-­‐service ships. All of

Plasma Thermal Conversion of Methane to Acetylene

International Nuclear Information System (INIS)

Fincke, James Russell; Anderson, Raymond Paul; Hyde, Timothy Allen; Detering, Brent Alan; Wright, Randy Ben; Bewley, Randy Lee; Haggard, Delon C; Swank, William David

2002-01-01

This paper describes a re-examination of a known process for the direct plasma thermal conversion of methane to acetylene. Conversion efficiencies (% methane converted) approached 100% and acetylene yields in the 90-95% range with 2-4% solid carbon production were demonstrated. Specificity for acetylene was higher than in prior work. Improvements in conversion efficiency, yield, and specificity were due primarily to improved injector design and reactant mixing, and minimization of temperature gradients and cold boundary layers. At the 60-kilowatt scale cooling by wall heat transfer appears to be sufficient to quench the product stream and prevent further reaction of acetylene resulting in the formation of heavier hydrocarbon products or solid carbon. Significantly increasing the quenching rate by aerodynamic expansion of the products through a converging-diverging nozzle led to a reduction in the yield of ethylene but had little effect on the yield of other hydrocarbon products. While greater product selectivity for acetylene has been demonstrated, the specific energy consumption per unit mass of acetylene produced was not improved upon. A kinetic model that includes the reaction mechanisms resulting in the formation of acetylene and heavier hydrocarbons, through benzene, is described

Synthesis of hydrogen-carbon clathrate material and hydrogen evolution therefrom at moderate temperatures and pressures

Science.gov (United States)

Lueking, Angela [State College, PA; Narayanan, Deepa [Redmond, WA

2011-03-08

A process for making a hydrogenated carbon material is provided which includes forming a mixture of a carbon source, particularly a carbonaceous material, and a hydrogen source. The mixture is reacted under reaction conditions such that hydrogen is generated and/or released from the hydrogen source, an amorphous diamond-like carbon is formed, and at least a portion of the generated and/or released hydrogen associates with the amorphous diamond-like carbon, thereby forming a hydrogenated carbon material. A hydrogenated carbon material including a hydrogen carbon clathrate is characterized by evolution of molecular hydrogen at room temperature at atmospheric pressure in particular embodiments of methods and compositions according to the present invention.

Laboratory Studies of Methane and Its Relationship to Prebiotic Chemistry.

Science.gov (United States)

Kobayashi, Kensei; Geppert, Wolf D; Carrasco, Nathalie; Holm, Nils G; Mousis, Olivier; Palumbo, Maria Elisabetta; Waite, J Hunter; Watanabe, Naoki; Ziurys, Lucy M

2017-08-01

To examine how prebiotic chemical evolution took place on Earth prior to the emergence of life, laboratory experiments have been conducted since the 1950s. Methane has been one of the key molecules in these investigations. In earlier studies, strongly reducing gas mixtures containing methane and ammonia were used to simulate possible reactions in the primitive atmosphere of Earth, producing amino acids and other organic compounds. Since Earth's early atmosphere is now considered to be less reducing, the contribution of extraterrestrial organics to chemical evolution has taken on an important role. Such organic molecules may have come from molecular clouds and regions of star formation that created protoplanetary disks, planets, asteroids, and comets. The interstellar origin of organics has been examined both experimentally and theoretically, including laboratory investigations that simulate interstellar molecular reactions. Endogenous and exogenous organics could also have been supplied to the primitive ocean, making submarine hydrothermal systems plausible sites of the generation of life. Experiments that simulate such hydrothermal systems where methane played an important role have consequently been conducted. Processes that occur in other Solar System bodies offer clues to the prebiotic chemistry of Earth. Titan and other icy bodies, where methane plays significant roles, are especially good targets. In the case of Titan, methane is both in the atmosphere and in liquidospheres that are composed of methane and other hydrocarbons, and these have been studied in simulation experiments. Here, we review the wide range of experimental work in which these various terrestrial and extraterrestrial environments have been modeled, and we examine the possible role of methane in chemical evolution. Key Words: Methane-Interstellar environments-Submarine hydrothermal systems-Titan-Origin of life. Astrobiology 17, 786-812.

Utilization of coalbed methane

Energy Technology Data Exchange (ETDEWEB)

Gustavson, J.B. [Gustavson Associates Inc., Boulder, CO (United States)

1996-02-01

Substantial progress has been made in capturing coalbed methane (CBM gas), which constitutes a valuable source of clean burning energy. It is of importance to study the various potential uses of coalbed methane and to understand the various technologies required, as well as their economics and any institutional constraints. In industrialised countries, the uses of coalbed methane are almost solely dependent on microeconomics; coalbed methane must compete for a market against natural gas and other energy sources - and frequently, coalbed methane is not competitive against other energy sources. In developing countries, on the other hand, particularly where other sources of energy are in short supply, coalbed methane economics yield positive results. Here, constraints to development of CBM utilization are mainly lack of technology and investment capital. Sociological aspects such as attitude and cultural habits, may also have a strong negative influence. This paper outlines the economics of coalbed methane utilization, particularly its competition with natural gas, and touches upon the many different uses to which coalbed methane may be applied. 24 refs., 4 figs.

Doses from radioactive methane

International Nuclear Information System (INIS)

Phipps, A.W.; Kendall, G.M.; Fell, T.P.; Harrison, J.D.

1990-01-01

A possible radiation hazard arises from exposure to methane labelled with either a 3 H or a 14 C nuclide. This radioactive methane could be released from a variety of sources, e.g. land burial sites containing radioactive waste. Standard assumptions adopted for vapours would not apply to an inert alkane like methane. This paper discusses mechanisms by which radioactive methane would irradiate tissues and provides estimates of doses. Data on skin thickness and metabolism of methane are discussed with reference to these mechanisms. It is found that doses are dominated by dose from the small fraction of methane which is inhaled and metabolised. This component of dose has been calculated under rather conservative assumptions. (author)

Methane reacts with heteropolyacids chemisorbed on silica to produce acetic acid under soft conditions

KAUST Repository

Sun, Miao

2013-01-16

Selective functionalization of methane at moderate temperature is of crucial economic, environmental, and scientific importance. Here, we report that methane reacts with heteropolyacids (HPAs) chemisorbed on silica to produce acetic acid under soft conditions. Specially, when chemisorbed on silica, H 4SiW12O40, H3PW12O 40, H4SiMo12O40, and H 3PMo12O40 activate the primary C-H bond of methane at room temperature and atmospheric pressure. With these systems, acetic acid is produced directly from methane, in a single step, in the absence of Pd and without adding CO. Extensive surface characterization by solid-state NMR spectroscopy, IR spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy suggests that C-H activation of methane is triggered by the protons in the HPA-silica interface with concerted reduction of the Keggin cage, leading to water formation and hydration of the interface. This is the simplest and mildest way reported to date to functionalize methane. © 2012 American Chemical Society.

Liquid hydrogen production via hydrogen sulfide methane reformation

Science.gov (United States)

Huang, Cunping; T-Raissi, Ali

Hydrogen sulfide (H 2S) methane (CH 4) reformation (H 2SMR) (2H 2S + CH 4 = CS 2 + 4H 2) is a potentially viable process for the removal of H 2S from sour natural gas resources or other methane containing gases. Unlike steam methane reformation that generates carbon dioxide as a by-product, H 2SMR produces carbon disulfide (CS 2), a liquid under ambient temperature and pressure-a commodity chemical that is also a feedstock for the synthesis of sulfuric acid. Pinch point analyses for H 2SMR were conducted to determine the reaction conditions necessary for no carbon lay down to occur. Calculations showed that to prevent solid carbon formation, low inlet CH 4 to H 2S ratios are needed. In this paper, we analyze H 2SMR with either a cryogenic process or a membrane separation operation for production of either liquid or gaseous hydrogen. Of the three H 2SMR hydrogen production flowsheets analyzed, direct liquid hydrogen generation has higher first and second law efficiencies of exceeding 80% and 50%, respectively.

Oxidative coupling of methane using inorganic membrane reactor

Energy Technology Data Exchange (ETDEWEB)

Ma, Y.H.; Moser, W.R.; Dixon, A.G. [Worcester Polytechnic Institute, MA (United States)] [and others

1995-12-31

The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.

Martian methane plume models for defining Mars rover methane source search strategies

Science.gov (United States)

Nicol, Christopher; Ellery, Alex; Lynch, Brian; Cloutis, Ed

2018-07-01

The detection of atmospheric methane on Mars implies an active methane source. This introduces the possibility of a biotic source with the implied need to determine whether the methane is indeed biotic in nature or geologically generated. There is a clear need for robotic algorithms which are capable of manoeuvring a rover through a methane plume on Mars to locate its source. We explore aspects of Mars methane plume modelling to reveal complex dynamics characterized by advection and diffusion. A statistical analysis of the plume model has been performed and compared to analyses of terrestrial plume models. Finally, we consider a robotic search strategy to find a methane plume source. We find that gradient-based techniques are ineffective, but that more sophisticated model-based search strategies are unlikely to be available in near-term rover missions.

Laboratory Studies of Methane and Its Relationship to Prebiotic Chemistry

Science.gov (United States)

Kobayashi, Kensei; Geppert, Wolf D.; Carrasco, Nathalie; Holm, Nils G.; Mousis, Olivier; Palumbo, Maria Elisabetta; Waite, J. Hunter; Watanabe, Naoki; Ziurys, Lucy M.

2017-08-01

To examine how prebiotic chemical evolution took place on Earth prior to the emergence of life, laboratory experiments have been conducted since the 1950s. Methane has been one of the key molecules in these investigations. In earlier studies, strongly reducing gas mixtures containing methane and ammonia were used to simulate possible reactions in the primitive atmosphere of Earth, producing amino acids and other organic compounds. Since Earth's early atmosphere is now considered to be less reducing, the contribution of extraterrestrial organics to chemical evolution has taken on an important role. Such organic molecules may have come from molecular clouds and regions of star formation that created protoplanetary disks, planets, asteroids, and comets. The interstellar origin of organics has been examined both experimentally and theoretically, including laboratory investigations that simulate interstellar molecular reactions. Endogenous and exogenous organics could also have been supplied to the primitive ocean, making submarine hydrothermal systems plausible sites of the generation of life. Experiments that simulate such hydrothermal systems where methane played an important role have consequently been conducted. Processes that occur in other Solar System bodies offer clues to the prebiotic chemistry of Earth. Titan and other icy bodies, where methane plays significant roles, are especially good targets. In the case of Titan, methane is both in the atmosphere and in liquidospheres that are composed of methane and other hydrocarbons, and these have been studied in simulation experiments. Here, we review the wide range of experimental work in which these various terrestrial and extraterrestrial environments have been modeled, and we examine the possible role of methane in chemical evolution.

Impact of methane flow through deformable lake sediments on atmospheric release

Science.gov (United States)

Scandella, B.; Juanes, R.

2010-12-01

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

C-13 isotopic studies of the surface catalysed reactions of methane

International Nuclear Information System (INIS)

Long, M.A.; He, S.J.X.; Adebajo, M.

1997-01-01

The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and 13 C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane 13 C, which show that methylation of aromatics such as naphthalene by the methane 13 C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

Science.gov (United States)

Alperin, M. J.; Blair, Neal E.; Albert, D. B.; Hoehler, T. M.; Martens, C. S.

1993-01-01

The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane

Controls on Gas Hydrate Formation and Dissociation

Energy Technology Data Exchange (ETDEWEB)

Miriam Kastner; Ian MacDonald

2006-03-03

The main objectives of the project were to monitor, characterize, and quantify in situ the rates of formation and dissociation of methane hydrates at and near the seafloor in the northern Gulf of Mexico, with a focus on the Bush Hill seafloor hydrate mound; to record the linkages between physical and chemical parameters of the deposits over the course of one year, by emphasizing the response of the hydrate mound to temperature and chemical perturbations; and to document the seafloor and water column environmental impacts of hydrate formation and dissociation. For these, monitoring the dynamics of gas hydrate formation and dissociation was required. The objectives were achieved by an integrated field and laboratory scientific study, particularly by monitoring in situ formation and dissociation of the outcropping gas hydrate mound and of the associated gas-rich sediments. In addition to monitoring with the MOSQUITOs, fluid flow rates and temperature, continuously sampling in situ pore fluids for the chemistry, and imaging the hydrate mound, pore fluids from cores, peepers and gas hydrate samples from the mound were as well sampled and analyzed for chemical and isotopic compositions. In order to determine the impact of gas hydrate dissociation and/or methane venting across the seafloor on the ocean and atmosphere, the overlying seawater was sampled and thoroughly analyzed chemically and for methane C isotope ratios. At Bush hill the pore fluid chemistry varies significantly over short distances as well as within some of the specific sites monitored for 440 days, and gas venting is primarily focused. The pore fluid chemistry in the tub-warm and mussel shell fields clearly documented active gas hydrate and authigenic carbonate formation during the monitoring period. The advecting fluid is depleted in sulfate, Ca Mg, and Sr and is rich in methane; at the main vent sites the fluid is methane supersaturated, thus bubble plumes form. The subsurface hydrology exhibits both

Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.

Science.gov (United States)

Kida, Masato; Jin, Yusuke; Takahashi, Nobuo; Nagao, Jiro; Narita, Hideo

2010-09-09

Dissociation behavior of methane-ethane mixed gas hydrate coexisting structures I and II at constant temperatures less than 223 K was studied with use of powder X-ray diffraction and solid-state (13)C NMR techniques. The diffraction patterns at temperatures less than 203 K showed both structures I and II simultaneously convert to Ih during the dissociation, but the diffraction pattern at temperatures greater than 208 K showed different dissociation behavior between structures I and II. Although the diffraction peaks from structure II decreased during measurement at constant temperatures greater than 208 K, those from structure I increased at the initial step of dissociation and then disappeared. This anomalous behavior of the methane-ethane mixed gas hydrate coexisting structures I and II was examined by using the (13)C NMR technique. The (13)C NMR spectra revealed that the anomalous behavior results from the formation of ethane-rich structure I. The structure I hydrate formation was associated with the dissociation rate of the initial methane-ethane mixed gas hydrate.

Lithium-ion induced conformational change of 5,17-bis(9-fluorenyl)-25,26,27,28-tetrapropoxy calix[4]arene resulting in an egg-shaped dimeric clathrate

DEFF Research Database (Denmark)

Faldt, A.; Krebs, Frederik C; Jørgensen, Mikkel

2000-01-01

Synthesis and structural investigation of a 5,17-bis(9-fluorenyl)-25,26,27,28-tetrapropoxy calix[4]arene and its lithium complex salt that forms a dimeric clathrate with a molecule of solvent inside a cavity. At least three different interactions were identified as being responsible for the forma...

Methane from benzene in argon dielectric barrier discharge

International Nuclear Information System (INIS)

Das, Tomi Nath; Dey, G.R.

2013-01-01

Highlights: ► Efficient on-line conversion of benzene to methane at room temperature. ► Absence of other H-atom donor suggests new type of chemistry. ► For parent loss > 90%, methane yield was ∼40% of limit due to H-atom availability. ► Surface moisture contributed ·OH radical for trace phenolic products’ formation. ► This method may emerge as an exploitable tactic for pollutants’ usable alterations. -- Abstract: A first-time account of direct, on-line, instantaneous and efficient chemical conversion of gas phase benzene to methane in argon Dielectric Barrier Discharge (DBD) is presented. In the absence of another overt hydrogen-donating source, potency of analogous parents toward methane generation is found to follow the order: benzene > toluene > p-xylene. Simultaneous production of trace amounts of phenolic surface deposits suggest (a) prompt decomposition of the parent molecules, including a large fraction yielding atomic transients (H-atom), (b) continuous and appropriate recombination of such parts, and (c) trace moisture in parent contributing ·OH radicals and additional H-atoms, which suitably react with the unreacted fraction of the parent, and also other intermediates. Results highlight Ar DBD to be a simple and exploitable technology for transforming undesirable hazardous aromatics to usable/useful low molecular weight open-chain products following the principles of green chemistry and engineering

Atmospheric methane removal by methane-oxidizing bacteria immobilized on porous building materials

NARCIS (Netherlands)

Ganendra, G; De Muynck, W; Ho, A.; Hoefman, S.; De Vos, P.; Boeckx, P.; Boon, N.

2014-01-01

Biological treatment using methane-oxidizing bacteria (MOB) immobilized on six porous carrier materials have been used to mitigate methane emission. Experiments were performed with different MOB inoculated in building materials at high (similar to 20 % (v/v)) and low (similar to 100 ppmv) methane

Response of the Black Sea methane budget to massive short-term submarine inputs of methane

DEFF Research Database (Denmark)

Schmale, O.; Haeckel, M.; McGinnis, D. F.

2011-01-01

A steady state box model was developed to estimate the methane input into the Black Sea water column at various water depths. Our model results reveal a total input of methane of 4.7 Tg yr(-1). The model predicts that the input of methane is largest at water depths between 600 and 700 m (7......% of the total input), suggesting that the dissociation of methane gas hydrates at water depths equivalent to their upper stability limit may represent an important source of methane into the water column. In addition we discuss the effects of massive short-term methane inputs (e. g. through eruptions of deep......-water mud volcanoes or submarine landslides at intermediate water depths) on the water column methane distribution and the resulting methane emission to the atmosphere. Our non-steady state simulations predict that these inputs will be effectively buffered by intense microbial methane consumption...

Methane oxidation and methane fluxes in the ocean surface layer and deep anoxic waters

Science.gov (United States)

Ward, B. B.; Kilpatrick, K. A.; Novelli, P. C.; Scranton, M. I.

1987-01-01

Measured biological oxidation rates of methane in near-surface waters of the Cariaco Basin are compared with the diffusional fluxes computed from concentration gradients of methane in the surface layer. Methane fluxes and oxidation rates were investigated in surface waters, at the oxic/anoxic interface, and in deep anoxic waters. It is shown that the surface-waters oxidation of methane is a mechanism which modulates the flux of methane from marine waters to the atmosphere.

Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

Science.gov (United States)

Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

2013-01-01

Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

Excimer-mediated photoionization of covalently-linked diaryl compounds: Energy thresholds for excimer formation and excimer-assisted photoionization of jet-cooled bis (9-Fluorenyl) methane

International Nuclear Information System (INIS)

Lee, Jae Kwang; Kang, Heun Kag; Cho, Han Joung; Boo, Bong Hyun; Lim, Edward C.

2001-01-01

Diarylakanes capable of adopting a face-to face arrangement of the two aromatic rings are ideal systems in which to probe the excited-state dynamics leading to excimer formation and the role of the singlet excimer in the photoionization of covalently linked bichromophoric molecules. Bis (9-eluorenyl) methane, BFM, is a good example of such diaryl compounds. Boo and co-workers have shown that BFM exhibits excrimer fluorescence in solution at ambient temperatures. An Arrhenius plot of the temperature-dependent excimer formation rate yielded activation energy of about 15 kJ·mol -1 . It has been proposed that the activation energy is related to the barrier for transforming the initial S 1 geometry to the face-to face (sandwich-pair) geometry of the intramolecular singlet excimer. This is accord with the study of an intramolecular excimer formation in jet-cooled 1, 3-diphenylpropane (DPP), and that of an intramolecular exciplex formation in 1-(9-anthryl)-3-(4-N, N-dimethylaniline) propane, which indicate that the energy threshold for such conformational changes is about 11 kJ·mol -1 .

High performance biological methanation in a thermophilic anaerobic trickle bed reactor.

Science.gov (United States)

Strübing, Dietmar; Huber, Bettina; Lebuhn, Michael; Drewes, Jörg E; Koch, Konrad

2017-12-01

In order to enhance energy efficiency of biological methanation of CO 2 and H 2 , this study investigated the performance of a thermophilic (55°C) anaerobic trickle bed reactor (ATBR) (58.1L) at ambient pressure. With a methane production rate of up to 15.4m 3 CH4 /(m 3 trickle bed ·d) at methane concentrations above 98%, the ATBR can easily compete with the performance of other mixed culture methanation reactors. Control of pH and nutrient supply turned out to be crucial for stable operation and was affected significantly by dilution due to metabolic water production, especially during demand-orientated operation. Considering practical applications, inoculation with digested sludge, containing a diverse biocenosis, showed high adaptive capacity due to intrinsic biological diversity. However, no macroscopic biofilm formation was observed at thermophilic conditions even after 313days of operation. The applied approach illustrates the high potential of thermophilic ATBRs as a very efficient energy conversion and storage technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Coalbed Methane Outreach Program

Science.gov (United States)

Coalbed Methane Outreach Program, voluntary program seeking to reduce methane emissions from coal mining activities. CMOP promotes profitable recovery/use of coal mine methane (CMM), addressing barriers to using CMM instead of emitting it to atmosphere.

Improved methane removal in exhaust gas from biogas upgrading process using immobilized methane-oxidizing bacteria.

Science.gov (United States)

Sun, Meng-Ting; Yang, Zhi-Man; Fu, Shan-Fei; Fan, Xiao-Lei; Guo, Rong-Bo

2018-05-01

Methane in exhaust gas from biogas upgrading process, which is a greenhouse gas, could cause global warming. The biofilter with immobilized methane-oxidizing bacteria (MOB) is a promising approach for methane removal, and the selections of inoculated MOB culture and support material are vital for the biofilter. In this work, five MOB consortia were enriched at different methane concentrations. The MOB-20 consortium enriched at the methane concentration of 20.0% (v/v) was then immobilized on sponge and two particle sizes of volcanic rock in biofilters to remove methane in exhaust gas from biogas upgrading process. Results showed that the immobilized MOB performed more admirable methane removal capacity than suspended cells. The immobilized MOB on sponge reached the highest methane removal efficiency (RE) of 35%. The rough surface, preferable hydroscopicity, appropriate pore size and particle size of support material might favor the MOB immobilization and accordingly methane removal. Copyright © 2018 Elsevier Ltd. All rights reserved.

Plasma-assisted partial oxidation of methane at low temperatures: numerical analysis of gas-phase chemical mechanism

Energy Technology Data Exchange (ETDEWEB)

Goujard, Valentin; Nozaki, Tomohiro; Yuzawa, Shuhei; Okazaki, Ken [Department of Mechanical and Control Engineering, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro, 1528552, Tokyo (Japan); Agiral, Anil, E-mail: tnozaki@mech.titech.ac.jp [Mesoscale Chemical Systems, MESA Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, PO Box 217, 7500 AE, Enschede (Netherlands)

2011-07-13

Methane partial oxidation was investigated using a plasma microreactor. The experiments were performed at 5 and 300 deg. C. Microreactor configuration allows an efficient evacuation of the heat generated by methane partial oxidation and dielectric barrier discharges, allowing at the same time a better temperature control. At 5 deg. C, liquid condensation of low vapour pressure compounds, such as formaldehyde and methanol, occurs. {sup 1}H-NMR analysis allowed us to demonstrate significant CH{sub 3}OOH formation during plasma-assisted partial oxidation of methane. Conversion and product selectivity were discussed for both temperatures. In the second part of this work, a numerical simulation was performed and a gas-phase chemical mechanism was proposed and discussed. From the comparison between the experimental results and the simulation it was found that CH{sub 3}OO{center_dot} formation has a determinant role in oxygenated compound production, since its fast formation disfavoured radical recombination. At 5 deg. C the oxidation leads mainly towards oxygenated compound formation, and plasma dissociation was the major phenomenon responsible for CH{sub 4} conversion. At 300 deg. C, higher CH{sub 4} conversion resulted from oxidative reactions induced by {center_dot}OH radicals with a chemistry predominantly oxidative, producing CO, H{sub 2}, CO{sub 2} and H{sub 2}O.

Protocol for Measuring the Thermal Properties of a Supercooled Synthetic Sand-water-gas-methane Hydrate Sample.

Science.gov (United States)

Muraoka, Michihiro; Susuki, Naoko; Yamaguchi, Hiroko; Tsuji, Tomoya; Yamamoto, Yoshitaka

2016-03-21

Methane hydrates (MHs) are present in large amounts in the ocean floor and permafrost regions. Methane and hydrogen hydrates are being studied as future energy resources and energy storage media. To develop a method for gas production from natural MH-bearing sediments and hydrate-based technologies, it is imperative to understand the thermal properties of gas hydrates. The thermal properties' measurements of samples comprising sand, water, methane, and MH are difficult because the melting heat of MH may affect the measurements. To solve this problem, we performed thermal properties' measurements at supercooled conditions during MH formation. The measurement protocol, calculation method of the saturation change, and tips for thermal constants' analysis of the sample using transient plane source techniques are described here. The effect of the formation heat of MH on measurement is very small because the gas hydrate formation rate is very slow. This measurement method can be applied to the thermal properties of the gas hydrate-water-guest gas system, which contains hydrogen, CO2, and ozone hydrates, because the characteristic low formation rate of gas hydrate is not unique to MH. The key point of this method is the low rate of phase transition of the target material. Hence, this method may be applied to other materials having low phase-transition rates.

Project identification for methane reduction options

Energy Technology Data Exchange (ETDEWEB)

Kerr, T.

1996-12-31

This paper discusses efforts directed at reduction in emission of methane to the atmosphere. Methane is a potent greenhouse gas, which on a 20 year timeframe may present a similar problem to carbon dioxide. In addition, methane causes additional problems in the form of smog and its longer atmospheric lifetime. The author discusses strategies for reducing methane emission from several major sources. This includes landfill methane recovery, coalbed methane recovery, livestock methane reduction - in the form of ruminant methane reduction and manure methane recovery. The author presents examples of projects which have implemented these ideas, the economics of the projects, and additional gains which come from the projects.

Non-oxidative conversion of methane into higher hydrocarbons over ...

Indian Academy of Sciences (India)

SOURABH MISHRA

2017-09-27

Sep 27, 2017 ... (Syn-gas, CO+H2) formation via steam reforming, dry reforming or partial oxidation of methane ... Micromeritics ASAP 2010 apparatus at liquid nitrogen tem- perature. Nitrogen (N2) was the adsorbate ... some runs were carried out in triplicate and mass balance for all the runs was measured. Runs with a ...

Biogeochemical processes controlling authigenic carbonate formation within the sediment column from the Okinawa Trough

Science.gov (United States)

Li, Jiwei; Peng, Xiaotong; Bai, Shijie; Chen, Zhiyan; Van Nostrand, Joy D.

2018-02-01

Authigenic carbonates are one type of conspicuous manifestation in seep environments that can provide long-term archives of past seepage activity and methane cycling in the oceans. Comprehensive investigations of the microbial community functional structure and their roles in the process of carbonate formation are, however, lacking. In this study, the mineralogical, geochemical, and microbial functional composition were examined in seep carbonate deposits collected from the west slope of the northern section of the Okinawa Trough (OT). The aim of this work was to explore the correspondence between the mineralogical phases and microbial metabolism during carbonate deposit formation. The mineralogical analyses indicated that authigenic carbonate minerals (aragonite, magnesium-rich calcite, dolomite, ankerite and siderite) and iron-bearing minerals (limonite, chlorite, and biotite) were present in these carbonate samples. The carbon and oxygen isotopic values of the carbonate samples varied between -51.1‰ to -4.7‰ and -4.8‰ to 3.7‰, respectively. A negative linear correlation between carbon and oxygen isotopic compositions was found, indicating a mixture of methane-derived diagenetic (low δ13C/high 18O) carbonates and detrital origin (high δ13C/low 18O) carbonates at the OT. GeoChip analyses suggested that various metabolic activities of microorganisms, including methanogenesis, methane oxidation, sulfite oxidation, sulfate reduction, and metal biotransformations, all occurred during the formation process. On the basis of these findings, the following model for the methane cycle and seep carbonate deposit formation in the sediment column at the OT is proposed: (1) in the upper oxidizing zone, aerobic methane oxidation was the main way of methane consumption; (2) in the sulfate methane transition zone, sulfate-dependent AOM (anaerobic oxidation of methane) consumes methane, and authigenic minerals such as aragonite, magnesium-calcite, and sulfide minerals

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

Science.gov (United States)

Shuai, Yanhua; Douglas, Peter M.J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-01-01

Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation

Changes in biochemical constituent of some organic waste materials under anaerobic methane fermentation

Energy Technology Data Exchange (ETDEWEB)

Prasad, C R; Gulati, K C; Idnani, M A

1970-10-01

Changes in the percentage composition of holocellulose, cellulose, hemicellulose, lignin, pentosans and methoxyl contents of organic materials after fermentation of various systems like cow dung alone, cowdung-gum arabic, cowdung-wheat straw, cowdung-groundnut shells and cowdung-sugarcane bagasse by methane organisms indicated that the systems which had holocellulose (lignin in a ratio of 3 : 1 or less before fermentation) showed a greater decrease of hemicellulose fraction than of cellulose fraction. The percentage of lignin (18.41-22.03) and pentosans (0.292-5.129) increased after fermentation, except in cowdung-gum arabic which showed decrease of pentosans content. Methoxyl contents also decreased after fermentation, indicating a positive role of methyl group of methoxyls in the formation of methane by methane formers.

Global Methane Initiative

Science.gov (United States)

The Global Methane Initiative promotes cost-effective, near-term methane recovery through partnerships between developed and developing countries, with participation from the private sector, development banks, and nongovernmental organizations.

Risk factors of methane hydrate resource development in the concentrated zones distributed in the eastern Nankai Trough

Science.gov (United States)

Yamamoto, K.; Nagakubo, S.

2009-04-01

, low pressure. Deformation and subsidence of the sea floor may be unavoidable but does not cause serious concern on the safety. Some have argued that hydrate dissociations in wide area may cause landslide due to weakened formation by dissociation. To manage the concern, the test site should be chosen carefully and formation property alternation should be well known. One common misunderstanding widespread in public is that methane hydrate is "unstable material." Indeed, the hydrate is stable in the original temperature and pressure conditions, and the endothermic process of hydrate dissociation leads negative feedback to the formation conditions from the altered states by artificial depressurization. Also the hydrate dissociation in the sandy sediments is governed by relatively slow heat and fluid transport phenomena in porous media, so the process is gradual. Therefore, a catastrophic chain reaction which many people imagine is surely unlikely. As mentioned above, at present, risks of methane hydrate resource development in the concentrated zones distributed in the eastern Nankai trough are not significant, and comparable or less serious than conventional oil and gas production, we concluded. Of course, this evaluation should be verified with offshore production tests in the future, and new knowledge should be reflected to the safe and environmentally friendly production system designs. The nature of unconsolidated formation after the hydrate dissociation is key issue of such investigation. MH21 consortium has studied the issue in many aspects, and will continue the investigation.

Liquid hydrogen production via hydrogen sulfide methane reformation

Energy Technology Data Exchange (ETDEWEB)

Huang, Cunping; T-Raissi, Ali [University of Central Florida, Florida Solar Energy Center, 1769 Clearlake Road, Cocoa, FL 32922 (United States)

2008-01-03

Hydrogen sulfide (H{sub 2}S) methane (CH{sub 4}) reformation (H{sub 2}SMR) (2H{sub 2}S + CH{sub 4} = CS{sub 2} + 4H{sub 2}) is a potentially viable process for the removal of H{sub 2}S from sour natural gas resources or other methane containing gases. Unlike steam methane reformation that generates carbon dioxide as a by-product, H{sub 2}SMR produces carbon disulfide (CS{sub 2}), a liquid under ambient temperature and pressure - a commodity chemical that is also a feedstock for the synthesis of sulfuric acid. Pinch point analyses for H{sub 2}SMR were conducted to determine the reaction conditions necessary for no carbon lay down to occur. Calculations showed that to prevent solid carbon formation, low inlet CH{sub 4} to H{sub 2}S ratios are needed. In this paper, we analyze H{sub 2}SMR with either a cryogenic process or a membrane separation operation for production of either liquid or gaseous hydrogen. Of the three H{sub 2}SMR hydrogen production flowsheets analyzed, direct liquid hydrogen generation has higher first and second law efficiencies of exceeding 80% and 50%, respectively. (author)

Formate Formation and Formate Conversion in Biological Fuels Production

Directory of Open Access Journals (Sweden)

Bryan R. Crable

2011-01-01

Full Text Available Biomethanation is a mature technology for fuel production. Fourth generation biofuels research will focus on sequestering CO2 and providing carbon-neutral or carbon-negative strategies to cope with dwindling fossil fuel supplies and environmental impact. Formate is an important intermediate in the methanogenic breakdown of complex organic material and serves as an important precursor for biological fuels production in the form of methane, hydrogen, and potentially methanol. Formate is produced by either CoA-dependent cleavage of pyruvate or enzymatic reduction of CO2 in an NADH- or ferredoxin-dependent manner. Formate is consumed through oxidation to CO2 and H2 or can be further reduced via the Wood-Ljungdahl pathway for carbon fixation or industrially for the production of methanol. Here, we review the enzymes involved in the interconversion of formate and discuss potential applications for biofuels production.

Manufacture of Methane Hydrate using Carbon Nano Tubes

International Nuclear Information System (INIS)

Park, Sung Seek

2010-02-01

Methane hydrate is formed by physical binding between water molecule and gas such as methane, ethane, propane, or carbon dioxide, etc., which is captured in the cavities of water molecule under the specific temperature and pressure. More than 99% of naturally produced methane hydrate consists of methane, and is widely dispersed in the continental slope and continental Shelf of the Pacific and the Atlantic, the Antarctica etc. The reserve of fossil fuel is 500 billion carbon ton and the reserve of methane is 360 million carbon ton. The reserve of gas hydrate is more than 1 trillion carbon ton, which is twice the fossil fuel. Therefore, natural gas hydrate as a kind of gas hydrate is expected to replace fossil fuel as new energy source of 21st century. Also 1 m 3 hydrate of pure methane can be decomposed to the maximum of 216 m 3 methane at standard condition. If these characteristics of hydrate are reversely utilized, natural gas is fixed into water in the form of hydrate solid. Therefore, the hydrate is considered to be a great way to transport and store natural gas in large quantity. Especially the transportation cost is known to be 18∼25% less than the liquefied transportation. However, when natural gas hydrate is artificially formed, its reaction time may be too long and the gas consumption in water becomes relatively low, because the reaction rate between water and gas is low. Therefore, for the practical purpose in the application, the present investigation focuses on the rapid production of hydrates and increases gas consumption by adding MWCNT and NaCl into pure water. The results show that the equilibrium pressure in seawater is more higher than that in pure water, and methane hydrate could be formed rapidly during pressurization if the subcooling is maintained at 9K or above in seawater and 8K or above in pure water, respectively. Also, amount of consumed gas volume in pure water is more higher that in seawater at the same experimental conditions

Uncertainty assessment of the breath methane concentration method to determine methane production of dairy cows

NARCIS (Netherlands)

Wu, Liansun; Groot Koerkamp, Peter W.G.; Ogink, Nico

2018-01-01

The breath methane concentration method uses the methane concentrations in the cow's breath during feed bin visits as a proxy for the methane production rate. The objective of this study was to assess the uncertainty of a breath methane concentration method in a feeder and its capability to measure

Biocatalytic conversion of methane to methanol as a key step for development of methane-based biorefineries.

Science.gov (United States)

Hwang, In Yeub; Lee, Seung Hwan; Choi, Yoo Seong; Park, Si Jae; Na, Jeong Geol; Chang, In Seop; Kim, Choongik; Kim, Hyun Cheol; Kim, Yong Hwan; Lee, Jin Won; Lee, Eun Yeol

2014-12-28

Methane is considered as a next-generation carbon feedstock owing to the vast reserves of natural and shale gas. Methane can be converted to methanol by various methods, which in turn can be used as a starting chemical for the production of value-added chemicals using existing chemical conversion processes. Methane monooxygenase is the key enzyme that catalyzes the addition of oxygen to methane. Methanotrophic bacteria can transform methane to methanol by inhibiting methanol dehydrogenase. In this paper, we review the recent progress made on the biocatalytic conversion of methane to methanol as a key step for methane-based refinery systems and discuss future prospects for this technology.

Calibration and validation of a numerical model against experimental data of methane hydrate formation and dissociation in a sandy porous medium

Science.gov (United States)

Yin, Z.; Moridis, G. J.; Chong, Z. R.; Linga, P.

2017-12-01

Methane hydrates (MH) are known to trap enormous amounts of CH4 in oceanic and permafrost-associated deposits, and are being considered as a potential future energy source. Several powerful numerical simulators were developed to describe the behavior of natural hydrate-bearing sediments (HBS). The complexity and strong nonlinearities in HBS do not allow analytical solutions for code validation. The only reliable method to develop confidence in these models is through comparisons to laboratory and/or field experiments. The objective of this study is to reproduce numerically the results from earlier experiments of MH formation and depressurization (and the corresponding fluid production) in 1.0L reactor involving unconsolidated sand, thus validating and calibrating the TOUGH+Hydrate v1.5 simulator. We faithfully describe the reactor geometry and the experimental process that involves both hydrate formation and dissociation. We demonstrate that the laboratory experiments can only be captured by a kinetic hydration model. There is an excellent agreement between observations and predictions (a) of the cumulative gas depletion (during formation) and production (during dissociation) and (b) of pressure over time. The temperature agreement is less satisfactory, and the deviations are attributed to the fixed locations of the limited number of sensors that cannot fully capture the hydrate heterogeneity. We also predict the spatial distributions over time of the various phase (gas, aqueous and hydrate) saturations. Thus, hydrates form preferentially along the outer boundary of the sand core, and the hydrate front moves inward leaving a significant portion of the sand at the center hydrate-free. During depressurization, dissociation advances again inward from the reactor boundary to the center of the reactor. As expected, methane gas accumulates initially at the locations of most intense dissociation, and then gradually migrates to the upper section of the reactor because of

Methane fluxes during the cold season: distribution and mass transfer in the snow cover of bogs

Science.gov (United States)

Smagin, A. V.; Shnyrev, N. A.

2015-08-01

Fluxes and profile distribution of methane in the snow cover and different landscape elements of an oligotrophic West-Siberian bog (Mukhrino Research Station, Khanty-Mansiisk autonomous district) have been studied during a cold season. Simple models have been proposed for the description of methane distribution in the inert snow layer, which combine the transport of the gas and a source of constant intensity on the soil surface. The formation rates of stationary methane profiles in the snow cover have been estimated (characteristic time of 24 h). Theoretical equations have been derived for the calculation of small emission fluxes from bogs to the atmosphere on the basis of the stationary profile distribution parameters, the snow porosity, and the effective methane diffusion coefficient in the snow layer. The calculated values of methane emission significantly (by 2-3 to several tens of times) have exceeded the values measured under field conditions by the closed chamber method (0.008-0.25 mg C/(m2 h)), which indicates the possibility of underestimating the contribution of the cold period to the annual emission cycle of bog methane.

Mechanics of coalbed methane production

Energy Technology Data Exchange (ETDEWEB)

Creel, J C; Rollins, J B [Crawley, Gillespie and Associates, Inc. (United Kingdom)

1994-12-31

Understanding the behaviour of coalbed methane reservoirs and the mechanics of production is crucial to successful management of coalbed methane resources and projects. This paper discusses the effects of coal properties and coalbed methane reservoir characteristics on gas production rates and recoveries with a review of completion techniques for coalbed methane wells. 4 refs., 17 figs.

Anaerobic methane oxidation rates at the sulfate-methane transition in marine sediments from Kattegat and Skagerrak (Denmark)

International Nuclear Information System (INIS)

Iversen, N.; Jorgensen, B.B.

1985-01-01

Concomitant radiotracer measurements were made of in situ rates of sulfate reduction and anaerobic methane oxidation in 2-3-m-long sediment cores. Methane accumulated to high concentrations (> 1 mM CH 4 ) only below the sulfate zone, at 1 m or deeper in the sediment. Sulfate reduction showed a broad maximum below the sediment surface and a smaller, narrow maximum at the sulfate-methane transition. Methane oxidation was low (0.002-0.1 nmol CH 4 cm -3 d -1 ) throughout the sulfate zone and showed a sharp maximum at the sulfate-methane transition, coinciding with the sulfate reduction maximum. Total anaerobic methane oxidation at two stations was 0.83 and 1.16 mmol CH 4 m -2 d -1 , of which 96% was confined to the sulfate-methane transition. All the methane that was calculated to diffuse up into the sulfate-methane transition was oxidized in this zone. The methane oxidation was equivalent to 10% of the electron donor requirement for the total measured sulfate reduction. A third station showed high sulfate concentrations at all depths sampled and the total methane oxidation was only 0.013 mmol m -2 d -1 . From direct measurements of rates, concentration gradients, and diffusion coefficients, simple calculations were made of sulfate and methane fluxes and of methane production rates

Methane-fueled vehicles: A promising market for coalbed methane

International Nuclear Information System (INIS)

Deul, M.

1993-01-01

The most acceptable alternative fuel for motor vehicles is compressed natural gas (CNG). An important potential source of such gas is coalbed methane, much of which is now being wasted. Although there are no technological impediments to the use of CNG it has not been adequately promoted for a variety of reasons: structural, institutional and for coalbed gas, legal. The benefits of using CNG fuel are manifold: clean burning, low cost, abundant, and usable in any internal combustion engine. Even though more than 30,000 CNG vehicles are now in use in the U.S.A., they are not readily available, fueling stations are not easily accessible, and there is general apathy on the part of the public because of negligence by such agencies as the Department of Energy, the Department of Transportation and the Environmental Protection Agency. The economic benefits of using methane are significant: 100,000 cubic feet of methane is equivalent to 800 gallons of gasoline. Considering the many millions of cubic feet methane wasted from coal mines conservation and use of this resource is a worthy national goal

Is methane a new therapeutic gas?

Directory of Open Access Journals (Sweden)

Liu Wenwu

2012-09-01

Full Text Available Abstract Background Methane is an attractive fuel. Biologically, methanogens in the colon can use carbon dioxide and hydrogen to produce methane as a by-product. It was previously considered that methane is not utilized by humans. However, in a recent study, results demonstrated that methane could exert anti-inflammatory effects in a dog small intestinal ischemia-reperfusion model. Point of view Actually, the bioactivity of methane has been investigated in gastrointestinal diseases, but the exact mechanism underlying the anti-inflammatory effects is required to be further elucidated. Methane can cross the membrane and is easy to collect due to its abundance in natural gas. Although methane is flammable, saline rich in methane can be prepared for clinical use. These seem to be good news in application of methane as a therapeutic gas. Conclusion Several problems should be resolved before its wide application in clinical practice.

On the atomistic mechanisms of alkane (methane-pentane) separation by distillation: a molecular dynamics study.

Science.gov (United States)

Zahn, Dirk

2007-11-01

Insights into the liquid-vapor transformation of methane-pentane mixtures were obtained from transition path sampling molecular dynamics simulations. This case study of the boiling of non-azeotropic mixtures demonstrates an unprejudiced identification of the atomistic mechanisms of phase separation in the course of vaporization which form the basis of distillation processes. From our simulations we observe spontaneous segregation events in the liquid mixture to trigger vapor nucleation. The formation of vapor domains stabilizes and further promotes the separation process by preferential evaporation of methane molecules. While this discrimination holds for all mixtures of different composition studied, a full account of the boiling process requires a more complex picture. At low methane concentration the nucleation of the vapor domains includes both methane and pentane molecules. The pentane molecules, however, tend to form small aggregates and undergo rapid re-condensation within picoseconds to nanoseconds scales. Accordingly, two aspects of selectivity accounting for methane-pentane separation in the course of liquid-vapor transformations were made accessible to molecular dynamics simulations: spontaneous segregation in the liquid phase leading to selective vapor nucleation and growth favoring methane vaporization and selective re-condensation of pentane molecules.

NMR and computational study of Ba8CuxGe46-x clathrate semiconductors

International Nuclear Information System (INIS)

Chen, Jing-Han; Sirusi Arvij, Ali; Zheng, Xiang; Rodriguez, Sergio Y.; Ross, Joseph H.

2014-01-01

Highlights: • Quadrupole NMR with first-principles calculations probes local site preferences. • Cu/Ge ratio is clarified vs. the ideal Zintl composition. • Modified Becke–Johnson exchange potential agrees well with NMR Knight shifts. - Abstract: Ba 8 Cu x Ge 46-x is a type-I clathrate material that forms as a semiconductor in a narrow composition range corresponding to the electron-balanced Zintl composition, with x = 5.3. We use NMR spectroscopy combined with ab initio electronic structure calculations to probe the electronic and structural behavior of these materials. Computational results based on a superstructure model for the atomic configuration of the alloy provide good agreement with the electric quadrupole-broadened NMR lineshapes. Modeling using the modified Becke–Johnson (TB-mBJ) exchange potential is also shown to agree well with experimental NMR Knight shifts. The results indicate that the Cu–Ge balance is the main factor determining the carrier density, within a narrow stability range near the ideal Zintl composition

Determination of soil-entrapped methane

Energy Technology Data Exchange (ETDEWEB)

Alberto, M.C.R.; Neue, H.U.; Lantin, R.S.; Aduna, J.B. [Soil and Water Sciences Division, Manila (Philippines)

1996-12-31

A sampling method was developed and modified to sample soil from paddy fields for entrapped methane determination. A 25-cm long plexiglass tube (4.4-cm i.d.) fitted with gas bag was used to sample soil and entrapped gases to a depth of 15-cm. The sampling tube was shaken vigorously to release entrapped gases. Headspace gas in sampling tube and gas bag was analyzed for methane. The procedure was verified by doing field sampling weekly at an irrigated ricefield in the IRRI Research Farm on a Maahas clay soil. The modified sampling method gave higher methane concentration because it eliminated gas losses during sampling. The method gave 98% {+-} 5 recovery of soil-entrapped methane. Results of field sampling showed that the early growth stage of the rice plant, entrapped methane increased irrespective of treatment. This suggests that entrapped methane increased irrespective of treatment. This suggests that entrapped methane was primarily derived from fermentation of soil organic matter at the early growth stage. At the latter stage, the rice plant seems to be the major carbon source for methane production. 7 refs., 4 figs., 4 tabs.

Metagenomic analysis of the rumen microbial community following inhibition of methane formation by a halogenated methane analogue

Directory of Open Access Journals (Sweden)

Stuart E Denman

2015-10-01

Full Text Available Japanese goats fed a diet of 50% Timothy grass and 50% concentrate with increasing levels of the anti-methanogenic compound, bromochloromethane (BCM were investigated with respect to the microbial shifts in the rumen. Microbial ecology methods identified many species that exhibited positive and negative responses to the increasing levels of BCM. The methane-inhibited rumen appeared to adapt to the higher H2 levels by shifting fermentation to propionate which was mediated by an increase in the population of hydrogen-consuming Prevotella and Selenomonas spp. Metagenomic analysis of propionate production pathways was dominated by genomic content from these species. Reductive acetogenic marker gene libraries and metagenomics analysis indicate that reductive acetogenic species do not play a major role in the BCM treated rumen.

Method for solid state crystal growth

Science.gov (United States)

Nolas, George S.; Beekman, Matthew K.

2013-04-09

A novel method for high quality crystal growth of intermetallic clathrates is presented. The synthesis of high quality pure phase crystals has been complicated by the simultaneous formation of both clathrate type-I and clathrate type-II structures. It was found that selective, phase pure, single-crystal growth of type-I and type-II clathrates can be achieved by maintaining sufficient partial pressure of a chemical constituent during slow, controlled deprivation of the chemical constituent from the primary reactant. The chemical constituent is slowly removed from the primary reactant by the reaction of the chemical constituent vapor with a secondary reactant, spatially separated from the primary reactant, in a closed volume under uniaxial pressure and heat to form the single phase pure crystals.

Enrichment of specific electro-active microorganisms and enhancement of methane production by adding granular activated carbon in anaerobic reactors.

Science.gov (United States)

Lee, Jung-Yeol; Lee, Sang-Hoon; Park, Hee-Deung

2016-04-01

Direct interspecies electron transfer (DIET) via conductive materials can provide significant benefits to anaerobic methane formation in terms of production amount and rate. Although granular activated carbon (GAC) demonstrated its applicability in facilitating DIET in methanogenesis, DIET in continuous flow anaerobic reactors has not been verified. Here, evidences of DIET via GAC were explored. The reactor supplemented with GAC showed 1.8-fold higher methane production rate than that without GAC (35.7 versus 20.1±7.1mL-CH4/d). Around 34% of methane formation was attributed to the biomass attached to GAC. Pyrosequencing of 16S rRNA gene demonstrated the enrichment of exoelectrogens (e.g. Geobacter) and hydrogenotrophic methanogens (e.g. Methanospirillum and Methanolinea) from the biomass attached to GAC. Furthermore, anodic and cathodic currents generation was observed in an electrochemical cell containing GAC biomass. Taken together, GAC supplementation created an environment for enriching the microorganisms involved in DIET, which increased the methane production rate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetic studies of methane-ethane mixed gas hydrates by neutron diffraction and Raman spectroscopy.

Science.gov (United States)

Murshed, M Mangir; Kuhs, Werner F

2009-04-16

In situ formations of CH(4)-C(2)H(6) mixed gas hydrates were made using high flux neutron diffraction at 270 K and 5 MPa. For this purpose, a feed gas composition of CH(4) and C(2)H(6) (95 mol% CH(4)) was employed. The rates of transformation of spherical grains of deuterated ice Ih into hydrates were measured by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. Phase fractions of the crystalline constituents were obtained from Rietveld refinements. A concomitant formation of structure type I (sI) and structure type II (sII) hydrates were observed soon after the gas pressure was applied. The initial fast formation of sII hydrate reached its maximum volume and started declining very slowly. The formation of sI hydrate followed a sigmoid growth kinetics that slowed down due to diffusion limitation. This observation has been interpreted in terms of a kinetically favored nucleation of the sII hydrate along with a slow transformation into sI. Both powder diffraction and Raman spectroscopic results suggest that a C(2)H(6)-rich sII hydrate was formed at the early part of the clathration, which slowly decreased to approximately 3% after a reaction of 158 days as confirmed by synchrotron XRD. The final persistence of a small portion of sII hydrate points to a miscibility gap between CH(4)-rich sI and C(2)H(6)-rich sII hydrates.

Methane accumulation and forming high saturations of methane hydrate in sandy sediments

Energy Technology Data Exchange (ETDEWEB)

Uchida, T.; Waseda, A. [JAPEX Research Center, Chiba (Japan); Fujii, T. [Japan Oil, Gas and Metals National Corp., Chiba (Japan). Upstream Technology Unit

2008-07-01

Methane supplies for marine gas hydrates are commonly attributed to the microbial conversion of organic materials. This study hypothesized that methane supplies were related to pore water flow behaviours and microscopic migration in intergranular pore systems. Sedimentology and geochemistry analyses were performed on sandy core samples taken from the Nankai trough and the Mallik gas hydrate test site in the Mackenzie Delta. The aim of the study was to determine the influence of geologic and sedimentolic controls on the formation and preservation of natural gas hydrates. Grain size distribution curves indicated that gas hydrate saturations of up to 80 per cent in pore volume occurred throughout the hydrate-dominant sand layers in the Nankai trough and Mallik areas. Water permeability measurements showed that the highly gas hydrate-saturated sands have a permeability of a few millidarcies. Pore-space gas hydrates occurred primarily in fine and medium-grained sands. Core temperature depression, core observations, and laboratory analyses of the hydrates confirmed the pore-spaces as intergranular pore fillings. Results of the study suggested that concentrations of gas hydrates may require a pore space large enough to occur within a host sediments, and that the distribution of porous and coarser-grained sandy sediments is an important factor in controlling the occurrence of gas hydrates. 11 refs., 4 figs.

OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

Energy Technology Data Exchange (ETDEWEB)

Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

1998-04-01

The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

The formation of nitrogeneous compounds in the γ-radiolyses of liquid nitrogen solutions of hydrogen, methane, and ethane

International Nuclear Information System (INIS)

Horigome, Keiichi; Hirokami, Shun-ichi; Sato, Shin

1978-01-01

The γ-radiolyses of liquid nitrogen solutions of hydrogen, methane, and ethane have been reinvestigated. A complete survey of nitrogen-containing products has been attempted. The nitrogeneous compounds observed were ammonia (0.7) and hydrogen azide (0.02) in the case of hydrogen, ammonia (0.3), hydrogen cyanide (0.1), methyl azide (0.01), and a polymer in the case of methane, and ammonia (0.3), hydrogen cyanide (0.05), acetonitrile (0.04), ethyl azide (0.01), and a polymer in the case of ethane. The values in parentheses are the G-values obtained at optimum conditions. The hydrolysis of the polymer obtained with methane gave formaldehyde in amounts which correspond to the fact that the G-value of the nitrogen atoms which were converted into the polymer is about 1.0. In order to explain these results, possible reaction mechanisms are discussed. (auth.)

Determination of Methane and Carbon Dioxide Formation Rate Constants for Semi-Continuously Fed Anaerobic Digesters

Directory of Open Access Journals (Sweden)

Jan Moestedt

2015-01-01

Full Text Available To optimize commercial-scale biogas production, it is important to evaluate the performance of each microbial step in the anaerobic process. Hydrolysis and methanogenesis are usually the rate-limiting steps during digestion of organic waste and by-products. By measuring biogas production and methane concentrations on-line in a semi-continuously fed reactor, gas kinetics can be evaluated. In this study, the rate constants of the fermentative hydrolysis step (kc and the methanogenesis step (km were determined and evaluated in a continuously stirred tank laboratory-scale reactor treating food and slaughterhouse waste and glycerin. A process additive containing Fe2+, Co2+ and Ni2+ was supplied until day 89, after which Ni2+ was omitted. The omission resulted in a rapid decline in the methanogenesis rate constant (km to 70% of the level observed when Ni2+ was present, while kc remained unaffected. This suggests that Ni2+ mainly affects the methanogenic rather than the hydrolytic microorganisms in the system. However, no effect was initially observed when using conventional process monitoring parameters such as biogas yield and volatile fatty acid concentration. Hence, formation rate constants can reveal additional information on process performance and km can be used as a complement to conventional process monitoring tools for semi-continuously fed anaerobic digesters.

Biocatalytic methanation of hydrogen and carbon dioxide in an anaerobic three-phase system.

Science.gov (United States)

Burkhardt, M; Koschack, T; Busch, G

2015-02-01

A new type of anaerobic trickle-bed reactor was used for biocatalytic methanation of hydrogen and carbon dioxide under mesophilic temperatures and ambient pressure in a continuous process. The conversion of gaseous substrates through immobilized hydrogenotrophic methanogenic archaea in a biofilm is a unique feature of this type of reactor. Due to the formation of a three-phase system on the carrier surface and operation as a plug flow reactor without gas recirculation, a complete reaction could be observed. With a methane concentration higher than c(CH4) = 98%, the product gas exhibits a very high quality. A specific methane production of P(CH4) = 1.49 Nm(3)/(m(3)(SV) d) was achieved at a hydraulic loading rate of LR(H2) = 6.0 Nm(3)/(m(3)(SV) d). The relation between trickle flow through the reactor and productivity could be shown. An application for methane enrichment in combination with biogas facilities as a source of carbon dioxide has also been positively proven. Copyright © 2014 Elsevier Ltd. All rights reserved.

Photocatalytic conversion of methane to methanol

Energy Technology Data Exchange (ETDEWEB)

Taylor, C.E.; Noceti, R.P.; D`Este, J.R. [Pittsburgh Energy Technology Center, PA (United States)

1995-12-31

A long-term goal of our research group is the exploration of novel pathways for the direct oxidation of methane to liquid fuels, chemicals, and intermediates. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol is attractive. The products of reaction, methanol and hydrogen, are both commercially desirable, methanol being used as is or converted to a variety of other chemicals, and the hydrogen could be utilized in petroleum and/or chemical manufacturing. Methane is produced as a by-product of coal gasification. Depending upon reactor design and operating conditions, up to 18% of total gasifier product may be methane. In addition, there are vast proven reserves of geologic methane in the world. Unfortunately, a large fraction of these reserves are in regions where there is little local demand for methane and it is not economically feasible to transport it to a market. There is a global research effort under way in academia, industry, and government to find methods to convert methane to useful, more readily transportable and storable materials. Methanol, the initial product of methane oxidation, is a desirable product of conversion because it retains much of the original energy of the methane while satisfying transportation and storage requirements. Investigation of direct conversion of methane to transportation fuels has been an ongoing effort at PETC for over 10 years. One of the current areas of research is the conversion of methane to methanol, under mild conditions, using light, water, and a semiconductor photocatalyst. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol, is attractive. Research in the laboratory is directed toward applying the techniques developed for the photocatalytic splitting of the water and the photochemical conversion of methane.

The effect of gamma irradiation and ethyl methan sulfonate on somatic embryo formation of soybean (Glycine max L.)

International Nuclear Information System (INIS)

Ragapadmi Purnamaningsih; Ika Mariska; Lestari, E.G.; Sri Hutami; Rossa Yunita

2014-01-01

Soybean is a source of protein and vegetable oil. Global climate change affect the productivity of soybean, so that new cultivars that have superior characteristic can be produced. In vitro techniques through somaclonal variation and mutation is one alternative for obtaining new varieties when genetic material as the material selection is not available. Mutation induction can be performed on embryogenic cell populations using gamma irradiation or chemical compounds, such as Ethyl Methane Sulfonate (EMS). Both of these methods have been widely used to increase the genetic diversity of plants and have produced new clones with superior characteristic. The main component that must be controlled in the implementation of these technologies is somatic cells regeneration after mutation treatment in order to get in vitro shoots. Regeneration methods which are successfully applied to certain varieties, often is not successfully for other varieties of the same species. Some factors that influence it, are such as explants source, genotype, medium composition, genotype, medium composition, etc. Somaclonal variation and mutation treatment can cause cell damage that is sometimes necessary need modifications of the regeneration method that has been produced before. The aim of the experiment was to get cell population and planlet mutation with gamma irradiation and Ethyl Methan Sulfonate (EMS). Young embryozygotic was used as explant came from young pod that was harvested at 12-20 days after fertilization of Willis, Burangrang and Baluran varieties and accession No B 3592. Embryogenic callus induction was done by using MS media with vitamin B5 added with 20 mg/l of 2,4-D and 3% sucrose. The callus were irradiated by gamma rays 400 rad or dilute in EMS solution with 0.1%, 0.3% and 0.5% concentration for 1, 2, and 3 hours. After mutation treatment, the callus were sub culture for seed somatic induction. The results showed that callus formation was influenced by plant genotype. All

A novel method for estimating methane emissions from underground coal mines: The Yanma coal mine, China

Science.gov (United States)

Ji, Zhong-Min; Chen, Zhi-Jian; Pan, Jie-Nan; Niu, Qing-He

2017-12-01

As the world's largest coal producer and consumer, China accounts for a relatively high proportion of methane emissions from coal mines. Several estimation methods had been established for the coal mine methane (CMM) emission. However, with large regional differences, various reservoir formation types of coalbed methane (CBM) and due to the complicated geological conditions in China, these methods may be deficient or unsuitable for all the mining areas (e.g. Jiaozuo mining area). By combing the CMM emission characteristics and considering the actual situation of methane emissions from underground coal mine, we found that the methane pre-drainage is a crucial reason creating inaccurate evaluating results for most estimation methods. What makes it so essential is the extensive pre-drainage quantity and its irrelevance with annual coal production. Accordingly, the methane releases were divided into two categories: methane pre-drainage and methane release during mining. On this basis, a pioneering method for estimating CMM emissions was proposed. Taking the Yanma coal mine in the Jiaozuo mining area as a study case, the evaluation method of the pre-drainage methane quantity was established after the correlation analysis between the pre-drainage rate and time. Thereafter, the mining activity influence factor (MAIF) was first introduced to reflect the methane release from the coal and rock seams around where affected by mining activity, and the buried depth was adopted as the predictor of the estimation for future methane emissions. It was verified in the six coal mines of Jiaozuo coalfield (2011) that the new estimation method has the minimum errors of 12.11%, 9.23%, 5.77%, -5.20%, -8.75% and 4.92% respectively comparing with other methods. This paper gives a further insight and proposes a more accurate evaluation method for the CMM emissions, especially for the coal seams with low permeability and strong tectonic deformation in methane outburst coal mines.

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

Science.gov (United States)

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

2003-12-01

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

Evaluation of two-phase thermophilic anaerobic methane fermentation for the treatment of garbage

International Nuclear Information System (INIS)

Park, Y.J.; Hong, F.; Japan Science and Technology Agency, Tokyo; Tsuno, H.; Hidaka, T.; Cheon, J.H.; Japan Science and Technology Agency, Tokyo

2004-01-01

Municipal solid wastes (MSW) in Japan are generally incinerated. However, in recent years, garbage has been recognized as a renewable energy source. This has resulted in an increase in the use of biological processes, such as anaerobic digestion, to treat organic waste such as sewage sludge and garbage. The two phases of anaerobic digestion are the acidogenic phase and the methane producing phase. Both differ significantly in their nutritional and physiological requirements. This study evaluated the effectiveness of treating garbage with the two-phase thermophilic methane fermentation system (TPS). The performance of the acid fermentation phase in TPS was examined with particular reference to operational parameters such as pH, hydraulic retention time and organic loading rate on volatile fatty acid fermentation. It was shown that TPS was more efficient than the single-phase thermophilic methane fermentation system (SPS). Acidification control in the first stage resulted in better stability of methane fermentation in the second stage. VFA formation was optimized at a pH of 6. The recovery ratios of VFAs and methane were achieved in the range of 42 to 44 per cent and 88 to 91 per cent of garbage by high organic loading rate respectively. 12 refs., 6 tabs., 4 figs

Genomic selection for methane emission

DEFF Research Database (Denmark)

de Haas, Yvette; Pryce, Jennie E; Wall, Eileen

2016-01-01

Climate change is a growing area of international concern, and it is well established that the release of greenhouse gases (GHG) is a contributing factor. Of the various GHG produced by ruminants, enteric methane (CH4 ) is the most important contributor. One mitigation strategy is to reduce methane...... emission through genetic selection. Our first attempt used beef cattle and a GWAS to identify genes associated with several CH4 traits in Angus beef cattle. The Angus population consisted of 1020 animals with phenotypes on methane production (MeP), dry matter intake (DMI), and weight (WT). Additionally......, two new methane traits: residual genetic methane (RGM) and residual phenotypic methane (RPM) were calculated by adjusting CH4 for DMI and WT. Animals were genotyped using the 800k Illumina Bovine HD Array. Estimated heritabilities were 0.30, 0.19 and 0.15 for MeP, RGM and RPM respectively...

Situation of methanization installations in Haute-Normandie. Phase 2: Assessment of the regional sector. Phase 3: Development perspectives for the methanization sector in Haute-Normandie. To understand methanization. Haute-Normandie Commission of expertise on methanization

International Nuclear Information System (INIS)

Convert, Mathilde

2012-10-01

A first report proposes an analysis of the situation of methanization installations in the Haute-Normandie region while recalling the national context. It briefly reports an analysis and assessment of waste flows, processed effluents, by-products and biomass displaying an energetic potential. It describes methanization installations by addressing the different steps of the methanization process, by presenting the different digestion indicators, by briefly evoking the issue of the return-to-soil of digestates, and by presenting various operational data. Financial aspects are then addressed (investments and subsidies, financial balance of farm-based and collective installations), and an overview of methanization projects in the region and development perspectives is proposed. The second report more precisely analyses development perspectives for the methanization sector in the region through a brief assessment of the methanizable organic substrate resource, a discussion of different associated challenges (energy, agronomic, environmental and societal), a discussion of development levers and brakes, and an analysis of competitions (related to the use of industrial by-products, between processing installations, and related to agricultural soils). Another document proposes an overview of various aspects of methanization: a tool for territorial development, regulatory framework, evolution of installations in the region, assets of methanization, and role of the regional commission of expertise on methanization

Methanization in Burgundy-Franche-Comte - Figures and benchmarks. Agricultural methanization in Franche-Comte - Reflection guide for projects. Methanization development in Burgundy - Assessment 2014. Biogas sector in Burgundy. Methanization development in Burgundy - How to develop a project in Burgundy

International Nuclear Information System (INIS)

Aucordonnier, Bertrand; SIBUE, Lionel; Granger, Sylvie; Pervenchon, Frank; Forgue, Isabelle; Lirzin, Frank; Aucordonnier, Bertand; Abrahamse, Philippe; Dondaine, Regis; Rousseau, Christophe; Fevre, Jean-Michel; Carbonnier, Arnaud; Gontier, Thomas; Lemaire, Sylvie; Gallois, Vincent; Lachaize, M.

2015-03-01

A first document proposes graphs, figures and maps which illustrate various aspects of the situation and development of methanization in France and in the Burgundy-Franche-Comte region (number and location of installations, production evolution, biomass origins, biogas valorisation). A second document presents methanization (basic principles, process types, valorisation), describes agricultural methanization (substrate origin, use of final energy, use of digestates) and proposes elements of thought for methanization development regarding waste origin, project definition, various concerns (energy, environment, agriculture), digestate use and quantities, methane use, and installation sizing. A publication then proposes a synthetic overview of methanization development in Burgundy: number of supported projects, installations (evolution of their number, used materials, production), and support activities. The next publication proposes an assessment and an overview of the biogas sector in Burgundy: presentation and recommendations, assessment in terms of jobs, activities and expertise, professional education and training. The last document recalls some elements related to the methanization technique, outlines some important issues (materials, valorisation type for biogas and for digestate) to be addressed for an agricultural methanization project, and evokes benefits of methanization and some economic aspects. It also briefly describes how to start a project in the region

Modeling of methane bubbles released from large sea-floor area: Condition required for methane emission to the atmosphere

OpenAIRE

Yamamoto, A.; Yamanaka, Y.; Tajika, E.

2009-01-01

Massive methane release from sea-floor sediments due to decomposition of methane hydrate, and thermal decomposition of organic matter by volcanic outgassing, is a potential contributor to global warming. However, the degree of global warming has not been estimated due to uncertainty over the proportion of methane flux from the sea-floor to reach the atmosphere. Massive methane release from a large sea-floor area would result in methane-saturated seawater, thus some methane would reach the atm...

Source Attribution of Methane Emissions in Northeastern Colorado Using Ammonia to Methane Emission Ratios

Science.gov (United States)

Eilerman, S. J.; Neuman, J. A.; Peischl, J.; Aikin, K. C.; Ryerson, T. B.; Perring, A. E.; Robinson, E. S.; Holloway, M.; Trainer, M.

2015-12-01

Due to recent advances in extraction technology, oil and natural gas extraction and processing in the Denver-Julesburg basin has increased substantially in the past decade. Northeastern Colorado is also home to over 250 concentrated animal feeding operations (CAFOs), capable of hosting over 2 million head of ruminant livestock (cattle and sheep). Because of methane's high Global Warming Potential, quantification and attribution of methane emissions from oil and gas development and agricultural activity are important for guiding greenhouse gas emission policy. However, due to the co-location of these different sources, top-down measurements of methane are often unable to attribute emissions to a specific source or sector. In this work, we evaluate the ammonia:methane emission ratio directly downwind of CAFOs using a mobile laboratory. Several CAFOs were chosen for periodic study over a 12-month period to identify diurnal and seasonal variation in the emission ratio as well as differences due to livestock type. Using this knowledge of the agricultural ammonia:methane emission ratio, aircraft measurements of ammonia and methane over oil and gas basins in the western US during the Shale Oil and Natural Gas Nexus (SONGNEX) field campaign in March and April 2015 can be used for source attribution of methane emissions.

Methane emissions from natural wetlands

Energy Technology Data Exchange (ETDEWEB)

Meyer, J.L. [Georgia Univ., Athens, GA (United States); Burke, R.A. Jr. [Environmental Protection Agency, Athens, GA (United States). Environmental Research Lab.

1993-09-01

Analyses of air trapped in polar ice cores in conjunction with recent atmospheric measurements, indicate that the atmospheric methane concentration increased by about 250% during the past two or three hundred years (Rasmussen and Khalil, 1984). Because methane is a potent ``greenhouse`` gas, the increasing concentrations are expected to contribute to global warning (Dickinson and Cicerone, 1986). The timing of the methane increase suggests that it is related to the rapid growth of the human population and associated industrialization and agricultural development. The specific causes of the atmospheric methane concentration increase are not well known, but may relate to either increases in methane sources, decreases in the strengths of the sinks, or both.

Cryptic Methane Emissions from Upland Forest Ecosystems

Energy Technology Data Exchange (ETDEWEB)

Megonigal, Patrick [Smithsonian Institution, Washington, DC (United States); Pitz, Scott [Johns Hopkins Univ., Baltimore, MD (United States); Smithsonian Institution, Washington, DC (United States)

2016-04-19

This exploratory research on Cryptic Methane Emissions from Upland Forest Ecosystems was motivated by evidence that upland ecosystems emit 36% as much methane to the atmosphere as global wetlands, yet we knew almost nothing about this source. The long-term objective was to refine Earth system models by quantifying methane emissions from upland forests, and elucidate the biogeochemical processes that govern upland methane emissions. The immediate objectives of the grant were to: (i) test the emerging paradigm that upland trees unexpectedly transpire methane, (ii) test the basic biogeochemical assumptions of an existing global model of upland methane emissions, and (iii) develop the suite of biogeochemical approaches that will be needed to advance research on upland methane emissions. We instrumented a temperate forest system in order to explore the processes that govern upland methane emissions. We demonstrated that methane is emitted from the stems of dominant tree species in temperate upland forests. Tree emissions occurred throughout the growing season, while soils adjacent to the trees consumed methane simultaneously, challenging the concept that forests are uniform sinks of methane. High frequency measurements revealed diurnal cycling in the rate of methane emissions, pointing to soils as the methane source and transpiration as the most likely pathway for methane transport. We propose the forests are smaller methane sinks than previously estimated due to stem emissions. Stem emissions may be particularly important in upland tropical forests characterized by high rainfall and transpiration, resolving differences between models and measurements. The methods we used can be effectively implemented in order to determine if the phenomenon is widespread.

Methane rising from the Deep: Hydrates, Bubbles, Oil Spills, and Global Warming

Science.gov (United States)

Leifer, I.; Rehder, G. J.; Solomon, E. A.; Kastner, M.; Asper, V. L.; Joye, S. B.

2011-12-01

Elevated methane concentrations in near-surface waters and the atmosphere have been reported for seepage from depths of nearly 1 km at the Gulf of Mexico hydrate observatory (MC118), suggesting that for some methane sources, deepsea methane is not trapped and can contribute to atmospheric greenhouse gas budgets. Ebullition is key with important sensitivity to the formation of hydrate skins and oil coatings, high-pressure solubility, bubble size and bubble plume processes. Bubble ROV tracking studies showed survival to near thermocline depths. Studies with a numerical bubble propagation model demonstrated that consideration of structure I hydrate skins transported most methane only to mid-water column depths. Instead, consideration of structure II hydrates, which are stable to far shallower depths and appropriate for natural gas mixtures, allows bubbles to survive to far shallower depths. Moreover, model predictions of vertical methane and alkane profiles and bubble size evolution were in better agreement with observations after consideration of structure II hydrate properties as well as an improved implementation of plume properties, such as currents. These results demonstrate the importance of correctly incorporating bubble hydrate processes in efforts to predict the impact of deepsea seepage as well as to understand the fate of bubble-transported oil and methane from deepsea pipeline leaks and well blowouts. Application to the DWH spill demonstrated the importance of deepsea processes to the fate of spilled subsurface oil. Because several of these parameters vary temporally (bubble flux, currents, temperature), sensitivity studies indicate the importance of real-time monitoring data.

Urban sources and emissions of nitrous oxide and methane in southern California, USA

Science.gov (United States)

Townsend-Small, A.; Pataki, D.; Tyler, S. C.; Czimczik, C. I.; Xu, X.; Christensen, L. E.

2012-12-01

Anthropogenic activities have resulted in increasing levels of greenhouse gases, including carbon dioxide, methane, and nitrous oxide. While global and regional emissions sources of carbon dioxide are relatively well understood, methane and nitrous oxide are less constrained, particularly at regional scales. Here we present the results of an investigation of sources and emissions of methane and nitrous oxide in Los Angeles, California, USA, one of Earth's largest urban areas. The original goal of the project was to determine whether isotopes are useful tracers of agricultural versus urban nitrous oxide and methane sources. For methane, we found that stable isotopes (carbon-13 and deuterium) and radiocarbon are good tracers of biogenic versus fossil fuel sources. High altitude observations of methane concentration, measured continuously using tunable laser spectroscopy, and isotope ratios, measured on discrete flask samples using mass spectrometry, indicate that the predominant methane source in Los Angeles is from fossil fuels, likely from "fugitive" emissions from geologic formations, natural gas pipelines, oil refining, or power plants. We also measured nitrous oxide emissions and isotope ratios from urban (landscaping and wastewater treatment) and agricultural sources (corn and vegetable fields). There was no difference in nitrous oxide isotope ratios between the different types of sources, although stable isotopes did differ between nitrous oxide produced in oxic and anoxic wastewater treatment tanks. Our nitrous oxide flux data indicate that landscaped turfgrass emits nitrous oxide at rates equivalent to agricultural systems, indicating that ornamental soils should not be disregarded in regional nitrous oxide budgets. However, we also showed that wastewater treatment is a much greater source of nitrous oxide than soils regionally. This work shows that global nitrous oxide and methane budgets are not easily downscaled to regional, urban settings, which has

Challenges related to methanization - Bibliographical synthesis by France Nature Environnement. Opinion of FNE on methanization: Which challenges and which desirable development? Methascope: assessment support tool for a methanization project

International Nuclear Information System (INIS)

Desaunay, Thomas; Mathien, Adeline; Dorioz, Camille; Saint-Aubin, Thibaud; Banaszuk, Agnes; Badereau, Benedicte de; Capiez, Nathalie; Zoffoli, Maxime

2014-12-01

A first document proposes a bibliographical synthesis on the various challenges related to methanization. It addresses the following issues: biogas and public policies, methanization as a natural process of transformation of organic matter, different installations for different territories, matters which can be used in methanization, biogas as a renewable and local energy which can be transformed according to needs, properties and uses of digestate, choice between composting and methanization, energetic crops, methanization and nitrates, regulation, potential risks and pollutions, economic profitability of projects. The second document states the FNE's opinion on methanization, its challenges and the associated desirable development. The third document is a guide which aims at providing knowledge on methanization, at easing dialogue between actors of a territory, and at elaborating a position and an opinion with respect to a specific methanization project on a territory

A two-dimensional model of the passive coastal margin deep sedimentary carbon and methane cycles

Directory of Open Access Journals (Sweden)

D. E. Archer

2012-08-01

Full Text Available We present a new geologic-time and basin-spatial scale model of the continental margin methane cycle. The model, SpongeBOB, is used to simulate evolution of the carbon cycle in a passive sedimentary continental margin in response to changing oceanographic and geologic forcing over a time scale of 200 million years. The geochemistry of the sediment column is altered by the addition of vertical high-permeability channels intended to mimic the effects of heterogeneity in the real sediment column due to faults, and produces results consistent with measured pore-water tracers SO₄²⁻ and ¹²⁹I. Pore water dissolved inorganic carbon (DIC concentrations are consistent with chemical weathering (CaCO₃ formation from igneous rocks at depth within the sediment column. The carbon isotopic composition of the DIC is consistent with a methane production efficiency from particulate organic carbon (POC of 50%, which is somewhat lower than redox balance with the H / C of organic matter in the model. The hydrate inventory in the model is somewhat less sensitive to temperature than our previous results with a one-dimensional model, quite sensitive to reasonable changes in POC, and extremely sensitive to the ability of methane bubbles to rise within the sediment column, and how far gas-phase methane can get through the sediment column before it redissolves when it reaches undersaturated conditions. Hydrate formation is also sensitive to deep respiration of migrating petroleum. Other phenomena which we simulated had only a small impact on the hydrate inventory, including thermogenic methane production and production/decomposition of dissolved organic carbon.

Coalbed methane: new frontier

Energy Technology Data Exchange (ETDEWEB)

Eaton, S.

2003-02-01

There are large numbers of stacked coal seams permeated with methane or natural gas in the Western Canadian Sedimentary Basin, and approximately 20 coalbed methane pilot projects are operating in the area, and brief descriptions of some of them were provided. Coalbed methane reserves have a long life cycle. A definition of coalbed methane can be a permeability challenged reservoir. It is not uncommon for coalbed methane wells to flow water for periods varying from 2 to 6 months after completion before the production of natural gas. A made-in-Canada technological solution is being developed by CDX Canada Inc., along with its American parent company. The techniques used by CDX are a marriage between coal mining techniques and oil and gas techniques. A brief description of coalification was provided. Nexen is participating in the production of gas from an Upper Mannville coal at 1 000-metres depth in a nine-well pilot project. The Alberta Foothills are considered prime exploration area since older coal is carried close to the surface by thrusting. CDX Canada uses cavitation completion in vertical wells. Cavitation consists in setting the casing above the coal seam and drilling ahead under balanced. The design of wells for coalbed methane gas is based on rock and fluid mechanics. Hydraulic fracturing completions is also used, as are tiltmeters. An enhanced coalbed methane recovery pilot project is being conducted by the Alberta Research Council at Fenn-Big Valley, located in central Alberta. It injects carbon dioxide, which shows great potential for the reduction of greenhouse gas emissions. 1 figs.

Nitrogen-fixing methane-utilizing bacteria

NARCIS (Netherlands)

Bont, de J.A.M.

1976-01-01

Methane occurs abundantly in nature. In the presence of oxygen this gas may be metabolized by bacteria that are able to use it as carbon and energy source. Several types of bacteria involved in the oxidation of methane have been described in literature. Methane-utilizing bacteria have in

Global diffusive fluxes of methane in marine sediments

Science.gov (United States)

Egger, Matthias; Riedinger, Natascha; Mogollón, José M.; Jørgensen, Bo Barker

2018-06-01

Anaerobic oxidation of methane provides a globally important, yet poorly constrained barrier for the vast amounts of methane produced in the subseafloor. Here we provide a global map and budget of the methane flux and degradation in diffusion-controlled marine sediments in relation to the depth of the methane oxidation barrier. Our new budget suggests that 45-61 Tg of methane are oxidized with sulfate annually, with approximately 80% of this oxidation occurring in continental shelf sediments (methane in steady-state diffusive sediments, we calculate that 3-4% of the global organic carbon flux to the seafloor is converted to methane. We further report a global imbalance of diffusive methane and sulfate fluxes into the sulfate-methane transition with no clear trend with respect to the corresponding depth of the methane oxidation barrier. The observed global mean net flux ratio between sulfate and methane of 1.4:1 indicates that, on average, the methane flux to the sulfate-methane transition accounts for only 70% of the sulfate consumption in the sulfate-methane transition zone of marine sediments.

Methane monitoring from space

Science.gov (United States)

Stephan, C.; Alpers, M.; Millet, B.; Ehret, G.; Flamant, P.

2017-11-01

Methane is one of the strongest anthropogenic greenhouse gases. It contributes by its radiative forcing significantly to the global warming. For a better understanding of climate changes, it is necessary to apply precise space-based measurement techniques in order to obtain a global view on the complex processes that control the methane concentration in the atmosphere. The MERLIN mission is a joint French-German cooperation, on a micro satellite mission for space-based measurement of spatial and temporal gradients of atmospheric methane columns on a global scale. MERLIN will be the first Integrated Path Differential Absorption LIDAR for greenhouse gas monitoring from space. In contrast to passive methane missions, the LIDAR instrument allows measurements at alllatitudes, all-seasons and during night.

A biomimetic methane-oxidising catalyst

Energy Technology Data Exchange (ETDEWEB)

Dalton, H [Warwick Univ., Coventry (United Kingdom). Dept. of Biological Sciences

1997-12-31

The diminishing resources of petroleum oil has meant that there has been considerable efforts in recent years to find a suitable substitute for gasoline as a transportation fuel. Methanol has been identified as a suitable substitute since it is a readily combustible fuel which can be manufactured from a number of different sources. Methane is commonly used as a starting material for the production of synthesis gas (CO + H{sub 2}) and hence methanol. It is well known that the cleavage of the C-H bond of methane is extremely difficult (bond energy is around 104 kcal/mol) and that fairly drastic conditions are required to convert methane into methanol. Temperatures around 1200 deg C and pressures of up to 100 atmospheres over metal catalysts in a series of reactions are required to effect this process. Efforts have been made to reduce the temperature and the number of steps by using lanthanide ruthenium oxide catalyst but such reactions are still thermodynamically endothermic. An energetically more efficient reaction would be the direct conversion of methane to methanol using oxygen as the oxidant: CH{sub 4} + 1/2O{sub 2} -> CH{sub 3}OH {Delta}H deg = - 30.7 kcal/mol. Such a direct oxidation route is manifest in the bacterially-mediated oxidation of methane by methanotrophic bacteria. These organisms effect the direct oxidation of methane to methanol by the enzyme methane monooxygenase (MMO) as part of the reaction sequences to oxidize methane to carbon dioxide. (14 refs.)

A biomimetic methane-oxidising catalyst

Energy Technology Data Exchange (ETDEWEB)

Dalton, H. [Warwick Univ., Coventry (United Kingdom). Dept. of Biological Sciences

1996-12-31

The diminishing resources of petroleum oil has meant that there has been considerable efforts in recent years to find a suitable substitute for gasoline as a transportation fuel. Methanol has been identified as a suitable substitute since it is a readily combustible fuel which can be manufactured from a number of different sources. Methane is commonly used as a starting material for the production of synthesis gas (CO + H{sub 2}) and hence methanol. It is well known that the cleavage of the C-H bond of methane is extremely difficult (bond energy is around 104 kcal/mol) and that fairly drastic conditions are required to convert methane into methanol. Temperatures around 1200 deg C and pressures of up to 100 atmospheres over metal catalysts in a series of reactions are required to effect this process. Efforts have been made to reduce the temperature and the number of steps by using lanthanide ruthenium oxide catalyst but such reactions are still thermodynamically endothermic. An energetically more efficient reaction would be the direct conversion of methane to methanol using oxygen as the oxidant: CH{sub 4} + 1/2O{sub 2} -> CH{sub 3}OH {Delta}H deg = - 30.7 kcal/mol. Such a direct oxidation route is manifest in the bacterially-mediated oxidation of methane by methanotrophic bacteria. These organisms effect the direct oxidation of methane to methanol by the enzyme methane monooxygenase (MMO) as part of the reaction sequences to oxidize methane to carbon dioxide. (14 refs.)

Methane in German hard coal mining

International Nuclear Information System (INIS)

Martens, P.N.; Den Drijver, J.

1995-01-01

Worldwide, hard coal mining is being carried out at ever increasing depth, and has, therefore, to cope with correspondingly increasing methane emissions are caused by coal mining. Beside carbon dioxide, chloro-fluoro-carbons (CFCs) and nitrogen oxides, methane is one of the most significant 'greenhouse' gases. It is mainly through the release of such trace gases that the greenhouse effect is brought about. Reducing methane emissions is therefore an important problem to be solved by the coal mining industry. This paper begins by highlighting some of the fundamental principles of methane in hard coal mining. The methane problem in German hard coal mining and the industry's efforts to reduce methane emissions are presented. The future development in German hard coal mining is illustrated by an example which shows how large methane volumes can be managed, while still maintaining high outputs at increasing depth. (author). 7 tabs., 10 figs., 20 refs

Microbial anaerobic methane cycling in the subseafloor at the Von Damm hydrothermal vent field, Mid-Cayman Rise

Science.gov (United States)

Huber, J. A.; Reveillaud, J. C.; Stepanauskas, R.; McDermott, J. M.; Sylva, S. P.; Seewald, J.

2013-12-01

The Mid-Cayman Rise (MCR) is Earth's deepest and slowest spreading mid-ocean ridge located in the western Caribbean. With an axial rift valley floor at a depth of ~4200-6500 m, it represents one of the deepest sections of ridge crest worldwide. In 2009, the world's deepest hydrothermal vents (Piccard at 4960 m) and an ultramafic-influenced system only 20 km away on top of an oceanic core complex (Von Damm at 2350 m) were discovered along the MCR. Each site is hosted in a distinct geologic setting with different thermal and chemical regimes. The Von Damm site is a particularly interesting location to examine chemolithoautotrophic subseafloor microbial communities due to the abundant hydrogen, methane, and organic compounds in the venting fluids. Here, we used a combination of stable isotope tracing, next-generation sequencing, and single cell techniques to determine the identity, activity, and genomic repertoire of subseafloor anaerobic archaea involved in methane cycling in hydrothermal fluids venting at the Von Damm site. Molecular sequencing of phylogenetic marker genes revealed the presence of diverse archaea that both generate and consume methane across a geochemical and thermal spectrum of vents. Stable isotope tracing experiments were used to detect biological utilization of formate and dissolved inorganic carbon, and methane generation at 70 °C under anaerobic conditions. Results indicate that methanogenesis with formate as a substrate is occurring at 70 °C at two Von Damm sites, Ginger Castle and the Main Orifice. The results are consistent with thermodynamic predictions for carbon speciation at the temperatures encountered at the ultramafic-hosted Von Damm, where formate is predicted to be thermodynamically stable, and may thus serve as a an important source of carbon. Diverse thermophilic methanogenic archaea belonging to the genera Methanothermococcus were detected at all vent sites with both 16S rRNA tag sequencing and single cell sorting. Other

Quantification of methane emissions from danish landfills

DEFF Research Database (Denmark)

Scheutz, Charlotte; Mønster, Jacob; Kjeldsen, Peter

2013-01-01

Whole-landfill methane emission was quantified using a tracer technique that combines controlled tracer gas release from the landfill with time-resolved concentration measurements downwind of the landfill using a mobile high-resolution analytical instrument. Methane emissions from 13 Danish...... landfills varied between 2.6 and 60.8 kg CH4 h–1. The highest methane emission was measured at the largest (in terms of disposed waste amounts) of the 13 landfills, whereas the lowest methane emissions (2.6-6.1 kgCH4 h–1) were measured at the older and smaller landfills. At two of the sites, which had gas...... collection, emission measurements showed that the gas collection systems only collected between 30-50% of the methane produced (assuming that the produced methane equalled the sum of the emitted methane and the collected methane). Significant methane emissions were observed from disposed shredder waste...

Methane anomalies in seawaters of the Ragay Gulf, Philippines: methane cycling and contributions to atmospheric greenhouse gases

International Nuclear Information System (INIS)

Heggie, D.T.; Evans, D.; Bishop, J.H.

1999-01-01

The vertical distribution of methane has been measured in the water column of a semi-enclosed basin, the Ragay Gulf, in the Philippines archipelago. The methane distribution is characterised by unusual mid-water and bottom-water plumes, between 80 and 100 m thick. The plumes are confined to water depths between about 100 and 220 m. where the temperature-depth (a proxy for seawater density) gradient is steepest. Plumes of high methane are 'trapped' within the main thermocline; these are local features, persisting over kilometre-scale distances. Geochemical and geological evidence suggests that the elevated methane concentrations are thermogenic in origin (although an oxidised biogenic origin cannot be ruled out for some of the methane anomalies), and have migrated from the sea floor into the overlying water. The mid and bottom-water methane maxima support fluxes of methane from depth into surface waters and, subsequently, from the oceans to the atmosphere. The average supersaturation of methane in the top 5 m of the sea, at nine locations, was 206±16.5%; range 178-237%. The average estimated sea-air flux was 101 nmole.cm -2 .y -1 and probably represents a minimum flux, because of low wind speeds of <10 knots. These fluxes, we suggest, are supported by seepage from the sea floor and represent naturally occurring fluxes of mostly fossil methane (in contrast to anthropogenic fossil methane), from the sea to the atmosphere. The estimated minimum fluxes of naturally occurring fossil methane are comparable to those biogenic fluxes measured elsewhere in the surface oceans, but are less than those naturally occurring methane inputs from sediments of the Barents Sea. Ragay Gulf fluxes are also less than anthropogenic fluxes measured in areas of petroleum exploration and development, such as the Texas and Louisiana, USA shelf areas

Quantification of the methane concentration using anaerobic oxidation of methane coupled to extracellular electron transfer

Science.gov (United States)

A biofilm anode acclimated with acetate, acetate+methane, and methane growth media for over three years produced a steady current density of 1.6-2.3 mA/m^2 in a microbial electrochemical cell (MxC) fed with methane as the sole electron donor. Geobacter was the dominant genus for...

The effects of fire on biogenic emissions of methane and nitric oxide from wetlands

Science.gov (United States)

Levine, Joel S.; Cofer, Wesley R., III; Sebacher, Daniel I.; Rhinehart, Robert P.; Winstead, Edward L.; Sebacher, Shirley; Hinkle, C. Ross; Schmalzer, Paul A.; Koller, Albert M., Jr.

1990-01-01

Enhanced emissions of methane (CH4) and nitric oxide (NO) were measured following three controlled burns in a Florida wetlands in 1987 and 1988. Wetlands are the major global source of methane resulting from metabolic activity of methanogenic bacteria. Methanogens require carbon dioxide, acetate, or formate for their growth and the metabolic production of methane. All three water-soluble compounds are produced in large concentrations during biomass burning. Postfire methane emissions exceeded 0.15 g CH 4/sq m per day. Preburn and postburn measurements of soil nutrients indicate significant postburn increases in soil ammonium, from 8.35 to 13.49 parts per million (ppm) in the upper 5 cm of the Juncus marsh and from 8.83 to 23.75 ppm in the upper 5 cm of the Spartina marsh. Soil nitrate concentrations were found to decrease in both marshes after the fire. These measurements indicate that the combustion products of biomass burning exert an important 'fertilizing' effect on the biosphere and on the biogenic production of environmentally significant atmospheric gases.

Titan's methane clock

Science.gov (United States)

Nixon, C. A.; Jennings, D. E.; Romani, P. N.; Teanby, N. A.; Irwin, P. G. J.; Flasar, F. M.

2010-04-01

Measurements of the 12C/13C and D/H isotopic ratios in Titan's methane show intriguing differences from the values recorded in the giant planets. This implies that either (1) the atmosphere was differently endowed with material at the time of formation, or (2) evolutionary processes are at work in the moon's atmosphere - or some combination of the two. The Huygens Gas Chromatograph Mass Spectrometer Instrument (GCMS) found 12CH4/13CH4 = 82 +/- 1 (Niemann et al. 2005), some 7% lower than the giant planets' value of 88 +/- 7 (Sada et al. 1996), which closely matches the terrestrial inorganic standard of 89. The Cassini Composite Infrared Spectrometer (CIRS) has previously reported 12CH4/13CH4 of 77 +/-3 based on nadir sounding, which we now revise upwards to 80 +/- 4 based on more accurate limb sounding. The CIRS and GCMS results are therefore in agreement about an overall enrichment in 13CH4 of ~10%. The value of D/H in Titan's CH4 has long been controversial: historical measurements have ranged from about 8-15 x 10-5 (e.g. Coustenis et al. 1989, Coustenis et al. 2003). A recent measurement based on CIRS limb data by Bezard et al. (2007) puts the D/H in CH4 at (13 +/- 1) x 10-5, very much greater than in Jupiter and Saturn, ~2 x 10-5 (Mahaffy et al. 1998, Fletcher et al. 2009). To add complexity, the 12C/13C and D/H vary among molecules in Titan atmosphere, typically showing enhancement in D but depletion in 13C in the daughter species (H2, C2H2, C2H6), relative to the photochemical progenitor, methane. Jennings et al. (2009) have sought to interpret the variance in carbon isotopes as a Kinetic Isotope Effect (KIE), whilst an explanation for the D/H in all molecules remains elusive (Cordier et al. 2008). In this presentation we argue that evolution of isotopic ratios in Titan's methane over time forms a ticking 'clock', somewhat analogous to isotopic ratios in geochronology. Under plausible assumptions about the initial values and subsequent replenishment, various

Study on gas hydrate as a new energy resource in the 21th century

Energy Technology Data Exchange (ETDEWEB)

Ryu, Byeong-Jae; Kwak Young-Hoon; Kim, Won-Sik [Korea Institute of Geology Mining and Materials, Taejon (KR)] (and others)

1999-12-01

Natural gas hydrate, a special type of clathrate hydrates, is a metastable solid compound which mainly consists of methane and water, and generally called as gas hydrate. It is stable in the specific low-temperature/high-pressure conditions. Gas hydrates play an important role as major reservoir of methane on the earth. On the other hand, the formation and dissociation of gas hydrates could cause the plugging in pipeline, gas kick during production, atmospheric pollution and geohazard. To understand the formation and dissociation of the gas hydrate, the experimental equilibrium conditions of methane hydrate were measured in pure water, 3 wt.% NaCl and MgCl{sub 2} solutions. The equilibrium conditions of propane hydrates were also measured in pure water. The relationship between methane hydrate formation time and overpressure was also analyzed through the laboratory work. The geophysical surveys using air-gun system and multibeam echo sounder were implemented to develop exploration techniques and to evaluate the gas hydrate potential in the East Sea, Korea. General indicators of submarine gas hydrates on seismic data is commonly inferred from the BSR developed parallel to the see floor, amplitude blanking at the upper part of the BSR, and phase reversal and decrease of the interval velocity at BSR. The field data were processed using Geobit 2.9.5 developed by KIGAM to detect the gas hydrate indicators. The accurate velocity analysis was performed by XVA (X-window based Velocity Analysis). Processing results show that the strong reflector occurred parallel to the sea floor were shown at about 1800 ms two way travel time. The interval velocity decrease at this strong reflector and at the reflection phase reversal corresponding to the reflection at the sea floor. Gas hydrate stability field in the study area was determined using the data of measured hydrate equilibrium condition, hydrothermal gradient and geothermal gradient. The depth of BSR detected in the seismic

A Second Glass Transition in Pressure Collapsed Type II Clathrate Hydrates.

Science.gov (United States)

Andersson, Ove; Häussermann, Ulrich

2018-04-19

Type II clathrate hydrates (CHs) M·17 H 2 O, with M = tetrahydrofuran (THF) or 1,3-dioxolane, are known to collapse, or amorphize, on pressurization to ∼1.3 GPa in the temperature range 77-140 K. On heating at 1 GPa, these pressure-amorphized CH states show a weak, stretched sigmoid-shaped, heat-capacity increase because of a glass transition. Here we use thermal conductivity and heat capacity measurements to show that also type II CH with M = cyclobutanone (CB) collapses on isothermal pressurization and undergoes a similar, weak, glass transition upon heating at 1 GPa. Furthermore, we reveal for both THF CH and CB CH a second, much more pronounced, glass transition at temperatures above the thermally weak glass transition on heating in the 0.2-0.7 GPa range. This result suggests the general occurrence of two glass transitions in water-rich (94 mol %) pressure-collapsed CHs. Because of a large increase in dielectric permittivity concurrently as the weak heat capacity increase, the first glass transition must be due to kinetic unfreezing of water molecules. The thermal features of the second glass transition, measured on isobaric temperature cycling, are typical of a glass-liquid-glass transition, which suggests that pressure-amorphized CHs transform reversibly to liquids.

Methane-bomb natural gas

International Nuclear Information System (INIS)

Anon.

1993-01-01

About 50% of the so-called 'greenhouse-effect' is not caused by CO 2 , but by more dangerous gases, among them is methane. Natural gas consists to about 98% of methane. In Austria result about 15% of the methane emissions from offtake, storage, transport (pipelines) and distribution from natural gas. A research study of the Research Centre Seibersdorf points out that between 2.5% and 3.6% of the employed natural gas in Austria emits. The impact of this emitted methane is about 29 times worse than the impact of CO 2 (caused for examples by petroleum burning). Nevertheless the Austrian CO 2 -commission states that an increasing use of natural gas would decrease the CO 2 -emissions - but this statement is suspected to be based on wrong assumptions. (blahsl)

Evaluation of Phytoremediation of Coal Bed Methane Product Water and Waters of Quality Similar to that Associated with Coal Bed Methane Reserves of the Powder River Basin, Montana and Wyoming

Energy Technology Data Exchange (ETDEWEB)

James Bauder

2008-09-30

U.S. emphasis on domestic energy independence, along with advances in knowledge of vast biogenically sourced coalbed methane reserves at relatively shallow sub-surface depths with the Powder River Basin, has resulted in rapid expansion of the coalbed methane industry in Wyoming and Montana. Techniques have recently been developed which constitute relatively efficient drilling and methane gas recovery and extraction techniques. However, this relatively efficient recovery requires aggressive reduction of hydrostatic pressure within water-saturated coal formations where the methane is trapped. Water removed from the coal formation during pumping is typically moderately saline and sodium-bicarbonate rich, and managed as an industrial waste product. Current approaches to coalbed methane product water management include: surface spreading on rangeland landscapes, managed irrigation of agricultural crop lands, direct discharge to ephermeral channels, permitted discharge of treated and untreated water to perennial streams, evaporation, subsurface injection at either shallow or deep depths. A Department of Energy-National Energy Technology Laboratory funded research award involved the investigation and assessment of: (1) phytoremediation as a water management technique for waste water produced in association with coalbed methane gas extraction; (2) feasibility of commercial-scale, low-impact industrial water treatment technologies for the reduction of salinity and sodicity in coalbed methane gas extraction by-product water; and (3) interactions of coalbed methane extraction by-product water with landscapes, vegetation, and water resources of the Powder River Basin. Prospective, greenhouse studies of salt tolerance and water use potential of indigenous, riparian vegetation species in saline-sodic environments confirmed the hypothesis that species such as Prairie cordgrass, Baltic rush, American bulrush, and Nuttall's alkaligrass will thrive in saline-sodic environments

Phase equilibrium condition measurements in nitrogen and air clathrate hydrate forming systems at temperatures below freezing point of water

International Nuclear Information System (INIS)

Yasuda, Keita; Oto, Yuya; Shen, Renkai; Uchida, Tsutomu; Ohmura, Ryo

2013-01-01

Highlights: • Phase equilibrium conditions in the nitrogen and modelled air hydrate forming systems are measured. • Measurements are conducted at temperatures below the freezing point of water. • Results have relevance to the air hydrate formation in the ice sheets. • Measured data are quantitatively compared with the previously reported values. • Range of the equilibrium measurements was from (242 to 268) K. -- Abstract: Contained in this paper are the three phase equilibrium conditions of the (ice + clathrate hydrate + guest-rich) vapour in the (nitrogen + water) and the modelled (air + water) systems at temperatures below the freezing point of water. The precise determination of the equilibrium conditions in those systems are of importance for the analysis of the past climate change using the cored samples from the ice sheets at Antarctica and Greenland because the air hydrates keep the ancient climate signals. The mole ratio of the modelled air composed of nitrogen and oxygen is 0.790:0.210. The equilibrium conditions were measured by the batch, isochoric procedure. The temperature range of the measurements in the nitrogen hydrate forming system is (244.05 < T < 266.55) K and the corresponding equilibrium pressure range is (7.151 < p < 12.613) MPa. The temperature range of the measurements in the modelled air hydrate forming system is (242.55 < T < 267.85) K, and the corresponding equilibrium pressure range is (6.294 < p < 12.144) MPa. The data obtained quantitatively compared with the previously reported data

Plasma catalytic process for CO2 methanation

International Nuclear Information System (INIS)

Nizio, Magdalena

2016-01-01

The limited resources of oil and natural gas, together with an increasing energy demand, forces us to seek more and more efficient and cleaner energy production alternatives. Hydrogen has been recently considered as a promising energy carrier. However, there are several inherent problems to the utilization of H 2 , from its transportation to its distribution. Transformation of the H 2 molecule by fixing into a carbon-containing compound, i.e. CH 4 , will offer the possibility of using the conventional transportation network. Indeed, the Sabatier reaction, which is highly exothermic, involves the reaction of carbon dioxide and hydrogen gas in order to produce methane and water. This process, called methanation, represents a feasible approach contributing to the reduction of the CO 2 emissions in our atmosphere, through a closed carbon cycle involving the valorization of CO 2 , i.e. from capture. However, below a temperature of 250 C, the conversion becomes practically close to 0 %, whereas at higher temperatures, i.e., (≥300 C), the co-existence of secondary reactions favours the formation of CO and H 2 . This is the reason why new catalysts and process conditions are continuously being investigated in order to maximize the methane selectivity at low reaction temperatures at atmospheric pressure. Therefore, by using catalysts combined to Dielectric Barrier Discharge plasmas (DBD), the activation of the methanation reaction can be enhanced and overcome the drawbacks of existing conventional processes. Several Ni-containing catalysts were prepared using various ceria-zirconia oxides as supports, with different Ce/Zr ratios. The results obtained in the adiabatic conditions at low temperatures (ranging between 100-150 C), in the presence of catalysts activated by plasma, are promising. Indeed, the conversion of CO 2 to CH 4 is about 85 % with a selectivity close to 100 %. The same conversion in the absence of the plasma activation of the catalyst is observed at 350 C

Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology

Energy Technology Data Exchange (ETDEWEB)

Michalis, Vasileios K.; Costandy, Joseph; Economou, Ioannis G., E-mail: ioannis.economou@qatar.tamu.edu [Chemical Engineering Program, Texas A and M University at Qatar, P.O. Box 23847, Doha (Qatar); Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K. [Environmental Research Laboratory, National Center for Scientific Research NCSR “Demokritos,” Aghia Paraskevi, Attiki GR-15310 (Greece)

2015-01-28

The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal–isobaric ensemble in order to determine the coexistence temperature (T{sub 3}) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T{sub 3}, is treated with long simulations in the range of 1000–4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T{sub 3} predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T{sub 3} of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.

Hydrate-based methane separation from coal mine methane gas mixture by bubbling using the scale-up equipment

International Nuclear Information System (INIS)

Cai, Jing; Xu, Chun-Gang; Xia, Zhi-Ming; Chen, Zhao-Yang; Li, Xiao-Sen

2017-01-01

Highlights: •Hydrate-based methane separation was achieved in the large scale using SHW-II. •Bubbling method was beneficial to reduce energy consumption. •The optimal conditions were determined. •The morphology and flow characteristic of hydrate formation were filmed. -- Abstract: In this work, the hydrate-based methane (CH 4 ) separation from coal mine methane (CMM) gas mixture was carried out by bubbling with a scale-up equipment (SHW-II). The influences of gas/liquid volume ratios (0.25 and 0.60), gas bubble sizes (diameter: 20, 50 and 100 μm) and gas flow rates (7.50, 16.13 and 21.50 mL/min/L) on gas consumption and CH 4 recovery were systematically investigated at 277.15 K and 1.50 MPa. The hydrate formation morphology was filmed by a camera and the hydrate structure was determined by powder X-ray diffraction (PXRD). Gas bubbles generated when gas mixture flowed into bulk solution through a bubble plate from the bottom of SHW-II. Initially, the gas hydrates formed at the bubble boundary and grew up as the shell around the bubble with the continuously rising of the gas bubble, and finally accumulated in the interface between the gaseous phase and solution. The experimental results showed that the THF/CH 4 /N 2 hydrate in SHW-II presented structure II (sII). The gas/liquid volume ratio, gas bubble size and gas flow rate had influences on gas consumption and CH 4 recovery. The increase of gas/liquid volume ratio resulted in the decrease of gas consumption and CH 4 recovery, while the increase of gas flow rate caused the decrease of gas consumption. Both the maximum gas consumption and CH 4 recovery were achieved at the gas bubble with diameter of 50 μm. The optimal operating condition for large-scale CH 4 separation via clatharate hydrate was comprehensively defined as the gas/liquid volume ratio of 0.25, the gas bubble diameter of 50 μm and the gas flow rate of 16.13 mL/min/L at 277.15 K and 1.50 MPa.

Simulations of atmospheric methane for Cape Grim, Tasmania, to constrain southeastern Australian methane emissions

Directory of Open Access Journals (Sweden)

Z. M. Loh

2015-01-01

Full Text Available This study uses two climate models and six scenarios of prescribed methane emissions to compare modelled and observed atmospheric methane between 1994 and 2007, for Cape Grim, Australia (40.7° S, 144.7° E. The model simulations follow the TransCom-CH4 protocol and use the Australian Community Climate and Earth System Simulator (ACCESS and the CSIRO Conformal-Cubic Atmospheric Model (CCAM. Radon is also simulated and used to reduce the impact of transport differences between the models and observations. Comparisons are made for air samples that have traversed the Australian continent. All six emission scenarios give modelled concentrations that are broadly consistent with those observed. There are three notable mismatches, however. Firstly, scenarios that incorporate interannually varying biomass burning emissions produce anomalously high methane concentrations at Cape Grim at times of large fire events in southeastern Australia, most likely due to the fire methane emissions being unrealistically input into the lowest model level. Secondly, scenarios with wetland methane emissions in the austral winter overestimate methane concentrations at Cape Grim during wintertime while scenarios without winter wetland emissions perform better. Finally, all scenarios fail to represent a~methane source in austral spring implied by the observations. It is possible that the timing of wetland emissions in the scenarios is incorrect with recent satellite measurements suggesting an austral spring (September–October–November, rather than winter, maximum for wetland emissions.

Anaerobic Oxidization of Methane in a Minerotrophic Peatland: Enrichment of Nitrite-Dependent Methane-Oxidizing Bacteria

Science.gov (United States)

Zhu, Baoli; van Dijk, Gijs; Fritz, Christian; Smolders, Alfons J. P.; Pol, Arjan; Jetten, Mike S. M.

2012-01-01

The importance of anaerobic oxidation of methane (AOM) as a methane sink in freshwater systems is largely unexplored, particularly in peat ecosystems. Nitrite-dependent anaerobic methane oxidation (n-damo) was recently discovered and reported to be catalyzed by the bacterium “Candidatus Methylomirabilis oxyfera,” which is affiliated with the NC10 phylum. So far, several “Ca. Methylomirabilis oxyfera” enrichment cultures have been obtained using a limited number of freshwater sediments or wastewater treatment sludge as the inoculum. In this study, using stable isotope measurements and porewater profiles, we investigated the potential of n-damo in a minerotrophic peatland in the south of the Netherlands that is infiltrated by nitrate-rich ground water. Methane and nitrate profiles suggested that all methane produced was oxidized before reaching the oxic layer, and NC10 bacteria could be active in the transition zone where countergradients of methane and nitrate occur. Quantitative PCR showed high NC10 bacterial cell numbers at this methane-nitrate transition zone. This soil section was used to enrich the prevalent NC10 bacteria in a continuous culture supplied with methane and nitrite at an in situ pH of 6.2. An enrichment of nitrite-reducing methanotrophic NC10 bacteria was successfully obtained. Phylogenetic analysis of retrieved 16S rRNA and pmoA genes showed that the enriched bacteria were very similar to the ones found in situ and constituted a new branch of NC10 bacteria with an identity of less than 96 and 90% to the 16S rRNA and pmoA genes of “Ca. Methylomirabilis oxyfera,” respectively. The results of this study expand our knowledge of the diversity and distribution of NC10 bacteria in the environment and highlight their potential contribution to nitrogen and methane cycles. PMID:23042166

Cu and Zn substituted silicon clathrates with the cubic type-II structure. Synthesis and characterization of Cs{sub 8}Na{sub 16}Cu{sub 3.8}Si{sub 132.2} and Cs{sub 8}Na{sub 16}Zn{sub 6.9}Si{sub 129.1}

Energy Technology Data Exchange (ETDEWEB)

Schaefer, Marion C.; Bobev, Svilen [Department of Chemistry and Biochemistry, University of Delaware, Newark, DE (United States)

2017-12-13

Studies in the systems Cs-Na-Cu-Si and Cs-Na-Zn-Si yielded the novel clathrates Cs{sub 8}Na{sub 16}(Cu,Si){sub 136} and Cs{sub 8}Na{sub 16}(Zn,Si){sub 136}, both with the cubic type-II structure [space group Fd anti 3m (no. 227), Pearson symbol cF160]. The structures of the title compounds were established from single-crystal X-ray diffraction methods, confirming the complete ordering of the Cs and Na guest atoms. The framework-building Si atoms are found to be randomly substituted by Cu atoms on framework site 96g, exclusively. In the structure of Cs{sub 8}Na{sub 16}(Zn,Si){sub 136}, the refinements indicate that the Zn and Si atoms co-occupy two of the three framework sites with notable preference for site 96g over site 32e. The corresponding refined compositions and unit cell parameters are as follows: Cs{sub 8}Na{sub 16}Cu{sub 3.8}Si{sub 132.2(1)} [a = 14.7583(15) Aa]; Cs{sub 8}Na{sub 16}Zn{sub 6.9}Si{sub 129.1(1)} [a = 14.7682(5) Aa], respectively. The type-II clathrates can be obtained only from experiments employing both Na and Cs, whereas work in the ternary Cs-Cu-Si, Cs-Zn-Si, Na-Cu-Si, and Na-Zn-Si systems failed to yield any clathrate phases. At the same conditions, exploratory studies in the K-Zn-Si and Rb-Zn-Si systems provided evidence that type-I clathrates are favored. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Methanation process utilizing split cold gas recycle

Science.gov (United States)

Tajbl, Daniel G.; Lee, Bernard S.; Schora, Jr., Frank C.; Lam, Henry W.

1976-07-06

In the methanation of feed gas comprising carbon monoxide and hydrogen in multiple stages, the feed gas, cold recycle gas and hot product gas is mixed in such proportions that the mixture is at a temperature sufficiently high to avoid carbonyl formation and to initiate the reaction and, so that upon complete reaction of the carbon monoxide and hydrogen, an excessive adiabatic temperature will not be reached. Catalyst damage by high or low temperatures is thereby avoided with a process that utilizes extraordinarily low recycle ratios and a minimum of investment in operating costs.

Methanization of industrial liquid effluents

International Nuclear Information System (INIS)

Frederic, S.; Lugardon, A.

2007-01-01

In a first part, this work deals with the theoretical aspects of the methanization of the industrial effluents; the associated reactional processes are detailed. The second part presents the technological criteria for choosing the methanization process in terms of the characteristics of the effluent to be treated. Some of the methanization processes are presented with their respective advantages and disadvantages. At last, is described the implementation of an industrial methanization unit. The size and the main choices are detailed: the anaerobic reactor, the control, the valorization aspects of the biogas produced. Some examples of industrial developments illustrate the different used options. (O.M.)

Elimination of methane in exhaust gas from biogas upgrading process by immobilized methane-oxidizing bacteria.

Science.gov (United States)

Wu, Ya-Min; Yang, Jing; Fan, Xiao-Lei; Fu, Shan-Fei; Sun, Meng-Ting; Guo, Rong-Bo

2017-05-01

Biogas upgrading is essential for the comprehensive utilization of biogas as substitute of natural gas. However, the methane in the biogas can be fully recovered during the upgrading process of biogas, and the exhaust gas produced during biogas upgrading may contain a very low concentration of methane. If the exhaust gas with low concentration methane releases to atmosphere, it will be harmful to environment. In addition, the utilization of large amounts of digestate produced from biogas plant is another important issue for the development of biogas industry. In this study, solid digestate was used to produce active carbon, which was subsequently used as immobilized material for methane-oxidizing bacteria (MOB) in biofilter. Biofilter with MOB immobilized on active carbon was used to eliminate the methane in exhaust gas from biogas upgrading process. Results showed porous active carbon was successfully made from solid digestate. The final methane elimination capacity of immobilized MOB reached about 13molh -1 m -3 , which was more 4 times higher than that of MOB without immobilization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Shock tube/laser absorption measurements of methane, acetylene and ethylene during the pyrolysis of n-pentane and iso-pentane

KAUST Repository

Sajid, Muhammad Bilal

2015-11-09

Pentane isomers are important constituents of distillate gasoline, compressed natural gas and liquefied petroleum gas. Pentane chemistry is integral component of the chemical kinetic mechanisms of larger hydrocarbons. Existing kinetic mechanisms differ in their predictions of the oxidative and pyrolysis behavior of pentane isomers. This work provides new species time-history data to validate and improve pentane chemistry models. Methane, acetylene and ethylene are measured during the high-temperature pyrolysis of n-pentane and iso-pentane. Experiments are performed behind reflected shock waves over 1400–2100 K and pressures near 1 atm. Methane and acetylene are measured using a quantum cascade laser operating near 8 µm, whereas ethylene is measured with a CO2 gas laser operating near 10.6 µm. A two-color technique is used to eliminate broadband interference caused by large hydrocarbons. Measurements are compared with predictions of existing chemical kinetic mechanisms which underpredict the formation of methane and acetylene but overpredict ethylene formation.

Effects of guest atomic species on the lattice thermal conductivity of type-I silicon clathrate studied via classical molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Kumagai, Tomohisa, E-mail: kumagai@criepi.denken.or.jp; Nakamura, Kaoru; Yamada, Susumu; Ohnuma, Toshiharu [Materials Science Research Laboratory, Central Research Institute of Electric Power Industry, 2-6-1 Nagasaka, Yokosuka, Kanagawa 240-0196 (Japan)

2016-08-14

The effects of guest atomic species in Si clathrates on the lattice thermal conductivity were studied using classical molecular dynamics calculations. The interaction between a host atom and a guest atom was described by the Morse potential function while that between host atoms was described by the Tersoff potential. The parameters of the potentials were newly determined for this study such that the potential curves obtained from first-principles calculations for the insertion of a guest atom into a Si cage were successfully reproduced. The lattice thermal conductivities were calculated by using the Green-Kubo method. The experimental lattice thermal conductivity of Ba{sub 8}Ga{sub 16}Si{sub 30} can be successfully reproduced using the method. As a result, the lattice thermal conductivities of type-I Si clathrates, M{sub 8}Si{sub 46} (M = Na, Mg, K, Ca Rb, Sr, Cs, or Ba), were obtained. It is found that the lattice thermal conductivities of M{sub 8}Si{sub 46}, where M is IIA elements (i.e., M = Mg, Ca, Sr, or Ba) tend to be lower than those of M{sub 8}Si{sub 46}, where M is IA elements (i.e., M = Na, K, Rb, or Cs). Those of {sup m}M{sub 8}Si{sub 46}, where m was artificially modified atomic weight were also obtained. The obtained lattice thermal conductivity can be regarded as a function of a characteristic frequency, f{sub c}. That indicates minimum values around f{sub c}=2-4 THz, which corresponds to the center of the frequencies of the transverse acoustic phonon modes associated with Si cages.

Mechanisms of Xenon Effect on Skin and Red Blood Cells

DEFF Research Database (Denmark)

Ponomarev, Alexander; Rodin, V.; Gurevich, Leonid

2017-01-01

The usage of Xenon (Xe) is known in anesthesia and biobanking areas. It is considered preservation effect of Xe is associated either with clathrate formation - solid gaseous structures or dissolution of Xe molecules in liquid phase without physical state modification (so-called hyperbarium) [1......]. This study is addressed to establish differences between hyberbarium or clathrate Xe actions as well as its applications on various bioobjects with anaerobic - red blood cells (RBCs) and aerobic (skin fragments) metabolism. Xe clathrates and hyperbarium storage were simulated under 277 K and 620-725 k...... to control (15.68 ± 1.11, CI95%). Skin fragments were harvested from rat tails and divided on hyberbarium, clathrate and dimetylsulfoxide cryopreserved as control group and stored for 7 days. Assessment was performed by point-score method including epidermal-dermal integrity various assays and engraftment...

Superconductivity in gallium-substituted Ba8Si46 clathrates

Science.gov (United States)

Li, Yang; Zhang, Ruihong; Liu, Yang; Chen, Ning; Luo, Z. P.; Ma, Xingqiao; Cao, Guohui; Feng, Z. S.; Hu, Chia-Ren; Ross, Joseph H., Jr.

2007-02-01

We report a joint experimental and theoretical investigation of superconductivity in Ga-substituted type-I silicon clathrates. We prepared samples of the general formula Ba8Si46-xGax , with different values of x . We show that Ba8Si40Ga6 is a bulk superconductor, with an onset at TC≈3.3K . For x=10 and higher, no superconductivity was observed down to T=1.8K . This represents a strong suppression of superconductivity with increasing Ga content, compared to Ba8Si46 with TC≈8K . Suppression of superconductivity can be attributed primarily to a decrease in the density of states at the Fermi level, caused by a reduced integrity of the sp3 -hybridized networks as well as the lowering of carrier concentration. These results are corroborated by first-principles calculations, which show that Ga substitution results in a large decrease of the electronic density of states at the Fermi level, which explains the decreased superconducting critical temperature within the BCS framework. To further characterize the superconducting state, we carried out magnetic measurements showing Ba8Si40Ga6 to be a type-II superconductor. The critical magnetic fields were measured to be HC1≈35Oe and HC2≈8.5kOe . We deduce the London penetration depth λ≈3700Å and the coherence length ξc≈200Å . Our estimate of the electron-phonon coupling reveals that Ba8Si40Ga6 is a moderate phonon-mediated BCS superconductor.

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

Science.gov (United States)

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

2015-12-01

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

Evaluation of methane emissions from Taiwanese paddies

International Nuclear Information System (INIS)

Liu, C.-W.; Wu, C.-Y.

2004-01-01

The main greenhouse gases are carbon dioxide, methane and nitrous oxide. Methane is the most important because the warming effect of methane is 21 times greater than that of carbon dioxide. Methane emitted from rice paddy fields is a major source of atmospheric methane. In this work, a methane emission model (MEM), which integrates climate change, plant growth and degradation of soil organic matter, was applied to estimate the emission of methane from rice paddy fields in Taiwan. The estimated results indicate that much methane is emitted during the effective tillering and booting stages in the first crop season and during the transplanting stage in the second crop season in a year. Sensitivity analysis reveals that the temperature is the most important parameter that governs the methane emission rate. The order of the strengths of the effects of the other parameters is soil pH, soil water depth (SWD) and soil organic matter content. The masses of methane emitted from rice paddy fields of Taiwan in the first and second crop seasons are 28,507 and 350,231 tons, respectively. The amount of methane emitted during the second crop season is 12.5 times higher than that emitted in the first crop season. With a 12% reduction in planted area during the second crop season, methane emission could be reduced by 21%. In addition, removal of rice straw left from the first crop season and increasing the depth of flooding to 25 cm are also strategies that could help reduce annual emission by up to 18%

Reducing methane emissions from ruminant animals

Energy Technology Data Exchange (ETDEWEB)

Mathison, G.W.; Okine, E.K.; McAllister, T.A.; Dong, Y.; Galbraith, J.; Dmytruk, O.I.N. [University of Alberta, Edmonton, AB (Canada). Dept. of Agriculture, Food and Nutrition Science

1998-09-01

In 1992 it was estimated that 30 x 10{sup 12}g more methane was emitted into the atmosphere than was removed, with animals being considered the largest single anthropogenic source. Ruminants produce 97% of the methane generated in enteric fermentation by animals. Estimates for methane emissions from animal wastes vary between 6 and 31% of that produced directly by the animal, with the most likely value being between 5 and 10% globally. Methane inhibitors can reduce methane emissions to zero in the short term but due to microbial adaptation the effects of these compounds are quickly neutralized and feed intake is often depressed. Methane emissions per unit of feed consumed from sheep and cattle fed hay diets appear to be quite similar but differences between other ruminants have been measured. The most practical way of influencing methane emissions per unit product is to increase productivity level since the proportion of feed energy required to just maintain the animal will be reduced, methane production falls with increased intake level, and the animal may go to market sooner. The most promising avenues for future research for reducing methanogenesis are the development of new products for reducing protozoal numbers in the rumen and the use of bacterocins or other compounds which specifically target methanogenic bacteria.

Wave-induced release of methane : littoral zones as a source of methane in lakes

OpenAIRE

Hofmann, Hilmar; Federwisch, Luisa; Peeters, Frank

2010-01-01

This study investigates the role of surface waves and the associated disturbance of littoral sediments for the release and later distribution of dissolved methane in lakes. Surface wave field, wave-induced currents, acoustic backscatter strength, and the concentration and distribution of dissolved methane were measured simultaneously in Lake Constance, Germany. The data indicate that surface waves enhance the release of dissolved methane in the shallow littoral zone via burst-like releases of...

Direct Activation Of Methane

KAUST Repository

Basset, Jean-Marie; Sun, Miao; Caps, Valerie; Pelletier, Jeremie; Abou-Hamad, Edy

2013-01-01

Heteropolyacids (HPAs) can activate methane at ambient temperature (e.g., 20.degree. C.) and atmospheric pressure, and transform methane to acetic acid, in the absence of any noble metal such as Pd). The HPAs can be, for example, those with Keggin

Methane emissions from coal mining

International Nuclear Information System (INIS)

Boyer, C.M.; Kelafant, J.R.; Kuuskraa, V.A.; Manger, K.C.; Kruger, D.

1990-09-01

The report estimates global methane emissions from coal mining on a country specific basis, evaluates the technologies available to degasify coal seams and assesses the economics of recovering methane liberated during mining. 33 to 64 million tonnes were liberated in 1987 from coal mining, 75 per cent of which came from China, the USSR, Poland and the USA. Methane emissions from coal mining are likely to increase. Emission levels vary between surface and underground mines. The methane currently removed from underground mines for safety reasons could be used in a number of ways, which may be economically attractive. 55 refs., 19 figs., 24 tabs

Gas-liquid equilibrium in mixtures of methane + m-xylene, and methane + m-cresol

Energy Technology Data Exchange (ETDEWEB)

Simnick, J J; Sebastian, H M; Lin, H M; Chao, K C

1979-01-01

Compositions of saturated equilibrium liquid and vapor phases as determined in a flow apparatus for methane + m-xylene mixtures at 370/sup 0/, 450/sup 0/, 520/sup 0/, and 600/sup 0/F (190/sup 0/, 230/sup 0/, 270/sup 0/, and 310/sup 0/C) and up to 200 atm, and for methane + m-cresol at 370/sup 0/, 520/sup 0/, 660/sup 0/, and 730/sup 0/F (190/sup 0/, 270/sup 0/, 350/sup 0/, and 390/sup 0/C) and up to 250 atm. Compared with published data on its solubility in benzene, methane appears to be more soluble in m-xylene at similar conditions but substantially less soluble in m-cresol. This difference indicates that the functional groups CH/sub 3/ and OH play different roles in determining the solubility of methane.

Electrocatalytic oxidation of methane: investigations of new catalysts to be used in a solid polymer electrolyte methane fuel-cell; Oxydation electrocatalytique du methane: recherche de catalyseurs en vue d'une application a une pile au methane a electrolyte polymere solide

Energy Technology Data Exchange (ETDEWEB)

Berthelot, S

1998-07-01

This thesis evaluated the performances of many catalysts facing the methane oxidation which is a critical step in methane fuel cells development. In a first part the study of the methane electro-oxidation has been realized by classical electrochemical technics on many electrodes to determine the most active ones. In a second part the in situ reflection infra-red spectroscopy allowed to identify, during the methane oxidation, the adsorbed species on the electrode and the reaction products. These results also help the understanding of the part of the concerned materials mechanisms in the methane oxidation and then to optimize them for a whole oxidation of the methane in carbon dioxide. The final objective is the use of the methane in a PEMFC fuel cell type. A comparison with the methanol and C2 hydrocarbons behaviour, such as the ethane the ethylene and the acetylene, has been done to evaluate the performances. (A.L.B.)

Controls on the methane released through ebullition affected by permafrost degradation

Science.gov (United States)

S.J. Klapstein; M.R. Turetsky; A.D. McGuire; J.W. Harden; C.I. Czimczik; X. Xu; J.P. Chanton; J.M. Waddington

2014-01-01

Permafrost thaw in peat plateaus leads to the flooding of surface soils and the formation of collapse scar bogs, which have the potential to be large emitters of methane (CH4) from surface peat as well as deeper, previously frozen, permafrost carbon (C). We used a network of bubble traps, permanently installed 20 cm and 60 cm beneath the moss surface, to examine...

Ebullitive methane emissions from oxygenated wetland streams

Science.gov (United States)

Crawford, John T.; Stanley, Emily H.; Spawn, Seth A.; Finlay, Jacques C.; Striegl, Robert G.

2014-01-01

Stream and river carbon dioxide emissions are an important component of the global carbon cycle. Methane emissions from streams could also contribute to regional or global greenhouse gas cycling, but there are relatively few data regarding stream and river methane emissions. Furthermore, the available data do not typically include the ebullitive (bubble-mediated) pathway, instead focusing on emission of dissolved methane by diffusion or convection. Here, we show the importance of ebullitive methane emissions from small streams in the regional greenhouse gas balance of a lake and wetland-dominated landscape in temperate North America and identify the origin of the methane emitted from these well-oxygenated streams. Stream methane flux densities from this landscape tended to exceed those of nearby wetland diffusive fluxes as well as average global wetland ebullitive fluxes. Total stream ebullitive methane flux at the regional scale (103 Mg C yr−1; over 6400 km2) was of the same magnitude as diffusive methane flux previously documented at the same scale. Organic-rich stream sediments had the highest rates of bubble release and higher enrichment of methane in bubbles, but glacial sand sediments also exhibited high bubble emissions relative to other studied environments. Our results from a database of groundwater chemistry support the hypothesis that methane in bubbles is produced in anoxic near-stream sediment porewaters, and not in deeper, oxygenated groundwaters. Methane interacts with other key elemental cycles such as nitrogen, oxygen, and sulfur, which has implications for ecosystem changes such as drought and increased nutrient loading. Our results support the contention that streams, particularly those draining wetland landscapes of the northern hemisphere, are an important component of the global methane cycle.

Determining Methane Leak Locations and Rates with a Wireless Network Composed of Low-Cost, Printed Sensors

Science.gov (United States)

Smith, C. J.; Kim, B.; Zhang, Y.; Ng, T. N.; Beck, V.; Ganguli, A.; Saha, B.; Daniel, G.; Lee, J.; Whiting, G.; Meyyappan, M.; Schwartz, D. E.

2015-12-01

We will present our progress on the development of a wireless sensor network that will determine the source and rate of detected methane leaks. The targeted leak detection threshold is 2 g/min with a rate estimation error of 20% and localization error of 1 m within an outdoor area of 100 m2. The network itself is composed of low-cost, high-performance sensor nodes based on printed nanomaterials with expected sensitivity below 1 ppmv methane. High sensitivity to methane is achieved by modifying high surface-area-to-volume-ratio single-walled carbon nanotubes (SWNTs) with materials that adsorb methane molecules. Because the modified SWNTs are not perfectly selective to methane, the sensor nodes contain arrays of variously-modified SWNTs to build diversity of response towards gases with adsorption affinity. Methane selectivity is achieved through advanced pattern-matching algorithms of the array's ensemble response. The system is low power and designed to operate for a year on a single small battery. The SWNT sensing elements consume only microwatts. The largest power consumer is the wireless communication, which provides robust, real-time measurement data. Methane leak localization and rate estimation will be performed by machine-learning algorithms built with the aid of computational fluid dynamics simulations of gas plume formation. This sensor system can be broadly applied at gas wells, distribution systems, refineries, and other downstream facilities. It also can be utilized for industrial and residential safety applications, and adapted to other gases and gas combinations.

Methane Group Ions in Saturn’s Outer Magnetosphere?

Science.gov (United States)

Sittler, E. C.; Hartle, R. E.; Cooper, J. F.; Johnson, R. E.; Smith, H.; Shappirio, M.; Reisenfeld, D. B.

2009-12-01

Yelle et al. [2008] have estimated from Cassini Ion Neutral Mass Spectrometer (INMS) measurements that methane is escaping from Titan’s upper atmosphere at the rate of 2.5-3.0×109 mol/cm2/s and in order to explain this loss rate Strobel [2008] has proposed a hydrodynamic escape model to explain such high loss rates. This translates to loss of 2.8×1027 methane mol/s. The consequence of this work is the formation of a methane torus around Saturn which will dissociate to CH3 and other fragments of methane. The CH3 will then become ionized to form CH3+ with pickup energies ≈ keV after which it can be detected by the Cassini Plasma Spectrometer (CAPS) Ion Mass Spectrometer (IMS). Up till now the ion composition within Saturn’s outer magnetosphere in the vicinity of Titan’s orbit have yielded negative results with water group ions W+ dominating. The water group ions probably result from the emission of fast neutrals from the Enceladus torus via charge exchange reactions but still gravitationally bound to Saturn [see Johnson et al., 2005 and Sittler et al. 2006] and then become ionized in the outer magnetosphere as ~≈keV pickup ions. The CAPS IMS produces two ion composition data products, one called Straight Through (ST) and the other Linear Electric Field (LEF). The first has a higher sensitivity, while the latter has a greater discrimination in time-of-flight (TOF). For ST data O+ and CH4+ have similar TOF with the primary discriminator being the O- fragment which appears at a different TOF than for mass 16 ions. One can also look for other discriminators called ghost peaks. In case of LEF W+ ions produce TOF peak close to that for atomic O+ and the methane will produce TOF close to that for atomic C+ which has a significantly different(shorter) TOF than O+. We will be reporting on our continual search for methane ions within Saturn’s outer magnetosphere. References: 1. Yelle, R. V., J. Cui and I.C.F. Müller-Wodarg, JGR, 2008. 2. Strobel, D. F., Icarus

Methane generated from graphite--tritium interaction

International Nuclear Information System (INIS)

Coffin, D.O.; Walthers, C.R.

1979-01-01

When hydrogen isotopes are separated by cryogenic distillation, as little as 1 ppM of methane will eventually plug the still as frost accumulates on the column packings. Elemental carbon exposed to tritium generates methane spontaneously, and yet some dry transfer pumps, otherwise compatible with tritium, convey the gas with graphite rotors. This study was to determine the methane production rate for graphite in tritium. A pump manufacturer supplied graphite samples that we exposed to tritium gas at 0.8 atm. After 137 days we measured a methane synthesis rate of 6 ng/h per cm 2 of graphite exposed. At this rate methane might grow to a concentration of 0.01 ppM when pure tritium is transferred once through a typical graphite--rotor transfer pump. Such a low methane level will not cause column blockage, even if the cryogenic still is operated continuously for many years

Rapid, Real-time Methane Detection in Ground Water Using a New Gas-Water Equilibrator Design

Science.gov (United States)

Ruybal, C. J.; DiGiulio, D. C.; Wilkin, R. T.; Hargrove, K. D.; McCray, J. E.

2014-12-01

Recent increases in unconventional gas development have been accompanied by public concern for methane contamination in drinking water wells near production areas. Although not a regulated pollutant, methane may be a marker contaminant for others that are less mobile in groundwater and thus may be detected later, or at a location closer to the source. In addition, methane poses an explosion hazard if exsolved concentrations reach 5 - 15% volume in air. Methods for determining dissolved gases, such as methane, have evolved over 60 years. However, the response time of these methods is insufficient to monitor trends in methane concentration in real-time. To enable rapid, real-time monitoring of aqueous methane concentrations during ground water purging, a new gas-water equilibrator (GWE) was designed that increases gas-water mass exchange rates of methane for measurement. Monitoring of concentration trends allows a comparison of temporal trends between sampling events and comparison of baseline conditions with potential post-impact conditions. These trends may be a result of removal of stored casing water, pre-purge ambient borehole flow, formation physical and chemical heterogeneity, or flow outside of well casing due to inadequate seals. Real-time information in the field can help focus an investigation, aid in determining when to collect a sample, save money by limiting costs (e.g. analytical, sample transport and storage), and provide an immediate assessment of local methane concentrations. Four domestic water wells, one municipal water well, and one agricultural water well were sampled for traditional laboratory analysis and compared to the field GWE results. Aqueous concentrations measured on the GWE ranged from non-detect to 1,470 μg/L methane. Some trends in aqueous methane concentrations measured on the GWE were observed during purging. Applying a paired t-test comparing the new GWE method and traditional laboratory analysis yielded a p-value 0

Methane hydrates in nature - Current knowledge and challenges

Science.gov (United States)

Collett, Timothy S.

2014-01-01

Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance

Methane Flux and Authigenic Carbonate in Shallow Sediments Overlying Methane Hydrate Bearing Strata in Alaminos Canyon, Gulf of Mexico

Directory of Open Access Journals (Sweden)

Joseph P. Smith

2014-09-01

Full Text Available In June 2007 sediment cores were collected in Alaminos Canyon, Gulf of Mexico across a series of seismic data profiles indicating rapid transitions between the presence of methane hydrates and vertical gas flux. Vertical profiles of dissolved sulfate, chloride, calcium, magnesium, and dissolved inorganic carbon (DIC concentrations in porewaters, headspace methane, and solid phase carbonate concentrations were measured at each core location to investigate the cycling of methane-derived carbon in shallow sediments overlying the hydrate bearing strata. When integrated with stable carbon isotope ratios of DIC, geochemical results suggest a significant fraction of the methane flux at this site is cycled into the inorganic carbon pool. The incorporation of methane-derived carbon into dissolved and solid inorganic carbon phases represents a significant sink in local carbon cycling and plays a role in regulating the flux of methane to the overlying water column at Alaminos Canyon. Targeted, high-resolution geochemical characterization of the biogeochemical cycling of methane-derived carbon in shallow sediments overlying hydrate bearing strata like those in Alaminos Canyon is critical to quantifying methane flux and estimating methane hydrate distributions in gas hydrate bearing marine sediments.

The influence of sulfate and nitrate on the methane formation by methanogenic archaea in freshwater sediments

NARCIS (Netherlands)

Scholten, J.C.M.

1999-01-01

In this thesis the effect of inorganic electron acceptors (sulfate and nitrate) on methane emission from freshwater sediments in the Netherlands was investigated. The chosen study area was a polder located between Leiden and Utrecht, and is representative for similar polders