Sample records for clathrate hydrate formation

  1. CO2-SO2 clathrate hydrate formation on early Mars

    Directory of Open Access Journals (Sweden)

    Chassefière E.


    Full Text Available Most sulfate minerals discovered on Mars are dated no earlier than the Hesperian. We showed, using a 1-D radiative-convective-photochemical model, that clathrate formation during the Noachian would have buffered the atmospheric CO2 pressure of early Mars at ~2 bar and maintained a global average surface temperature ~230 K. Because clathrates trap SO2 more favorably than CO2, all volcanically outgassed sulfur would have been trapped in Noachian Mars cryosphere, preventing a significant formation of sulfate minerals during the Noachian and inhibiting carbonates from forming at the surface in acidic water resulting from the local melting of the SO2- rich cryosphere. The massive formation of sulfate minerals at the surface of Mars during the Hesperian could be the consequence of a drop of the CO2 pressure below a 2-bar threshold value at the late Noachian-Hesperian transition, which would have released sulfur gases into the atmosphere from both the Noachian sulfur-rich cryosphere and still active Tharsis volcanism. Our hypothesis could allow to explain the formation of chaotic terrains and outflow channels, and the occurrence of episodic warm episodes facilitated by the release of SO2 to the atmosphere. These episodes could explain the formation of valley networks and the degradation of impact craters, but remain to be confirmed by further modeling.

  2. Overview: Nucleation of clathrate hydrates (United States)

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


    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.

  3. Clathrate hydrate tuning for technological purposes (United States)

    di Profio, Pietro; Germani, Raimondo; Savelli, Gianfranco


    Gas hydrates are being increasingly considered as convenient media for gas storage and transportation as the knowledge of their properties increases, in particular as relates to methane and hydrogen. Clathrate hydrates may also represent a feasible sequestration technology for carbon dioxide, due to a well defined P/T range of stability, and several research programs are addressing this possibility. Though the understanding of the molecular structure and supramolecular interactions which are responsible of most properties of hydrates have been elucitated in recent years, the underlying theoretical physico-chemical framework is still poor, especially as relates to the role of "conditioners" (inhibitors and promoters) from the molecular/supramolecular point of view. In the present communication we show some results from our research approach which is mainly focused on the supramolecular properties of clathrate hydrate systems - and their conditioners - as a way to get access to a controlled modulation of the formation, dissociation and stabilization of gas hydrates. In particular, this communication will deal with: (a) a novel, compact apparatus for studying the main parameters of formation and dissociation of gas hydrates in a one-pot experiment, which can be easily and rapidly carried out on board of a drilling ship;[1] (b) the effects of amphiphile molecules (surfactants) as inhibitors or promoters of gas hydrate formation;[2] (c) a novel nanotechnology for a reliable and quick production of hydrogen hydrates, and its application to fuel cells;[3,4] and (d) the development of a clathrate hydrate tecnology for the sequestration and geological storage of man-made CO2, possibly with concomitant recovery of natural gas from NG hydrate fields. Furthermore, the feasibility of catalyzing the reduction of carbon dioxide to energy-rich species by hydrates is being investigated. [1] Di Profio, P., Germani, R., Savelli, G., International Patent Application PCT/IT2006

  4. Investigating the Metastability of Clathrate Hydrates for Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Carolyn Ann [Colorado School of Mines, Golden, CO (United States)


    Important breakthrough discoveries have been achieved from the DOE award on the key processes controlling the synthesis and structure-property relations of clathrate hydrates, which are critical to the development of clathrate hydrates as energy storage materials. Key achievements include: (i) the discovery of key clathrate hydrate building blocks (stable and metastable) leading to clathrate hydrate nucleation and growth; (ii) development of a rapid clathrate hydrate synthesis route via a seeding mechanism; (iii) synthesis-structure relations of H2 + CH4/CO2 binary hydrates to control thermodynamic requirements for energy storage and sequestration applications; (iv) discovery of a new metastable phase present during clathrate hydrate structural transitions. The success of our research to-date is demonstrated by the significant papers we have published in high impact journals, including Science, Angewandte Chemie, J. Am. Chem. Soc. Intellectual Merits of Project Accomplishments: The intellectual merits of the project accomplishments are significant and transformative, in which the fundamental coupled computational and experimental program has provided new and critical understanding on the key processes controlling the nucleation, growth, and thermodynamics of clathrate hydrates containing hydrogen, methane, carbon dioxide, and other guest molecules for energy storage. Key examples of the intellectual merits of the accomplishments include: the first discovery of the nucleation pathways and dominant stable and metastable structures leading to clathrate hydrate formation; the discovery and experimental confirmation of new metastable clathrate hydrate structures; the development of new synthesis methods for controlling clathrate hydrate formation and enclathration of molecular hydrogen. Broader Impacts of Project Accomplishments: The molecular investigations performed in this project on the synthesis (nucleation & growth)-structure-stability relations of clathrate

  5. 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


    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......) equilibrium data are presented for the ternary system of water-cyclopentane-carbon dioxide at temperatures ranging from 285.2K down to 275.5K.New four-phase H-Lw-La-V equilibrium data for the quaternary system water-THF-cyclopentane-carbon dioxide are presented in the temperature range from 275.1K to 286.6K....... 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....

  6. Methane Clathrate Hydrate Prospecting (United States)

    Duxbury, N.; Romanovsky, V.


    A method of prospecting for methane has been devised. The impetus for this method lies in the abundance of CH4 and the growing shortages of other fuels. The method is intended especially to enable identification of subpermafrost locations where significant amounts of methane are trapped in the form of methane gas hydrate (CH4(raised dot)6H2O). It has been estimated by the U.S. Geological Survey that the total CH4 resource in CH4(raised dot) 6H2O exceeds the energy content of all other fossil fuels (oil, coal, and natural gas from non-hydrate sources). Also, CH4(raised dot)6H2O is among the cleanest-burning fuels, and CH4 is the most efficient fuel because the carbon in CH4 is in its most reduced state. The method involves looking for a proxy for methane gas hydrate, by means of the combination of a thermal-analysis submethod and a field submethod that does not involve drilling. The absence of drilling makes this method easier and less expensive, in comparison with prior methods of prospecting for oil and natural gas. The proposed method would include thermoprospecting in combination with one more of the other non-drilling measurement techniques, which could include magneto-telluric sounding and/or a subsurface-electrical-resistivity technique. The method would exploit the fact that the electrical conductivity in the underlying thawed region is greater than that in the overlying permafrost.

  7. Desalination utilizing clathrate hydrates (LDRD final report).

    Energy Technology Data Exchange (ETDEWEB)

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy (Sandia National Laboratories, Albuquerque, NM); Greathouse, Jeffery A. (Sandia National Laboratories, Albuquerque, NM); Majzoub, Eric H. (University of Missouri, Columbia, MO)


    Advances are reported in several aspects of clathrate hydrate desalination fundamentals necessary to develop an economical means to produce municipal quantities of potable water from seawater or brackish feedstock. These aspects include the following, (1) advances in defining the most promising systems design based on new types of hydrate guest molecules, (2) selection of optimal multi-phase reactors and separation arrangements, and, (3) applicability of an inert heat exchange fluid to moderate hydrate growth, control the morphology of the solid hydrate material formed, and facilitate separation of hydrate solids from concentrated brine. The rate of R141b hydrate formation was determined and found to depend only on the degree of supercooling. The rate of R141b hydrate formation in the presence of a heat exchange fluid depended on the degree of supercooling according to the same rate equation as pure R141b with secondary dependence on salinity. Experiments demonstrated that a perfluorocarbon heat exchange fluid assisted separation of R141b hydrates from brine. Preliminary experiments using the guest species, difluoromethane, showed that hydrate formation rates were substantial at temperatures up to at least 12 C and demonstrated partial separation of water from brine. We present a detailed molecular picture of the structure and dynamics of R141b guest molecules within water cages, obtained from ab initio calculations, molecular dynamics simulations, and Raman spectroscopy. Density functional theory calculations were used to provide an energetic and molecular orbital description of R141b stability in both large and small cages in a structure II hydrate. Additionally, the hydrate of an isomer, 1,2-dichloro-1-fluoroethane, does not form at ambient conditions because of extensive overlap of electron density between guest and host. Classical molecular dynamics simulations and laboratory trials support the results for the isomer hydrate. Molecular dynamics simulations

  8. 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)


    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.

  9. Volatile inventories in clathrate hydrates formed in the primordial nebula. (United States)

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


    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

  10. Reaction coordinate of incipient methane clathrate hydrate nucleation. (United States)

    Barnes, Brian C; Knott, Brandon C; Beckham, Gregg T; Wu, David T; Sum, Amadeu K


    Nucleation from solution is a ubiquitous phenomenon with relevance to myriad scientific disciplines, including pharmaceuticals, biomineralization, and disease. One prominent example is the nucleation of clathrate hydrates, multicomponent crystalline inclusion compounds relevant to the energy industry where they block pipelines and also constitute a potential vast energy resource. Despite their importance, the molecular mechanism of incipient hydrate formation remains unknown. Herein, we employ advanced molecular simulation tools (pB histogram, equilibrium path sampling) to provide a statistical-mechanical basis for extracting physical insight into the molecular steps by which clathrates form. Through testing the Mutually Coordinated Guest (MCG) order parameter, we demonstrate that both guest (methane) and host (water) structuring are crucial to accurately describe the nucleation of hydrates and determine a critical nucleus size of MCG-1 = 16 at 255 K and 500 bar. Equipped with a validated (and novel) reaction coordinate, subsequent equilibrium path sampling simulations yield the free energy barrier and nucleation rate. The resulting quantitative nucleation process is described by the MCG clustering mechanism. This constitutes a significant advance in the field of hydrates research, as the fitness of a molecular descriptor has never been statistically verified. More broadly, this work has significance to a wide range of multicomponent nucleation contexts wherein the formation mechanism depends on contributions from both solute and solvent.

  11. Complex admixtures of clathrate hydrates in a water desalination method (United States)

    Simmons, Blake A [San Francisco, CA; Bradshaw, Robert W [Livermore, CA; Dedrick, Daniel E [Berkeley, CA; Anderson, David W [Riverbank, CA


    Disclosed is a method that achieves water desalination by utilizing and optimizing clathrate hydrate phenomena. Clathrate hydrates are crystalline compounds of gas and water that desalinate water by excluding salt molecules during crystallization. Contacting a hydrate forming gaseous species with water will spontaneously form hydrates at specific temperatures and pressures through the extraction of water molecules from the bulk phase followed by crystallite nucleation. Subsequent dissociation of pure hydrates yields fresh water and, if operated correctly, allows the hydrate-forming gas to be efficiently recycled into the process stream.

  12. Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition. (United States)

    Alavi, Saman; Ripmeester, J A


    Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

  13. The strength and rheology of methane clathrate hydrate (United States)

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


    Methane clathrate hydrate (structure I) is found to be very strong, based on laboratory triaxial deformation experiments we have carried out on samples of synthetic, high-purity, polycrystalline material. Samples were deformed in compressional creep tests (i.e., constant applied stress, ??), at conditions of confining pressure P = 50 and 100 MPa, strain rate 4.5 ?? 10-8 ??? ?? ??? 4.3 ?? 10-4 s-1, temperature 260 ??? T ??? 287 K, and internal methane pressure 10 ??? PCH4 ??? 15 MPa. At steady state, typically reached in a few percent strain, methane hydrate exhibited strength that was far higher than expected on the basis of published work. In terms of the standard high-temperature creep law, ?? = A??ne-(E*+PV*)/RT the rheology is described by the constants A = 108.55 MPa-n s-1, n = 2.2, E* = 90,000 J mol-1, and V* = 19 cm3 mol-1. For comparison at temperatures just below the ice point, methane hydrate at a given strain rate is over 20 times stronger than ice, and the contrast increases at lower temperatures. The possible occurrence of syntectonic dissociation of methane hydrate to methane plus free water in these experiments suggests that the high strength measured here may be only a lower bound. On Earth, high strength in hydrate-bearing formations implies higher energy release upon decomposition and subsequent failure. In the outer solar system, if Titan has a 100-km-thick near-surface layer of high-strength, low-thermal conductivity methane hydrate as has been suggested, its interior is likely to be considerably warmer than previously expected.

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

    Directory of Open Access Journals (Sweden)

    Beatrice Castellani


    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.

  15. Evaluation of the possible presence of clathrate hydrates in Europa's icy shell or seafloor (United States)

    Prieto-Ballesteros, Olga; Kargel, Jeffrey S.; Fernández-Sampedro, Maite; Selsis, Franck; Martínez, Eduardo Sebastián; Hogenboom, David L.


    lower salinity would allow all these clathrates to sink, except that CH 4 clathrate would still float. Many geological processes may be driven or affected by the formation, presence, and destruction of clathrates in Europa such as explosive cryomagmatic activity [Stevenson, D.J., 1982. Volcanism and igneous processes in small icy satellites. Nature 298, 142-144], partial differentiation of the crust driven by its clathration, or the local retention of heat within or beneath clathrate-rich layers because of the low thermal conductivity of clathrate hydrates [Ross, R.G., Kargel, J.S., 1998. Thermal conductivity of Solar System ices, with special reference to martian polar caps. In: Schmitt, B., De Berg, C., Festou, M. (Eds.), Solar System Ices. Kluwer Academic, Dordrecht, pp. 33-62]. On the surface, destabilization of these minerals and compounds, triggered by fracture decompression or heating could result in formation of chaotic terrain morphologies, a mechanism that also has been proposed for some martian chaotic terrains [Tanaka, K.L., Kargel, J.S., MacKinnon, D.J., Hare, T.M., Hoffman, N., 2002. Catastrophic erosion of Hellas basin rim on Mars induced by magmatic intrusion into volatile-rich rocks. Geophys. Res. Lett. 29 (8); Kargel, J.S., Prieto-Ballesteros, O., Tanaka K.L., 2003. Is clathrate hydrate dissociation responsible for chaotic terrains on Earth, Mars, Europa, and Triton? Geophys. Res. 5. Abstract 14252]. Models of the evolution of the ice shell of Europa might take into account the presence of clathrate hydrates because if gases are vented from the silicate interior to the water ocean, they first would dissolve in the ocean and then, if the gas concentrations are sufficient, may crystallize. If any methane releases occur in Europa by hydrothermal or biological activity, they also might form clathrates. Then, from both geological and astrobiological perspectives, future missions to Europa should carry instrumentation capable of clathrate hydrate detection.

  16. 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


    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.

  17. Vibrational Raman spectra of hydrogen clathrate hydrates from density functional theory (United States)

    Ramya, K. R.; Venkatnathan, Arun


    Hydrogen clathrate hydrates are promising sources of clean energy and are known to exist in a sII hydrate lattice, which consists of H2 molecules in dodecahedron (512) and hexakaidecahedron (51264) water cages. The formation of these hydrates which occur in extreme thermodynamic conditions is known to be considerably reduced by an inclusion of tetrahydrofuran (THF) in cages of these hydrate lattice. In this present work, we employ the density functional theory with a dispersion corrected (B97-D) functional to characterize vibrational Raman modes in the cages of pure and THF doped hydrogen clathrate hydrates. Our calculations show that the symmetric stretch of the H2 molecule in the 51264H2.THF cage is blueshifted compared to the 51264H2 cage. However, all vibrational modes of water molecules are redshifted which suggest reduced interaction between the H2 molecule and water molecules in the 51264H2.THF cage. The symmetric and asymmetric O-H stretch of water molecules in 512H2, 51264H2, and 51264H2.THF cages are redshifted compared with the corresponding guest free cages due to interactions between encapsulated H2 molecules and water molecules of the cages. The low frequency modes contain contributions from contraction and expansion of water cages and vibration of water molecules due to hydrogen bonding and these modes could possibly play an important role in the formation of the hydrate lattice.

  18. Phase Behaviour and Structural Aspects of Ternary Clathrate Hydrate Systems. The Role of Additives

    NARCIS (Netherlands)

    Mooijer-Van den Heuvel, M.M.


    In this study an experimental and modelling approach is applied to obtain fundamental insight into the phase behaviour of ternary systems, in which clathrate hydrates are formed. Proper interpretation of the phase behaviour requires knowledge on the clathrate hydrate structure in these systems,

  19. Permanent Sequestration of Emitted Gases in the Form of Clathrate Hydrates (United States)

    Duxbury, N.; Romanovsky, V.


    Underground sequestration has been proposed as a novel method of permanent disposal of harmful gases emitted into the atmosphere as a result of human activity. The method was conceived primarily for disposal of carbon dioxide (CO2, greenhouse gas causing global warming), but could also be applied to CO, H2S, NOx, and chorofluorocarbons (CFCs, which are super greenhouse gases). The method is based on the fact that clathrate hydrates (e.g., CO2 6H2O) form naturally from the substances in question (e.g., CO2) and liquid water in the pores of sub-permafrost rocks at stabilizing pressures and temperatures. The proposed method would be volumetrically efficient: In the case of CO2, each volume of hydrate can contain as much as 184 volumes of gas. Temperature and pressure conditions that favor the formation of stable clathrate hydrates exist in depleted oil reservoirs that lie under permafrost. For example, CO2-6H2O forms naturally at a temperature of 0 C and pressure of 1.22 MPa. Using this measurement, it has been calculated that the minimum thickness of continuous permafrost needed to stabilize CO2 clathrate hydrate is only about 100 m, and the base of the permafrost is known to be considerably deeper at certain locations (e.g., about 600 m at Prudhoe Bay in Alaska). In this disposal method, the permafrost layers over the reservoirs would act as impermeable lids that would prevent dissociation of the clathrates and diffusion of the evolved gases up through pores.

  20. Molecular Dynamics Simulations of Clathrate Hydrates on Specialised Hardware Platforms

    Directory of Open Access Journals (Sweden)

    Christian R. Trott


    Full Text Available Classical equilibrium molecular dynamics (MD simulations have been performed to investigate the computational performance of the Simple Point Charge (SPC and TIP4P water models applied to simulation of methane hydrates, and also of liquid water, on a variety of specialised hardware platforms, in addition to estimation of various equilibrium properties of clathrate hydrates. The FPGA-based accelerator MD-GRAPE 3 was used to accelerate substantially the computation of non-bonded forces, while GPU-based platforms were also used in conjunction with CUDA-enabled versions of the LAMMPS MD software packages to reduce computational time dramatically. The dependence of molecular system size and scaling with number of processors was also investigated. Considering performance relative to power consumption, it is seen that GPU-based computing is quite attractive.

  1. NH3 as unique non-classical content-former within clathrate hydrates. (United States)

    Maşlakcı, Zafer; Devlin, J Paul; Uras-Aytemiz, Nevin


    High quality FTIR spectra of aerosols of NH3-THF and NH3-TMO binary clathrate hydrates (CHs) have been measured. Our recently developed all-vapor sub-second approach to clathrate-hydrate formation combined with computational studies has been used to identify vibrational spectroscopic signatures of NH3 within the gas hydrates. The present study shows that there are three distinct NH3 types, namely, classical small-cage NH3, nonclassical small-cage NH3, and NH3 within the hydrate network. The network ammonia does not directly trigger the non-classical CH structure. Rather, the ammonia within the network structure perturbs the water bonding, introducing orientational defects that are stabilized by small and/or large cage guest molecules through H-bonding. This unusual behavior of NH3 within CHs opens a possibility for catalytic action of NH3 during CH-formation. Furthermore, impacts over time of the small-cage NH3-replacement molecules CO2 and CH4 on the structure and composition of the ternary CHs have been noted.

  2. Massively parallel molecular dynamics simulation of formation of clathrate-hydrate precursors at planar water-methane interfaces: insights into heterogeneous nucleation. (United States)

    English, Niall J; Lauricella, Marco; Meloni, Simone


    The formation of methane-hydrate precursors at large planar water-methane interfaces has been studied using massively parallel molecular dynamics in systems of varying size from around 10 000 to almost 7 × 10(6) molecules. This process took two distinct steps. First, the concentration of solvated methane clusters increases just inside the aqueous domain via slow diffusion from the methane-water interface, forming "clusters" of solvated methane molecules. Second, the re-ordering process of solvated methane and water molecules takes place in a manner very roughly consistent with the "blob" hypothesis, although with important differences, to form hydrate precursors, necessary for subsequent hydrate nucleation and crystallisation. It was found that larger system sizes serve to promote the formation rate of precursors.

  3. Meso-Scale Clathrate Experiments: Effect of Grain Size on Formation Pathways (United States)

    Leeman, J. R.; Elwood-Madden, M.; Alford, J.; Phelps, T. J.; Rawn, C.


    Clathrates, or gas hydrates result from a guest gas molecule populating a cavity in a cage of water molecules. Gas hydrates naturally occur on Earth under low temperature and moderate pressure environments such as seafloor or permafrost sediments. Gas hydrates are a large sink of methane, a major greenhouse gas and a possible energy reserve. A release from these reservoirs has been hypothesized to have had a major role in climate change throughout geologic time as clathrates are sensitive to pressure and temperature. Hydrates can also be used as a storage technology for both transport and sequestration of carbon. To properly utilize hydrates a thorough understanding of formation characteristics/preferences is essential. Gas hydrates are predicted to show a preference of forming in materials with a large grain size. Verification of this model could aid prediction of natural clathrate reservoirs and make methane production from hydrates economically viable. Predicting the location and extent of clathrate reservoirs throughout geologic time will also aid paleo-climate modeling and improve the accuracy of models of modern global change A mesoscale gas hydrate formation experiment was designed within ORNL’s Seafloor Process Simulator (SPS) to determine how sediment grain-size and synthetic mesh planes affect hydrate formation pathways. The 72-liter pressure vessel was fitted with a sediment column which was vertically split with one-half of the cylindrical vessel containing sand of 500 microns and half containing silt of 65 microns. Inside the column a diffuser injected gas into both sediments at equal flow rates and the formation of clathrate was tracked with both ‘bulk’ pressure/temperature data from the vessel and via approximately 150 sensors embedded in each of four fiber optic planes, which were placed at four levels in the sediment column. Experiments concluded that clathrate formation is more likely to occur in coarse materials due to the high porosity and

  4. Preservation of carbon dioxide clathrate hydrate in the presence of trehalose under freezer conditions (United States)

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


    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.

  5. Preservation of carbon dioxide clathrate hydrate in the presence of trehalose under freezer conditions. (United States)

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


    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.

  6. Thermodynamic Properties of Hydrogen + Tetra-n-Butyl Ammonium Bromide Semi-Clathrate Hydrate

    Directory of Open Access Journals (Sweden)

    Shunsuke Hashimoto


    Full Text Available Thermodynamic stability and hydrogen occupancy on the hydrogen + tetra-n-butyl ammonium bromide semi-clathrate hydrate were investigated by means of Raman spectroscopic and phase equilibrium measurements under the three-phase equilibrium condition. The structure of mixed gas hydrates changes from tetragonal to another structure around 95 MPa and 292 K depending on surrounding hydrogen fugacity. The occupied amount of hydrogen in the semi-clathrate hydrate increases significantly associated with the structural transition. Tetra-n-butyl ammonium bromide semi-clathrate hydrates can absorb hydrogen molecules by a pressure-swing without destroying the hydrogen bonds of hydrate cages at 15 MPa or over.

  7. On the application of binary correction factors in lattice distortion calculations for methane clathrate hydrates (United States)

    Lasich, Matthew; Mohammadi, Amir H.; Bolton, Kim; Vrabec, Jadran; Ramjugernath, Deresh


    The lattice distortion theory of Zele and co-workers is an attractive method for amending calculated phase equilibria of clathrate hydrates, since only two molecular computations are required. The perturbation energy between the empty and loaded clathrate hydrate lattice is the quantity of interest. The effect of binary correction factors applied to the Lorentz and Berthelot combining rules for the intermolecular interaction between gas and water particles is investigated. There are clear trends for the perturbation energy and lattice constant in terms of the binary correction factors, although there is significant sensitivity to the force field parameterization of the gas species.

  8. Selective occupancy of methane by cage symmetry in TBAB ionic clathrate hydrate. (United States)

    Muromachi, Sanehiro; Udachin, Konstantin A; Alavi, Saman; Ohmura, Ryo; Ripmeester, John A


    Methane trapped in the two distinct dodecahedral cages of the ionic clathrate hydrate of TBAB was studied by single crystal XRD and MD simulation. The relative CH4 occupancies over the cage types were opposite to those of CO2, which illustrates the interplay between the cage symmetry and guest shape and dynamics, and thus the gas selectivity.

  9. Measurement of Clathrate Hydrate Thermodynamic Stability in the Presence of Ammonia (United States)

    Dunham, Marc


    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.

  10. Raman spectra of vibrational and librational modes in methane clathrate hydrates using density functional theory (United States)

    Ramya, K. R.; Pavan Kumar, G. V.; Venkatnathan, Arun


    The sI type methane clathrate hydrate lattice is formed during the process of nucleation where methane gas molecules are encapsulated in the form of dodecahedron (512CH4) and tetrakaidecahedron (51262CH4) water cages. The characterization of change in the vibrational modes which occur on the encapsulation of CH4 in these cages plays a key role in understanding the formation of these cages and subsequent growth to form the hydrate lattice. In this present work, we have chosen the density functional theory (DFT) using the dispersion corrected B97-D functional to characterize the Raman frequency vibrational modes of CH4 and surrounding water molecules in these cages. The symmetric and asymmetric C-H stretch in the 512CH4 cage is found to shift to higher frequency due to dispersion interaction of the encapsulated CH4 molecule with the water molecules of the cages. However, the symmetric and asymmetric O-H stretch of water molecules in 512CH4 and 51262CH4 cages are shifted towards lower frequency due to hydrogen bonding, and interactions with the encapsulated CH4 molecules. The CH4 bending modes in the 512CH4 and 51262CH4 cages are blueshifted, though the magnitude of the shifts is lower compared to modes in the high frequency region which suggests bending modes are less affected on encapsulation of CH4. The low frequency librational modes which are collective motion of the water molecules and CH4 in these cages show a broad range of frequencies which suggests that these modes largely contribute to the formation of the hydrate lattice.

  11. Micro-Tomographic Investigation of Ice and Clathrate Formation and Decomposition under Thermodynamic Monitoring

    Directory of Open Access Journals (Sweden)

    Stefan Arzbacher


    Full Text Available Clathrate hydrates are inclusion compounds in which guest molecules are trapped in a host lattice formed by water molecules. They are considered an interesting option for future energy supply and storage technologies. In the current paper, time lapse 3D micro computed tomographic (µCT imaging with ice and tetrahydrofuran (THF clathrate hydrate particles is carried out in conjunction with an accurate temperature control and pressure monitoring. µCT imaging reveals similar behavior of the ice and the THF clathrate hydrate at low temperatures while at higher temperatures (3 K below the melting point, significant differences can be observed. Strong indications for micropores are found in the ice as well as the THF clathrate hydrate. They are stable in the ice while unstable in the clathrate hydrate at temperatures slightly below the melting point. Significant transformations in surface and bulk structure can be observed within the full temperature range investigated in both the ice and the THF clathrate hydrate. Additionally, our results point towards an uptake of molecular nitrogen in the THF clathrate hydrate at ambient pressures and temperatures from 230 K to 271 K.

  12. Clathrate hydrates as possible source of episodic methane releases on Mars (United States)

    Karatekin, Özgür; Gloesener, Elodie; Temel, Orkun


    Methane has been shown to vary with location and time in the Martian atmosphere, with abundances of up to tens of parts-per-billion by volume (ppbv). Since methane is short-lived on geological time scales, its presence implies the existence of an active, current source of methane that is yet to be understood. In this study we investigate the destabilization of subsurface reservoirs of clathrate hydrates as a possible geological source of methane. Clathrate hydrates are crystalline compounds constituted by cages of hydrogen-bonded water molecules, inside of which guest gas molecules are trapped. We show the present-day maps of methane clathrate stability zones, in particular in the vicinity of Gale Crater where the Sample Analysis at Mars (SAM) suite on the Curiosity rover has made in situ measurements of atmospheric methane, during more than 3 years. Curiosity has observed spikes of elevated methane levels of 7 ppbv on four sequential observations over a 2-month period. The possibility of episodic releases consistent with curiosity observations from a subsurface clathrate source, is investigated using a gas transport through porous Martian regolith considering different depths of reservoirs. Transport of the released methane spike into the atmosphere is simulated using the PlanetWRF model.

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

  14. Molecular mechanism of formation of the face-sharing double cages in structure-I methane hydrate (United States)

    Liu, Jinxiang; Hou, Jian; Liu, Haiying; Liu, Mengyuan; Xu, Jiafang; Chen, Gang; Zhang, Jun


    Despite the potential applications and ubiquity of clathrate hydrates, the molecular mechanism of formation of these compounds is not yet well-understood. In this work, the formation mechanism of the face-sharing double cages in structure-I hydrate was studied by density functional theory calculations, which is responsible to the hydrate nucleation and growth. The results show that the clathrate cages favor to form one after another, and the 512 cages are thermodynamically feasible in the beginning. The water-water and water-methane interactions mostly dominate the formation of the clathrate cages, while the methane-methane interactions have little effect on the formation process.

  15. Search for memory effects in methane hydrate: structure of water before hydrate formation and after hydrate decomposition. (United States)

    Buchanan, Piers; Soper, Alan K; Thompson, Helen; Westacott, Robin E; Creek, Jefferson L; Hobson, Greg; Koh, Carolyn A


    Neutron diffraction with HD isotope substitution has been used to study the formation and decomposition of the methane clathrate hydrate. Using this atomistic technique coupled with simultaneous gas consumption measurements, we have successfully tracked the formation of the sI methane hydrate from a water/gas mixture and then the subsequent decomposition of the hydrate from initiation to completion. These studies demonstrate that the application of neutron diffraction with simultaneous gas consumption measurements provides a powerful method for studying the clathrate hydrate crystal growth and decomposition. We have also used neutron diffraction to examine the water structure before the hydrate growth and after the hydrate decomposition. From the neutron-scattering curves and the empirical potential structure refinement analysis of the data, we find that there is no significant difference between the structure of water before the hydrate formation and the structure of water after the hydrate decomposition. Nor is there any significant change to the methane hydration shell. These results are discussed in the context of widely held views on the existence of memory effects after the hydrate decomposition.

  16. Experimental Studies of the Growth Kinetics of Methane Clathrate Hydrates & Superfluid Hydrodynamics on the Nanoscale (United States)

    Botimer, Jeffrey David

    This thesis details the experimental findings of three distinct research projects. The first studies the growth kinetics of methane clathrate hydrates grown under the influence of multiple factors including surfactants, porous media, substrate wetting properties, and salt content. The second investigates the flow behaviors of superfluid helium through single, high aspect ratio nanopipes. The third models the frequency response of a quartz tuning fork in high pressure normal and superfluid helium and demonstrates how quartz tuning forks can be used as cheap, small, in situ, cryogenic pressure gauges. The first project reports studies of the kinetics of growth of methane hydrates from liquid water containing small amounts of surfactant (water and solid phase in the reaction vessel, or in situ micro-Raman measurements or in situ NMR measurements. These diagnostics show that the uptake of methane and the conversion of liquid water to a solid phase do not occur simultaneously; the uptake of gas always lags the visual and spectroscopic signatures of the disappearance of liquid water and the formation of solid. The evidence suggests that the SDS causes water to form an intermediate immobile solid-like state before combining with the methane to form hydrate. The growth mechanism is related to the surfactant and disappears for low SDS concentrations (pipe lengths (1-30mm), and pipe radii (130--230nm). As a function of pressure we observe two distinct flow regimes above and below a critical pressure Pc. For P The second project studies pressure driven flow of superfluid helium through single high aspect ratio glass nanopipes into a vacuum has been studied for a wide range of pressure drop (0--30 atm), reservoir temperature (0.8--2.5K), pipe lengths (1--30mm), and pipe radii (130--230nm). As a function of pressure we observe two distinct flow regimes above and below a critical pressure Pc. For P.

  17. 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.


    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......, and the residuals of a selected correlation results lead to define the probable outliers. This method not only contributes to outliers diagnostics but also identifies the range of applicability of the applied model and quality of the existing experimental data. The available correlation in the literature...... 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...

  18. Major occurrences and reservoir concepts of marine clathrate hydrates: Implications of field evidence (United States)

    Booth, J.S.; Winters, W.J.; Dillon, William P.; Clennell, M.B.; Rowe, M.M.


    This paper is part of the special publication Gas hydrates: relevance to world margin stability and climatic change (eds J.P. Henriet and J. Mienert). Questions concerning clathrate hydrate as an energy resource, as a factor in modifying global climate and as a triggering mechanism for mass movements invite consideration of what factors promote hydrate concentration, and what the quintessential hydrate-rich sediment may be. Gas hydrate field data, although limited, provide a starting point for identifying the environments and processes that lead to more massive concentrations. Gas hydrate zones are up to 30 m thick and the vertical range of occurrence at a site may exceed 200 m. Zones typically occur more than 100m above the phase boundary. Thicker zones are overwhelmingly associated with structural features and tectonism, and often contain sand. It is unclear whether an apparent association between zone thickness and porosity represents a cause-and-effect relationship. The primary control on the thickness of a potential gas hydrate reservoir is the geological setting. Deep water and low geothermal gradients foster thick gas hydrate stability zones (GHSZs). The presence of faults, fractures, etc. can favour migration of gas-rich fluids. Geological processes, such as eustacy or subsidence, may alter the thickness of the GHSZ or affect hydrate concentratiion. Tectonic forces may promote injection of gas into the GHSZ. More porous and permeable sediment, as host sediment properties, increase storage capacity and fluid conductivity, and thus also enhance reservoir potential.

  19. The HD molecule in small and medium cages of clathrate hydrates: Quantum dynamics studied by neutron scattering measurements and computation

    Energy Technology Data Exchange (ETDEWEB)

    Colognesi, Daniele; Celli, Milva; Ulivi, Lorenzo, E-mail: [Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi, via Madonna del Piano 10, I-50019 Sesto Fiorentino (Italy); Powers, Anna; Xu, Minzhong [Department of Chemistry, New York University, New York, New York 10003 (United States); Bačić, Zlatko, E-mail: [Department of Chemistry, New York University, New York, New York 10003 (United States); NYU-ECNU Center for Computational Chemistry at NYU Shanghai, Shanghai 200062 (China)


    We report inelastic neutron scattering (INS) measurements on molecular hydrogen deuteride (HD) trapped in binary cubic (sII) and hexagonal (sH) clathrate hydrates, performed at low temperature using two different neutron spectrometers in order to probe both energy and momentum transfer. The INS spectra of binary clathrate samples exhibit a rich structure containing sharp bands arising from both the rotational transitions and the rattling modes of the guest molecule. For the clathrates with sII structure, there is a very good agreement with the rigorous fully quantum simulations which account for the subtle effects of the anisotropy, angular and radial, of the host cage on the HD microscopic dynamics. The sH clathrate sample presents a much greater challenge, due to the uncertainties regarding the crystal structure, which is known only for similar crystals with different promoter, but nor for HD (or H{sub 2}) plus methyl tert-butyl ether (MTBE-d12)

  20. 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. ... the hydrate formation operating conditions (temperature and pressure) including drawing the logarithm of pressure changes curve in terms of gas temperature which is one of the most common ...

  1. Modeling the THF clathrate hydrate dynamics by combining molecular dynamics and quasi-elastic neutron scattering (United States)

    Pefoute, Eric; Martin-Gondre, Ludovic; Ollivier, Jacques; Soetens, Jean-Christophe; Russina, Margarita; Desmedt, Arnaud


    The dynamics of the THF molecule encapsulated in the type II clathrate hydrate matches the MD-QENS observation time (typically 0.1-10 ps) between 100 K and 270 K. Spatial and time characteristics of the THF molecule's dynamics obtained by means of MD simulations are in agreement with those experimentally determined by means of quasielastic neutron scattering. A detailed model of the THF dynamics is then proposed through the calculations of MD-derived properties. Reorientational relaxation has been observed on a timescale of 0.7 ± 0.1 ps at 270 K with activation energy of 3.0 ± 0.3 kJ/mol in addition to a highly damped rotational excitation occurring in the plane of the THF molecule with a period of ca. 2 ps. Moreover, the anisotropic cage energy landscape of the THF clathrate hydrate is revealed through a comprehensive investigation of THF orientational distribution functions, revealing the occurrence of preferred orientation of the THF molecule within the cage.

  2. Global-density fluctuations in methane clathrate hydrates in externally applied electromagnetic fields (United States)

    Waldron, Conor J.; English, Niall J.


    Non-equilibrium molecular-dynamics simulations of bulk methane clathrate hydrates have been conducted in a range of externally applied electromagnetic (e/m) fields. Studies into frequencies of system(or "global")-mass-density fluctuations showed that these clathrates have three major modes: the dominant one is attributable to water molecules' librations and occurs at 720 cm-1, regardless of any applied e/m fields. One of the more minor system-density fluctuations arises at 10-12 cm-1 and is caused by the propagation of local-density fluctuations; again, this is independent of e/m fields. The final density fluctuation is caused by e/m fields, and it only becomes apparent for field strengths of 1.2 V/nm or higher. The frequency of this mode is always twice the frequency of the applied e/m field. It was shown that the main qualitative features of the translational and librational densities of states (DOSs) were unaffected by the application of e/m fields; however, a slight coupling effect was observed, producing a peak in all DOSs at the frequency of the applied field. This study showed that e/m fields below a certain intensity threshold do not lead to any marked structural distortion or dissociation effect on pre-existing bulk clathrates, in which the hydrogen-bonding structure of the lattice remains intact. This is verified by system-density and configurational-energy values as well as radial distribution functions.

  3. 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.


    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

  4. Kinetics measurements and in situ Raman spectroscopy of formation of hydrogen-tetrabutylammonium bromide semi-hydrates

    NARCIS (Netherlands)

    Trueba, A.T.; Radović, I.R.; Zevenbergen, J.F.; Kroon, M.C.; Peters, C.J.


    The kinetics of formation of H2-TBAB semi-clathrate hydrates was studied in this work in order to elucidate their potential for H2 storage. The influence of pressure (5-16 MPa), TBAB concentration (2.6 mol% and 3.7 mol%) and formation method (T-cycle method and T-constant method) on the hydrate

  5. Benzene solubility in ionic liquids: working toward an understanding of liquid clathrate formation. (United States)

    Pereira, Jorge F B; Flores, Luis A; Wang, Hui; Rogers, Robin D


    The solubility of benzene in 15 imidazolium, pyrrolidinium, pyridinium, and piperidinium ionic liquids has been determined; the resulting, benzene-saturated ionic liquid solutions, also known as liquid clathrates, were examined with (1) H and (19) F nuclear magnetic resonance spectroscopy to try and understand the molecular interactions that control liquid clathrate formation. The results suggest that benzene interacts primarily with the cation of the ionic liquid, and that liquid clathrate formation (and benzene solubility) is controlled by the strength of the cation-anion interactions, that is, the stronger the cation-anion interaction, the lower the benzene solubility. Other factors that were determined to be important in the final amount of benzene in any given liquid clathrate phase included attractive interactions between the anion and benzene (when significant), and larger steric or free volume demands of the ions, both of which lead to greater benzene solubility. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Molecular storage of ozone in a clathrate hydrate: an attempt at preserving ozone at high concentrations.

    Directory of Open Access Journals (Sweden)

    Takahiro Nakajima

    Full Text Available This paper reports an experimental study of the formation of a mixed O(3+ O(2+ CO(2 hydrate and its frozen storage under atmospheric pressure, which aimed to establish a hydrate-based technology for preserving ozone (O(3, a chemically unstable substance, for various industrial, medical and consumer uses. By improving the experimental technique that we recently devised for forming an O(3+ O(2+ CO(2 hydrate, we succeeded in significantly increasing the fraction of ozone contained in the hydrate. For a hydrate formed at a system pressure of 3.0 MPa, the mass fraction of ozone was initially about 0.9%; and even after a 20-day storage at -25°C and atmospheric pressure, it was still about 0.6%. These results support the prospect of establishing an economical, safe, and easy-to-handle ozone-preservation technology of practical use.

  7. Determining the flux of methane into Hudson Canyon at the edge of methane clathrate hydrate stability (United States)

    Weinsten, A.; Navarrete, L; Ruppel, Carolyn D.; Weber, T.C.; Leonte, M.; Kellermann, M.; Arrington, E.; Valentine, D.L.; Scranton, M.L; Kessler, John D.


    Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern US Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady-state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6 – 24 kmol methane per day). These analyses suggest this methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH. This article is protected by copyright. All rights reserved.

  8. Rapid gas hydrate formation process (United States)

    Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.


    The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

  9. Effects of Water in Synthetic Lubricant Systems and Clathrate Formation: A Literature Search and Review

    Energy Technology Data Exchange (ETDEWEB)

    Rohatgi, Ngoc Dung T.


    An extensive literature search and a confidential survey were critically analyzed to determine the effects of water on the stability of hydrofluorocarbon/synthetic lubricant systems and to identify key areas requiring further investigation. Following are highlights from the analysis: Clathrate hydrates are solid solutions formed when water molecules are linked through hydrogen bonding creating cavities that can enclose various guest molecules from hydrate formers, such as hydrofluorocarbons R-32, R-125, R-134a, R-407C and R-410A. The four methods for preventing clathrate formation were drying the gas, heating it, reducing its pressure, or using inhibitors. The hydrolysis of polyolester lubricants was mostly acid-catalyzed and its reaction rate constant typically followed the Arrhenius equation of an activated process. Hydrolytic stability improved with hindered molecular structures, and with the presence of acid catcher additives and desiccants. Water vapor can effect the adsorption of long-chain fatty acids and the chemistry of formation of protective oxide film. However, these effects on lubrication can be either positive or negative. Fifty to sixty percent of the moisture injected into an air-conditioning system remained in the refrigerant and the rest mixed with the compressor oil. In an automotive air-conditioning system using R-134a, ice would form at 0 C evaporating temperature when the water content in the vapor refrigerant on the low-pressure side was more than 350 ppm. Moisture would cause the embrittlement of polyethylene terephthalate and the hydrolysis of polyesters, but would reduce the effect of amine additives on fluoroelastomer rubbers. The reactions of water with refrigerants and lubricants would cause formicary and large-pit corrosion in copper tubes, as well as copper plating and sludge formation. Moreover, blockage of capillary tubes increased rapidly in the presence of water. Twenty-four companies responded to the survey. From the responses

  10. The Early Development of Inorganic Clathrates (United States)

    Pouchard, Michel; Cros, Christian

    In this chapter the authors relate the discovery of the first inorganic clathrates, Na8Si46 and NaxSi136 (3 ≤ x ≤ 11), whose cage-like structures were determined by comparison with those of the two most classical gas and liquid clathrate hydrates. The main characteristics of clathrate compounds are recalled and a brief review of clathrate hydrates is given. The different polyhedral cages and their arrangements in the so-called type I structure (Na8Si46) and type II structure (NaxSi136) are described in details. The synthesis, composition and structure of other inorganic clathrates of silicon, germanium and tin with potassium, rubidium and cesium as guest atoms are reported. The crystal structure (type I or type II) and corresponding composition is closely related to the size of the guest alkali atoms. The formation of the characteristic polyhedral cages with a majority of pentagonal faces is discussed, and results from the arrangement of all the tetrahedrons in eclipsed position. The relation between clathrate structures and those of clathrasils (silica-based clathrates), Frank-Kasper alloys and fullerene forms of carbon is also discussed. The first measurements of the physical properties of inorganic clathrates are reviewed, including electrical conductivity, thermal properties, high pressure behavior, NMR and ESR investigations. The ability for the silicon, germanium and tin host lattices to form non-stoichiometric and mixed frameworks with elements of neighboring groups is briefly described, giving rise to a large variety of new inorganic clathrates with ionic guest-host interactions and semiconducting properties.

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

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


    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.

  12. Proton dynamics in the perchloric acid clathrate hydrate HClO4.5.5H2O. (United States)

    Desmedt, Arnaud; Stallmach, Frank; Lechner, Ruep E; Cavagnat, Dominique; Lassègues, Jean-Claude; Guillaume, François; Grondin, Joseph; Gonzalez, Miguel A


    In the perchloric acid clathrate hydrate HClO4.5.5H2O, the perchlorate anions are contained inside an aqueous host crystalline matrix, positively charged because of the presence of delocalized acidic protons. Our experimental results demonstrate that the microscopic mechanisms of proton conductivity in this system are effective on a time scale ranging from nanosecond to picosecond. In the present paper, we discuss more specifically on the relaxation processes occurring on a nanosecond time scale by combining high-resolution quasielastic neutron scattering and 1H pulse-field-gradient nuclear magnetic resonance experiments. The combination of these two techniques allows us to probe proton dynamics in both space and time domains. The existence of two types of proton dynamical processes has been identified. The slowest one is associated to long-range translational diffusion of protons between crystallographic oxygen sites and has been precisely characterized with a self-diffusion coefficient of 3.5 x 10(-8) cm2/s at 220 K and an activation energy of 29.2+/-1.4 kJ/mol. The fastest dynamical process is due to water molecules' reorientations occurring every 0.7 ns at 220 K with an activation energy of 17.4+/-1.5 kJ/mol. This powerful multitechnique approach provides important information required to understand the microscopic origin of proton transport in an ionic clathrate hydrate. (c) 2004 American Institute of Physics

  13. Competing quantum effects in the free energy profiles and diffusion rates of hydrogen and deuterium molecules through clathrate hydrates. (United States)

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


    Clathrate hydrates hold considerable promise as safe and economical materials for hydrogen storage. Here we present a quantum mechanical study of H2 and D2 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 H2 and D2 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 H2 and D2 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.

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

    CERN Document Server

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


    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 profoundly affected by competing quantum effects: above 25 K, zero-point energy (ZPE) perpendicular to the reaction path for diffusion between cavities decreases the ...

  15. New Insights on Gas Hydroquinone Clathrates Using in Situ Raman Spectroscopy: Formation/Dissociation Mechanisms, Kinetics, and Capture Selectivity. (United States)

    Coupan, Romuald; Péré, Eve; Dicharry, Christophe; Torré, Jean-Philippe


    Hydroquinone (HQ) is known to form organic clathrates with different gaseous species over a wide range of pressures and temperatures. However, the enclathration reaction involving HQ is not fully understood. This work offers new elements of understanding HQ clathrate formation and dissociation mechanisms. The kinetics and selectivity of the enclathration reaction were also investigated. The focus was placed on HQ clathrates formed with CO2 and CH4 as guest molecules for potential use in practical applications for the separation of a CO2/CH4 gas mixture. The structural transition from the native form (α-HQ) to the clathrate form (β-HQ), as well as the reverse process, were tracked using in situ Raman spectroscopy. The clathrate formation was conducted at 323 K and 3.0 MPa, and the dissociation was conducted at 343 K and 1.0 kPa. The experiments with CH4 confirmed that a small amount of gas can fill the α-HQ before the phase transition from α- to β-HQ begins. The dissociation of the CO2-HQ clathrates highlighted the presence of a clathrate structure with no guest molecules. We can therefore conclude that HQ clathrate formation and dissociation are two-step reactions that pass through two distinct reaction intermediates: guest-loaded α-HQ and guest-free β-HQ. When an equimolar CO2/CH4 gas mixture is put in contact with either the α-HQ or the guest-free β-HQ, the CO2 is preferentially captured. Moreover, the guest-free β-HQ can retain the CO2 quicker and more selectively.

  16. Phase Behaviour, Thermodynamics and Kinetics of Clathrate Hydrate Systems of Carbon Dioxide in Presence of Tetrahydrofuran and Electrolytes

    NARCIS (Netherlands)

    Mohamad Sabil, K. Bin


    In view of the possibilities for new development of carbon dioxide hydrate processes, this study focused on experimental measurements to obtain fundamental insight into the phase behaviour and the kinetic of formation of carbon dioxide hydrate forming systems. These data are essential for the

  17. Kinetic measurements and in situ Raman spectroscopy study of the formation of TBAF semi-hydrates with hydrogen and carbon dioxide

    NARCIS (Netherlands)

    Trueba, A.T.; Radović, I.R.; Zevenbergen, J.F.; Peters, C.J.; Kroon, M.C.


    The kinetics of formation of semi-clathrate hydrates of tetra n-butyl ammonium fluoride (TBAF) with hydrogen (H2) and carbon dioxide (CO2) were studied in order to elucidate their potential for H 2 storage as well as for CO2 sequestration. The influence of pressure, TBAF concentration (1.8 mol% and

  18. Study of hydrogen-molecule guests in type II clathrate hydrates using a force-matched potential model parameterised from ab initio molecular dynamics (United States)

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


    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.

  19. Understanding Carbon Dioxide Solubility in Ionic Liquids by Exploring the Link with Liquid Clathrate Formation. (United States)

    Kelley, Steven P; Flores, Luis A; Shannon, Matthew S; Bara, Jason E; Rogers, Robin D


    The solubilities of the quadrupolar molecules benzene and CO2 in various ionic liquids (ILs) are compared in order to determine the connection between aromatic liquid clathrate formation and CO2 dissolution in ILs. It was found that both CO2 Henry's law constants and benzene solubility are remarkably well correlated with each other and with IL molar volume, suggesting both phenomena depend more on the strength of interionic interactions between the ions of an IL rather than the identity of either ion. However, IL ion-quadrupole interactions were found to have an effect for dicyanamide ([N(CN)2 ]- ), where solubility of CO2 and benzene are affected by destabilizing and stabilizing interactions with [N(CN)2 ]- , respectively. The results suggest both solubility phenomena are related to the incorporation of the solute into an IL host network. Aromatic liquid clathrate formation thus has potential as a facile experimental probe for predicting the relative ability of ILs to physisorb CO2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Massively-Parallel Molecular Dynamics Simulation of Clathrate Hydrates on Blue Gene Platforms

    Directory of Open Access Journals (Sweden)

    Niall J. English


    Full Text Available Massively-parallel classical equilibrium molecular dynamics (MD simulations have been performed to investigate the computational performance of the Simple Point Charge (SPC model and single-particle model of Molinero et al. applied to simulation of methane hydrates, using systems consisting of several million particles, on a variety of Blue Gene/L, P and Q platforms. It was found that the newer Blue Gene/Q platform offers attractive performance for massively-parallel simulation.

  1. Influence of temperature on methane hydrate formation. (United States)

    Zhang, Peng; Wu, Qingbai; Mu, Cuicui


    During gas hydrate formation process, a phase transition of liquid water exists naturally, implying that temperature has an important influence on hydrate formation. In this study, methane hydrate was formed within the same media. The experimental system was kept at 1.45, 6.49, and 12.91 °C respectively, and then different pressurization modes were applied in steps. We proposed a new indicator, namely the slope of the gas flow rates against time (dν g /dt), to represent the intrinsic driving force for hydrate formation. The driving force was calculated as a fixed value at the different stages of formation, including initial nucleation/growth, secondary nucleation/growth, and decay. The amounts of gas consumed at each stage were also calculated. The results show that the driving force during each stage follows an inverse relation with temperature, whereas the amount of consumed gas is proportional to temperature. This opposite trend indicates that the influences of temperature on the specific formation processes and final amounts of gas contained in hydrate should be considered separately. Our results also suggest that the specific ambient temperature under which hydrate is formed should be taken into consideration, when explaining the formation of different configurations and saturations of gas hydrates in natural reservoirs.

  2. 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


    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.

  3. [In situ Raman spectroscopic observation of micro-processes of methane hydrate formation and dissociation]. (United States)

    Liu, Chang-Ling; Ye, Yu-Guang; Meng, Qing-Guo; Lü, Wan-Jun; Wang, Fei-Fei


    Micro laser Raman spectroscopic technique was used for in situ observation of the micro-processes of methane hydrate formed and decomposed in a high pressure transparent capillary. The changes in clathrate structure of methane hydrate were investigated during these processes. The results show that, during hydrate formation, the Raman peak (2 917 cm(-1)) of methane gas gradually splits into two peaks (2 905 and 2 915 cm(-1)) representing large and small cages, respectively, suggesting that the dissolved methane molecules go into two different chemical environments. In the meantime, the hydrogen bonds interaction is strengthened because water is changing from liquid to solid state gradually. As a result, the O-H stretching vibrations of water shift to lower wavenumber. During the decomposition process of methane hydrates, the Raman peaks of the methane molecules both in the large and small cages gradually clear up, and finally turn into a single peak of methane gas. The experimental results show that laser Raman spectroscopy can accurately demonstrate some relevant information of hydrate crystal structure changes during the formation and dissociation processes of methane hydrate.

  4. Surfactant effects on SF6 hydrate formation. (United States)

    Lee, Bo Ram; Lee, Ju Dong; Lee, Hyun Ju; Ryu, Young Bok; Lee, Man Sig; Kim, Young Seok; Englezos, Peter; Kim, Myung Hyun; Kim, Yang Do


    Sulfur hexafluoride (SF(6)) has been widely used in a variety of industrial processes, but it is one of the most potent greenhouse gases. For this reason, it is necessary to separate or collect it from waste gas streams. One separation method is through hydrate crystal formation. In this study, SF(6) hydrate was formed in aqueous surfactant solutions of 0.00, 0.01, 0.05, 0.15 and 0.20 wt% to investigate the effects of surfactants on the hydrate formation rates. Three surfactants, Tween 20 (Tween), sodium dodecyl sulfate (SDS) and linear alkyl benzene sulfonate (LABS), were tested in a semi-batch stirred vessel at the constant temperature and pressures of 276.2 K and 0.78 MPa, respectively. All surfactants showed kinetic promoter behavior for SF(6) hydrate formation. It was also found that SF(6) hydrate formation proceeded in two stages with the second stage being the most rapid. In situ Raman spectroscopy analysis revealed that the increased gas consumption rate with the addition of surfactant was possibly due to the increased gas filling rate in the hydrate cavity.

  5. Experimental Investigation of Effect on Hydrate Formation in Spray Reactor

    Directory of Open Access Journals (Sweden)

    Jianzhong Zhao


    Full Text Available The effects of reaction condition on hydrate formation were conducted in spray reactor. The temperature, pressure, and gas volume of reaction on hydrate formation were measured in pure water and SDS solutions at different temperature and pressure with a high-pressure experimental rig for hydrate formation. The experimental data and result reveal that additives could improve the hydrate formation rate and gas storage capacity. Temperature and pressure can restrict the hydrate formation. Lower temperature and higher pressure can promote hydrate formation, but they can increase production cost. So these factors should be considered synthetically. The investigation will promote the advance of gas storage technology in hydrates.

  6. Controls on Gas Hydrate Formation and Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Miriam Kastner; Ian MacDonald


    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

  7. Controlling superstructural ordering in the clathrate-I Ba8M16P30 (M = Cu, Zn) through the formation of metal-metal bonds. (United States)

    Dolyniuk, J; Whitfield, P S; Lee, K; Lebedev, O I; Kovnir, K


    Order-disorder-order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu-Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16-x Zn x P30 with 0 Cu-Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm3n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba-Cu-Zn-P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu-Zn bonds. For the compounds with the highest Zn content, a disorder-order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu-Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30.

  8. Kinetics of formation and dissociation of gas hydrates (United States)

    Manakov, A. Yu; Penkov, N. V.; Rodionova, T. V.; Nesterov, A. N.; Fesenko, E. E., Jr.


    The review covers a wide range of issues related to the nucleation, growth and dissociation of gas hydrates. The attention is focused on publications of the last 10-15 years. Along with the mathematical models used to describe these processes, the results of relevant experimental studies are surveyed. Particular sections are devoted to the gas hydrate self-preservation effect, the water memory effect in the hydrate formation, development of catalysts for hydrate formation and the effect of substances dissolved in the aqueous phase on the formation of hydrates. The main experimental techniques used to study gas hydrates are briefly considered. The bibliography includes 230 references.

  9. Modeling thermodynamic properties of propane or tetrahydrofuran mixed with carbon dioxide or methane in structure-II clathrate hydrates

    NARCIS (Netherlands)

    Fang, Bin; Ning, Fulong; Cao, Pinqiang; Peng, Li; Wu, Jianyang; Zhang, Zhun; Vlugt, T.J.H.; Kjelstrup, Signe


    A sound knowledge of thermodynamic properties of sII hydrates is of great importance to understand the stability of sII gas hydrates in petroleum pipelines and in natural settings. Here, we report direct molecular dynamics (MD) simulations of the thermal expansion coefficient, the

  10. Further chemical studies on controlling gas hydrate formation

    Energy Technology Data Exchange (ETDEWEB)

    Kelland, M.A.; Svartaas, T.M.; Dybvik, L.A. [Rogalandsforskning, Stavanger (Norway)


    Gas hydrates are clathrates in which water molecules form a hydrogen bonded network enclosing roughly spherical cavities that are filled with gas molecules. They are a menace to the oil industry in several areas, one example being their potential blocking of production lines and processing equipment. This paper reviews new technology for combating the problem. Natural gas hydrates form in several structures depending on the gas molecules, their size relative to the cavity, and the relative stability of the structures. At high pressures, gas hydrates can be stable well above the melting point of ice. Pipeline blocking can be overcome in many ways: (1) insulate the pipeline, (2) reduce pressure, (3) remove water, (4) use chemicals. These techniques are expensive. Today only thermodynamic inhibitors such as methanol or ethylene glycol are used, but cheaper methods are sought for. Kinetic Inhibitors are chemicals able to (1) delay hydrate nucleation, or (2) delay hydrate crystal growth. Anti-Agglomerators are chemicals able to prevent agglomeration of hydrates. The suitability of the various inhibitor types are discussed. It is concluded from laboratory tests that the best kinetic inhibitors are chemicals (5000 ppm) which prevent hydrate nucleation for several days at ca. 10{sup o}C subcooling, or chemicals that delay visual hydrate growth for 24 hrs at 10 {sup o}C subcooling. The best anti-agglomerators are chemicals preventing agglomeration at 30-40% water cuts at from 3{sup o}C upwards and so far tested in the pressure range 40-95 bar. 5 refs., 18 figs.

  11. Nucleation rate analysis of methane hydrate from molecular dynamics simulations. (United States)

    Yuhara, Daisuke; Barnes, Brian C; Suh, Donguk; Knott, Brandon C; Beckham, Gregg T; Yasuoka, Kenji; Wu, David T; Sum, Amadeu K


    Clathrate hydrates are solid crystalline structures most commonly formed from solutions that have nucleated to form a mixed solid composed of water and gas. Understanding the mechanism of clathrate hydrate nucleation is essential to grasp the fundamental chemistry of these complex structures and their applications. Molecular dynamics (MD) simulation is an ideal method to study nucleation at the molecular level because the size of the critical nucleus and formation rate occur on the nano scale. Various analysis methods for nucleation have been developed through MD to analyze nucleation. In particular, the mean first-passage time (MFPT) and survival probability (SP) methods have proven to be effective in procuring the nucleation rate and critical nucleus size for monatomic systems. This study assesses the MFPT and SP methods, previously used for monatomic systems, when applied to analyzing clathrate hydrate nucleation. Because clathrate hydrate nucleation is relatively difficult to observe in MD simulations (due to its high free energy barrier), these methods have yet to be applied to clathrate hydrate systems. In this study, we have analyzed the nucleation rate and critical nucleus size of methane hydrate using MFPT and SP methods from data generated by MD simulations at 255 K and 50 MPa. MFPT was modified for clathrate hydrate from the original version by adding the maximum likelihood estimate and growth effect term. The nucleation rates calculated by MFPT and SP methods are within 5%, and the critical nucleus size estimated by the MFPT method was 50% higher, than values obtained through other more rigorous but computationally expensive estimates. These methods can also be extended to the analysis of other clathrate hydrates.

  12. Genesis and geometry of the Meiklejohn Peak lime mud-mound, Bare Mountain Quadrangle, Nevada, USA: Ordovician limestone with submarine frost heave structures—a possible response to gas clathrate hydrate evolution (United States)

    Krause, Federico F.


    . Zebra banded rocks are also accompanied by snout and socket structures and, in some instances, are folded and sheared by curving kink bands. Zebra and stromatactis limestone structures found throughout the mud-mound resemble frost heave and cryoturbation structures identified in both Holocene and Pleistocene cryosols, and in laboratory experiments with advancing freezing fronts in clay-size sediment. Significantly, modern occurrences of methane clathrate hydrate (methane-charged ice) display parallel and digitate layering similar in depositional appearance to that of zebra and stromatactis limestone from Meiklejohn Peak. Early carbonate cements are also commonly associated with these modern clathrate hydrate deposits. Consequently, gas clathrate hydrates may have been the propping agent for zebra and stromatactis structures observed in the mud-mound. In this scenario, carbonate cements would have precipitated and stabilized these structures, both with the consolidation and dissociation of gas clathrate hydrates, and with the oxidation and reduction of associated gases. Stable δ13C and δ18O isotope ratios collected from mudstone and spar of zebra and stromatactis structures indicate that they were lithified in equilibrium with Ordovician seawater. The δ13C isotope ratios recorded at Meiklejohn Peak are similar to δ13C isotopic ratios obtained from ∑CO 2 evolving from modern seafloor. These isotopic ratios may indicate that frost heave structures in the Meiklejohn Peak mud-mound are the result of consolidation and dissociation of carbon dioxide clathrate hydrates. Even though the bulk of gas clathrate hydrates identified to date in modern ocean floors are composed of methane, carbon dioxide clathrate hydrates are known from the modern seafloor of the Okinawa Trough. They may also be common in areas of abundant carbonate sediment accumulation, as suggested by recent observations from the Great Australian Bight.

  13. Resolving CO2 and methane hydrate formation kinetics

    NARCIS (Netherlands)

    Golombok, M.; Ineke, E.; Luzardo, J.C.R.; He, Y.Y.; Zitha, P.


    We analyse the kinetics of CO2 and methane hydrate formation. The characteristic formation times are associated with different steps of the formation process. Conditions for minimising these rate times are identified while maintaining a regime where CO2 hydrate is formed and methane remains

  14. Synergistic kinetic inhibition of natural gas hydrate formation

    DEFF Research Database (Denmark)

    Daraboina, Nagu; Malmos, Christine; von Solms, Nicolas


    Rocking cells were used to investigate the natural gas hydrate formation and decomposition in the presence of kinetic inhibitor, Luvicap. In addition, the influence of poly ethylene oxide (PEO) and NaCl on the performance of Luvicap was investigated using temperature ramping and isothermal...... experiments. Luvicap decreased the hydrate nucleation temperature in ramping and increased the hydrate nucleation time at fixed temperatures. The presence of PEO and NaCl enhanced the nucleation inhibition strength of Luvicap. However the addition of Luvicap promoted the hydrate growth after nucleation. PEO...... does not affect hydrate growth whereas NaCl reduced the hydrate growth both in the presence and absence of Luvicap. In addition complex two-stage hydrate growth was observed in the presence of Luvicap. Moreover, the hydrate formed in the presence of inhibitor took longer time/higher temperature...

  15. Hydrate bearing clayey sediments: Formation and gas production concepts

    KAUST Repository

    Jang, Jaewon


    Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO2single bondCH4 replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.

  16. Methane clathrates in the solar system. (United States)

    Mousis, Olivier; Chassefière, Eric; Holm, Nils G; Bouquet, Alexis; Waite, Jack Hunter; Geppert, Wolf Dietrich; Picaud, Sylvain; Aikawa, Yuri; Ali-Dib, Mohamad; Charlou, Jean-Luc; Rousselot, Philippe


    We review the reservoirs of methane clathrates that may exist in the different bodies of the Solar System. Methane was formed in the interstellar medium prior to having been embedded in the protosolar nebula gas phase. This molecule was subsequently trapped in clathrates that formed from crystalline water ice during the cooling of the disk and incorporated in this form into the building blocks of comets, icy bodies, and giant planets. Methane clathrates may play an important role in the evolution of planetary atmospheres. On Earth, the production of methane in clathrates is essentially biological, and these compounds are mostly found in permafrost regions or in the sediments of continental shelves. On Mars, methane would more likely derive from hydrothermal reactions with olivine-rich material. If they do exist, martian methane clathrates would be stable only at depth in the cryosphere and sporadically release some methane into the atmosphere via mechanisms that remain to be determined. In the case of Titan, most of its methane probably originates from the protosolar nebula, where it would have been trapped in the clathrates agglomerated by the satellite's building blocks. Methane clathrates are still believed to play an important role in the present state of Titan. Their presence is invoked in the satellite's subsurface as a means of replenishing its atmosphere with methane via outgassing episodes. The internal oceans of Enceladus and Europa also provide appropriate thermodynamic conditions that allow formation of methane clathrates. In turn, these clathrates might influence the composition of these liquid reservoirs. Finally, comets and Kuiper Belt Objects might have formed from the agglomeration of clathrates and pure ices in the nebula. The methane observed in comets would then result from the destabilization of clathrate layers in the nuclei concurrent with their approach to perihelion. Thermodynamic equilibrium calculations show that methane-rich clathrate

  17. Ethylene Separation via Hydrate Formation in W/O Emulsions

    Directory of Open Access Journals (Sweden)

    Yong Pan


    Full Text Available An hybrid absorption-hydration method was adopted to recover C2H4 from C2H4/CH4 binary gas mixtures and the hydrate formation conditions of C2H4/CH4 mixtures was studied experimentally in diesel in water (w/o emulsions. Span 20 at a concentration of 1.0 wt% in the aqueous phase was added to form water in diesel emulsions before hydrate formation and then hydrate in diesel slurry was separated after hydrate formation. The influences of initial gas-liquid volume ratio (53–142, pressure (3.4–5.4 MPa, temperature (274.15–278.15 K, water cuts (10–30 vol%, and the mole fraction of C2H4 in feed gas (13.19–80.44 mol% upon the C2H4 separation efficiency were systematically investigated. The experimental results show that ethylene can be enriched in hydrate slurry phase with high separation factor (S and recovery ratio (R. Most hydrate formation finished in 20 min, after that, the hydrate formation rate became very slow. The conclusion is useful for determining the suitable operation conditions when adopting an absorption-hydration method to separate C2H4/CH4.

  18. Effect of additives on formation of natural gas hydrate

    Energy Technology Data Exchange (ETDEWEB)

    C.S. Zhang; S.S. Fan; D.Q. Liang; K.H. Guo [Chinese Academy of Sciences, Guangzhou (China). Guangzhou Center for Gas Hydrate Research, Guangzhou Institute of Energy Conversion


    The formation of natural gas hydrate (NGH) is studied in this work. Kinetics data of hydrate formation with no agitation were collected at various concentrations of the aqueous solutions with different additives such as alkylpolyglucside, sodium dodecyl benzene sulfonate and potassium oxalate monohydrate. Various kinds of additive increased the formation rates of NGH and its storage capacity and reduced the induction time of NGH formation. Moreover, the storage capacity, the induction time and the hydrate formation rate were influenced by the concentration of the aqueous solution. 24 refs., 7 figs., 4 tabs.

  19. Characteristics of SF{sub 6} gas hydrate formation mechanisms (kinetics) and surfactants effects on hydrate formation rate

    Energy Technology Data Exchange (ETDEWEB)

    Lee, B.; Lee, H.; Kim, Y.D. [Pusan National Univ., Busan (Korea, Republic of). School of Materials Science and Engineering; Kim, Y.S.; Lee, J.D. [Korea Inst. of Industrial Technology, Busan (Korea, Republic of). Advanced Energy Resource Development Team


    Sulfur hexafluoride (SF{sub 6}) is used as an insulating gas in a variety of industrial applications, and is a potent greenhouse gas (GHG). Gas hydrates are stable crystalline compounds formed by water and natural gas molecules that have relatively large cavities that can be occupied by guest molecules. SF{sub 6} gas is able to form hydrates at relatively mild conditions. This study investigated the hydrate formation mechanisms of SF{sub 6} gas, and presented a potential hydration treatment for the gas. The effects of surface active agents on SF{sub 6} gas hydrate formation were examined experimentally using Tween 20, sodium dodecyl sulfate (SDS) and linear alkyl benzene sulfonate (LABS). The surfactants showed promoter behaviour for SF{sub 6} gas hydrate formation. Formation rates occurred in 2 stages, with rates rapidly increasing during the second phase. The inflection point occurred approximately 30 minutes after the hydrate nucleation point. Results indicated the existence of a critical concentration of surfactants. It was concluded that SF{sub 6} gas hydrate formation rates were increased by the addition of surfactants. Further studies are needed to investigate 2-stage hydrate formation rates. 18 refs., 4 figs.

  20. Separation of water through gas hydrate formation

    DEFF Research Database (Denmark)

    Boch Andersen, Torben; Thomsen, Kaj


    Gas hydrate is normally recognized as a troublemaker in the oil and gas industry. However, gas hydrate has some interesting possibilities when used in connection with separation of water. Nordic Sugar has investigated the possibility of using gas hydrates for concentration of sugar juice. The goal...... of the project was to formulate an alternative separation concept, which can replace the traditional water evaporation process in the sugar production. Work with the separation concept showed that gas hydrates can be used for water separation. The process is not suitable for sugar production because of large...

  1. Alloys of clathrate allotropes for rechargeable batteries (United States)

    Chan, Candace K; Miller, Michael A; Chan, Kwai S


    The present disclosure is directed at an electrode for a battery wherein the electrode comprises clathrate alloys of silicon, germanium or tin. In method form, the present disclosure is directed at methods of forming clathrate alloys of silicon, germanium or tin which methods lead to the formation of empty cage structures suitable for use as electrodes in rechargeable type batteries.

  2. Antifreezes act as catalysts for methane hydrate formation from ice. (United States)

    McLaurin, Graham; Shin, Kyuchul; Alavi, Saman; Ripmeester, John A


    Contrary to the thermodynamic inhibiting effect of methanol on methane hydrate formation from aqueous phases, hydrate forms quickly at high yield by exposing frozen water-methanol mixtures with methanol concentrations ranging from 0.6-10 wt% to methane gas at pressures from 125 bars at 253 K. Formation rates are some two orders of magnitude greater than those obtained for samples without methanol and conversion of ice is essentially complete. Ammonia has a similar catalytic effect when used in concentrations of 0.3-2.7 wt%. The structure I methane hydrate formed in this manner was characterized by powder X-ray diffraction and Raman spectroscopy. Steps in the possible mechanism of action of methanol were studied with molecular dynamics simulations of the Ih (0001) basal plane exposed to methanol and methane gas. Simulations show that methanol from a surface aqueous layer slowly migrates into the ice lattice. Methane gas is preferentially adsorbed into the aqueous methanol surface layer. Possible consequences of the catalytic methane hydrate formation on hydrate plug formation in gas pipelines, on large scale energy-efficient gas hydrate formation, and in planetary science are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Methane hydrate formation in confined nanospace can surpass nature. (United States)

    Casco, Mirian E; Silvestre-Albero, Joaquín; Ramírez-Cuesta, Anibal J; Rey, Fernando; Jordá, Jose L; Bansode, Atul; Urakawa, Atsushi; Peral, Inma; Martínez-Escandell, Manuel; Kaneko, Katsumi; Rodríguez-Reinoso, Francisco


    Natural methane hydrates are believed to be the largest source of hydrocarbons on Earth. These structures are formed in specific locations such as deep-sea sediments and the permafrost based on demanding conditions of high pressure and low temperature. Here we report that, by taking advantage of the confinement effects on nanopore space, synthetic methane hydrates grow under mild conditions (3.5 MPa and 2 °C), with faster kinetics (within minutes) than nature, fully reversibly and with a nominal stoichiometry that mimics nature. The formation of the hydrate structures in nanospace and their similarity to natural hydrates is confirmed using inelastic neutron scattering experiments and synchrotron X-ray powder diffraction. These findings may be a step towards the application of a smart synthesis of methane hydrates in energy-demanding applications (for example, transportation).

  4. Two-component, ab initio potential energy surface for CO2—H2O, extension to the hydrate clathrate, CO2@(H2O)20, and VSCF/VCI vibrational analyses of both (United States)

    Wang, Qingfeng Kee; Bowman, Joel M.


    We report an ab initio, full-dimensional, potential energy surface (PES) for CO2—H2O, in which two-body interaction energies are fit using a basis of permutationally invariant polynomials and combined with accurate potentials for the non-interacting monomers. This approach which we have termed "plug and play" is extended here to improve the precision of the 2-body fit in the long range. This is done by combining two separate fits. One is a fit to 47 593 2-body energies in the region of strong interaction and approaching the long range, and the second one is a fit to 6244 2-body energies in the long range. The two fits have a region of overlap which permits a smooth switch from one to the other. All energies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ level of theory. Properties of the full PES, i.e., stationary points, harmonic frequencies of the global minimum, etc., are shown to be in excellent agreement with direct CCSD(T)-F12b/aug-cc-pVTZ results. Diffusion Monte Carlo calculations of the dimer zero-point energy (ZPE) are performed, and a dissociation energy, D0, of 787 cm-1 is obtained using that ZPE, De, and the rigorous ZPEs of the monomers. Using a benchmark De, D0 is 758 cm-1. Vibrational self-consistent field (VSCF)/virtual state configuration interaction (VCI) MULTIMODE calculations of intramolecular fundamentals are reported and are in good agreement with available experimental results. Finally, the full dimer PES is combined with an existing ab initio water potential to develop a potential for the CO2 hydrate clathrate CO2(H2O)20(512 water cage). A full normal-mode analysis of this hydrate clathrate is reported as are local-monomer VSCF/VCI calculations of the fundamentals of CO2.

  5. Two-component, ab initio potential energy surface for CO2-H2O, extension to the hydrate clathrate, CO2@(H2O)20, and VSCF/VCI vibrational analyses of both. (United States)

    Wang, Qingfeng Kee; Bowman, Joel M


    We report an ab initio, full-dimensional, potential energy surface (PES) for CO2-H2O, in which two-body interaction energies are fit using a basis of permutationally invariant polynomials and combined with accurate potentials for the non-interacting monomers. This approach which we have termed "plug and play" is extended here to improve the precision of the 2-body fit in the long range. This is done by combining two separate fits. One is a fit to 47 593 2-body energies in the region of strong interaction and approaching the long range, and the second one is a fit to 6244 2-body energies in the long range. The two fits have a region of overlap which permits a smooth switch from one to the other. All energies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ level of theory. Properties of the full PES, i.e., stationary points, harmonic frequencies of the global minimum, etc., are shown to be in excellent agreement with direct CCSD(T)-F12b/aug-cc-pVTZ results. Diffusion Monte Carlo calculations of the dimer zero-point energy (ZPE) are performed, and a dissociation energy, D0, of 787 cm-1 is obtained using that ZPE, De, and the rigorous ZPEs of the monomers. Using a benchmark De, D0 is 758 cm-1. Vibrational self-consistent field (VSCF)/virtual state configuration interaction (VCI) MULTIMODE calculations of intramolecular fundamentals are reported and are in good agreement with available experimental results. Finally, the full dimer PES is combined with an existing ab initio water potential to develop a potential for the CO2 hydrate clathrate CO2(H2O)20(512 water cage). A full normal-mode analysis of this hydrate clathrate is reported as are local-monomer VSCF/VCI calculations of the fundamentals of CO2.

  6. Static formation and dissociation of methane+methylcyclohexane hydrate for gas hydrate production and regasification

    Energy Technology Data Exchange (ETDEWEB)

    He, S. [Chinese Academy of Science, Guangzhou Institute of Energy Conversion, Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou (China); Graduate University of Chinese Academy of Science, Beijing (China); Liang, D.; Li, D. [Chinese Academy of Science, Guangzhou Institute of Energy Conversion, Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou (China); Chinese Academy of Science, Guangzhou Institute of Energy Conversion, Guangzhou Center for Gas Hydrate Research, Guangzhou (China); Ma, L. [Chinese Academy of Science, Guangzhou Institute of Energy Conversion, Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou (China)


    The formation and decomposition of methane+methylcyclohexane (MCH) hydrate in a static batch reactor, which was also designed as a high-pressure microwave reactor, were investigated. The addition of 300 ppm sodium dodecyl sulfate (SDS) provides continuous formation of CH{sub 4}+MCH hydrate under static conditions. Increasing the initial pressure within the narrow range of 2.7 to 4.6 MPa at 274 K enhances the formation rate by even several times. The gas storage capacity can be largely improved with partial coexisting of sI CH{sub 4} hydrate. Unlike a stirred formation, an increase of nonaqueous MCH inhibits the static formation of sH hydrate. The following regasification by 2.45 GHz microwave heating indicates that the dissociation is rate-controlled by the parallel connection of efficient internal heating and conventional external heating. The multiphase convection characterized by osmotic dehydration and driven by intensified regasification is considered as the dominant mechanism affecting the quiescent dissociation. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Using magnetic resonance imaging to monitor CH4 hydrate formation and spontaneous conversion of CH4 hydrate to CO2 hydrate in porous media. (United States)

    Baldwin, Bernard A; Stevens, Jim; Howard, James J; Graue, Arne; Kvamme, Bjorn; Aspenes, Erick; Ersland, Geir; Husebø, Jarle; Zornes, David R


    Magnetic resonance imaging was used to monitor and quantify methane hydrate formation and exchange in porous media. Conversion of methane hydrate to carbon dioxide hydrate, when exposed to liquid carbon dioxide at 8.27 MPa and approximately 4 degrees C, was experimentally demonstrated with MRI data and verified by mass balance calculations of consumed volumes of gases and liquids. No detectable dissociation of the hydrate was measured during the exchange process.

  8. Inorganic and methane clathrates: Versatility of guest–host compounds for energy harvesting

    Energy Technology Data Exchange (ETDEWEB)

    Krishna, Lakshmi; Koh, Carolyn A.



    This review article evaluates the structure–property relations of inorganic clathrates and clathrate hydrates and their potential role in energy harvesting. There is potential cross-fertilization between the two research areas.

    Guest–host clathrate compounds exhibit unique structural and physical properties, which lead to their versatile roles in energy applications. Prominent classes of clathrate compounds are gas hydrates and inorganic clathrates. That said, there is limited cross-fertilization between the clathrate hydrate and inorganic clathrate communities, with researchers in the respective fields being less informed on the other field. Yet the structures and unique guest–host interactions in both these compounds are common important features of these clathrates. Common features and procedures can inspire and inform development between the compound classes, which may be important to the technological advancements for the different clathrate materials, e.g., structure characterization techniques and guest–host dynamics in which the “guest” tends to be imprisoned in the host structure, until external forces are applied. Conversely, the diversity in chemical compositions of these two classes of materials leads to the different applications from methane capture and storage to converting waste heat to electricity (thermoelectrics). This article highlights the structural and physical similarities and differences of inorganic and methane clathrates. The most promising state-of-the-art applications of the clathrates are highlighted for harvesting energy from methane (clathrate) hydrate deposits under the ocean and for inorganic clathrates as promising thermoelectric materials.

  9. Formation of methane nano-bubbles during hydrate decomposition and their effect on hydrate growth. (United States)

    Bagherzadeh, S Alireza; Alavi, Saman; Ripmeester, John; Englezos, Peter


    Molecular dynamic simulations are performed to study the conditions for methane nano-bubble formation during methane hydrate dissociation in the presence of water and a methane gas reservoir. Hydrate dissociation leads to the quick release of methane into the liquid phase which can cause methane supersaturation. If the diffusion of methane molecules out of the liquid phase is not fast enough, the methane molecules agglomerate and form bubbles. Under the conditions of our simulations, the methane-rich quasi-spherical bubbles grow to become cylindrical with a radius of ∼11 Å. The nano-bubbles remain stable for about 35 ns until they are gradually and homogeneously dispersed in the liquid phase and finally enter the gas phase reservoirs initially set up in the simulation box. We determined that the minimum mole fraction for the dissolved methane in water to form nano-bubbles is 0.044, corresponding to about 30% of hydrate phase composition (0.148). The importance of nano-bubble formation to the mechanism of methane hydrate formation, growth, and dissociation is discussed.

  10. 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


    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.

  11. Clathrates - An Exploration of the Chemistry of Caged Compounds

    Indian Academy of Sciences (India)

    MRI images. But, at times this toxic heavy metal (Gd) may react with bio molecules as the chelate winds its way through the body. But, encapsulating the Gd in- side a fullerene is safer and such endohedral fullerenes offer additional advantages in the medical field. Gas Hydrates. Gas Hydrates, also called water clathrates, ...

  12. Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments (United States)

    Bigalke, N.; Deusner, C.; Kossel, E.; Schicks, J. M.; Spangenberg, E.; Priegnitz, M.; Heeschen, K. U.; Abendroth, S.; Thaler, J.; Haeckel, M.


    The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. The process aims at maintaining the in situ hydrate saturation and structure and causing limited impact on soil hydraulic properties and geomechanical stability. However, to increase hydrate conversion yields and rates it must potentially be assisted by thermal stimulation or depressurization. Further, secondary formation of CO2-rich hydrates from pore water and injected CO2 enhances hydrate conversion and CH4 production yields [1]. Technical stimulation and secondary hydrate formation add significant complexity to the bulk conversion process resulting in spatial and temporal effects on hydraulic and geomechanical properties that cannot be predicted by current reservoir simulation codes. In a combined experimental and numerical approach, it is our objective to elucidate both hydraulic and mechanical effects of CO2 injection and CH4-CO2-hydrate conversion in CH4-hydrate bearing soils. For the experimental approach we used various high-pressure flow-through systems equipped with different online and in situ monitoring tools (e.g. Raman microscopy, MRI and ERT). One particular focus was the design of triaxial cell experimental systems, which enable us to study sample behavior even during large deformations and particle flow. We present results from various flow-through high-pressure experimental studies on different scales, which indicate that hydraulic and geomechanical properties of hydrate-bearing sediments are drastically altered during and after injection of CO2. We discuss the results in light of the competing processes of hydrate dissociation, hydrate conversion and secondary hydrate formation. Our results will also contribute to the understanding of effects of temperature and pressure changes leading to dissociation of gas hydrates in ocean and permafrost systems. [1] Deusner C, Bigalke N, Kossel E

  13. Controlling superstructural ordering in the clathrate-I Ba 8 M 16 P 30 (M = Cu, Zn) through the formation of metal–metal bonds

    Energy Technology Data Exchange (ETDEWEB)

    Dolyniuk, J.; Whitfield, P. S.; Lee, K.; Lebedev, O. I.; Kovnir, K.


    Order–disorder–order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu–Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16-xZnxP30 with 0 < x < 1.6 (10% Zn/Mtotal), but vanishes at greater substitution concentrations. Higher Zn concentrations (up to 35% Zn/Mtotal) resulted in the additional substitution of Zn for P in Ba8M16+yP30-y (M = Cu, Zn) with 0 ≤ y ≤ 1. This causes the formation of Cu–Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm[3 with combining macron]n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba–Cu–Zn–P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu–Zn bonds. For the compounds with the highest Zn content, a disorder–order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu–Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30.

  14. Investigation of hydrate formation and transportability in multiphase flow systems (United States)

    Grasso, Giovanny A.

    The oil and gas industry is moving towards offshore developments in more challenging environments, where evaluating hydrate plugging risks to avoid operational/safety hazards becomes more difficult (Sloan, 2005). Even though mechanistic models for hydrate plug formation have been developed, components for a full comprehensive model are still missing. Prior to this work, research efforts were focused on flowing hydrate particles with relatively little research on hydrate accumulation, leaving hydrate deposition in multiphase flow an unexplored subject. The focus of this thesis was to better understand hydrate deposition as a form of accumu- lation in pipelines. To incorporate the multiphase flow effect, hydrate formation experiments were carried out at varying water cut (WC) from 15 to 100 vol.%, liquid loading (LL) from 50 to 85 vol.%, mixture velocity (vmix) from 0.75 to 3 m/s, for three fluids systems (100 % WC, water in Conroe crude oil emulsions and King Ranch condensate + water) on the ExxonMobil flowloop (4 in. nominal size and 314 ft. long) at Friendswood, TX. For the 100 % WC flowloop tests, hydrate particle distribution transitions beyond a critical hydrate volume concentration, observed values were between 8.2 to 29.4 vol.%, causing a sudden increase in pressure drop (DP). A revised correlation of the transition as a function of Reynolds number and liquid loading was developed. For Conroe emulsions, DP starts increasing at higher hydrate concentrations than King Ranch condensate, many times at 10 vol.%. Experiments with King Ranch show higher relative DP (10 to 25) than Conroe (2 to 10) performed at the same vmix and LL. Cohesive force measurements between cyclopentane hydrate particles were reduced from a value of 3.32 mN/m to 1.26 mN/m when 6 wt.% Conroe was used and to 0.41 mN/m when 5 wt.% Caratinga crude oil was used; similar values were obtained when extracted asphaltenes were used. King Ranch condensate (11 wt.%) did not significantly change the

  15. Numerical analysis of wellbore instability in gas hydrate formation during deep-water drilling (United States)

    Zhang, Huaiwen; Cheng, Yuanfang; Li, Qingchao; Yan, Chuanliang; Han, Xiuting


    Gas hydrate formation may be encountered during deep-water drilling because of the large amount and wide distribution of gas hydrates under the shallow seabed of the South China Sea. Hydrates are extremely sensitive to temperature and pressure changes, and drilling through gas hydrate formation may cause dissociation of hydrates, accompanied by changes in wellbore temperatures, pore pressures, and stress states, thereby leading to wellbore plastic yield and wellbore instability. Considering the coupling effect of seepage of drilling fluid into gas hydrate formation, heat conduction between drilling fluid and formation, hydrate dissociation, and transformation of the formation framework, this study established a multi-field coupling mathematical model of the wellbore in the hydrate formation. Furthermore, the influences of drilling fluid temperatures, densities, and soaking time on the instability of hydrate formation were calculated and analyzed. Results show that the greater the temperature difference between the drilling fluid and hydrate formation is, the faster the hydrate dissociates, the wider the plastic dissociation range is, and the greater the failure width becomes. When the temperature difference is greater than 7°C, the maximum rate of plastic deformation around the wellbore is more than 10%, which is along the direction of the minimum horizontal in-situ stress and associated with instability and damage on the surrounding rock. The hydrate dissociation is insensitive to the variation of drilling fluid density, thereby implying that the change of the density of drilling fluids has a minimal effect on the hydrate dissociation. Drilling fluids that are absorbed into the hydrate formation result in fast dissociation at the initial stage. As time elapses, the hydrate dissociation slows down, but the risk of wellbore instability is aggravated due to the prolonged submersion in drilling fluids. For the sake of the stability of the wellbore in deep

  16. A prediction method of natural gas hydrate formation in deepwater gas well and its application

    Directory of Open Access Journals (Sweden)

    Yanli Guo


    Full Text Available To prevent the deposition of natural gas hydrate in deepwater gas well, the hydrate formation area in wellbore must be predicted. Herein, by comparing four prediction methods of temperature in pipe with field data and comparing five prediction methods of hydrate formation with experiment data, a method based on OLGA & PVTsim for predicting the hydrate formation area in wellbore was proposed. Meanwhile, The hydrate formation under the conditions of steady production, throttling and shut-in was predicted by using this method based on a well data in the South China Sea. The results indicate that the hydrate formation area decreases with the increase of gas production, inhibitor concentrations and the thickness of insulation materials and increases with the increase of thermal conductivity of insulation materials and shutdown time. Throttling effect causes a plunge in temperature and pressure in wellbore, thus leading to an increase of hydrate formation area.

  17. Full-dimensional, high-level ab initio potential energy surfaces for H2(H2O) and H2(H2O)2 with application to hydrogen clathrate hydrates. (United States)

    Homayoon, Zahra; Conte, Riccardo; Qu, Chen; Bowman, Joel M


    New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H2(H2O) two-body and H2(H2O)2 three-body potentials. The database for H2(H2O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are compared to computationally faster ones obtained via "purified" symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H2, H2O, and (H2O)2, to obtain full PESs for H2(H2O) and H2(H2O)2. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H2(H2O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H2@(H2O)20. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H2 from the calculated equilibrium structure.

  18. Hydrogen-bond vibrational and energetic dynamical properties in sI and sII clathrate hydrates and in ice Ih: Molecular dynamics insights (United States)

    Chakraborty, Somendra Nath; English, Niall J.


    Equilibrium molecular dynamics (MD) simulations have been performed on cubic (sI and sII) polymorphs of methane hydrate, and hexagonal ice (ice Ih), to study the dynamical properties of hydrogen-bond vibrations and hydrogen-bond self-energy. It was found that hydrogen-bond energies are greatest in magnitude in sI hydrates, followed by sII, and their energies are least in magnitude in ice Ih. This is consistent with recent MD-based findings on thermal conductivities for these various materials [N. J. English and J. S. Tse, Phys. Rev. Lett. 103, 015901 (2009)], in which the lower thermal conductivity of sI methane hydrate was rationalised in terms of more strained hydrogen-bond arrangements. Further, modes for vibration and energy-transfer via hydrogen bonds in sI hydrate were found to occur at higher frequencies vis-à-vis ice Ih and sII hydrate in both the water-librational and OH⋯H regions because of the more strained nature of hydrogen bonds therein.

  19. Effect of three representative surfactants on methane hydrate formation rate and induction time

    Directory of Open Access Journals (Sweden)

    Mostafa keshavarz Moraveji


    Full Text Available The effects of three types of surfactants on methane hydrate formation process were investigated. Three different classes of surfactants involving anionic (sodium dodecyl sulfonate, cationic (hexadecyl trimethyl ammonium bromide and non-ionic (poly oxy ethylene (40 octyl phenyl ether have been used. Thermodynamics of hydrate formation, formation rate, kinetic constants and induction time in the presence of surfactants with various concentrations were analyzed. Critical micelle concentrations (CMCs of these surfactants in water were determined by induction time measurements in various concentrations under methane hydrate formation conditions. The critical micelle concentration (CMC at the methane hydrate formation conditions for SDS, HTABr and TritonX-405 solutions were obtained at 450, 380 and 950 ppm, respectively. The experimental results indicated that hydrate formation rate increased with the use of surfactants for all concentrations and induction time decreased. It was found that for surfactants, CMC at hydrate formation conditions was less than CMC at ambient conditions.

  20. Methane hydrate synthesis from ice: Influence of pressurization and ethanol on optimizing formation rates and hydrate yield (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Kumar Saw V.


    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.

  2. Methane hydrate formation in partially water-saturated Ottawa sand (United States)

    Waite, W.F.; Winters, W.J.; Mason, D.H.


    Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.

  3. Study on Prompt Methane Hydrate Formation Derived by Addition of Ionic Liquid


    Kitajima, Takashi; Ohtsubo, Naoto; Hashimoto, Shunsuke; Makino, Takashi; Kodama, Daisuke; Ohgaki, Kazunari


    Aims: The objective of this study is to establish the fundamental model on methane hydrate formation and to accelerate the rate of methane hydrate formation with a small amount of ionic liquid and to investigate the effect of ionic liquid on hydrate formation. Study Design: Experimental study containing modeling. Place and Duration of Study: The present study was held between April 2010 and February 2012 at Division of Chemical Engineering, Department of Materials Engineering Science, Osaka U...

  4. The effect of hydrate formation on the elastic properties of unconsolidated sediment (United States)

    Rydzy, Marisa B.

    Natural gas hydrates exist in unconsolidated marine or permafrost sediments and can adopt many morphologies. In this study, the effect of hydrate formation on the wave velocities of unconsolidated sediment was investigated in a series of laboratory studies, with particular focus on the extent to which the initial water saturation controls the manner in which hydrate is distributed, and thus the extent to which hydrate formation increases the wave velocity in sands. Ultrasonic p- and s-wave velocities (vp, vs) were measured in conjunction with magnetic resonance imaging (MRI) in hydrate-bearing Ottawa Sand F110 during hydrate formation and dissociation. vp and vs were determined as functions of gas hydrate saturation (Sh). Hydrates were formed out of solution using tetrahydrofuran (THF) and through CH 4 injection into partially water-saturated samples. For the latter, samples with low and high initial water saturation (Swi) were tested. The recorded velocities exhibited a noticeable dependence on Swi. At low Swi (~20%) the hydrate stiffened the sediment and increased the ultrasonic velocities dramatically. Comparing measured velocities to those calculated with existing rock physics models links the initial water saturation, which determines the gas-water distribution in the sediment and hence the location of initial hydrate formation, to the evolution of wave velocity during hydrate formation. We concluded that at low Swi, the water is evenly distributed and located at the grain contacts. The resulting hydrate cements the grains, dramatically increasing the wave velocities even at low hydrate saturations. To test the dependence of the initial water distribution on the initial water saturation, micro X-ray CT images were also acquired of partially saturated glass-bead packs without hydrate but with varying amounts of water. At low water saturations, water occurred as bridges between adjacent glass beads or was located at the glass-bead contacts. At high water

  5. Formation and Dissociation of Methane Hydrates from Seawater in Consolidated Sand: Mimicking Methane Hydrate Dynamics beneath the Seafloor

    Directory of Open Access Journals (Sweden)

    Prasad B. Kerkar


    Full Text Available Methane hydrate formation and dissociation kinetics were investigated in seawater-saturated consolidated Ottawa sand-pack under sub-seafloor conditions to study the influence of effective pressure on formation and dissociation kinetics. To simulate a sub-seafloor environment, the pore-pressure was varied relative to confining pressure in successive experiments. Hydrate formation was achieved by methane charging followed by sediment cooling. The formation of hydrates was delayed with increasing degree of consolidation. Hydrate dissociation by step-wise depressurization was instantaneous, emanating preferentially from the interior of the sand-pack. Pressure drops during dissociation and in situ temperature controlled the degree of endothermic cooling within sediments. In a closed system, the post-depressurization dissociation was succeeded by thermally induced dissociation and pressure-temperature conditions followed theoretical methane-seawater equilibrium conditions and exhibited excess pore pressure governed by the pore diameter. These post-depressurization equilibrium values for the methane hydrates in seawater saturated consolidated sand-pack were used to estimate the enthalpy of dissociation of 55.83 ± 1.41 kJ/mol. These values were found to be lower than those reported in earlier literature for bulk hydrates from seawater (58.84 kJ/mol and pure water (62.61 kJ/mol due to excess pore pressure generated within confined sediment system under investigation. However, these observations could be significant in the case of hydrate dissociation in a subseafloor environment where dissociation due to depressurization could result in an instantaneous methane release followed by slow thermally induced dissociation. The excess pore pressure generated during hydrate dissociation could be higher within fine-grained sediments with faults and barriers present in subseafloor settings which could cause shifting in geological layers.

  6. Molecular dynamics simulation of the intercalation behaviors of methane hydrate in montmorillonite. (United States)

    Yan, KeFeng; Li, XiaoSen; Xu, ChunGang; Lv, QiuNan; Ruan, XuKe


    The formation and mechanism of CH4 hydrate intercalated in montmorillonite are investigated by molecular dynamics (MD) simulation. The formation process of CH4 hydrate in montmorillonite with 1 ~ 8 H2O layers is observed. In the montmorillonite, the "surface H2O" constructs the network by hydrogen bonds with the surface Si-O ring of clay, forming the surface cage. The "interlayer H2O" constructs the network by hydrogen bonds, forming the interlayer cage. CH4 molecules and their surrounding H2O molecules form clathrate hydrates. The cation of montmorillonite has a steric effect on constructing the network and destroying the balance of hydrogen bonds between the H2O molecules, distorting the cage of hydrate in clay. Therefore, the cages are irregular, which is unlike the ideal CH4 clathrate hydrates cage. The pore size of montmorillonite is another impact factor to the hydrate formation. It is quite easier to form CH4 hydrate nucleation in montmorillonite with large pore size than in montmorillonite with small pore. The MD work provides the constructive information to the investigation of the reservoir formation for natural gas hydrate (NGH) in sediments.

  7. Formation of nitrous oxide (N2O) hydrate in soil mineral suspensions with electrolytes (United States)

    Kyung, D.; Enkh-Amgalan, T.; Lee, W.


    We have identified the effects of solid surface (illite, nontronite, sphalerite, kaolinite) and electrolyte (NaCl, KCl, CaCl2, MgCl2) types on the formation of N2O hydrate in this study. The hydrate formation experiments were conducted at hydrate forming condition (273.3K and 30 bar) by injecting N2O gas into the soil mineral suspensions with and without electrolytes in a 50mL pressurized vessel. The formation of N2O hydrate in aqueous electrolyte solutions was slower than that in deionized water. Ion charge and size were significant factors affecting N2O hydrate formation kinetic in electrolytes solutions. The addition of soil mineral suspensions accelerated the formation of N2O hydrate in the electrolyte solutions. Surface area and ionic strength of soil minerals highly influenced on formation kinetic of N2O hydrate. The hydrate formation times in the solid suspensions without electrolytes were very similar to that in the deionized water. The results obtained from this research could be indirectly applied to the fate of N2O sequestered into geological formations as well as its storage as a form of N2O hydrate.

  8. Characteristics of CO2 Hydrate Formation and Dissociation in Glass Beads and Silica Gel

    Directory of Open Access Journals (Sweden)

    Qingping Li


    Full Text Available CO2 hydrate formation and dissociation is crucial for hydrate-based CO2 capture and storage. Experimental and calculated phase equilibrium conditions of carbon dioxide (CO2 hydrate in porous medium were investigated in this study. Glass beads were used to form the porous medium. The experimental data were generated using a graphical method. The results indicated the decrease of pore size resulted in the increase of the equilibrium pressure of CO2 hydrate. Magnetic resonance imaging (MRI was used to investigate the priority formation site of CO2 hydrate in different porous media, and the results showed that the hydrate form firstly in BZ-02 glass beads under the same pressure and temperature. An improved model was used to predict CO2 hydrate equilibrium conditions, and the predictions showed good agreement with experimental measurements.

  9. Towards a fundamental understanding of natural gas hydrates. (United States)

    Koh, Carolyn A


    Gas clathrate hydrates were first identified in 1810 by Sir Humphrey Davy. However, it is believed that other scientists, including Priestley, may have observed their existence before this date. They are solid crystalline inclusion compounds consisting of polyhedral water cavities which enclathrate small gas molecules. Natural gas hydrates are important industrially because the occurrence of these solids in subsea gas pipelines presents high economic loss and ecological risks, as well as potential safety hazards to exploration and transmission personnel. On the other hand, they also have technological importance in separation processes, fuel transportation and storage. They are also a potential fuel resource because natural deposits of predominantly methane hydrate are found in permafrost and continental margins. To progress with understanding and tackling some of the technological challenges relating to natural gas hydrate formation, inhibition and decomposition one needs to develop a fundamental understanding of the molecular mechanisms involved in these processes. This fundamental understanding is also important to the broader field of inclusion chemistry. The present article focuses on the application of a range of physico-chemical techniques and approaches for gaining a fundamental understanding of natural gas hydrate formation, decomposition and inhibition. This article is complementary to other reviews in this field, which have focused more on the applied, engineering and technological aspects of clathrate hydrates.

  10. Laboratory formation of non-cementing, methane hydrate-bearing sands (United States)

    Waite, William F.; Bratton, Peter M.; Mason, David H.


    Naturally occurring hydrate-bearing sands often behave as though methane hydrate is acting as a load-bearing member of the sediment. Mimicking this behavior in laboratory samples with methane hydrate likely requires forming hydrate from methane dissolved in water. To hasten this formation process, we initially form hydrate in a free-gas-limited system, then form additional hydrate by circulating methane-supersaturated water through the sample. Though the dissolved-phase formation process can theoretically be enhanced by increasing the pore pressure and flow rate and lowering the sample temperature, a more fundamental concern is preventing clogs resulting from inadvertent methane bubble formation in the circulation lines. Clog prevention requires careful temperature control throughout the circulation loop.

  11. Isotopic fractionation of guest gas at the formation of methane and ethane hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Hachikubo, A.; Ozeki, T.; Kosaka, T.; Sakagami, H.; Minami, H.; Nunokawa, Y.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan); Kida, M. [Advanced Industrial Science and Technology, Sapporo (Japan); Krylov, A. [All-Russia Inst. for Geology and Mineral Resources of the Ocean, St. Petersburg (Russian Federation)


    Gas fractionation can occur between light and heavy guest molecules when equilibrium pressures in the hydrates differ. This study investigated the effect of temperature on the isotopic fractionation of gas molecules during the formation of synthetic methane-ethane gas hydrates prepared in a pressurized cell. The experiments were conducted in a temperature ranging between 223.2 and 278.2 K. The study showed that methane and ethane values in the hydrate phase were smaller than those observed in the gas phase, and that heavy molecules were more unstable within the hydrate. The isotopic composition of the residual and hydrate-bonded gases were also measured and compared. Results showed that the hydrate-bound molecules of the hydrates were lower than those observed in the residual gas during the formation process. Isotopic fractionation was used to identify the gas origin of the natural gas hydrates. Isotopic differences between the hydrate-bound and surrounding gases will help researchers determine when the hydrate was formed. However, further studies are needed to determine the effects of pressure, salinity, and formation rate on the process of isotopic fractionation. The study also demonstrated that fractionation was effective at lower temperatures. 13 refs., 3 figs.

  12. Volume change associated with formation and dissociation of hydrate in sediment (United States)

    Ruppel, Carolyn; Lee, J.Y.; Santamarina, J.C.


    Gas hydrate formation and dissociation in sediments are accompanied by changes in the bulk volume of the sediment and can lead to changes in sediment properties, loss of integrity for boreholes, and possibly regional subsidence of the ground surface over areas where methane might be produced from gas hydrate in the future. Experiments on sand, silts, and clay subject to different effective stress and containing different saturations of hydrate formed from dissolved phase tetrahydrofuran are used to systematically investigate the impact of gas hydrate formation and dissociation on bulk sediment volume. Volume changes in low specific surface sediments (i.e., having a rigid sediment skeleton like sand) are much lower than those measured in high specific surface sediments (e.g., clay). Early hydrate formation is accompanied by contraction for all soils and most stress states in part because growing gas hydrate crystals buckle skeletal force chains. Dilation can occur at high hydrate saturations. Hydrate dissociation under drained, zero lateral strain conditions is always associated with some contraction, regardless of soil type, effective stress level, or hydrate saturation. Changes in void ratio during formation-dissociation decrease at high effective stress levels. The volumetric strain during dissociation under zero lateral strain scales with hydrate saturation and sediment compressibility. The volumetric strain during dissociation under high shear is a function of the initial volume average void ratio and the stress-dependent critical state void ratio of the sediment. Other contributions to volume reduction upon hydrate dissociation are related to segregated hydrate in lenses and nodules. For natural gas hydrates, some conditions (e.g., gas production driven by depressurization) might contribute to additional volume reduction by increasing the effective stress.

  13. Constraining Hydrate-Mediated Transfer of the Greenhouse Gases CO2 and CH4 to the Ocean at Controlled Thermodynamic and Hydrodynamic Forcing


    Bigalke, Nikolaus Karl


    At pressures and temperatures prevailing in the ocean at a few hundred meters depth transfer of methane and carbon dioxide into and within the water column are influenced by the thermodynamic and kinetic stability of clathrates formed by these two greenhouse gases. Thus, a better understanding of hydrate formation and stability is essential to assess the contribution of submarine methane seepage to climate change, the hazard potential of submarine gas hydrate deposits and the feasibility and ...

  14. Gas hydrate phase equilibria measurement techniques and phase rule considerations

    Energy Technology Data Exchange (ETDEWEB)

    Beltran, Juan G. [Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, ON (Canada); Bruusgaard, Hallvard [Department of Chemical Engineering, McGill University, Montreal, QC (Canada); Servio, Phillip, E-mail: [Department of Chemical Engineering, McGill University, Montreal, QC (Canada)


    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.

  15. Computational Approach for Gas Hydrate Formation and Corresponding Physical Property Changes (United States)

    Hu, D.; Keehm, Y.


    Gas hydrate is a solid substance composed of water and hydrocarbon (mainly methane). It occurs worldwide in the oceanic and polar sediments where temperature is low enough and pressure is sufficiently high to crystallize the methane into gas hydrate. Gas hydrate has drawn great attention because it can be future energy resource, a global warming factor and a hazard in ocean structures such as oil platforms. However, the formation of gas hydrate and corresponding physical property changes are not well known, since the detailed hydrates formation mechanism at the pore scale are poorly understood. In this paper, we try various phenomenological formation models on pore microstructure of beach sands obtained by the X-ray microtomographic technique, and calculate physical properties of hydrate-bearing sediments as functions of gas hydrate saturation. Then we compare the results to lab experiments by KIGAM (Korea Institute of Geoscience and Mineral Resources) and AIST (Advanced Industrial Science and Technology of Japan), which were obtained from a similar experiment setup, but the permeability trends along hydrate saturation were quite different. As a preliminary result, among the various nucleation and growth models, the KIGAM's results agree well with G-2 model, where the nucleation and growth of hydrate occur at the pore throats; while AIST's results seem to match the G-3 model, which is growth-dominant one. Although more complete conclusion will be possible by more results from ongoing pore-scale modeling, this computational approach show that it can be a robust tool for analyzing the hydrate formation mechanism for a given sediment and estimating quantitative relations between hydrate saturation and physical properties of hydrate-bearing sediments.

  16. Effect of electrolytes and soil mineral surfaces on N2O hydrate formation kinetics (United States)

    Kyung, D.; Ha, S.; Lee, W.


    Nitrous oxide (N2O) is one of the main greenhouse gases (GHGs) defined by IPCC (Intergovernmental Panel on Climate Change) and its global warming potential (GWP) is 310 times higher than that of carbon dioxide (CO2). Gas hydrates are unique crystalline compounds that trap suitable guest gas molecules (size between 0.35 and 0.9 nm) stably inside the hydrogen-bonded water cages via van der Waals interaction under high pressure and low temperature conditions. N2O has similar properties (e.g. van der Waals diameter, molar mass, density, etc.) with CO2 except for polarity and it was revealed that both N2O and CO2 can be formed as hydrate s-I in natural environment. In this study, we have identified the effect of electrolytes (NaCl, KCl, CaCl2, MgCl2) and solid surfaces (illite, nontronite, sphalerite, kaolinite, montmorillonite) on the N2O hydrate formation kinetics. The hydrate formation experiments were conducted by injecting N2O gas into the soil mineral suspensions with and without electrolytes in a 50mL pressurized vessel. The formation of N2O hydrate in aqueous electrolyte solutions was slower than that in deionized water. Ion charge and size were significant factors affecting N2O hydrate formation kinetic in electrolytes solutions. The addition of soil mineral suspensions accelerated the formation of N2O hydrate in the electrolyte solutions. Surface area and ionic strength of soil minerals highly influenced on formation kinetic of N2O hydrate. The hydrate formation times in the solid suspensions without electrolytes were very similar to that in the deionized water. The results obtained from this research could be indirectly applied to the fate of N2O sequestered into geological formations as well as its storage as a form of N2O hydrate.

  17. Inhibition of Methane Hydrate Formation by Ice-Structuring Proteins

    DEFF Research Database (Denmark)

    Jensen, Lars; Ramløv, Hans; Thomsen, Kaj


    In the oil and gas industry there is ample motivation for moving toward greener kinetic inhibitors of gas hydrates as many of those used today suffer from poor biodegradability. In this work, we have investigated experimentally whether ice-structuring proteins (ISPs) found in fish and insect......, 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......-known kinetic hydrate inhibitor. The results revealed that adding ISP in sufficient amounts caused the appearance of an initial nonlinear growth period. At a certain point during the growth process the growth pattern changed to linear which is identical to the growth observed for methane hydrate in the absence...

  18. The elastic wave velocity response of methane gas hydrate formation in vertical gas migration systems (United States)

    Bu, Q. T.; Hu, G. W.; Ye, Y. G.; Liu, C. L.; Li, C. F.; Best, A. I.; Wang, J. S.


    Knowledge of the elastic wave velocities of hydrate-bearing sediments is important for geophysical exploration and resource evaluation. Methane gas migration processes play an important role in geological hydrate accumulation systems, whether on the seafloor or in terrestrial permafrost regions, and their impact on elastic wave velocities in sediments needs further study. Hence, a high-pressure laboratory apparatus was developed to simulate natural continuous vertical migration of methane gas through sediments. Hydrate saturation (S h) and ultrasonic P- and S-wave velocities (V p and V s) were measured synchronously by time domain reflectometry (TDR) and by ultrasonic transmission methods respectively during gas hydrate formation in sediments. The results were compared to previously published laboratory data obtained in a static closed system. This indicated that the velocities of hydrate-bearing sediments in vertical gas migration systems are slightly lower than those in closed systems during hydrate formation. While velocities increase at a constant rate with hydrate saturation in the closed system, P-wave velocities show a fast-slow-fast variation with increasing hydrate saturation in the vertical gas migration system. The observed velocities are well described by an effective-medium velocity model, from which changing hydrate morphology was inferred to cause the fast-slow-fast velocity response in the gas migration system. Hydrate forms firstly at the grain contacts as cement, then grows within the pore space (floating), then finally grows into contact with the pore walls again. We conclude that hydrate morphology is the key factor that influences the elastic wave velocity response of methane gas hydrate formation in vertical gas migration systems.

  19. Effect of different surfactants on methane hydrate formation rate, stability and storage capacity

    Energy Technology Data Exchange (ETDEWEB)

    H. Ganji; M. Manteghian; K. Sadaghiani zadeh; M.R. Omidkhah; H. Rahimi Mofrad [Tarbiat Modares University, Tehran (Iran). Department of Chemical Engineering, Faculty of Engineering


    The effects of anionic surfactants sodium dodecyl sulfate (SDS) and linear alkyl benzene sulfonate (LABS), cationic surfactant cetyl trimethyl ammonium bromide (CTAB) and non-ionic surfactant ethoxylated nonylphenol (ENP) on the formation, dissociation and storage capacity of methane hydrate have been investigated. Each surfactant was tested with 3 concentrations 300, 500 and 1000 ppm and it has been found that SDS, when prepared with these three concentrations speeds up the hydrate formation rate effectively. LABS increases the hydrate formation rate at 500 and 1000 ppm but decreases it at 300 ppm. CTAB and ENP have promotion effect on hydrate formation rate at 1000 ppm but decrease it at 300 and 500 ppm. Hydrate stability tests have been performed at three temperatures 268.2, 270.2 and 272.2 K with and without surfactant promoters. The results show that all tested additives increase the dissociation rate of methane hydrate below the ice point. CTAB has the minimum and LABS the maximum effect on the methane hydrate dissociation rate. Experimental results on hydrate gas content revealed that maximum storage capacity of 165 V/V is obtained with 1000 ppm of CTAB in water. 25 refs., 8 figs.

  20. Determining the mechanism and parameters of hydrate formation and loss in glucose. (United States)

    Scholl, Sarah K; Schmidt, Shelly J


    Water-solid interactions are known to play a major role in the chemical and physical stability of food materials. Despite its extensive use throughout the food industry, the mechanism and parameters of hydrate formation and loss in glucose are not well characterized. Hydrate formation in alpha-anhydrous glucose (α-AG) and hydrate loss in glucose monohydrate (GM) were studied under equilibrium conditions at various relative humidity (RH) values using saturated salt slurries for 1 y. The mechanism of hydrate formation and hydrate loss were determined through mathematical modeling of Dynamic Vapor Sorption data and Raman spectroscopy was used to confirm the mechanisms. The critical temperature for hydrate loss in GM was determined using thermogravimetric analysis (TGA). The moisture sorption profiles of α-AG and GM were also studied under dynamic conditions using an AquaSorp Isotherm Generator. Hydrate formation was observed at and above 68% RH at 25 °C and the conversion of α-AG to GM can best be described as following a nucleation mechanism, however, diffusion and/or geometric contraction mechanisms were also observed by Raman spectroscopy subsequent to the coalescence of initial nucleation sites. Hydrate loss was observed to occur at and below 11% RH at 25 °C during RH storage and at 70 °C during TGA. The conversion of GM to α-AG follows nucleation and diffusion mechanisms. Hydrate formation was evident under dynamic conditions in α-AG and GM prior to deliquescence. This research is the first to report hydrate formation and loss parameters for crystalline α-AG and GM during extended storage at 25 ˚C. © 2014 Institute of Food Technologists®

  1. Water Transfer Characteristics during Methane Hydrate Formation Processes in Layered Media

    Directory of Open Access Journals (Sweden)

    Yousheng Deng


    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.

  2. Hydrate Formation/Dissociation in (Natural Gas + Water + Diesel Oil Emulsion Systems

    Directory of Open Access Journals (Sweden)

    Chang-Yu Sun


    Full Text Available Hydrate formation/dissociation of natural gas in (diesel oil + water emulsion systems containing 3 wt% anti-agglomerant were performed for five water cuts: 5, 10, 15, 20, and 25 vol%. The natural gas solubilities in the emulsion systems were also examined. The experimental results showed that the solubility of natural gas in emulsion systems increases almost linearly with the increase of pressure, and decreases with the increase of water cut. There exists an initial slow hydrate formation stage for systems with lower water cut, while rapid hydrate formation takes place and the process of the gas-liquid dissolution equilibrium at higher water cut does not appear in the pressure curve. The gas consumption amount due to hydrate formation at high water cut is significantly higher than that at low water cut. Fractional distillation for natural gas components also exists during the hydrate formation process. The experiments on hydrate dissociation showed that the dissociation rate and the amount of dissociated gas increase with the increase of water cut. The variations of temperature in the process of natural gas hydrate formation and dissociation in emulsion systems were also examined.

  3. Gas Hydrate Formation Amid Submarine Canyon Incision: Investigations From New Zealand's Hikurangi Subduction Margin (United States)

    Crutchley, G. J.; Kroeger, K. F.; Pecher, I. A.; Mountjoy, J. J.; Gorman, A. R.


    We investigate gas hydrate system dynamics beneath a submarine canyon on New Zealand's Hikurangi subduction margin using seismic reflection data and petroleum systems modeling. High seismic velocities just above the base of gas hydrate stability (BGHS) indicate that concentrated gas hydrates exist beneath the canyon. Two-dimensional gas hydrate formation modeling shows how the process of canyon incision at this location alters the distribution and concentration of gas hydrate. The key modeling result is that free gas is trapped beneath the gas hydrate layer and then "captured" into a concentrated gas hydrate deposit as a result of a downward-shift in the BGHS driven by canyon incision. Our study thus provides new insight into the functioning of this process. From our data, we also conceptualize two other models to describe how canyons could significantly change gas hydrate distribution and concentration. One scenario is related to deflection of fluid flow pathways from over-pressured regions at the BGHS toward the canyon, and the other is based on relationships between simultaneous seafloor uplift and canyon incision. The relationships and processes described are of global relevance because of considerations of gas hydrate as an energy resource and the influence of both submarine canyons and gas hydrate systems on seafloor biodiversity.

  4. Measurements of Water Permeability in Unconsolidated Porous Media with Methane Hydrate Formation

    Directory of Open Access Journals (Sweden)

    Xiao-Sen Li


    Full Text Available Permeability is one of the key factors that determine the fluids flow capacity and production potential of hydrate deposits. In this study, an experimental setup is developed to investigate the flow properties of the porous media, and the permeabilities to water are measured in the unconsolidated porous media with or without hydrate deposition in the pores. A specialized method of precisely controlling the amount of injected methane gas is employed to form methane hydrate in the core sample, and the hydrate formation process is described by the change characteristics of the gas and hydrate saturations. It is found that the residual gas plays an obstructive role in the water flow and it tends to slightly reduce the water permeability in the porous media, especially under high pressure conditions. After hydrate formation in the core sample, relatively steady flow state can be obtained under suitable water injection rate Q at which hydrate dissociation rate is very slow. The absolute permeability of the porous sample is reduced from 49.2 to 1.2 Darcies when the hydrate saturation increases from 0 to 9.3% in this study, indicating a strong dependence of k on the hydrate saturation.

  5. Methane Hydrate Distribution from Prolonged and Repeated Formation in Natural and Compacted Sand Samples: X-Ray CT Observations

    Directory of Open Access Journals (Sweden)

    Emily V. L. Rees


    Full Text Available 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.

  6. 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.


    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.

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

    National Research Council Canada - National Science Library

    Kumar Saw, V; Udayabhanu, G; Mandal, A; Laik, S


      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...

  8. Hydration characteristics and structure formation of cement pastes containing metakaolin

    Directory of Open Access Journals (Sweden)

    Dvorkin Leonid


    Full Text Available Metakaolin (MK is one of the most effective mineral admixtures for cement-based composites. The deposits of kaolin clays are wide-spread in the world. Metakaolin is comparable to silica fume as an active mineral admixture for cement-based composites. In this paper, the rheological and mechanical properties of cement paste containing metakaolin are investigated. The effect of MK is more evident at “tight” hydration conditions within mixtures with low water-cement ratio, provided by application of superplasticizers. The cement is replaced with 0 to 15% metakaolin, and superplasticizer content ranged from 0 to 1.5% by weight of cementitious materials (i.e. cement and metakaolin. An equation is derived to describe the relationship between the metakaolin and superplasticizer content and consistency of pastes. There is a linear dependence between metakalolin content and water demand. Second-degree polynomial describe the influence of superplasticizer content. The application of SP and MK may produce cement-water suspensions with water-retaining capacity at 50-70% higher than control suspensions. The investigation of initial structure forming of cement pastes with SP-MK composite admixture indicates the extension of coagulation structure forming phase comparing to the pastes without additives. Crystallization stage was characterized by more intensive strengthening of the paste with SP-MK admixture comparing to the paste without admixtures and paste with SP. Results on the porosity parameters for hardened cement paste indicate a decrease in the average diameter of pores and refinement of pore structure in the presence of metakaolin. A finer pore structure associated with an increase in strength. X-ray analysis data reveal a growing number of small-crystalline low-alkaline calcium hydrosilicates and reducing portlandite content, when MK dosage increases. Scanning electron microscopy (SEM data confirm, that hardened cement paste containing MK has

  9. Evaluation of the geological relationships to gas hydrate formation and stability

    Energy Technology Data Exchange (ETDEWEB)

    Krason, J.; Finley, P.


    The summaries of regional basin analyses document that potentially economic accumulations of gas hydrates can be formed in both active and passive margin settings. The principal requirement for gas hydrate formation in either setting is abundant methane. Passive margin sediments with high sedimentation rates and sufficient sedimentary organic carbon can generate large quantities of biogenic methane for hydrate formation. Similarly, active margin locations near a terrigenous sediment source can also have high methane generation potential due to rapid burial of adequate amounts of sedimentary organic matter. Many active margins with evidence of gas hydrate presence correspond to areas subject to upwelling. Upwelling currents can enhance methane generation by increasing primary productivity and thus sedimentary organic carbon. Structural deformation of the marginal sediments at both active and passive sites can enhance gas hydrate formation by providing pathways for migration of both biogenic and thermogenic gas to the shallow gas hydrate stability zone. Additionally, conventional hydrocarbon traps may initially concentrate sufficient amounts of hydrocarbons for subsequent gas hydrate formation.

  10. Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens (United States)

    Waite, William F.; Spangenberg, E.K.


    Marine sands highly saturated with gas hydrates are potential energy resources, likely forming from methane dissolved in pore water. Laboratory fabrication of gas hydrate-bearing sands formed from dissolved-phase methane usually requires 1–2 months to attain the high hydrate saturations characteristic of naturally occurring energy resource targets. A series of gas hydrate formation tests, in which methane-supersaturated water circulates through 100, 240, and 200,000 cm3 vessels containing glass beads or unconsolidated sand, show that the rate-limiting step is dissolving gaseous-phase methane into the circulating water to form methane-supersaturated fluid. This implies that laboratory and natural hydrate formation rates are primarily limited by methane availability. Developing effective techniques for dissolving gaseous methane into water will increase formation rates above our observed (1 ± 0.5) × 10−7 mol of methane consumed for hydrate formation per minute per cubic centimeter of pore space, which corresponds to a hydrate saturation increase of 2 ± 1% per day, regardless of specimen size.

  11. Formation of Structured Water and Gas Hydrate by the Use of Xenon Gas in Vegetable Tissue (United States)

    Ando, Hiroko; Suzuki, Toru; Kawagoe, Yoshinori; Makino, Yoshio; Oshita, Seiichi

    Freezing is a valuable technique for food preservation. However, vegetables are known to be softening remarkably after freezing and thawing process. It is expected to find alternative technique instead of freezing. Recently, the application of structured water and/or gas hydrate had been attempted to prolong the preservation of vegetable. In this study, the formation process of structure water and/or gas hydrate in pure water and carrot tissue was investigated by using NMR relaxation times, T1 and T2, of which applying condition was up to 0.4MPa and 0.8MPa at 5oC. Under the pressure of 0.4MPa, no gas hydrate was appeared, however, at 0.8MPa, formation of gas hydrate was recognized in both water and carrot tissue. Once the gas hydrate formation process in carrot tissue started, T1 and T2 increased remarkably. After that, as the gas hydrate developed, then T1 and T2 turned to decrease. Since this phenomenon was not observed in pure water, it is suggested that behavior of NMR relaxation time just after the formation of gas hydrate in carrot tissue may be peculiar to compartment system such as inter and intracellular spaces.

  12. Flows due to pressure induced dissociation-formation of gas hydrates (United States)

    Agudo, J. R.; Kwon, S.; Saur, R.; Loekman, S.; Luzi, G.; Rauh, C.; Wierschem, A.; Delgado, A.


    During the last decade, Gas Hydrates (GH) have attracted the interest of the scientific community for engineering applications. Carbon dioxide hydrate (CO2H), for instance, may play an important role for capture and sequestration methods in order to reduce global climate change. Despite the extensive literature, the transport phenomena involved during CO2H formation are not yet fully understood. CO2 transfer from gas or liquid phase to the bulk of water is expected to happen not only by molecular diffusion but also driven by natural convective currents induced by CO2 dissolution in water. Using particle tracer methods, we experimentally characterize the flow velocity of the bulk of water during CO2H formation. For that purpose, CO2H is grown inside an optical cell with a volume of 12 mL at various pressures and temperatures. Due to CO2 dissolution, convection currents are noticed prior to hydrate formation. Our experimental results point to a significant correlation between this process and the subsequent hydrate formation. Two well-differentiated hydrate growth patterns were observed depending on the hydrate induction time and the corresponding CO2 concentration distribution inside water. For long induction times, CO2 can be provided from the water phase resulting in rapid growth. Short induction times resulted in slow growth at the interface creating a solid barrier accompanied by a significant drop in the flow velocity. In some cases, the hydrate layer appeared to be unstable and convection could restart.

  13. Gas Hydrate Research Database and Web Dissemination Channel

    Energy Technology Data Exchange (ETDEWEB)

    Micheal Frenkel; Kenneth Kroenlein; V Diky; R.D. Chirico; A. Kazakow; C.D. Muzny; M. Frenkel


    To facilitate advances in application of technologies pertaining to gas hydrates, a United States database containing experimentally-derived information about those materials was developed. The Clathrate Hydrate Physical Property Database (NIST Standard Reference Database {number_sign} 156) was developed by the TRC Group at NIST in Boulder, Colorado paralleling a highly-successful database of thermodynamic properties of molecular pure compounds and their mixtures and in association with an international effort on the part of CODATA to aid in international data sharing. Development and population of this database relied on the development of three components of information-processing infrastructure: (1) guided data capture (GDC) software designed to convert data and metadata into a well-organized, electronic format, (2) a relational data storage facility to accommodate all types of numerical and metadata within the scope of the project, and (3) a gas hydrate markup language (GHML) developed to standardize data communications between 'data producers' and 'data users'. Having developed the appropriate data storage and communication technologies, a web-based interface for both the new Clathrate Hydrate Physical Property Database, as well as Scientific Results from the Mallik 2002 Gas Hydrate Production Research Well Program was developed and deployed at

  14. Effect of bubble formation on the dissociation of methane hydrate in water: a molecular dynamics study. (United States)

    Yagasaki, Takuma; Matsumoto, Masakazu; Andoh, Yoshimichi; Okazaki, Susumu; Tanaka, Hideki


    We investigate the dissociation of methane hydrate in liquid water using molecular dynamics simulations. As dissociation of the hydrate proceeds, methane molecules are released into the aqueous phase and eventually they form bubbles. It is shown that this bubble formation, which causes change in the methane concentration in the aqueous phase, significantly affects the dissociation kinetics of methane hydrate. A large system size employed in this study makes it possible to analyze the effects of the change in the methane concentration and the formation of bubbles on the dissociation kinetics in detail. It is found that the dissociation rate decreases with time until the bubble formation and then it turns to increase. It is also demonstrated that methane hydrate can exist as a metastable superheated solid if there exists no bubble.

  15. Illuminating solid gas storage in confined spaces - methane hydrate formation in porous model carbons. (United States)

    Borchardt, Lars; Nickel, Winfried; Casco, Mirian; Senkovska, Irena; Bon, Volodymyr; Wallacher, Dirk; Grimm, Nico; Krause, Simon; Silvestre-Albero, Joaquín


    Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores.

  16. Research on Gas Hydrate Plug Formation under Pipeline-Like Conditions

    Directory of Open Access Journals (Sweden)

    Florian Stephan Merkel


    Full Text Available Hydrates of natural gases like methane have become subject of great interest over the last few decades, mainly because of their potential as energy resource. The exploitation of these natural gases from gas hydrates is seen as a promising mean to solve future energetic problems. Furthermore, gas hydrates play an important role in gas transportation and gas storage: in pipelines, particularly in tubes and valves, gas hydrates are formed and obstruct the gas flow. This phenomenon is called “plugging” and causes high operational expenditure as well as precarious safety conditions. In this work, research on the formation of gas hydrates under pipeline-like conditions, with the aim to predict induction times as a mean to evaluate the plugging potential, is described.

  17. Gas hydrate, fluid flow and free gas: Formation of the bottom-simulating reflector (United States)

    Haacke, R. Ross; Westbrook, Graham K.; Hyndman, Roy D.


    Gas hydrate in continental margins is commonly indicated by a prominent bottom-simulating seismic reflector (BSR) that occurs a few hundred metres below the seabed. The BSR marks the boundary between sediments containing gas hydrate above and free gas below. Most of the reflection amplitude is caused by the underlying free gas. Gas hydrate can occur without a BSR, however, and the controls on its formation are not well understood. Here we describe two complementary mechanisms for free gas accumulation beneath the gas hydrate stability zone (GHSZ). The first is the well-recognised hydrate recycling mechanism that generates gas from dissociating hydrate when the base of the GHSZ moves upward relative to hydrate-bearing sediment. The second is a recently identified mechanism in which the relationship between the advection and diffusion of dissolved gas with the local solubility curve allows the liquid phase to become saturated in a thick layer beneath the GHSZ when hydrate is present near its base. This mechanism for gas production (called the solubility-curvature mechanism) is possible in systems where the influence of diffusion becomes important relative to the influence of advection and where the gas-water solubility decreases to a minimum several hundred metres below the GHSZ. We investigate a number of areas in which gas hydrate occurs to determine where gas formation is dominated by the solubility-curvature mechanism and where it is dominated by hydrate recycling. We show that the former is dominant in areas with low rates of upward fluid flow (such as old, rifted continental margins), low rates of seafloor uplift, and high geothermal gradient and/or pressure. Conversely, free-gas formation is dominated by hydrate recycling where there are rapid rates of upward fluid flow and seabed uplift (such as in subduction zone accretionary wedges). Using these two mechanisms to investigate the formation of free gas beneath gas hydrate in continental margins, we are able

  18. Biosurfactant as a Promoter of Methane Hydrate Formation: Thermodynamic and Kinetic Studies. (United States)

    Arora, Amit; Cameotra, Swaranjit Singh; Kumar, Rajnish; Balomajumder, Chandrajit; Singh, Anil Kumar; Santhakumari, B; Kumar, Pushpendra; Laik, Sukumar


    Natural gas hydrates (NGHs) are solid non-stoichiometric compounds often regarded as a next generation energy source. Successful commercialization of NGH is curtailed by lack of efficient and safe technology for generation, dissociation, storage and transportation. The present work studied the influence of environment compatible biosurfactant on gas hydrate formation. Biosurfactant was produced by Pseudomonas aeruginosa strain A11 and was characterized as rhamnolipids. Purified rhamnolipids reduced the surface tension of water from 72 mN/m to 36 mN/m with Critical Micelle Concentration (CMC) of 70 mg/l. Use of 1000 ppm rhamnolipids solution in C type silica gel bed system increased methane hydrate formation rate by 42.97% and reduced the induction time of hydrate formation by 22.63% as compared to water saturated C type silica gel. Presence of rhamnolipids also shifted methane hydrate formation temperature to higher values relative to the system without biosurfactant. Results from thermodynamic and kinetic studies suggest that rhamnolipids can be applied as environment friendly methane hydrate promoter.

  19. Exploring the formation of multiple layer hydrates for a complex pharmaceutical compound. (United States)

    Zhao, Xin S; Siepmann, J Ilja; Xu, Wei; Kiang, Y-H; Sheth, Agam R; Karaborni, Sami


    The pharmaceutical compound A, 3-{2-oxo-3-[3-(5,6,7,8-tetrahydro[1,8]naphthyridin-2-yl)propyl]imidazolidin-1-yl}-3(S)-(6-methoxypyridin-3-yl)propionic acid, is known to exist in five different crystalline forms that differ in the hydration state ranging from the anhydrous desolvate over hemihydrate, dihydrate, and tetrahydrate forms to the pentahydrate. The formation of the higher hydrates and the concomitant lattice expansion leads to undesirable tablet cracking at higher humidities. In this work, particle-based simulation techniques are used to explore the hydrate formation of compound A as a function of humidity. It is found that a simulation strategy employing Monte Carlo simulations in the isobaric-isothermal and Gibbs ensembles and transferable force fields, which are not parametrized against any experimental data for compound A, is able to yield satisfactory crystal structures for the anhydrate and pentahydrate and to predict the existence of all five hydrates.

  20. Experimental investigation of gas hydrate formation, plugging and transportability in partially dispersed and water continuous systems (United States)

    Vijayamohan, Prithvi

    As oil/gas subsea fields mature, the amount of water produced increases significantly due to the production methods employed to enhance the recovery of oil. This is true especially in the case of oil reservoirs. This increase in the water hold up increases the risk of hydrate plug formation in the pipelines, thereby resulting in higher inhibition cost strategies. A major industry concern is to reduce the severe safety risks associated with hydrate plug formation, and significantly extending subsea tieback distances by providing a cost effective flow assurance management/safety tool for mature fields. Developing fundamental understanding of the key mechanistic steps towards hydrate plug formation for different multiphase flow conditions is a key challenge to the flow assurance community. Such understanding can ultimately provide new insight and hydrate management guidelines to diminish the safety risks due to hydrate formation and accumulation in deepwater flowlines and facilities. The transportability of hydrates in pipelines is a function of the operating parameters, such as temperature, pressure, fluid mixture velocity, liquid loading, and fluid system characteristics. Specifically, the hydrate formation rate and plugging onset characteristics can be significantly different for water continuous, oil continuous, and partially dispersed systems. The latter is defined as a system containing oil/gas/water, where the water is present both as a free phase and partially dispersed in the oil phase (i.e., entrained water in the oil). Since hydrate formation from oil dispersed in water systems and partially dispersed water systems is an area which is poorly understood, this thesis aims to address some key questions in these systems. Selected experiments have been performed at the University of Tulsa flowloop to study the hydrate formation and plugging characteristics for the partially dispersed water/oil/gas systems as well as systems where the oil is completely dispersed

  1. Interfacial properties of methane/aqueous VC-713 solution under hydrate formation conditions. (United States)

    Peng, Bao-Zi; Sun, Chang-Yu; Liu, Peng; Liu, Yan-Tao; Chen, Jun; Chen, Guang-Jin


    The interfacial tensions between methane and aqueous solutions of different contents of VC-713 (a terpolymer of N-vinylpyrrolidone, N-vinylcaprolactam, and dimethylamino-ethyl-methacrylate) were measured at different temperatures and pressures in the hydrate formation region. The surface adsorption free energies of methane were calculated accordingly in order to investigate the effect of this kinetic inhibitor on the nucleation of hydrate. The results show that the presence of VC-713 lowers the interfacial tension, increasing the concentration of methane on the surface of the aqueous phase, and thus promotes nucleation of hydrate at the gas/liquid interface. Additionally, the measured interfacial tension data suggest that VC-713 tends not to form micelles in water. Subsequently, the lateral growth rate of hydrate film on the surface of a methane bubble suspended in the aqueous phase was measured at different pressures to investigate the effect of VC-713 on the growth of hydrate. The results show that the lateral growth rate of hydrate film from aqueous VC-713 solution is much lower than that from pure water, demonstrating that VC-713 significantly inhibits the hydrate growth. The mechanism of the inhibition is also discussed.

  2. Kinetics of Methane Hydrate Formation in an Aqueous Solution with and without Kinetic Promoter (SDS by Spray Reactor

    Directory of Open Access Journals (Sweden)

    Yaqin Tian


    Full Text Available Hydrate formation apparatus reported so far was mainly concentrated in stirred-tank batch environments. It was difficult to produce the high gas storage hydrate efficiently. Some nonstirred technology has been attracting more attention by researchers. This work proposed a new apparatus for hydrate formation by spraying water into a gaseous phase with a fine nozzle. It can get sufficient contact surface area for gas-liquid reaction. Methane hydrate formation experiments have been conducted using pure water and sodium dodecyl sulfate (SDS aqueous solution for comparison at 277.15 K. The experiments were conducted at 7.0 and 6.0 MPa, respectively. Kinetics of methane hydrate formation have been investigated by methane consumption per mole of water and reaction rate. The mechanism of hydrate formation and kinetics property by spraying atomization were studied with the theory of crystal chemistry.

  3. Combustion of Methane Hydrate (United States)

    Roshandell, Melika

    A significant methane storehouse is in the form of methane hydrates on the sea floor and in the arctic permafrost. Methane hydrates are ice-like structures composed of water cages housing a guest methane molecule. This caged methane represents a resource of energy and a potential source of strong greenhouse gas. Most research related to methane hydrates has been focused on their formation and dissociation because they can form solid plugs that complicate transport of oil and gas in pipelines. This dissertation explores the direct burning of these methane hydrates where heat from the combustion process dissociates the hydrate into water and methane, and the released methane fuels the methane/air diffusion flame heat source. In contrast to the pipeline applications, very little research has been done on the combustion and burning characteristics of methane hydrates. This is the first dissertation on this subject. In this study, energy release and combustion characteristics of methane hydrates were investigated both theoretically and experimentally. The experimental study involved collaboration with another research group, particularly in the creation of methane hydrate samples. The experiments were difficult because hydrates form at high pressure within a narrow temperature range. The process can be slow and the resulting hydrate can have somewhat variable properties (e.g., extent of clathration, shape, compactness). The experimental study examined broad characteristics of hydrate combustion, including flame appearance, burning time, conditions leading to flame extinguishment, the amount of hydrate water melted versus evaporated, and flame temperature. These properties were observed for samples of different physical size. Hydrate formation is a very slow process with pure water and methane. The addition of small amounts of surfactant increased substantially the hydrate formation rate. The effects of surfactant on burning characteristics were also studied. One finding

  4. 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.


    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.

  5. Observation of the growth characteristics of gas hydrate in the quiescent-type formation method using surfactant (United States)

    Asaoka, Tatsunori; Ikeda, Koya


    We have observed the growth behavior of gas hydrate with addition of surfactants by several observation methods, and we discuss the mechanism of gas hydrate formation along the wall surface. From observation using colored water, the water moves up through the porous hydrate structure and unreacted water remains in the middle of the porous hydrate. In contrast to previous studies which observed growth from the side, we observed the growth behavior from the top. The hydrate height agrees well with that of water pulled up by capillary action. These results confirm that the driving force for hydrate growth in the vertical direction is capillary action. We discuss the driving force for hydrate growth in the horizontal direction. We suggest that the driving force in the horizontal direction is different because the initial concentration of the surfactant solution affects the growth behavior in the horizontal direction while it does not affect the hydrate height.

  6. Hydration, hydration, hydration

    National Research Council Canada - National Science Library

    Miller, Veronica S; Bates, Graham P


    .... Although the importance of adequate hydration in combating heat stress is universally recognized, studies in a range of worker groups have demonstrated a disturbingly poor hydration level in a high...

  7. In-situ visual observation for the formation and dissociation of methane hydrates in porous media by magnetic resonance imaging. (United States)

    Zhao, Jiafei; Lv, Qin; Li, Yanghui; Yang, Mingjun; Liu, Weiguo; Yao, Lei; Wang, Shenglong; Zhang, Yi; Song, Yongchen


    In this work, magnetic resonance imaging (MRI) was employed to observe the in-situ formation and dissociation of methane hydrates in porous media. Methane hydrate was formed in a high-pressure cell with controlled temperature, and then the hydrate was dissociated by thermal injection. The process was photographed by the MRI, and the pressure was recorded. The images confirmed that the direct visual observation was achieved; these were then employed to provide detailed information of the nucleation, growth, and decomposition of the hydrate. Moreover, the saturation of methane hydrate during the dissociation was obtained from the MRI intensity data. Our results showed that the hydrate saturation initially decreased rapidly, and then slowed down; this finding is in line with predictions based only on pressure. The study clearly showed that MRI is a useful technique to investigate the process of methane hydrate formation and dissociation in porous media. Copyright © 2015 Elsevier Inc. All rights reserved.

  8. Effect of interlayer ions on methane hydrate formation in clay sediments. (United States)

    Yeon, Sun-Hwa; Seol, Jiwoong; Seo, Young-ju; Park, Youngjune; Koh, Dong-Yeun; Park, Keun-Pil; Huh, Dae-Gee; Lee, Jaehyoung; Lee, Huen


    Natural methane hydrates occurring in marine clay sediments exhibit heterogeneous phase behavior with high complexity, particularly in the negatively charged interlayer region. To date, the real clay interlayer effect on natural methane hydrate formation and stability remains still much unanswered, even though a few computer simulation and model studies are reported. We first examined the chemical shift difference of 27Al, 29Si, and 23Na between dry clay and clay containing intercalated methane hydrates (MH) in the interlayer. We also measured the solid-state 13C MAS NMR spectra of MH in Na-montmorillonite (MMT) and Ca-montmorillonite (MMT) to reveal abnormal methane popularity established in the course of intercalation and further performed cryo-TEM and XRD analyses to identify the morphology and layered structure of the intercalated methane hydrate. The present findings strongly suggest that the real methane amount contained in natural MH deposits should be reevaluated under consideration of the compositional, structural, and physical characteristics of clay-rich sediments. Furthermore, the intercalated methane hydrate structure should be seriously considered for developing the in situ production technologies of the deep-ocean methane hydrate.

  9. Grain scale study of hydrate formation in sediments from methane gas : role of capillarity

    Energy Technology Data Exchange (ETDEWEB)

    Behseresht, J.; Peng, Y.; Prodanovic, M.; Bryant, S.L. [Texas Univ. at Austin, Austin, TX (United States)


    There are varying estimates of the amount of methane hydrate in ocean sediments and in permafrost regions. The difficulty in determining the growth habit and the spatial distribution of hydrate within the hydrate stability zone (HSZ) contribute to this variability. The mode in which methane is transported in the HSZ is thought to affect the spatial distribution of hydrate. A predictive, mechanistic model of transport is therefore needed. This paper focused on the contribution of capillarity-controlled fluid displacement to transport. Because gas, water and hydrate phases are known to coexist within the HSZ, the phenomena associated with two-phase flow was studied. The conference paper described mechanistic grain-scale models for the capillarity-controlled displacement of brine by gas. The model was extended to account heuristically for displacement of sediment grains by the pressure imbalance between gas and water phases. The paper discussed the implications of model predictions for water and gas availability for hydrate formation. The paper discussed the geometric models of sediments, the network model of drainage of the model sediment, wetting phase connectivity, and wetting phase trapping. It also discussed the level set method (LSM) for interface tracking including the progressive quasi-static (PQS) algorithm and the PQS fluid displacement coupled with grain displacement. It was concluded that LSM/PQS accurately predicted critical curvature for drainage. 22 refs., 1 tab., 9 figs.

  10. The influence of temperature, pressure, salinity and capillary force on the formation of methane hydrate

    Directory of Open Access Journals (Sweden)

    Zhenhao Duan


    Full Text Available We present here a thermodynamic model for predicting multi-phase equilibrium of methane hydrate liquid and vapor phases under conditions of different temperature, pressure, salinity and pore sizes. The model is based on the 1959 van der Waals–Platteeuw model, angle-dependent ab initio intermolecular potentials, the DMW-92 equation of state and Pitzer theory. Comparison with all available experimental data shows that this model can accurately predict the effects of temperature, pressure, salinity and capillary radius on the formation and dissociation of methane hydrate. Online calculations of the p–T conditions for the formation of methane hydrate at given salinities and pore sizes of sediments are available on:

  11. Adsorption of water and carbon dioxide on hematite and consequences for possible hydrate formation. (United States)

    Kvamme, Bjørn; Kuznetsova, Tatiana; Kivelae, Pilvi-Helina


    The interest in carbon dioxide for enhanced oil recovery is increasing proportional to the decline in naturally driven oil production and also due to the increasing demand for reduced emission of carbon dioxide into the atmosphere. Transport of carbon dioxide in offshore pipelines involves high pressure and low temperatures, conditions which may lead to formation of hydrates from residual water dissolved in carbon dioxide and carbon dioxide. The critical question is whether the water at certain temperatures and pressures will drop out as liquid droplets first, and then form hydrates, or alternatively, adsorb on the pipeline surfaces, and subsequently form hydrates heterogeneously. In this work, we used several different basis sets of density functional theory in ab initio calculations to estimate the charge distribution of hematite (the dominating component of rust) crystals. These rust particles were embedded in water and chemical potential for adsorbed water molecules was estimated through thermodynamic integration and compared to similar estimates for water clusters of the same size. While the generated charges were not unique, the use of high order approximations and different basis sets provides a range of likely charge distributions. Values obtained for the chemical potential of water in different surroundings indicated that it would be thermodynamically favorable for water to adsorb on hematite, and that evaluation of potential carbon dioxide hydrate formation conditions and kinetics should be based on this formation mechanism. Depending on the basis set and approximations, the estimated gain for water to adsorb on the hematite surface rather than condense as droplets varied between -1.7 kJ mole(-1) and -3.4 kJ mole(-1). The partial charge distribution on the hematite surface is incompatible with the hydrate structure, and thus hydrates will be unable to attach to the surface. The behavior of water outside the immediate vicinity of hematite (beyond 3

  12. Geological evolution and analysis of confirmed or suspected gas hydrate localities: Volume 13: Basin analysis, formation and stability of gas hydrates of the Nankai Trough: Topical report

    Energy Technology Data Exchange (ETDEWEB)

    Ciesnik, M.; Krason, J.


    Geological factors controlling the formation, stability, and distribution of gas hydrates were investigated by basin analysis of the Nankai Trough region. The Nankai Trough is located beneath the western Pacific, south of the Japanese islands Shikoku and central Kyushu. Geological, geophysical, and geochemical data from the region were assembled and critically evaluated to develop consistent interpretations of the relationships of geological environments and gas hydrates. This study was performed for the US Department of Energy Morgantown Energy Technology Center by Geoexplorers International, Inc., as part of a worldwide evaluation of 21 offshore sites where the presence of gas hydrates has been confirmed or inferred. 60 refs., 26 figs., 1 tab.

  13. Natural gas hydrate formation and inhibition in gas/crude oil/aqueous systems

    DEFF Research Database (Denmark)

    Daraboina, Nagu; Pachitsas, Stylianos; von Solms, Nicolas


    in comparison with that in pure water. This observed hydrate inhibition potential shows significant variation depending on the type of crude oil. The influence of crude oil composition (saturates, aromatics, resins and asphaltenes) on this behavior was probably due to the existence of a combination of different...... inhibition mechanisms and potentially a competition among inhibition-promotion mechanisms. Moreover, the hydrate formation time has been determined at different water cuts in each crude oil and it was found that the inhibition capability increases with an increase in the oil content. The effect...... can contribute to the safe operation of sub sea pipelines in the oil and gas industry....

  14. Cage occupancies in the high pressure structure H methane hydrate: a neutron diffraction study. (United States)

    Tulk, C A; Klug, D D; dos Santos, A M; Karotis, G; Guthrie, M; Molaison, J J; Pradhan, N


    A neutron diffraction study was performed on the CD(4) : D(2)O structure H clathrate hydrate to refine its CD(4) fractional cage occupancies. Samples of ice VII and hexagonal (sH) methane hydrate were produced in a Paris-Edinburgh press and in situ neutron diffraction data collected. The data were analyzed with the Rietveld method and yielded average cage occupancies of 3.1 CD(4) molecules in the large 20-hedron (5(12)6(8)) cages of the hydrate unit cell. Each of the pentagonal dodecahedron (5(12)) and 12-hedron (4(3)5(6)6(3)) cages in the sH unit cell are occupied with on average 0.89 and 0.90 CD(4) molecules, respectively. This experiment avoided the co-formation of Ice VI and sH hydrate, this mixture is more difficult to analyze due to the proclivity of ice VI to form highly textured crystals, and overlapping Bragg peaks of the two phases. These results provide essential information for the refinement of intermolecular potential parameters for the water-methane hydrophobic interaction in clathrate hydrates and related dense structures.

  15. Prediction of Gas Hydrate Formation Conditions in Aqueous Solutions of Single and Mixed Electrolytes

    DEFF Research Database (Denmark)

    Zuo, You-Xiang; Stenby, Erling Halfdan


    In this paper, the extended Patel-Teja equation of state was modified to describe non-ideality of the liquid phase containing water and electrolytes accurately. The modified Patel-Teja equation of state (MPT EOS) was utilized to develop a predictive method for gas hydrate equilibria. The new meth...... predicted the gas hydrate formation conditions in aqueous solutions of single and mixed electrolytes. The agreement between experimental data and predictions was found to be excellent.......In this paper, the extended Patel-Teja equation of state was modified to describe non-ideality of the liquid phase containing water and electrolytes accurately. The modified Patel-Teja equation of state (MPT EOS) was utilized to develop a predictive method for gas hydrate equilibria. The new method...

  16. Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria (United States)

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


    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.

  17. Molecular dynamics study of methane hydrate formation at a water/methane interface. (United States)

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


    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.

  18. Crystal structure, stability and spectroscopic properties of methane and CO2 hydrates. (United States)

    Martos-Villa, Ruben; Francisco-Márquez, Misaela; Mata, M Pilar; Sainz-Díaz, C Ignacio


    Methane hydrates are highly present in sea-floors and in other planets and their moons. Hence, these compounds are of great interest for environment, global climate change, energy resources, and Cosmochemistry. The knowledge of stability and physical-chemical properties of methane hydrate crystal structure is important for evaluating some new green becoming technologies such as, strategies to produce natural gas from marine methane hydrates and simultaneously store CO2 as hydrates. However, some aspects related with their stability, spectroscopic and other chemical-physical properties of both hydrates are not well understood yet. The structure and stability of crystal structure of methane and CO2 hydrates have been investigated by means of calculations with empirical interatomic potentials and quantum-mechanical methods based on Hartree-Fock and Density Functional Theory (DFT) approximations. Molecular Dynamic simulations have been also performed exploring different configurations reproducing the experimental crystallographic properties. Spectroscopic properties have also been studied. Frequency shifts of the main vibration modes were observed upon the formation of these hydrates, confirming that vibration stretching peaks of C-H at 2915cm(-1) and 2905cm(-1) are due to methane in small and large cages, respectively. Similar effect is observed in the CO2 clathrates. The guest-host binding energy in these clathrates calculated with different methods are compared and discussed in terms of adequacy of empirical potentials and DFT methods for describing the interactions between gas guest and the host water cage, proving an exothermic nature of methane and CO2 hydrates formation process. Copyright © 2013 Elsevier Inc. All rights reserved.

  19. The big fat LARS - a LArge Reservoir Simulator for hydrate formation and gas production (United States)

    Beeskow-Strauch, Bettina; Spangenberg, Erik; Schicks, Judith M.; Giese, Ronny; Luzi-Helbing, Manja; Priegnitz, Mike; Klump, Jens; Thaler, Jan; Abendroth, Sven


    Simulating natural scenarios on lab scale is a common technique to gain insight into geological processes with moderate effort and expenses. Due to the remote occurrence of gas hydrates, their behavior in sedimentary deposits is largely investigated on experimental set ups in the laboratory. In the framework of the submarine gas hydrate research project (SUGAR) a large reservoir simulator (LARS) with an internal volume of 425 liter has been designed, built and tested. To our knowledge this is presently a word-wide unique set up. Because of its large volume it is suitable for pilot plant scale tests on hydrate behavior in sediments. That includes not only the option of systematic tests on gas hydrate formation in various sedimentary settings but also the possibility to mimic scenarios for the hydrate decomposition and subsequent natural gas extraction. Based on these experimental results various numerical simulations can be realized. Here, we present the design and the experimental set up of LARS. The prerequisites for the simulation of a natural gas hydrate reservoir are porous sediments, methane, water, low temperature and high pressure. The reservoir is supplied by methane-saturated and pre-cooled water. For its preparation an external gas-water mixing stage is available. The methane-loaded water is continuously flushed into LARS as finely dispersed fluid via bottom-and-top-located sparger. The LARS is equipped with a mantle cooling system and can be kept at a chosen set temperature. The temperature distribution is monitored at 14 reasonable locations throughout the reservoir by Pt100 sensors. Pressure needs are realized using syringe pump stands. A tomographic system, consisting of a 375-electrode-configuration is attached to the mantle for the monitoring of hydrate distribution throughout the entire reservoir volume. Two sets of tubular polydimethylsiloxan-membranes are applied to determine gas-water ratio within the reservoir using the effect of permeability

  20. Dry Climate as Major Factor Controlling Formation of Hydrated Sulfate Minerals in Valles Marineris on Mars (United States)

    Szynkiewicz, A.


    In this study, a model for the formation of hydrated sulfate salts (Mg-Ca-Na sulfates) in the Rio Puerco watershed of New Mexico, a terrestrial analog site from the semi-arid Southwest U.S., was used to assess the origin and climate condition that may have controlled deposition of hydrated sulfates in Valles Marineris on Mars. In this analog site, the surface accumulation of sulfate minerals along canyon walls, slopes and valley surfaces closely resemble occurrences of hydrated sulfates in Valles Marineris on Mars. Significant surface accumulations of Mg-Ca-Na sulfates are a result of prevailing semiarid conditions and a short-lived hydrological cycle that mobilizes sulfur present in the bedrock as sulfides, sulfate minerals, and atmospheric deposition. Repeating cycles of salt dissolution and re-precipitation appear to be the underpinning processes that serve to transport sulfate from bedrock to sulfate salts (e.g., efflorescences) and into surface water. This process occurs in the shallow surface environment and is not accompanied by deep groundwater flow because of prevailing dry conditions and low annual precipitation. Generally, close resemblance of surface occurrence and mineralogical composition of sulfate salts between the studied terrestrial analog and Valles Marineris suggest that a similar sulfate cycle, involving limited water activity during formation of hydrated sulfates, was once present in Valles Marineris. Measured as efflorescence, the distributed surface mass of hydrated sulfates in Valles Marineris is relatively small (4 to 42%) when compared to terrestrial settings with higher surface accumulation of sulfate minerals such as the White Sands gypsum dune field. Under semi-arid conditions similar to the studied analog in the Rio Pueurco watershed, it would take only 100 to 1,000 years to activate an equivalent flux of aqueous sulfate in Valles Marineris, when comparing terrestrial annual sulfate fluxes from the Rio Puerco watershed with the amount

  1. Hydrate formation during wet granulation studied by spectroscopic methods and multivariate analysis

    DEFF Research Database (Denmark)

    Jørgensen, Anna; Rantanen, Jukka; Karjalainen, Milja


    ) Raman spectroscopy was compared with near-infrared spectroscopy (NIR) in following hydrate formation of drugs during wet granulation (off-line). To perform an at-line process analysis, the effect of water addition was monitored by NIR spectroscopy and principal components analysis (PCA). The changes...... gave information related to the drug molecule itself. The XRPD confirmed the spectroscopic results. PCA with three principal components explained 99.9 of the spectral variation in the second derivative NIR spectra. CONCLUSIONS: Both CCD Raman and NIR spectroscopic methods can be applied to monitoring...... in the crystal arrangements were verified by using X-ray powder diffraction (XRPD). RESULTS: Hydrate formation of theophylline and caffeine could be followed by CCD Raman spectroscopy. The NIR and Raman spectroscopic results were consistent with each other. NIR revealed the state of water, and Raman spectroscopy...

  2. Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids. (United States)

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong


    Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.


    Directory of Open Access Journals (Sweden)

    Kaziliunas A.


    Full Text Available Preparation of phosphogypsum to produce the binders requires a much higher input than preparation of natural gypsum stone. This makes it uncompetitive material. The investigations presented therein are meant to reduce this input by looking for the ways of rendering impurities harmless. Soluble acid orthophosphates are the main harmful impurity of phosphogypsum. The studies show that dry insoluble calcium orthophosphates hydrates (1.09 % and 2.18 % P2O5 in gypsum have little effect on W/C, setting times and soundness of Portland cement pastes. Insoluble calcium orthophosphates hydrates {CaHPO4∙2H2O, Ca8(HPO42(PO44∙5H2O and Ca9(HPO4(PO45(OH∙4H2O} formed in acidic medium (pH = 4.2 - 5.9 have been destroyed in alkaline medium and reduce standard compressive strength of cement up to 28 %. Calcium orthophosphates hydrates of hydroxyapatite group are stable in alcaline medium, while in dry state they reduce the standard compressive strength of cement until 10 %, but their suspensions prolong setting times of Portland cement as soluble orthophosphates – 2 - 3 times. Alkalis in cement increase pH of paste, but do not change the process of formation of calcium orthophosphates hydrates of hydroxyapatite group: it takes place through an intermediate phase - CaHPO4·2H2O, whose transformation into apatite lasts for 2 - 3 months.

  4. Study of ethane hydrate formation kinetics using the chemical affinity model with and without presence of surfactants (United States)

    Karimi, Reza; Varaminian, Farshad; Izadpanah, Amir A.


    In this article, we examine ethane hydrate formation kinetics with and without the presence of various surfactants. Firstly, the influences of stirring rate and initial pressure without the presence of surfactants are studied. The effects of four surfactants containing Sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), Polyoxyethylene (20) sorbitanmonopalmitate (Tween® 40), and TritonX-100 (TX-100) on ethane hydrate formation kinetics were experimentally investigated. Then the chemical affinity model is applied to model the ethane hydrate formation kinetics with and without surfactants. The kinetic parameters of the chemical affinity model were computed for the ethane hydrate formation with and without surfactants. We will see that the results of the modeling are in good agreement with the experimental data.

  5. Evaluation of the geological relationships to gas hydrate formation and stability. Progress report, June 16--September 30, 1988

    Energy Technology Data Exchange (ETDEWEB)

    Krason, J.; Finley, P.


    The summaries of regional basin analyses document that potentially economic accumulations of gas hydrates can be formed in both active and passive margin settings. The principal requirement for gas hydrate formation in either setting is abundant methane. Passive margin sediments with high sedimentation rates and sufficient sedimentary organic carbon can generate large quantities of biogenic methane for hydrate formation. Similarly, active margin locations near a terrigenous sediment source can also have high methane generation potential due to rapid burial of adequate amounts of sedimentary organic matter. Many active margins with evidence of gas hydrate presence correspond to areas subject to upwelling. Upwelling currents can enhance methane generation by increasing primary productivity and thus sedimentary organic carbon. Structural deformation of the marginal sediments at both active and passive sites can enhance gas hydrate formation by providing pathways for migration of both biogenic and thermogenic gas to the shallow gas hydrate stability zone. Additionally, conventional hydrocarbon traps may initially concentrate sufficient amounts of hydrocarbons for subsequent gas hydrate formation.

  6. A study of the methane hydrate formation by in situ turbidimetry

    Energy Technology Data Exchange (ETDEWEB)

    Herri, J.M.


    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.

  7. Effects of excipients on hydrate formation in wet masses containing theophylline

    DEFF Research Database (Denmark)

    Airaksinen, Sari; Luukkonen, Pirjo; Jørgensen, Anna


    Transformations between solid phases in dosage forms can lead to instability in drug release. Thus, it is important to understand mechanisms and kinetics of phase transformations and factors that may influence them. During wet granulation theophylline shows pseudopolymorphic changes that may alter...... is able to take large amounts of water into its internal structure, it was able to inhibit the formation of theophylline monohydrate only at low moisture contents, not at the amounts of water needed to form granules. Both the spectroscopic methods used could identify the hydrate formation even though...

  8. Thermodynamic modeling of phase equilibria of semi-clathrate hydrates of CO2, CH4, or N2+tetra-n-butylammonium bromide aqueous solution

    DEFF Research Database (Denmark)

    Eslamimanesh, Ali; Mohammadi, Amir H.; Richon, Dominique


    concentration in aqueous solution. The Peng–Robinson (PR-EoS) equation of state along with re-tuned parameters of Mathias–Copeman alpha function is applied for calculation of the fugacity of gaseous hydrate former. For determination of the activity coefficient of the non-electrolyte species in the aqueous phase...

  9. The effects of ice on methane hydrate nucleation: a microcanonical molecular dynamics study. (United States)

    Zhang, Zhengcai; Guo, Guang-Jun


    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.

  10. SEM imaging of gas hydrate formation processes and growth textures and comparison to natural hydrates of marine and permafrost origin

    Energy Technology Data Exchange (ETDEWEB)

    Stern, Laura; Circone, Susan; Kirby, Stephen; Durham, William


    Cryogenic scanning electron microscopy provides an excellent means for examining grain morphologies, grain contacts, phase distributions, and pore characteristics within gas-hydratebearing samples of both natural and laboratory origin. Here, we use SEM to observe a variety of laboratory-synthesized sI and sII gas hydrates of known composition and pressure-temperature histories. We show images that convey the diversity of textures observed at various extents of hydrate growth in single-phase gas hydrate systems and hydrate/sediment assemblages, including transient morphologies that are limited primarily to early-to-mid stages of reaction. The resulting textures of fully reacted and/or annealed samples are then followed through increasingly complex laboratory or ocean-floor processes, including compaction, compression, partial dissociation, or partial dissolution. Lastly, we compare the observed features to those developed within natural gashydrate-bearing samples recovered from both marine and permafrost settings. We find that labsynthesized samples can be produced to yield remarkably similar textures, phase distributions, and grain contacts to those found in some hydrate-bearing materials recovered from natural settings. (Author)

  11. A new experimental facility for investigating the formation and properties of gas hydrates under simulated seafloor conditions

    Energy Technology Data Exchange (ETDEWEB)

    Phelps, Tommy J.; Peters, David J.; Marshall, Simon L.; West, Olivia R.; Liang, Liyuan; Blencoe, James G.; Alexiades, Vasilios; Jacobs, Gary K.; Naney, Michael T.; Heck, Jack L.


    A seafloor process simulator (SPS) has been developed for experimental investigations of the physical, geochemical, and microbiological processes affecting the formation and stability of methane and carbon dioxide hydrates at temperatures and pressures corresponding to ocean depths of 2 km. The SPS is a corrosion-resistant pressure vessel whose salient characteristics are: (i) an operating range suitable for study of methane and carbon dioxide hydrates; (ii) numerous access and observation ports, and (iii) a large (0.0722 m3) internal volume. Initial experiments have shown that the SPS can be used to produce large amounts of high-purity methane hydrate over a wide range of experimental conditions.

  12. An Experimental and Theoretical Study of CO2 Hydrate Formation Systems

    DEFF Research Database (Denmark)

    Tzirakis, Fragkiskos

    Appendix E) using as promoters tetra-n-butyl ammonium salts of bromide, fluoride and cyclopentane in collaboration with MINESParisTech in France. These chemicals are well known for their reduction capabilities of hydrate formation pressure. The results are in good accordance with the literature. Moreover......, the simultaneous combination of these chemicals achieved greater pressure reduction than if they were used separately. Then, experimental uncertainties were measured (for pressure/temperature transducers and gas chromatograph) and calculated (for the inserted quantities of water and chemicals). The uncertainties...

  13. The combined effect of thermodynamic promoters tetrahydrofuran and cyclopentane on the kinetics of flue gas hydrate formation

    DEFF Research Database (Denmark)

    Daraboina, Nagu; von Solms, Nicolas


    Carbon dioxide (CO2) capture through hydrate crystallization is a promising method among the new approaches for mitigating carbon emissions into the atmosphere. In this work, we investigate a combination of tetrahydrofuran (THF) and cyclopentane (CP) on the kinetics of flue gas (CO2:20 mol %/N2...... of these two promoters is favorable both thermodynamically and kinetically for hydrate formation from flue gas....

  14. Formation of Sclerotic Hydrate Deposits in a Pipe for Extraction of a Gas from a Dome Separator (United States)

    Urazov, R. R.; Chiglinstev, I. A.; Nasyrov, A. A.


    The theory of formation of hydrate deposits on the walls of a pipe for extraction of a gas from a dome separator designed for the accident-related collection of hydrocarbons on the ocean floor is considered. A mathematical model has been constructed for definition of a steady movement of a gas in such a pipe with gas-hydrate deposition under the conditions of changes in the velocity, temperature, pressure, and moisture content of the gas flow.

  15. Study of formation and stability conditions of gas hydrates in drilling fluids; Etude des conditions de formation et de stabilite des hydrates de gaz dans les fluides de forage

    Energy Technology Data Exchange (ETDEWEB)

    Kharrat, M.


    Drilling fluids are complex media, in which solid particles are in suspension in a water-in-oil emulsion. The formation of gas hydrates in these fluids during off shore drilling operations has been suspected to be the cause of serious accidents. The purpose of this thesis is the study of the formation conditions as well as the stability of gas hydrates in complex fluids containing water-in-oil emulsions. The technique of high-pressure differential scanning calorimetry was used to characterise the conditions of hydrates formation and dissociation. Special attention has first been given to the validation of thermodynamic measurements in homogeneous solutions, in the pressure range 4 to 12 Mpa; the results were found to be in good agreement with literature data, as well as with modelling results. The method was then applied to water-in-oil emulsion, used as a model for real drilling fluids. It was proven that thermodynamics of hydrate stability are not significantly influenced by the state of dispersion of the water phase. On the other hand, the kinetics of formation and the amount of hydrates formed are highly increased by the dispersion. Applying the technique to real drilling fluids confirmed the results obtained in emulsions. Results interpretation allowed giving a representation of the process of hydrate formation in emulsion. Empirical modelling was developed to compute the stability limits of methane hydrate in the presence of various inhibitors, at pressures ranging from ambient to 70 MPa. Isobaric phase diagrams were constructed, that allow predicting the inhibiting efficiency of sodium chloride and calcium chloride at constant pressure, from 0,25 to 70 MPa. (author)

  16. Increasing the sensitivity of headspace analysis of low volatility solutes through water removal by hydrate formation. (United States)

    Hu, Hui-Chao; Chai, Xin-Sheng; Wei, Chao-Hai; Barnes, Donald


    This paper reports on the development of a new headspace analytical technique that is based on water removal by hydrate formation (WRHF). By adding anhydrous salt, the liquid water in an aqueous sample will be removed leaving behind volatile analytes that are fully vaporized at temperatures well below their boiling points. With WRHF, the amount of sample in the headspace can be significantly increased, thereby dramatically improving the detection sensitivity. The technique reduces the risk of possible column damage in gas chromatography (GC) systems. The technique was applied to the determination of phenol at different stages of a coking wastewater treatment plant. The results showed that up to mL-levels of sample solution can be used in WRHF HS-GC analysis when 5g of CaCl2 were used as the anhydrous salt. The detection sensitivity for phenol content was 500 times greater than that in earlier HS-GC work that did not incorporate hydrate formation. The proposed WRHF headspace analysis technique is simple and practical, making it a useful tool for quantifying low concentrations of volatile analytes in aqueous samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Nanobelt formation of magnesium hydroxide sulfate hydrate via a soft chemistry process. (United States)

    Zhou, Zhengzhi; Sun, Qunhui; Hu, Zeshan; Deng, Yulin


    The nanobelt formation of magnesium hydroxide sulfate hydrate (MHSH) via a soft chemistry approach using carbonate salt and magnesium sulfate as reactants was successfully demonstrated. X-ray diffraction (XRD), energy dispersion X-ray spectra (EDS), selected area electron diffraction (SAED), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analysis revealed that the MHSH nanobelts possessed a thin belt structure (approximately 50 nm in thickness) and a rectangular cross profile (approximately 200 nm in width). The MHSH nanobelts suffered decomposition under electron beam irradiation during TEM observation and formed MgO with the pristine nanobelt morphology preserved. The formation process of the MHSH nanobelts was studied by tracking the morphology of the MHSH nanobelts during the reaction. A possible chemical reaction mechanism is proposed.

  18. Temperature- and pressure-dependent structural transformation of methane hydrates in salt environments (United States)

    Shin, Donghoon; Cha, Minjun; Yang, Youjeong; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Ahn, Docheon; Im, Junhyuck; Lee, Yongjae; Han, Oc Hee; Yoon, Ji-Ho


    Understanding the stability of volatile species and their compounds under various surface and subsurface conditions is of great importance in gaining insights into the formation and evolution of planetary and satellite bodies. We report the experimental results of the temperature- and pressure-dependent structural transformation of methane hydrates in salt environments using in situ synchrotron X-ray powder diffraction, solid-state nuclear magnetic resonance, and Raman spectroscopy. We find that under pressurized and concentrated brine solutions methane hydrate forms a mixture of type I clathrate hydrate, ice, and hydrated salts. Under a low-pressure condition, however, the methane hydrates are decomposed through a rapid sublimation of water molecules from the surface of hydrate crystals, while NaCl · 2H2O undergoes a phase transition into a crystal growth of NaCl via the migration of salt ions. In ambient pressure conditions, the methane hydrate is fully decomposed in brine solutions at temperatures above 252 K, the eutectic point of NaCl · 2H2O.

  19. Formation of hydrate films on the surface of calcium silicate and aluminate in the presence of polyelectrolytes (United States)

    Kurochkina, G. N.


    To elucidate the mechanism of moistening and overmoistening of soils and mineral soil components capable of chemical hydration, the sorption of water vapor has been studied in combination with synchronous conductometric measurements. Effect of organic polyelectrolyte molecules on the hydration kinetics and the formation of hydrate films on their surface has been revealed for dehydrated calcium silicate and aluminate simulating minor soil components. The plotting of sorption-desorption curves has shown that hydrate-polymer films formed by aliphatic or aromatic polyelectrolytes with different functional groups (-COOH,-OH,-NH2,-CONH, etc.) significantly vary in dispersion and structure. The changes in dispersion during hydration are frequently not correlated with the amount of resulting hydrates, the content of which is controlled by the crystallochemical features of sorbents, the structure and activity of the polymer functional groups, and the conditions of sorption kinetic studies. It has been shown that the formation of low-permeable surface organomineral layers is typical for aliphatic polyelectrolytes, while more permeable layers determining the water-physical and structure-forming properties of soils are typical for aromatic polyelectrolytes.

  20. Molecular dynamics study on the nucleation of methane + tetrahydrofuran mixed guest hydrate. (United States)

    Wu, Jyun-Yi; Chen, Li-Jen; Chen, Yan-Ping; Lin, Shiang-Tai


    The nucleation of methane (CH4), tetrahydrofuran (THF), and CH4 + THF hydrates are investigated by microsecond MD simulations. These three systems exhibit distinct structural developments in the aqueous phase quantified by the formation of cage structures of hydrogen bonded water molecules. The development of a cluster of cages in the CH4 system is limited by the scarce CH4 molecules in the solution, while in the THF system it is limited by the short lifetime of cages. In the CH4 + THF mixed guest system, a small cluster of caged CH4 molecules can be rapidly stabilized by abundant neighboring cages of THF molecules. Therefore, the induction time of the CH4 + THF mixed guest system is found to be significantly shorter than that of the pure CH4 and pure THF systems. Furthermore, the structure of cages found in the initially formed cage clusters are often different from the typical 5(12)6(n) (n = 0, 2, 3, 4) cages observed in clathrate hydrate systems. The cluster of cages may grow or transform into structure I or II clathrate hydrate in the later stages.

  1. Silicon clathrates for lithium ion batteries: A perspective (United States)

    Warrier, Pramod; Koh, Carolyn A.


    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.

  2. Silicon clathrates for lithium ion batteries: A perspective

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  3. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns


    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

  4. Acoustic Investigations of Gas and Gas Hydrate Formations, Offshore Southwestern Black Sea* (United States)

    Kucuk, H. M.; Dondurur, D.; Ozel, O.; Atgin, O.; Sinayuc, C.; Merey, S.; Parlaktuna, M.; Cifci, G.


    The Black Sea is a large intercontinental back-arc basin with relatively high sedimentation rate. The basin was formed as two different sub-basins divided by Mid-Black Sea Ridge. The ridge is completely buried today and the Black Sea became a single basin in the early Miocene that is currently anoxic. Recent acoustic investigations in the Black Sea indicate potential for gas hydrate formation and gas venting. A total of 2500 km multichannel seismic, Chirp sub-bottom profiler and multibeam bathymetry data were collected during three different expeditions in 2010 and 2012 along the southwestern margin of the Black Sea. Box core sediment samples were collected for gas cromatography analysis. Wide spread BSRs and multiple BSRs are observed in the seismic profiles and may be categorized into two different types: cross-cutting BSRs (transecting sedimentary strata) and amplitude BSRs (enhanced reflections). Both types mimic the seabed reflection with polarity reversal. Some undulations of the BSR are observed along seismic profiles probably caused by local pressure and/or temperature changes. Shallow gas sources and chimney vents are clearly indicated by bright reflection anomalies in the seismic data. Gas cromatography results indicate the presence of methane and various components of heavy hydrocarbons, including Hexane. These observations suggest that the gas forming hydrate in the southwestern Black Sea may originate from deeper thermogenic hydrocarbon sources. * This study is supported by 2214-A programme of The Scientific and Technological Research Council of Turkey (TÜBITAK).

  5. On the Theory of Formation of a Gas Hydrate in a Heat-Insulated Space Compacted with Methane (United States)

    Shagapov, V. Sh.; Chiglintseva, A. S.; Belova, S. V.


    The formation of a gas hydrate in a closed adiabatic space saturated with snow and a gas in the initial state is considered. The formation of a gas hydrate in this gas-snow system in the case where in the initial state it has a negative temperature was investigated. It was established that, depending on the initial snow saturation of the indicated system, a gas hydrate can be formed in it at both negative and positive temperatures as well as at the melting point of ice. It is shown that there exists any initial snow saturation of the gas-snow system at which the hydrate saturation of the heat-insulated space reaches a maximum value depending on its initial temperature and pressure. It was established that the intensity of hydrate formation in this space increases with increase in the pressure in it and decrease in its temperature. Charts of different possible final states of the gas-snow system depending on its initial temperature, pressure, and snow saturation were constructed.

  6. Weak interactions between water and clathrate-forming gases at low pressures

    Energy Technology Data Exchange (ETDEWEB)

    Thurmer, Konrad; Yuan, Chunqing; Kimmel, Gregory A.; Kay, Bruce D.; Smith, R. Scott


    Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10-1 mbar methane or 10-5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~107 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10-5 mbar methane does not alter their morphology, suggesting that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water-gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~43 K and isobutane desorbs near ~100 K. Similar desorption temperatures were observed for desorption from amorphous solid water.

  7. Thermodynamic analysis of hydrates formation in drilling activities; Analise termodinamica da formacao de hidratos em atividades de perfuracao

    Energy Technology Data Exchange (ETDEWEB)

    Baptista, Joao Marcelo Mussi; Rossi, Luciano Fernando dos Santos; Morales, Rigoberto E.M. [Universidade Tecnologica Federal do Parana (UTFPR), Curitiba, PR (Brazil)], e-mail:, e-mail:, e-mail:


    The present work has for objective to present an analysis of hydrates formation in drilling activities. This analysis presents a study of the state conditions for gas hydrates formation in inhibitors containing systems (salts and alcohols, separately). To describe the nonidealities of liquid phase in electrolytic solutions, the activity coefficient model of Debye-Hueckel is used, as [4], and to describe the influence of alcohols in the activity of water, the UNQUAC model is used, as Parrish and Prausnitz. The hydrate phase is described by thermodynamic statistic model of van der Waals and Platteeuw, and the gaseous phase fugacities are modeled by the Peng-Robinson Equation of State. Some results are presented for saline inhibitors, and for methanol and ethyleneglycol. (author)

  8. Role of excipients in hydrate formation kinetics of theophylline in wet masses studied by near-infrared spectroscopy

    DEFF Research Database (Denmark)

    Jørgensen, Anna C; Airaksinen, Sari; Karjalainen, Milja


    . Anhydrous theophylline was chosen as the hydrate-forming model drug compound and two excipients, silicified microcrystalline cellulose (SMCC) and alpha-lactose monohydrate, with different water absorbing properties, were used in formulation. An early stage of wet massing was studied with anhydrous...... theophylline and its 1:1 (w/w) mixtures with alpha-lactose monohydrate and SMCC with 0.1g/g of purified water. The changes in the state of water were monitored using near-infrared spectroscopy, and the conversion of the crystal structure was verified using X-ray powder diffraction (XRPD). SMCC decreased...... the hydrate formation rate by absorbing water, but did not inhibit it. The results suggest that alpha-lactose monohydrate slightly increased the hydrate formation rate in comparison with a mass comprising only anhydrous theophylline....

  9. Numerical simulation of an alternative to prevent hydrates formation in a bypass section

    Energy Technology Data Exchange (ETDEWEB)

    Almeida, Lucilla Coelho; Oliveira Junior, Joao Americo Aguirre; Fonte, Clarissa Bergman [Engineering Simulation and Scientific Software Ltda. (ESSS), Florianopolis, SC (Brazil); Silva, Fabricio Soares da; Moraes, Carlos Alberto Capela [Petroleo Brasileiro S.A. (PETROBRAS), Rio de Janeiro, RJ (Brazil)


    This work presents the use of Computational Fluid Dynamics to evaluate the feasibility of MEG (monoethylene glycol) injection as an alternative to prevent hydrate formation in a bypass section, present in an inlet module of a separation device of a subsea separation system. As the bypass section is open to the main pipeline, MEG will probably be dragged due to secondary flows generated by the main flow stream. The MEG removal rate is estimated, as well as the internal heat transfer between the currents and the heat loss to the external environment in order to estimate the temperature in the equipment. In a first step, the MEG removal was evaluated considering the heat transfer between the liquid phase (composed of water, oil and MEG) and the gas phase as well as the heat transfer by forced convection to the external environment. In a second step, the influence of a thermal insulation layer around the bypass line, reducing the heat loss to the external environment, was studied. Both simulations (with or without thermal insulation) showed the establishment of secondary flows in the open connection between the main line and bypass line, promoting the removal of MEG from the bypass section and enabling other components of the liquid phase and/or gas to enter in the bypass line. This MEG removal is faster when thermal isolation was considered, due to the fact that higher temperatures are established in the bypass, maintaining the liquid phase with lower densities and viscosities. With regard to temperature, the insulation was able to keep higher temperatures at the bypass line than those obtained without insulation, indicating that the combination of MEG injection and thermal insulation may be able to avoid the critical condition for hydrate formation. (author)

  10. Experimental study on hydration damage mechanism of shale from the Longmaxi Formation in southern Sichuan Basin, China

    Directory of Open Access Journals (Sweden)

    Xiangjun Liu


    Full Text Available As a serious problem in drilling operation, wellbore instability restricts efficient development of shale gas. The interaction between the drilling fluid and shale with hydration swelling property would have impact on the generation and propagation mechanism of cracks in shale formation, leading to wellbore instability. In order to investigate the influence of the hydration swelling on the crack propagation, mineral components and physicochemical properties of shale from the Lower Silurian Longmaxi Formation (LF were investigated by using the XRD analysis, cation exchange capabilities (CEC analysis, and SEM observation, and we researched the hydration mechanism of LF shale. Results show that quartz and clay mineral are dominated in mineral composition, and illite content averaged 67% in clay mineral. Meanwhile, CEC of the LF shale are 94.4 mmol/kg. The process of water intruding inside shale along microcracks was able to be observed through high power microscope, meanwhile, the hydration swelling stress would concentrate at the crack tip. The microcracks would propagate, bifurcate and connect with each other, with increase of water immersing time, and it would ultimately develop into macro-fracture. Moreover, the macrocracks extend and coalesce along the bedding, resulting in the rock failure into blocks. Hydration swelling is one of the major causes that lead to wellbore instability of the LF shale, and therefore improving sealing capacity and inhibition of drilling fluid system is an effective measure to stabilize a borehole.

  11. 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)


    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

  12. 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


    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

  13. Methane hydrate formation in turbidite sediments of northern Cascadia, IODP Expedition 311 (United States)

    Torres, M.E.; Trehu, A.M.; Cespedes, N.; Kastner, M.; Wortmann, U.G.; Kim, J.-H.; Long, P.; Malinverno, A.; Pohlman, J.W.; Riedel, M.; Collett, T.


    Expedition 311 of the Integrated Ocean Drilling Program (IODP) to northern Cascadia recovered gas-hydrate bearing sediments along a SW-NE transect from the first ridge of the accretionary margin to the eastward limit of gas-hydrate stability. In this study we contrast the gas gas-hydrate distribution from two sites drilled ~ 8??km apart in different tectonic settings. At Site U1325, drilled on a depositional basin with nearly horizontal sedimentary sequences, the gas-hydrate distribution shows a trend of increasing saturation toward the base of gas-hydrate stability, consistent with several model simulations in the literature. Site U1326 was drilled on an uplifted ridge characterized by faulting, which has likely experienced some mass wasting events. Here the gas hydrate does not show a clear depth-distribution trend, the highest gas-hydrate saturation occurs well within the gas-hydrate stability zone at the shallow depth of ~ 49??mbsf. Sediments at both sites are characterized by abundant coarse-grained (sand) layers up to 23??cm in thickness, and are interspaced within fine-grained (clay and silty clay) detrital sediments. The gas-hydrate distribution is punctuated by localized depth intervals of high gas-hydrate saturation, which preferentially occur in the coarse-grained horizons and occupy up to 60% of the pore space at Site U1325 and > 80% at Site U1326. Detailed analyses of contiguous samples of different lithologies show that when enough methane is present, about 90% of the variance in gas-hydrate saturation can be explained by the sand (> 63????m) content of the sediments. The variability in gas-hydrate occupancy of sandy horizons at Site U1326 reflects an insufficient methane supply to the sediment section between 190 and 245??mbsf. ?? 2008 Elsevier B.V.

  14. Desalination of Produced Water via Gas Hydrate Formation and Post Treatment


    Niu, Jing


    This study presents a two-step desalination process, in which produced water is cleaned by forming gas hydrate in it and subsequently dewatering the hydrate to remove the residual produced water trapped in between the hydrate crystals. All experiments were performed with pressure in the range of 450 to 800psi and temperature in the range of -1 to 1°C using CO? as guest molecule for the hydrate crystals. The experiments were conducted using artificial produced waters containing different amoun...

  15. Modeling of tri-chloro-fluoro-methane hydrate formation in a w/o emulsion submitted to steady cooling

    Energy Technology Data Exchange (ETDEWEB)

    Avendano-Gomez, Juan Ramon; Limas-Ballesteros, Roberto [Laboratorio de Investigacion en Ingenieria Quimica Ambiental, SEPI-ESIQIE, Instituto Politecnico Nacional, Unidad Profesional Adolfo Lopez Mateos, Zacatenco, Edificio 8, 3. piso 07738, Mexico DF (Mexico); Garcia-Sanchez, Fernando [Laboratorio de Termodinamica, Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico DF (Mexico)


    The aim of this work is to study the modeling of the thermal evolution inside an hydrate forming system which is submitted to an imposed steady cooling. The study system is a w/o emulsion where the formulation considers the CCl{sub 3}F as the hydrate forming molecule dissolved in the oil phase. The hydrate formation occurs in the aqueous phase of the emulsion, i.e. in the dispersed phase. The model equation is based on the resolution of the continuity equation in terms of a heat balance for the dispersed phase. The crystallization of the CCl{sub 3}F hydrate occurs at supercooling conditions (T{sub c}hydrate crystallization. Three time intervals characterize the evolution of temperature during the steady cooling of the w/o emulsion: (1) steady cooling, (2) hydrate formation with a release of heat, (3) a last interval of steady cooling. (author)

  16. Study of electrical conductivity response upon formation of ice and gas hydrates from salt solutions by a second generation high pressure electrical conductivity probe. (United States)

    Sowa, Barbara; Zhang, Xue Hua; Kozielski, Karen A; Dunstan, Dave E; Hartley, Patrick G; Maeda, Nobuo


    We recently reported the development of a high pressure electrical conductivity probe (HP-ECP) for experimental studies of formation of gas hydrates from electrolytes. The onset of the formation of methane-propane mixed gas hydrate from salt solutions was marked by a temporary upward spike in the electrical conductivity. To further understand hydrate formation a second generation of window-less HP-ECP (MkII), which has a much smaller heat capacity than the earlier version and allows access to faster cooling rates, has been constructed. Using the HP-ECP (MkII) the electrical conductivity signal responses of NaCl solutions upon the formation of ice, tetrahydrofuran hydrates, and methane-propane mixed gas hydrate has been measured. The concentration range of the NaCl solutions was from 1 mM to 3M and the driving AC frequency range was from 25 Hz to 5 kHz. This data has been used to construct an "electrical conductivity response phase diagrams" that summarize the electrical conductivity response signal upon solid formation in these systems. The general trend is that gas hydrate formation is marked by an upward spike in the conductivity at high concentrations and by a drop at low concentrations. This work shows that HP-ECP can be applied in automated measurements of hydrate formation probability distributions of optically opaque samples using the conductivity response signals as a trigger.

  17. Direct Observation of THF Hydrate Formation in Porous Microstructure Using Magnetic Resonance Imaging

    Directory of Open Access Journals (Sweden)

    Di Liu


    Full Text Available The porous microstructure of hydrates governs the mechanical strength of the hydrate-bearing sediment. To investigate the growth law and microstructure of hydrates in porous media, the growth process of tetrahydrofuran (THF hydrate under different concentration of THF solution is directly observed using Magnetic Resonance Imaging (MRI. The images show that the THF hydrate grows as different models under different concentration of THF solution (19%, 11.4% and 5.7% by weight at 1 °C. When the concentration is 19% (stoichiometric molar ratio of THF/H2O = 1:17, the THF hydrate grows as cementing model. However, with the decreasing concentration of THF, the growth model transfers from cementing model to floating model. The results show that the growth of the THF hydrate was influenced by the dissolved quantity of THF in the water. The extension of the observed behavior to methane hydrate could have implications in understanding their role in seafloor and permafrost stability.

  18. Kinetic of formation for single carbon dioxide and mixed carbon dioxide and tetrahydrofuran hydrates in water and sodium chloride aqueous solution

    NARCIS (Netherlands)

    Sabil, K.M.; Duarte, A.R.C.; Zevenbergen, J.F.; Ahmad, M.M.; Yusup, S.; Omar, A.A.; Peters, C.J.


    A laboratory-scale reactor system is built and operated to measure the kinetic of formation for single and mixed carbon dioxide-tetrahydrofuran hydrates. The T-cycle method, which is used to collect the kinetic data, is briefly discussed. For single carbon dioxide hydrate, the induction time

  19. Analysis of formation pressure test results in the Mount Elbert methane hydrate reservoir through numerical simulation (United States)

    Kurihara, M.; Sato, A.; Funatsu, K.; Ouchi, H.; Masuda, Y.; Narita, H.; Collett, T.S.


    Targeting the methane hydrate (MH) bearing units C and D at the Mount Elbert prospect on the Alaska North Slope, four MDT (Modular Dynamic Formation Tester) tests were conducted in February 2007. The C2 MDT test was selected for history matching simulation in the MH Simulator Code Comparison Study. Through history matching simulation, the physical and chemical properties of the unit C were adjusted, which suggested the most likely reservoir properties of this unit. Based on these properties thus tuned, the numerical models replicating "Mount Elbert C2 zone like reservoir" "PBU L-Pad like reservoir" and "PBU L-Pad down dip like reservoir" were constructed. The long term production performances of wells in these reservoirs were then forecasted assuming the MH dissociation and production by the methods of depressurization, combination of depressurization and wellbore heating, and hot water huff and puff. The predicted cumulative gas production ranges from 2.16??106m3/well to 8.22??108m3/well depending mainly on the initial temperature of the reservoir and on the production method.This paper describes the details of modeling and history matching simulation. This paper also presents the results of the examinations on the effects of reservoir properties on MH dissociation and production performances under the application of the depressurization and thermal methods. ?? 2010 Elsevier Ltd.

  20. Clathrate compounds and method of manufacturing (United States)

    Nolas, George S [Tampa, FL; Witanachchi, Sarath [Tampa, FL; Mukherjee, Pritish [Tampa, FL


    The present invention comprises new materials, material structures, and processes of fabrication of such that may be used in technologies involving the conversion of light to electricity and/or heat to electricity, and in optoelectronics technologies. The present invention provide for the fabrication of a clathrate compound comprising a type II clathrate lattice with atoms of silicon and germanium as a main framework forming lattice spacings within the framework, wherein the clathrate lattice follows the general formula Si.sub.136-yGe.sub.y, where y indicates the number of Ge atoms present in the main framework and 136-y indicates the number of Si atoms present in the main framework, and wherein y>0.

  1. Contribution of oceanic gas hydrate dissociation to the formation of Arctic Ocean methane plumes

    Energy Technology Data Exchange (ETDEWEB)

    Reagan, M.; Moridis, G.; Elliott, S.; Maltrud, M.


    Vast quantities of methane are trapped in oceanic hydrate deposits, and there is concern that a rise in the ocean temperature will induce dissociation of these hydrate accumulations, potentially releasing large amounts of carbon into the atmosphere. Because methane is a powerful greenhouse gas, such a release could have dramatic climatic consequences. The recent discovery of active methane gas venting along the landward limit of the gas hydrate stability zone (GHSZ) on the shallow continental slope (150 m - 400 m) west of Svalbard suggests that this process may already have begun, but the source of the methane has not yet been determined. This study performs 2-D simulations of hydrate dissociation in conditions representative of the Arctic Ocean margin to assess whether such hydrates could contribute to the observed gas release. The results show that shallow, low-saturation hydrate deposits, if subjected to recently observed or future predicted temperature changes at the seafloor, can release quantities of methane at the magnitudes similar to what has been observed, and that the releases will be localized near the landward limit of the GHSZ. Both gradual and rapid warming is simulated, along with a parametric sensitivity analysis, and localized gas release is observed for most of the cases. These results resemble the recently published observations and strongly suggest that hydrate dissociation and methane release as a result of climate change may be a real phenomenon, that it could occur on decadal timescales, and that it already may be occurring.

  2. Experimental study of methane replacement in gas hydrate by carbon dioxide. (United States)

    Voronov, V P; Gorodetskii, E E; Muratov, A R


    The process of replacement of methane molecules in clathrate hydrate by carbon dioxide is studied experimentally. The dependence of the replacement extent on the concentration of the gas mixture coexisting with the hydrate is determined. The kinetics of the replacement is governed by two relaxation modes with a characteristic time ratio of about 10.

  3. Clathrate Sequestration: State-of-the-Art Review and New Technical Approaches

    Directory of Open Access Journals (Sweden)

    Annick Nago


    Full Text Available This paper focuses on reviewing the currently available solutions for natural gas production from methane hydrate deposits using CO2 sequestration. Methane hydrates are ice-like materials, which form at low temperature and high pressure and are located in permafrost areas and oceanic environments. They represent a huge hydrocarbon resource, which could supply the entire world for centuries. Fossil-fuel-based energy is still a major source of carbon dioxide emissions which contribute greatly to the issue of global warming and climate change. Geological sequestration of carbon dioxide appears as the safest and most stable way to reduce such emissions for it involves the trapping of CO2 into hydrocarbon reservoirs and aquifers. Indeed, CO2 can also be sequestered as hydrates while helping dissociate the in situ methane hydrates. The studies presented here investigate the molecular exchange between CO2 and CH4 that occurs when methane hydrates are exposed to CO2, thus generating the release of natural gas and the trapping of carbon dioxide as gas clathrate. These projects include laboratory studies on the synthesis, thermodynamics, phase equilibrium, kinetics, cage occupancy, and the methane recovery potential of the mixed CO2–CH4 hydrate. An experimental and numerical evaluation of the effect of porous media on the gas exchange is described. Finally, a few field studies on the potential of this new gas hydrate recovery technique are presented.

  4. Ternary phase behaviour and vesicle formation of a sodium N-lauroylsarcosinate hydrate/1-decanol/water system (United States)

    Akter, Nasima; Radiman, Shahidan; Mohamed, Faizal; Rahman, Irman Abdul; Reza, Mohammad Imam Hasan


    The phase behaviour of a system composed of amino acid-based surfactant (sodium N-lauroylsarcosinate hydrate), 1-decanol and deionised water was investigated for vesicle formation. Changing the molar ratio of the amphiphiles, two important aggregate structures were observed in the aqueous corner of the phase diagram. Two different sizes of microemulsions were found at two amphiphile-water boundaries. A stable single vesicle lobe was found for 1∶2 molar ratios in 92 wt% water with vesicles approximately 100 nm in size and with high zeta potential value. Structural variation arises due to the reduction of electrostatic repulsions among the ionic headgroups of the surfactants and the hydration forces due to adsorbed water onto monolayer's. The balance of these two forces determines the aggregate structures. Analysis was followed by the molecular geometrical structure. These findings may have implications for the development of drug delivery systems for cancer treatments, as well as cosmetic and food formulations.

  5. Binary Alkali-Metal Silicon Clathrates by Spark Plasma Sintering: Preparation and Characterization (United States)

    Veremchuk, Igor; Beekman, Matt; Antonyshyn, Iryna; Schnelle, Walter; Baitinger, Michael; Nolas, George S.; Grin, Yuri


    The binary intermetallic clathrates K8-xSi46 (x = 0.4; 1.2), Rb6.2Si46, Rb11.5Si136 and Cs7.8Si136 were prepared from M4Si4 (M = K, Rb, Cs) precursors by spark-plasma route (SPS) and structurally characterized by Rietveld refinement of PXRD data. The clathrate-II phase Rb11.5Si136 was synthesized for the first time. Partial crystallographic site occupancy of the alkali metals, particularly for the smaller Si20 dodecahedra, was found in all compounds. SPS preparation of Na24Si136 with different SPS current polarities and tooling were performed in order to investigate the role of the electric field on clathrate formation. The electrical and thermal transport properties of K7.6Si46 and K6.8Si46 in the temperature range 4–700 K were investigated. Our findings demonstrate that SPS is a novel tool for the synthesis of intermetallic clathrate phases that are not easily accessible by conventional synthesis techniques. PMID:28773710

  6. Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium-Nitrate Example. (United States)

    Jin, Geng Bang; Lin, Jian; Estes, Shanna L; Skanthakumar, S; Soderholm, L


    The influence of countercations (A n+ ) in directing the composition of monomeric metal-ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of A n+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A + hydration enthalpies found for two related series of thorium (Th)-nitrate molecular compounds obtained by evaporating acidic aqueous Th-nitrate solutions in the presence of A + counterions. Analyses of their chemical composition and solid-state structures demonstrate that A + not only affects the overall solid-state packing of the Th-nitrato complexes but also influences the composition of the Th-nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A + hydration enthalpies, such that the A + with smaller hydration enthalpies associate with less hydrated and more anionic Th-nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of A n+ , opens a new avenue for the design and synthesis of targeted metal-ligand complexes.

  7. Cisplatin enhances the formation of DNA single- and double-strand breaks by hydrated electrons and hydroxyl radicals. (United States)

    Rezaee, Mohammad; Sanche, Léon; Hunting, Darel J


    The synergistic interaction of cisplatin with ionizing radiation is the clinical rationale for the treatment of several cancers including head and neck, cervical and lung cancer. The underlying molecular mechanism of the synergy has not yet been identified, although both DNA damage and repair processes are likely involved. Here, we investigate the indirect effect of γ rays on strand break formation in a supercoiled plasmid DNA (pGEM-3Zf-) covalently modified by cisplatin. The yields of single- and double-strand breaks were determined by irradiation of DNA and cisplatin/DNA samples with (60)Co γ rays under four different scavenging conditions to examine the involvement of hydrated electrons and hydroxyl radicals in inducing the DNA damage. At 5 mM tris in an N2 atmosphere, the presence of an average of two cisplatins per plasmid increased the yields of single- and double-strand breaks by factors of 1.9 and 2.2, respectively, relative to the irradiated unmodified DNA samples. Given that each plasmid of 3,200 base pairs contained an average of two cisplatins, this represents an increase in radiosensitivity of 3,200-fold on a per base pair basis. When hydrated electrons were scavenged by saturating the samples with N2O, these enhancement factors decreased to 1.5 and 1.2, respectively, for single- and double-strand breaks. When hydroxyl radicals were scavenged using 200 mM tris, the respective enhancement factors were 1.2 and 1.6 for single- and double-strand breaks, respectively. Furthermore, no enhancement in DNA damage by cisplatin was observed after scavenging both hydroxyl radicals and hydrated electrons. These findings show that hydrated electrons can induce both single- and double-strand breaks in the platinated DNA, but not in unmodified DNA. In addition, cisplatin modification is clearly an extremely efficient means of increasing the formation of both single- and double-strand breaks by the hydrated electrons and hydroxyl radicals created by ionizing

  8. Investigating the influence of lithologic heterogeneity on gas hydrate formation and methane recycling at the base of the gas hydrate stability zone in channelized systems

    Energy Technology Data Exchange (ETDEWEB)

    Daigle, Hugh; Nole, Michael; Cook, Ann; Malinverno, Alberto


    In marine environments, gas hydrate preferentially accumulates in coarse-grained sediments. At the meso- to micro-scale, however, hydrate distribution in these coarse-grained units is often heterogeneous. We employ a methane hydrate reservoir simulator coupling heat and mass transfer as well as capillary effects to investigate how capillary controls on methane solubility affect gas and hydrate accumulations in reservoirs characterized by graded bedding and alternating sequences of coarse-grained sands and fine-grained silt and clay. Simulations bury a channelized reservoir unit encased in homogeneous, fine-grained material characterized by small pores (150 nm) and low permeability (~1 md in the absence of hydrate). Pore sizes within each reservoir bed between vary between coarse sand and fine silt. Sands have a median pore size of 35 microns and a lognormal pore size distribution. We also investigate how the amount of labile organic carbon (LOC) affects hydrate growth due to microbial methanogenesis within the sediments. In a diffusion-dominated system, methane movies into reservoir layers along spatial gradients in dissolved methane concentration. Hydrate grows in such a way as to minimize these concentration gradients by accumulating slower in finer-grained reservoir layers and faster in coarser-grained layers. Channelized, fining-upwards sediment bodies accumulate hydrate first along their outer surfaces and thence inward from top to bottom. If LOC is present in thin beds within the channel, higher saturations of hydrate will be distributed more homogeneously throughout the unit. When buried beneath the GHSZ, gas recycling can occur only if enough hydrate is present to form a connected gas phase upon dissociation. Simulations indicate that this is difficult to achieve for diffusion-dominated systems, especially those with thick GHSZs and/or small amounts of LOC. However, capillary-driven fracturing behavior may be more prevalent in settings with thick GHSZs.

  9. Gas Hydrates as a CH4 Source and a CO2 Sink: New Approaches Based on Fundamental Research (United States)

    Schicks, J. M.; Spangenberg, E.; Erzinger, J.


    hydrates: Differential scanning calorimetric measurements for the determination of the specific enthalpy of dissociation, determination of stability fields for pure and multicomponent systems, CH4 - CO2 -exchange reaction in clathrate hydrates and CO2 -hydrate formation in sediments under different pressure and temperature conditions were studied. Based on these fundamental data, new concepts for methane production and combined CO2 - sequestration will be presented and discussed. Reference: S.R. Dallimore, T.S. Collet (Eds.), 2005. Scientific Results from the Mallik 2002 Gas Hydrate Production Research Well Program, Mackenzie Delta, Northwest Territories, Canada, Geological Survey of Canada, WO H. Lee, Y. Seo, Y.-T. Seo, I.L. Moudrakovski, J.A. Ripmeester, 2003. Angewandte Chemie International Edition, 42, 5049-5051 A. Graue, B. Kvamme, 2006. Conference Paper presented at the Offshore Technology Conference in Houston, Texas, U.S.A., 1-4 May 2006 J.M. Schicks, R. Naumann, J. Erzinger, K.C. Hester, Caroly A. Koh, E.D. Sloan, 2006. Journal of Physical Chemistry, 110, 11468-11474

  10. On the activation energy for the formation of a critical size water cluster in structure I and structure II gas hydrates


    Høvring, Eirik


    Master's thesis in Petroleum engineering In the present thesis, experiments have been performed in order to study the activation energy for the formation of a stable, critical size water cluster in structure I and structure II gas hydrates. This activation energy represents an energy barrier for the nucleation process forming the required particle (nuclei) size to trigger macroscopic hydrate growth. The experiments were carried out in different laboratory high pressure cells, but of eq...

  11. On the activation energy for the formation of a critical size water cluster in structure I and structure II gas hydrates


    Høvring, Eirik


    In the present thesis, experiments have been performed in order to study the activation energy for the formation of a stable, critical size water cluster in structure I and structure II gas hydrates. This activation energy represents an energy barrier for the nucleation process forming the required particle (nuclei) size to trigger macroscopic hydrate growth. The experiments were carried out in different laboratory high pressure cells, but of equal size and geometry. Studies were conducte...

  12. Kinetics of organic matter degradation, microbial methane generation, and gas hydrate formation in anoxic marine sediments (United States)

    Wallmann, K.; Aloisi, G.; Haeckel, M.; Obzhirov, A.; Pavlova, G.; Tishchenko, P.


    Seven sediment cores were taken in the Sea of Okhotsk in a south-north transect along the slope of Sakhalin Island. The retrieved anoxic sediments and pore fluids were analyzed for particulate organic carbon (POC), total nitrogen, total sulfur, dissolved sulfate, sulfide, methane, ammonium, iodide, bromide, calcium, and total alkalinity. A novel method was developed to derive sedimentation rates from a steady-state nitrogen mass balance. Rates of organic matter degradation, sulfate reduction, methane turnover, and carbonate precipitation were derived from the data applying a steady-state transport-reaction model. A good fit to the data set was obtained using the following new rate law for organic matter degradation in anoxic sediments: R={K}/{C(DIC)+C(CH)+K}·kx·POC The rate of particulate organic carbon degradation ( RPOC) was found to depend on the POC concentration, an age-dependent kinetic constant ( kx) and the concentration of dissolved metabolites. Rates are inhibited at high dissolved inorganic carbon (DIC) and dissolved methane (CH 4) concentrations. The best fit to the data was obtained applying an inhibition constant KC of 35 ± 5 mM. The modeling further showed that bromide and iodide are preferentially released during organic matter degradation in anoxic sediments. Carbonate precipitation is driven by the anaerobic oxidation of methane (AOM) and removes one third of the carbonate alkalinity generated via AOM. The new model of organic matter degradation was further tested and extended to simulate the accumulation of gas hydrates at Blake Ridge. A good fit to the available POC, total nitrogen, dissolved ammonium, bromide, iodide and sulfate data was obtained confirming that the new model can be used to simulate organic matter degradation and methane production over the entire hydrate stability zone (HSZ). The modeling revealed that most of the gas hydrates accumulating in Blake Ridge sediments are neither formed by organic matter degradation within the

  13. Kinetics of methane hydrate decomposition studied via in situ low temperature X-ray powder diffraction. (United States)

    Everett, S Michelle; Rawn, Claudia J; Keffer, David J; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy J


    Gas hydrate is known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Based on results from the decomposition of three nominally similar methane hydrate samples, the kinetics of two regions, 180-200 and 230-260 K, within the overall decomposition range 140-260 K, were studied by in situ low temperature X-ray powder diffraction. The kinetic rate constants, k(a), and the reaction mechanisms, n, for ice formation from methane hydrate were determined by the Avrami model within each region, and activation energies, E(a), were determined by the Arrhenius plot. E(a) determined from the data for 180-200 K was 42 kJ/mol and for 230-260 K was 22 kJ/mol. The higher E(a) in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

  14. Formation of magnesium silicate hydrate (M-S-H) cement pastes using sodium hexametaphosphate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Tingting [Faculty of Infrastructure Engineering, Dalian University of Technology, Dalian 116024 (China); Department of Materials, Centre for Advanced Structural Ceramics, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Department of Civil and Environmental Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Vandeperre, Luc J. [Department of Materials, Centre for Advanced Structural Ceramics, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Cheeseman, Christopher R., E-mail: [Department of Civil and Environmental Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom)


    Magnesium silicate hydrate (M-S-H) gel is formed by the reaction of brucite with amorphous silica during sulphate attack in concrete and M-S-H is therefore regarded as having limited cementing properties. The aim of this work was to form M-S-H pastes, characterise the hydration reactions and assess the resulting properties. It is shown that M-S-H pastes can be prepared by reacting magnesium oxide (MgO) and silica fume (SF) at low water to solid ratio using sodium hexametaphosphate (NaHMP) as a dispersant. Characterisation of the hydration reactions by x-ray diffraction and thermogravimetric analysis shows that brucite and M-S-H gel are formed and that for samples containing 60 wt.% SF and 40 wt.% MgO all of the brucites react with SF to form M-S-H gel. These M-S-H cement pastes were found to have compressive strengths in excess of 70 MPa.

  15. Inhibition of hydrate formation by kinetic inhibitors. Literature study; Inhibierung von Erdgashydraten durch kinetische Inhibitoren. Literaturstudie

    Energy Technology Data Exchange (ETDEWEB)

    Eberhardt, E.; Meyn, V.; Rahimian, I. [Institut fuer Erdoel- und Erdgasforschung, Clausthal-Zellerfeld (Germany)


    The aim of this study was to represent the state-of-the art of the inhibition of gas hydrates. Corresponding to recent publications the kinetic inhibition was considered in particular. Special inhibitors were validated using a set of criteria derived from different experimental test methods. Best results were obtained by the application of terpolymer VC-713 especially in relation to nucleation and crystal growth, followed by PVCap (polyvinylcaprolactame) and THI (threshold hydrate inhibitor), the chemical structure of which is derived from the antifreeze glycopeptids of antarcitc winter flounder. (orig.) [German] Die vorliegende Literaturstudie gibt den derzeitigen Stand der Kenntnis zur Inhibierung von Gashydraten wieder. Entsprechend der neueren Literatur wird insbesondere auf die kinetische Inhibierung eingegangen. Zur Beurteilung der verschiedenen Inhibitoren werden Bewertungskriterien zur Validierung der mit unterschiedlichen Untersuchungsmethoden erzielten experimentellen Ergebnisse angegeben. Anhand dieser Vorgehensweise zeigte sich, dass mit dem Terpolymer VC-713 die besten Ergebnisse, insbesondere im Hinblick auf Keimbildung und Wachstum, erzielt werden konnten. Sehr gute Ergebnisse wurden auch mit dem Polyvinylcaprolactam (PVCap) und den aus den Antigefrierpeptiden der antarktischen Winterflunder abgeleiteten Threshold Hydrate Inhibitoren (THI) erhalten. (orig.)

  16. Miniaturized biosignature analysis reveals implications for the formation of cold seep carbonates at Hydrate Ridge (off Oregon, USA

    Directory of Open Access Journals (Sweden)

    T. Leefmann


    Full Text Available Methane-related carbonates from Hydrate Ridge typically show several macroscopically distinguishable mineral phases, namely whitish aragonite, lucent aragonite, and gray micrite. The relationship of these phases to particular microorganisms or biogeochemical processes is as yet unclear. We used a miniaturized biomarker technique on mg samples, combined with factor analysis and subsequent electron microprobe analysis, to study lipid biomarkers and chemical compositions of the individual phases. This allows us to identify particular mechanisms involved in the formation of the different carbonate precipitates. Our combined analysis of biomarkers and petrographic traits shows that most of the lipids related to the anaerobic oxidation of methane (>90% by weight are concentrated within only a minor compartment (~20% by volume of the Hydrate Ridge carbonates, the whitish aragonite. The patterns indicate that the whitish aragonite represents fossilized biofilms of methanotrophic consortia containing mainly archaea of the ANME-2 group and sulfate reducing bacteria, whereas the precipitation of the lucent aragonite may have lacked the immediate proximity of microorganisms during formation. By contrast, the gray micrite formed by incorporation of allochthonous organic and inorganic matter during carbonate precipitation induced by the anaerobic oxidation of methane involving ANME-1 archaea.

  17. Investigation of Methane Hydrate Formation in a Recirculating Flow Loop: Modeling of the Kinetics and Tests of Efficiency of Chemical Additives on Hydrate Inhibition Étude de la formation de l'hydrate de méthane dans une conduite de recirculation : modélisation de la cinétique et tests d'efficacité d'additifs chimiques inhibiteurs d'hydrates de gaz

    Directory of Open Access Journals (Sweden)

    Peytavy J. L.


    Full Text Available Gas hydrates can be formed when light gases, such as the components of natural gas, come into contact with water under particular conditions of temperature and pressure. These solid compounds give rise to problems in natural gas and oil industry because they can plug pipelines and process equipment. To prevent hydrate formation methanol and glycols are commonly and extensively used as inhibitors. Today, the thermodynamic equilibria of hydrate formation are well known, but the kinetics of gas hydrate formation and growth has to be studied in order to find means of controlling these processes and to explore the mechanisms for hydrate formation that follows non equilibrium laws. The present work deals with the kinetics of methane hydrate formation studied in a laboratory loop where the liquid blend saturated with methane is circulated up to a pressure of 75 bar. Pressure is maintained at a constant value during experimental runs by means of methane gas make-up. First the effects of pressure (35-75 bar, liquid velocity (0. 5-3 m/s, liquid cooling temperature ramp (2-15°C/h, and liquid hydrocarbon amount (0-96%, on hydrate formation kinetics are investigated. Then a new method is proposed to predict firstly the thermodynamic conditions (pressure and temperature at the maximum values of the growth rate of methane hydrate and secondly the methane hydrate growth rate. A good agreement is found between calculated and experimental data. Finally the evaluation of the efficiency of some kinetic additives and some surfactants developed to avoid either nucleation or crystal growth and agglomeration of methane hydrates is tested based on the proposed experimental procedure. Les hydrates de gaz des composés légers du gaz naturel se forment lorsque ceux-ci entrent en contact avec l'eau dans certaines conditions de température et de pression. Ces composés solides sont nuisibles pour les industries gazière et pétrolière car des bouchons solides peuvent

  18. Changes in the solid state of anhydrous and hydrated forms of sodium naproxen under different grinding and environmental conditions: Evidence of the formation of new hydrated forms. (United States)

    Censi, Roberta; Rascioni, Riccardo; Di Martino, Piera


    The aim of the present work was to investigate the solid state change of the anhydrous and hydrate solid forms of sodium naproxen under different grinding and environmental conditions. Grinding was carried out manually in a mortar under the following conditions: at room temperature under air atmosphere (Method A), in the presence of liquid nitrogen under air atmosphere (Method B), at room temperature under nitrogen atmosphere (Method C), and in the presence of liquid nitrogen under nitrogen atmosphere (Method D). Among the hydrates, the following forms were used: a dihydrate form (DSN) obtained by exposing the anhydrous form at 55% RH; a dihydrate form (CSN) obtained by crystallizing sodium naproxen from water; the tetrahydrate form (TSN) obtained by exposing the anhydrous form at 75% RH. The metastable monohydrate form (MSN), previously described in the literature, was not used because of its high physical instability. The chemical stability during grinding was firstly assessed and proven by HPLC. Modification of the particle size and shape, and changes in the solid state under different grinding methods were evaluated by scanning electron microscopy, and X-ray powder diffractometry and thermogravimetry, respectively. The study demonstrated the strong influence of starting form, grinding and environmental conditions on particle size, shape and solid state of recovered sodium naproxen forms. In particular, it was demonstrated that in the absence of liquid nitrogen (Methods A and C), either at air or at nitrogen atmosphere, the monohydrate form (MSN) was obtained from any hydrates, meaning that these grinding conditions favored the dehydration of superior hydrates. The grinding process carried out in the presence of liquid nitrogen (Method B) led to further hydration of the starting materials: new hydrate forms were identified as one pentahydrate form and one hexahydrate form. The hydration was caused by the condensation of the atmospheric water on sodium naproxen

  19. Photosensitive Cationic Azobenzene Surfactants: Thermodynamics of Hydration and the Complex Formation with Poly(methacrylic acid). (United States)

    Montagna, Maria; Guskova, Olga


    In this computational work, we investigate the photosensitive cationic surfactants with the trimethylammonium or polyamine hydrophilic head and the azobenzene-containing hydrophobic tail. The azobenzene-based molecules are known to undergo a reversible trans-cis-trans isomerization reaction when subjected to UV-visible light irradiation. Combining the density functional theory and the all-atom molecular dynamics simulations, the structural and the hydration properties of the trans- and the cis-isomers and their interaction with the oppositely charged poly(methacrylic acid) in aqueous solution are investigated. We establish and quantify the correlations of the molecular structure and the isomerization state of the surfactants and their hydrophilicity/hydrophobicity and the self-assembling altered by light. For this reason, we compare the hydration free energies of the trans- and the cis-isomers. Moreover, the investigations of the interaction strength between the azobenzene molecules and the polyanion provide additional elucidations of the recent experimental and theoretical studies on the light triggered reversible deformation behavior of the microgels and the polymer brushes loaded with azobenzene surfactants.

  20. Optimum potassium chloride concentration to reduce hydration capacity of clay formations; Concentracao otima de cloreto de potassio para reduzir a capacidade de hidratacao das formacoes argilosas

    Energy Technology Data Exchange (ETDEWEB)

    Machado, Jose Carlos Vieira [PETROBRAS, Salvador, BA (Brazil). Centro de Recursos Humanos Norte-Nordeste. Setor de Programas de Perfuracao; Oliveira, Manoel Martins de [PETROBRAS, BA (Brazil). Distrito de Perfuracao. Div. de Tecnicas de Perfuracao


    An experimental method for ascertaining the optimal concentration of potassium chloride for reducing the hydration and dispersion capacity of clayey formations sensitive to water-based fluids is described. Under this method, filtering time for disperse systems prepared from clayey formation samples is measured. A discussion is offered on theoretical aspects of hydration, expansion, and dispersion of clayey rocks in response to the variations in stress equilibrium states produced by these phenomena when a hole (well) is opened in the rock. The state of the art of this technological branch is also described. (author) 10 refs., 5 figs., 4 tabs.

  1. Vacancy ordering and superstructure formation in dry and hydrated strontium tantalate perovskites: A TEM perspective

    DEFF Research Database (Denmark)

    Ashok, Anuradha M.; Haavik, Camilla; Norby, Poul


    Crystal structures of Sr4(Sr2Ta2)O11 and Sr4(Sr1.92Ta2.08)O11.12, synthesized by solid state reaction technique in dry and hydrated state have been studied mainly using Transmission Electron Microscopy. Due to the lesser ability of X-rays to probe details in oxygen sublattice, the change in crystal...... symmetry due to ordering of oxygen vacancies could be detected better using Transmission Electron Microscopy. After detailed analysis through TEM, it was observed that no major change occurs in the cation sublattice. The TEM observations are compared with XRD data and discussed. The crystal symmetries...... structure. © 2014 Elsevier Ltd....

  2. Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn)

    Energy Technology Data Exchange (ETDEWEB)

    Dolyniuk, Juli-Anna [Department of Chemistry, The University of California, Davis, One Shields Avenue Davis CA 95616 USA; Zaikina, Julia V. [Department of Chemistry, The University of California, Davis, One Shields Avenue Davis CA 95616 USA; Kaseman, Derrick C. [Department of Materials Science and Engineering, The University of California, Davis, One Shields Avenue Davis CA 95616 USA; Sen, Sabyasachi [Department of Materials Science and Engineering, The University of California, Davis, One Shields Avenue Davis CA 95616 USA; Kovnir, Kirill [Department of Chemistry, The University of California, Davis, One Shields Avenue Davis CA 95616 USA


    A new clathrate type has been discovered in the Ba/Cu/Zn/P system. The crystal structure of the Ba8M24P28+δ (M=Cu/Zn) clathrate is composed of the pentagonal dodecahedra common to clathrates along with a unique 22-vertex polyhedron with two hexagonal faces capped by additional partially occupied phosphorus sites. This is the first example of a clathrate compound where the framework atoms are not in tetrahedral or trigonal-pyramidal coordination. In Ba8M24P28+δ a majority of the framework atoms are five- and six-coordinated, a feature more common to electron-rich intermetallics. The crystal structure of this new clathrate was determined by a combination of X-ray and neutron diffraction and was confirmed with solid-state 31P NMR spectroscopy. Based on chemical bonding analysis, the driving force for the formation of this new clathrate is the excess of electrons generated by a high concentration of Zn atoms in the framework. The rattling of guest atoms in the large cages results in a very low thermal conductivity, a unique feature of the clathrate family of compounds.

  3. Le problème des hydrates dans le contexte de la production et du transport polyphasiques des pétroles bruts et des gaz naturels. Première partie : physico-chimie de la formation et de la dissociation des hydrates Hydrates Problem Within the Framework of Multiphase Production and Transport of Crude Oils and Natural Gases. Part One: Physical-Chemistry of Hydrates Formation and Dissociation

    Directory of Open Access Journals (Sweden)

    Behar E.


    Full Text Available L'exploitation en mer des gisements de combustibles fossiles fluides a amplifié le besoin d'accroître nos connaissances sur les hydrates qui sont susceptibles de boucher les installations de production, de traitement et de transport. Dans cette publication, la structure moléculaire des hydrates I, II et H est rappelée, ensuite l'analyse physico-chimique de leur formation est succinctement décrite tant sur les plans thermodynamique que cinétique. Enfin, les remèdes possibles aux problèmes rencontrés par les compagnies opératrices sont indiqués, essentiellement les inhibiteurs thermodynamiques classiques tels que les alcools ou les sels qui diminuent la température de formation des hydrates, et les additifs dispersants qui évitent la croissance et/ou l'agglomération des cristaux. Pour terminer, une boucle pilote de circulation originale est présentée, ses caractéristiques qui permettent la validation des additifs dispersants dans des conditions hydrodynamiques et physico-chimiques représentatives étant soulignées. Offshore exploitation of fossil fluid fuels has emphasized the need of improving our knowledge on hydrates which can plug production, treatment and transport facilities. In this paper, the molecular structure of I, II and H hydrates is recalled, then the physical-chemistry of their formation is briefly reviewed from both the thermodynamic and the kinetic points of view. Finally, the possible remedies to the problems met by operating companies are described, mainly classical thermodynamic inhibitors such as alcohols or salts which decrease the hydrates formation temperature, and dispersant additives which avoid crystals growth and/or agglomeration. At last an original circulation loop at pilot scale is presented, its characteristics which allow the testing of dispersant additives under representative hydrodynamic and physico-chemical conditions being outlined.

  4. New Insights into Solid Form Stability and Hydrate Formation: o-Phenanthroline HCl and Neocuproine HCl

    Directory of Open Access Journals (Sweden)

    Doris E. Braun


    Full Text Available The moisture- and temperature dependent stabilities and interrelation pathways of the practically relevant solid forms of o-phenanthroline HCl (1 and neocuproine HCl (2 were investigated using thermal analytical techniques (HSM, DSC and TGA and gravimetric moisture sorption/desorption studies. The experimental stability data were correlated with the structural changes observed upon dehydration and the pairwise interaction and lattice energies calculated. For 1 the monohydrate was identified as the only stable form under conditions of RH typically found during production and storage, but at RH values >80% deliquescence occurs. The second compound, 2, forms an anhydrate and two different hydrates, mono- (2-Hy1 and trihydrate (2-Hy3. The 2-Hy1 structure was solved from SCXRD data and the anhydrate structure derived from a combination of PXRD and CSP. Depending on the environmental conditions (moisture either 2-Hy1 or 2-Hy3 is the most sable solid form of 2 at RT. The monohydrates 1-Hy1 and 2-Hy1 show a high enthalpic stabilization (≥20 kJ mol−1 relative to the anhydrates. The anhydrates are unstable at ambient conditions and readily transform to the monohydrates even in the presence of traces of moisture. This study demonstrates how the right combination of experiment and theory can unravel the properties and interconversion pathways of solid forms.

  5. Radiosensitization of DNA by Cisplatin Adducts Results from an Increase in the Rate Constant for the Reaction with Hydrated Electrons and Formation of Pt(I). (United States)

    Behmand, B; Marignier, J-L; Mostafavi, M; Wagner, J R; Hunting, D J; Sanche, L


    Pulse radiolysis measurements of the decay of hydrated electrons in solutions containing different concentrations of the oligonucleotide GTG with and without a cisplatin adduct show that the presence of a cisplatin moiety accelerates the reaction between hydrated electrons and the oligonucleotide. The rate constant of the reaction is found to be 2.23 × 10(10) mol(-1) L s(-1), which indicates that it is diffusion controlled. In addition, we show for the first time the formation of a Pt(I) intermediate as a result of the reaction of hydrated electrons with GTG-cisplatin. A putative reaction mechanism is proposed, which may form the basis of the radiosensitization of cancer cells in concomitant chemoradiation therapy with cisplatin.

  6. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)



    The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

  7. Ethane clathrates using different water-ethane models: Molecular dynamics (United States)

    Torres-García, G.; Luis, D. P.; Odriozola, G.; López-Lemus, J.


    Ethane clathrates are studied in a temperature window where the stable-unstable transition takes place by means of molecular dynamics simulations in an isothermal-isobaric ensemble. For this purpose a temperature range [200-440] K and a pressure of 2 MPa are considered. Firstly, structural analysis of the ethane clathrates is carried out at a fixed temperature of 200 K, where clathrates are stable for all considered water models. Here, it is found that structural properties of all stable clathrates do not strongly depend on the water model. As a next step, temperature is increased upon the clathrate turns unstable. This decomposition temperature is found by monitoring coordination numbers, total number of hydrogen-bonds, potential energy, potential of mean force and mean-square displacements. All properties consistently point out to the same temperature at which the stable-unstable transition takes place for each water model. As a part of our results, we notice that by using the standard Lorentz-Berthelot combining rules, the obtained temperature at which the clathrate becomes unstable is higher than the experimental reference value for all used water models. However, we have found that a reasonable way to approach the experimental-decomposition temperature is by including a re-scaling factor in the combining rules in such a way that both methyl-oxygen size and interaction energy turned out decreased. Our data indicates that the decomposition temperature is sensitive to both parameters.

  8. Hydrate prevention during formation test of gas in deep water; Prevencao de formacao de hidratos durante teste de formacao de poco de gas em lamina d'agua profunda

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, Renato Cunha [PETROBRAS, Rio de Janeiro, RJ (Brazil)


    This work shows a scenery of formation test in deep water, for a well of gas, for which, there were made simulations with objective of identifying possible pairs of points (Pressure x Temperature), favorable to the hydrates formation. Besides, they were made comparisons of the values obtained in the simulation with the values registered during the formation test for the well Alfa of the field Beta. Of ownership of those information, we made an evaluation of the real needs of injection of inhibitors with intention of preventing the hydrates formation in each phase of the test. In an including way, the work has as objective recommends the volumes of hydrates inhibitors to be injected in each phase of a test of formation of well of gas in deep water, in way to assure that the operations are made without there is risk of hydrates formation. (author)

  9. The influences of skin visco-elasticity, hydration level and aging on the formation of wrinkles: a comprehensive and objective approach. (United States)

    Choi, Jae Woo; Kwon, Soon Hyo; Huh, Chang Hun; Park, Kyoung Chan; Youn, Sang Woong


    Various skin parameters including skin visco-elasticity and hydration level affect the formation of wrinkles. The aim of this study was to investigate the comprehensive and objective relationship between age, skin visco-elasticity, hydration level, and the occurrence of wrinkles using bioengineering equipments for the first time. A total number of 97 healthy women were included in this study. Age, Fitzpatrick skin type, skin mechanical parameters obtained with Cutometer(R0~R9), hydration level measured with Corneometer, as well as wrinkle parameters (SEsm, SEr, SEsc, and SEw) assessed with Visioscan, were analyzed with the Pearson's correlation test. The skin fluidity (R6) increased while the elastic recovery ratio (R7) decreased with the age. The wrinkle parameter (SEw) also increased with the age. The higher skin hysteresis values (R4 and R9) coincided with the higher SEw values. Skin hydration significantly lowered the hysteresis (R9), the wrinkles (SEw), and the depth of wrinkle furrows (R3mr). The elderly have less elastic skin and more wrinkles. Skin hysteresis most closely related with the degree of wrinkles. Drier skin showed more wrinkles and deeper furrows, with wider intervals. On the basis of these objective findings, we propose several skin parameters associated with wrinkles, and hypothesize the mechanism of wrinkle generation. © 2012 John Wiley & Sons A/S.

  10. Hydrate formation in drilling fluids: prevention and countering; Formacao de hidratos em fluidos de perfuracao: prevencao e controle

    Energy Technology Data Exchange (ETDEWEB)

    Villas Boas, Mario Barbosa [PETROBRAS, Macae, RJ (Brazil). Distrito de Perfuracao do Sudeste. Setor de Fluidos de Perfuracao


    The possibility of hydrates forming during deep water well drilling is analyzed under conditions typical of the state of Rio de Janeiro`s coastal ocean bed. Relying on an extensive review of technical literature, an effort has been made to ascertain the conditions which favor the occurrence of such hydrates in gas-contaminated water-based drilling muds. Based on this study, methods are proposed for preventing and countering this problem. (author) 58 refs., 10 figs.

  11. Hydration lubrication

    National Research Council Canada - National Science Library

    Klein, Jacob


    The hydration lubrication paradigm, whereby hydration layers are both strongly held by the charges they surround, and so can support large pressures without being squeezed out, and at the same time...

  12. Melting Process of Clathrate in a Rectangular Cell (United States)

    Chiba, Takashi; Okada, Masashi; Matsumoto, Koji

    In order to clarify the mechanism of heat transfer during melting of a clathrate in rectangular cells, two melting processes, namely, two-dimensional melting process with natural convection from a vertical wall and one-dimensional melting process by heat conduction from an upper horizontal wall, are studied experimentally. The R-141b was used for generating clathrate. One experiment was carried out by melting the clathrate filled into a 150mm high and 100mm wide rectangular cell from a vertical wall. And in the other experiment, the clathrate was melted from the upper horizontal wall of a rectangular cell with 88mm height and 180mm width. The temperature distributions in cells were measured. The melting front was measured by pictures taken on fixed times. The concentration of freon in the melt was measured by gas-chromatography. The following results are obtained. (1) In the melting process, the clathrate decomposes into an emulsion region which is a water-freon mixture and a liquid freon region under the emulsion. (2) Concentration gradient of freon in the emulsion plyas an important role in the natural convection in the melt. The Nusselt number on the heated vertical wall is depressed by the concentration gradients.

  13. Implementation of subsea system to monitor in-situ temperature and formation pressure in methane hydrates sediments for the production test in 2017, offshore Japan (United States)

    Nishimoto, K.


    The methane hydrates phase changes, from solid to fluid, is governed by pressure drop and heat transportation through a geological formation. For the world's first offshore production test of methane hydrates conducted in 2013, the MH21 research team installed distributed temperature sensing (DTS) cables and array type resistance temperature devices (RTD) behind the casings of the monitoring wells. The temperature monitoring was continued over the period of 18 months. As a result, the thermal response of the methane hydrate-bearing sediment during depressurization was observed, and the obtained data was used to evaluate the methane dissociation behavior and to estimate the dissociation front radius from a producer well. The second offshore production test is planned in the same area in 2017 with the extended period up to one month. Two sets of a pair of monitoring and producer well were drilled in 2016. A pair of monitoring and producer wells is only 20m apart. An improved monitoring system is prepared for the second test with additional pressure measurement capability with new features of subsea system. The planed formation pressure measurement is expected to contribute not only for the evaluation of methane hydrate phase changes and estimation of its areal distribution but also the analyzing the interference in the vicinity of the producer wells from the geo-mechanical point of view. The DTS resolution was improved with longer averaging time than the previously utilized system. To accomplish the continuous acquisition up running over longer than 18 months to cover pre-flow and post-flow periods, the subsea acquisition system was equipped with an exchangeable subsea batteries by ROV. As for the surface communication method, the acoustic transponder was added in the subsea system. In this technical presentation, the improvements on the monitoring system are discussed and the scientific objectives for new measurements such as formation pressure are presented.

  14. Experimental Study of Methane Hydrates in Coal

    Directory of Open Access Journals (Sweden)

    Smirnov Vyacheslav


    Full Text Available The possibility of gas hydrate formation in porous space of coal has been studied. The experiments conducted have proven the possibility of methane gas hydrate formation in moist coal. It has been demonstrated that the decomposition points of methane gas hydrates in coal are near to the phase equilibrium curve for bulk methane hydrate. Only part of water absorbed by coal can be involved in the methane gas hydrate formation. With the increase in gas pressure increases the amount of gas hydrate formed in natural coal. For formation of hydrates at a positive temperature, the pressure in the system has to be at least 2 MPa. At the same time the speed of formation and decomposition of gas hydrates in coal is big enough.

  15. A possible reason behind the initial formation of pentagonal dodecahedron cavities in sI-methane hydrate nucleation: A DFT study (United States)

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


    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.

  16. Natural Gas Hydrates as CH4 Source and CO2 Sink - What do SO2 Impurities do? (United States)

    Beeskow-Strauch, B.; Schicks, J. M.; Spangenberg, E.; Erzinger, J.


    The large amounts of gas hydrates stored in natural reservoirs are thought to be a promising future energy source. The recently discussed idea of methane extraction from these formations, together with the subsequent storage of CO2 in form of gas hydrates is an elegant approach to bring forward. A number of experiments have been performed on lab scale showing the replacement of CH4 by CO2 and vice versa. For instance, Graue and Kvamme (2006) demonstrated with Magnetic Resonance Images of core plug experiments the possibility of CH4 extraction by using liquid CO2. Laser Raman investigations of Schicks et al. (2007) showed, on the other hand, the ineffectiveness and slowness of the CH4 exchange reaction with gaseous CO2. After 120 hours, only 20% CH4 were exchanged for CO2. Natural methane hydrates which include often higher hydrocarbons tend to be even more stable than pure methane hydrates (Schicks et al., 2006). Contrary to lab conditions, industrial emitted CO2 contains - despite much effort to clean it - traces of impurities. For instance, CO2 emitted from the state-of-the-art Vattenfall Oxyfuel pilot plant in Schwarze Pumpe should reach a quality of >99.7% CO2 but still contains small amounts of N2, Ar, O2, SOx and NOx (pers. comm. Dr. Rolland). Here we present a microscopic and laser Raman study in a p-T range of 1 to 4 MPa and 271 to 280K focussing on CO2 hydrate formation and CH4-exchange reaction in the presence of 1% SO2. The experiments have been performed in a small-scale cryocell. The Raman spectra show that CO2 and SO2 occupy both large and small cages of the hydrate lattice. SO2 occurs strongly enriched in the hydrate clathrate, compared to its concentration in the feed gas which causes a strong acidification of the liquid phase after hydrate dissociation. Our study reveals that the hydrate formation rate from impure CO2 is similar to that of pure CO2 hydrate but that the stability of the CO2-SO2-hydrate exceeds that of pure CO2 hydrate. The improved

  17. Gas hydrate formation in deep-sea sediments - on the role of sediment-mechanical process determination; Gashydratbildung in Tiefseesedimenten - zur Rolle der sedimentmechanischen Prozesssteuerung

    Energy Technology Data Exchange (ETDEWEB)

    Feeser, V. [Kiel Univ. (Germany). Geologisch-Palaeontologisches Inst.


    Slope failures in gas hydrate regions are encountered throughout the oceans. The stability of seafloor slopes can be assessed and predicted by means of calculation methods based on mechanical laws and parameters which describe the deformation behaviour and/or mechanical strength of the slope-forming sediments. Thermodynamic conditions conducive to the formation of gas hydrates in marine sediments differ from conditions prevailing in exclusively water-filled systems. The present contribution describes the relevant energetic conditions on the basis of a simple spherical model giving due consideration to petrographic parameters. Depending on pore size distribution, lithological stress conditions, pore water pressure, and sediment strength gas hydrates will either develop as a cementing phase or as segregated lenses. (MSK) [Deutsch] In den Weltmeeren ereignen sich immer wieder Hangrutschungen in Gashydratgebieten. Die zur Beurteilung und Prognonse von Hangstabilitaeten zu verwendenden Berechnungsverfahren erfordern Stoffgesetze und Parameter, welche das Deformations-und/oder Festigkeitsverhalten der hangbildenden Sedimente beschreiben. Die thermodynamischen Bildungsbedingungen von Gashydraten in marinen Sedimenten unterscheiden sich von den Bedingungen in ausschliesslich wassergefuellten Systemen. Unter Einbeziehung petrographischer Eigenschaften werden die energetischen Bedingungen beschrieben. Dazu dient ein einfaches Kugelmodell. Je nach vorhandenem Porenraumspektrum, lithostatischen Spannungsverhaeltnissen, Porenwasserdruck und Sedimentfestigkeit wachsen Gashydrate als Porenraumzement oder als segregierte Linsen.


    Energy Technology Data Exchange (ETDEWEB)

    Frank R. Rack; Tim Francis; Peter Schultheiss; Philip E. Long; Barry M. Freifeld


    The primary activities accomplished during this quarter were continued efforts to develop plans for Phase 2 of this cooperative agreement based on the evolving operational planning for IODP Expedition 311, which will use the JOIDES Resolution to study marine methane hydrates along the Cascadia margin, offshore Vancouver Island. IODP Expedition 311 has been designed to further constrain the models for the formation of marine gas hydrate in subduction zone accretionary prisms. The objectives include characterizing the deep origin of the methane, its upward transport, its incorporation in gas hydrate, and its subsequent loss to the seafloor. The main attention of this expedition is on the widespread seafloor-parallel layer of dispersed gas hydrate located just above the base of the predicted stability field. In a gas hydrate formation model, methane is carried upward through regional sediment or small-scale fracture permeability, driven by the tectonic consolidation of the accretionary prism. The upward moving methane is incorporated into the gas hydrate clathrate as it enters the methane hydrate stability zone. Also important is the focusing of a portion of the upward methane flux into localized plumes or channels to form concentrations of near-seafloor gas hydrate. The amount of gas hydrate in local concentrations near the seafloor is especially important for understanding the response of marine gas hydrate to climate change. The expedition includes coring and downhole measurements at five sites across the Northern Cascadia accretionary prism. The sites will track the history of methane in an accretionary prism from (1) its production by mainly microbiological processes over a thick sediment vertical extent, (2) its upward transport through regional or locally focused fluid flow, (3) its incorporation in the regional hydrate layer above the BSR or in local concentrations at or near the seafloor, (4) methane loss from the hydrate by upward diffusion, and (5) methane

  19. Clathrates-An Exploration of the Chemistry of Caged Compounds

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 9; Issue 7. Clathrates – An Exploration of the Chemistry of Caged Compounds. Srivathsa Vaidya. General Article Volume 9 Issue 7 July 2004 pp 18-31. Fulltext. Click here to view fulltext PDF. Permanent link:

  20. Association among active seafloor deformation, mound formation, and gas hydrate growth and accumulation within the seafloor of the Santa Monica Basin, offshore California (United States)

    Paull, C.K.; Normark, W.R.; Ussler, W.; Caress, D.W.; Keaten, R.


    Seafloor blister-like mounds, methane migration and gas hydrate formation were investigated through detailed seafloor surveys in Santa Monica Basin, offshore of Los Angeles, California. Two distinct deep-water (??? 800??m water depth) topographic mounds were surveyed using an autonomous underwater vehicle (carrying a multibeam sonar and a chirp sub-bottom profiler) and one of these was explored with the remotely operated vehicle Tiburon. The mounds are > 10??m high and > 100??m wide dome-shaped bathymetric features. These mounds protrude from crests of broad anticlines (~ 20??m high and 1 to 3??km long) formed within latest Quaternary-aged seafloor sediment associated with compression between lateral offsets in regional faults. No allochthonous sediments were observed on the mounds, except slumped material off the steep slopes of the mounds. Continuous streams of methane gas bubbles emanate from the crest of the northeastern mound, and extensive methane-derived authigenic carbonate pavements and chemosynthetic communities mantle the mound surface. The large local vertical displacements needed to produce these mounds suggests a corresponding net mass accumulation has occurred within the immediate subsurface. Formation and accumulation of pure gas hydrate lenses in the subsurface is proposed as a mechanism to blister the seafloor and form these mounds. ?? 2008 Elsevier B.V. All rights reserved.

  1. Report: Fourth International Conference on Gas Hydrates, held at Yokohama, Japan, 19-23 May 2002

    Digital Repository Service at National Institute of Oceanography (India)

    Karisiddaiah, S.M.

    formations, while Dr. L. Stern presented ne insights into the phenomena of anomalous or self- preservation of gas hydrates. JOUR.GEOL.SOC.INDIA, VOL.61, JAN. 2001 Posters on hydrate formation and prevention in pipelines and hydrate based...

  2. Tropospheric impact of methane emissions from clathrates in the Arctic Region


    Bhattacharyya, S.; Cameron-Smith, P.; Bergmann, D; Reagan, M; Elliott, S.; Moridis, G.


    A highly potent greenhouse gas, methane, is locked in the solid phase as ice-like deposits containing a mixture of water and gas (mostly methane) called clathrates in both ocean sediments and underneath permafrost regions. Clathrates are stable under high pressures and low temperatures. In a warming climate, increases in ocean temperatures could lead to dissociation of the clathrates and release methane into the ocean and subsequently the atmosphere. This is of part...

  3. Formation of low-T hydrated silicates in modern microbialites from Mexico and implications for microbial fossilization

    Directory of Open Access Journals (Sweden)

    Nina eZeyen


    Full Text Available Microbialites are organo-sedimentary rocks found in abundance throughout the geological record back to ~3.5 Ga. Interpretations of the biological and environmental conditions under which they formed rely on comparisons with modern microbialites. Therefore, a better characterization of diverse modern microbialites is crucial to improve such interpretations. Here, we studied modern microbialites from three Mexican alkaline crater lakes: Quechulac, La Preciosa and Atexcac. The geochemical analyses of water solutions showed that they were supersaturated to varying extents with several mineral phases, including aragonite, calcite, hydromagnesite, as well as hydrated Mg-silicates. Consistently, X-ray diffraction and Fourier transform infrared spectroscopy analyses revealed that microbialites are composed of a diversity of mineral phases including aragonite and sometimes calcite, hydromagnesite, and more interestingly, a poorly-crystalline hydrated silicate phase. Coupling of scanning electron microscopy with energy dispersive X-ray spectrometry microanalyses on polished sections showed that this latter phase is abundant, authigenic, magnesium-rich and sometimes associated with iron and manganese. This mineral phase is similar to kerolite, a hydrated poorly crystalline talc-like phase (Mg3Si4O10(OH2·nH2O. Diverse microfossils were permineralized by this silicate phase. Some of them were imaged in 3D by FIB-tomography showing that their morphologically was exquisitely preserved down to the few nm-scale. The structural and chemical features of these fossils were further studied using a combination of transmission electron microscopy and scanning transmission X-ray microscopy at the carbon and magnesium K-edges and iron L2,3-edges. These results showed that organic carbon is pervasively associated with kerolite. Overall, it is suggested that the poorly-crystalline hydrated magnesium-rich silicate forms in many alkaline lakes and has a strong potential

  4. Formation of low-T hydrated silicates in modern microbialites from Mexico and implications for microbial fossilization (United States)

    Zeyen, Nina; Benzerara, Karim; Li, Jinhua; Groleau, Alexis; Balan, Etienne; Robert, Jean-Louis; Esteve, Imene; Tavera, Rosaluz; Moreira, David; Lopez-Garcia, Purificacion


    Microbialites are organo-sedimentary rocks found in abundance throughout the geological record back to ~3.5 Ga. Interpretations of the biological and environmental conditions under which they formed rely on comparisons with modern microbialites. Therefore, a better characterization of diverse modern microbialites is crucial to improve such interpretations. Here, we studied modern microbialites from three Mexican alkaline crater lakes: Quechulac, La Preciosa and Atexcac. The geochemical analyses of water solutions showed that they were supersaturated to varying extents with several mineral phases, including aragonite, calcite, hydromagnesite, as well as hydrated Mg-silicates. Consistently, X-ray diffraction and Fourier transform infrared spectroscopy analyses revealed that microbialites are composed of a diversity of mineral phases including aragonite and sometimes calcite, hydromagnesite, and more interestingly, a poorly-crystalline hydrated silicate phase. Coupling of scanning electron microscopy with energy dispersive X-ray spectrometry microanalyses on polished sections showed that this latter phase is abundant, authigenic, magnesium-rich and sometimes associated with iron and manganese. This mineral phase is similar to kerolite, a hydrated poorly crystalline talc-like phase (Mg3Si4O10(OH)2·nH2O). Diverse microfossils were permineralized by this silicate phase. Some of them were imaged in 3D by FIB-tomography showing that their morphologically was exquisitely preserved down to the few nm-scale. The structural and chemical features of these fossils were further studied using a combination of transmission electron microscopy and scanning transmission X-ray microscopy at the carbon and magnesium K-edges and iron L2,3-edges. These results showed that organic carbon is pervasively associated with kerolite. Overall, it is suggested that the poorly-crystalline hydrated magnesium-rich silicate forms in many alkaline lakes and has a strong potential for fossilization of

  5. [Progress in Raman spectroscopic measurement of methane hydrate]. (United States)

    Xu, Feng; Zhu, Li-hua; Wu, Qiang; Xu, Long-jun


    Complex thermodynamics and kinetics problems are involved in the methane hydrate formation and decomposition, and these problems are crucial to understanding the mechanisms of hydrate formation and hydrate decomposition. However, it was difficult to accurately obtain such information due to the difficulty of measurement since methane hydrate is only stable under low temperature and high pressure condition, and until recent years, methane hydrate has been measured in situ using Raman spectroscopy. Raman spectroscopy, a non-destructive and non-invasive technique, is used to study vibrational modes of molecules. Studies of methane hydrate using Raman spectroscopy have been developed over the last decade. The Raman spectra of CH4 in vapor phase and in hydrate phase are presented in this paper. The progress in the research on methane hydrate formation thermodynamics, formation kinetics, decomposition kinetics and decomposition mechanism based on Raman spectroscopic measurements in the laboratory and deep sea are reviewed. Formation thermodynamic studies, including in situ observation of formation condition of methane hydrate, analysis of structure, and determination of hydrate cage occupancy and hydration numbers by using Raman spectroscopy, are emphasized. In the aspect of formation kinetics, research on variation in hydrate cage amount and methane concentration in water during the growth of hydrate using Raman spectroscopy is also introduced. For the methane hydrate decomposition, the investigation associated with decomposition mechanism, the mutative law of cage occupancy ratio and the formulation of decomposition rate in porous media are described. The important aspects for future hydrate research based on Raman spectroscopy are discussed.

  6. Dynamic hydration shell restores Kauzmann's 1959 explanation of how the hydrophobic factor drives protein folding (United States)

    Baldwin, Robert L.


    Kauzmann's explanation of how the hydrophobic factor drives protein folding is reexamined. His explanation said that hydrocarbon hydration shells are formed, possibly of clathrate water, and they explain why hydrocarbons have uniquely low solubilities in water. His explanation was not universally accepted because of skepticism about the clathrate hydration shell. A revised version is given here in which a dynamic hydration shell is formed by van der Waals (vdw) attraction, as proposed in 1985 by Jorgensen et al. [Jorgensen WL, Gao J, Ravimohan C (1985) J Phys Chem 89:3470–3473]. The vdw hydration shell is implicit in theories of hydrophobicity that contain the vdw interaction between hydrocarbon C and water O atoms. To test the vdw shell model against the known hydration energetics of alkanes, the energetics should be based on the Ben-Naim standard state (solute transfer between fixed positions in the gas and liquid phases). Then the energetics are proportional to n, the number of water molecules correlated with an alkane by vdw attraction, given by the simulations of Jorgensen et al. The energetics show that the decrease in entropy upon hydration is the root cause of hydrophobicity; it probably results from extensive ordering of water molecules in the vdw shell. The puzzle of how hydrophobic free energy can be proportional to nonpolar surface area when the free energy is unfavorable and the only known interaction (the vdw attraction) is favorable, is resolved by finding that the unfavorable free energy is produced by the vdw shell. PMID:25157156

  7. Ft-Ir Spectroscopic Study Of Co(1-Propanethiol)2Ni(Cn)4·Benzene Clathrate

    National Research Council Canada - National Science Library

    D. Türköz; Z. Kartal; S. Bahçeli


    By vibrational spectroscopy of the new Hofmann-propanethiol-type clathrate Co(1-propanethiol) Ni(CN) ·Benzene it is shown that its structure is similar structure to those of other Hofmanntype clathrates.

  8. Kondo-like phonon scattering in thermoelectric clathrates


    Ikeda, M.; Euchner, H.; Yan, X.; Tomes, P.; Prokofiev, A; Prochaska, L.; Lientschnig, G.; Svagera, R.; Hartmann, S.; Gati, E.; Lang, M.; Paschen, S.


    Crystalline solids are generally known as excellent heat conductors, amorphous materials or glasses as thermal insulators. It has thus come as a surprise that certain crystal structures defy this paradigm. A prominent example are type-I clathrates and other materials with guest-host structures. They sustain low-energy Einstein-like modes in their phonon spectra, but are also prone to various types of disorder and phonon-electron scattering and thus the mechanism responsible for their ultralow...

  9. Global Assessment of Methane Gas Hydrates: Outreach for the public and policy makers (United States)

    Beaudoin, Yannick


    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

  10. Ductile flow of methane hydrate (United States)

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


    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.

  11. Thermodynamic inhibitor performance extender that, effectively and economically prevent hydrate formation in the oil field production systems

    Energy Technology Data Exchange (ETDEWEB)

    Allenson, Stephen; Johnston, Angela [Nalco Energy Services, Sugar Land, TX (United States)


    This paper presents the development of a new additive that was developed to improve the effectiveness of the treatment two to four fold when added to the thermodynamic hydrate inhibitor (THI). Consequently, the THI/additive treatment can now enable the system to handle two to four times the amount of water production or can allow treatment of the same amount of water at half to quarter the dosage of THI. This new additive extends the performance of the THI and allows for a significant increase in production or a significant drop in the amount of THI usage with a corresponding drop in cost. This paper will further discuss the overall process of THI enhancement and will present several case studies where the enhanced THI has been successfully applied. (author)


    Energy Technology Data Exchange (ETDEWEB)

    John H. Cohen; Thomas E. Williams; Ali G. Kadaster; Bill V. Liddell


    The ''Methane Hydrate Production from Alaskan Permafrost'' project is a three-year endeavor being conducted by Maurer Technology Inc. (MTI), Noble, and Anadarko Petroleum, in partnership with the U.S. DOE National Energy Technology Laboratory (NETL). The project's goal is to build on previous and ongoing R&D in the area of onshore hydrate deposition. The project team plans to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope includes drilling and coring one well on Anadarko leases in FY 2003 during the winter drilling season. A specially built on-site core analysis laboratory will be used to determine some of the physical characteristics of the hydrates and surrounding rock. Prior to going to the field, the project team designed and conducted a controlled series of coring tests for simulating coring of hydrate formations. A variety of equipment and procedures were tested and modified to develop a practical solution for this special application. This Topical Report summarizes these coring tests. A special facility was designed and installed at MTI's Drilling Research Center (DRC) in Houston and used to conduct coring tests. Equipment and procedures were tested by cutting cores from frozen mixtures of sand and water supported by casing and designed to simulate hydrate formations. Tests were conducted with chilled drilling fluids. Tests showed that frozen core can be washed out and reduced in size by the action of the drilling fluid. Washing of the core by the drilling fluid caused a reduction in core diameter, making core recovery very difficult (if not impossible). One successful solution was to drill the last 6 inches of core dry (without fluid circulation). These tests demonstrated that it will be difficult to capture core when drilling in permafrost or hydrates without implementing certain safeguards. Among the coring tests was a simulated hydrate

  13. Potential impact on climate of the exploitation of methane hydrate deposits offshore

    Digital Repository Service at National Institute of Oceanography (India)

    Glasby, G.P.

    weather patterns, distribution of ecosystems, sea level change and patterns of disease (Anon, 2001a,b). The control of greenhouse gases is therefore likely to become a matter of critical concern in the future. Only now are models becoming available...–175 * Current address: 42 Warminster Cresent, Sheffield S8 9NW. E-mail address: (G.P. Glasby). 2. Stability and occurrence of methane hydrates Methane hydrate has a clathrate structure in which...

  14. Thermodynamic Stability of Structure H Hydrates Based on the Molecular Properties of Large Guest Molecules

    Directory of Open Access Journals (Sweden)

    Ryo Ohmura


    Full Text Available This paper report analyses of thermodynamic stability of structure-H clathrate hydrates formed with methane and large guest molecules in terms of their gas phase molecular sizes and molar masses for the selection of a large guest molecule providing better hydrate stability. We investigated the correlation among the gas phase molecular sizes, the molar masses of large molecule guest substances, and the equilibrium pressures. The results suggest that there exists a molecular-size value for the best stability. Also, at a given molecule size, better stability may be available when the large molecule guest substance has a larger molar mass.

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

    CERN Document Server

    Kriger, Y G; Chekhova, G N


    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

  16. Gas hydrates

    Digital Repository Service at National Institute of Oceanography (India)

    Ramprasad, T.

    . faulting and fluid migration, and 4. trapping of free gas beneath a hydrate seal. Experiments are being conducted to assess the impact of gas hydrate on sediment behavior, particularly with respect to slope failure and other potential geohazards....K. Paull, R. Matsumoto, P.J. Wallace, and W.P. Dillon (Eds.), Proceedings ODP, Scientific Results, v. 164 College Station, TX (Ocean Drilling Program), pp. 179-191. Dallimore, S. R., T. Uchida, and T. S. Collett, 1999, Summary, in S. R. Dallimore, T...

  17. Physical properties of sediment containing methane gas hydrate (United States)

    Winters, W.J.; Waite, W.F.; Mason, D.H.; Gilbert, L.Y.


    A study conducted by the US Geological Survey (USGS) on the formation, behavior, and properties of mixtures of gas hydrate and sediment is presented. The results show that the properties of host material influence the type and quantity of hydrates formed. The presence of hydrate during mechanical shear tests affects the measured sediment pore pressure. Sediment shear strength may be increased more than 500 percent by intact hydrate, but greatly weakened if the hydrate dissociates.

  18. Gas Hydrate Petroleum System Analysis (United States)

    Collett, T. S.


    In a gas hydrate petroleum system, the individual factors that contribute to the formation of gas hydrate accumulations, such as (1) gas hydrate pressure-temperature stability conditions, (2) gas source, (3) gas migration, and (4) the growth of the gas hydrate in suitable host sediment can identified and quantified. The study of know and inferred gas hydrate accumulations reveal the occurrence of concentrated gas hydrate is mostly controlled by the presence of fractures and/or coarser grained sediments. Field studies have concluded that hydrate grows preferentially in coarse-grained sediments because lower capillary pressures in these sediments permit the migration of gas and nucleation of hydrate. Due to the relatively distal nature of the deep marine geologic settings, the overall abundance of sand within the shallow geologic section is usually low. However, drilling projects in the offshore of Japan, Korea, and in the Gulf of Mexico has revealed the occurrence of significant hydrate-bearing sand reservoirs. The 1999/2000 Japan Nankai Trough drilling confirmed occurrence of hydrate-bearing sand-rich intervals (interpreted as turbidite fan deposits). Gas hydrate was determined to fill the pore spaces in these deposits, reaching saturations up to 80% in some layers. A multi-well drilling program titled "METI Toaki-oki to Kumano-nada" also identified sand-rich reservoirs with pore-filling hydrate. The recovered hydrate-bearing sand layers were described as very-fine- to fine-grained turbidite sand layers measuring from several centimeters up to a meter thick. However, the gross thickness of the hydrate-bearing sand layers were up to 50 m. In 2010, the Republic of Korea conducted the Second Ulleung Basin Gas Hydrate (UBGH2) Drilling Expedition. Seismic data clearly showed the development of a thick, potential basin wide, sedimentary sections characterized by mostly debris flows. The downhole LWD logs and core data from Site UBGH2-5 reveal that each debris flows is

  19. Well log characterization of natural gas hydrates (United States)

    Collett, Timothy S.; Lee, Myung W.


    In the last 25 years we have seen significant advancements in the use of downhole well logging tools to acquire detailed information on the occurrence of gas hydrate in nature: From an early start of using wireline electrical resistivity and acoustic logs to identify gas hydrate occurrences in wells drilled in Arctic permafrost environments to today where wireline and advanced logging-while-drilling tools are routinely used to examine the petrophysical nature of gas hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. The most established and well known use of downhole log data in gas hydrate research is the use of electrical resistivity and acoustic velocity data (both compressional- and shear-wave data) to make estimates of gas hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. New downhole logging tools designed to make directionally oriented acoustic and propagation resistivity log measurements have provided the data needed to analyze the acoustic and electrical anisotropic properties of both highly inter-bedded and fracture dominated gas hydrate reservoirs. Advancements in nuclear-magnetic-resonance (NMR) logging and wireline formation testing have also allowed for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids (i.e., free-water along with clay and capillary bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms controlling the formation and occurrence of gas hydrate in nature along with data on gas hydrate reservoir properties (i.e., permeabilities) needed to accurately predict gas production rates for various gas hydrate

  20. NMR and transport measurements of copper chalcogenide and clathrate compounds (United States)

    Sirusi Arvij, Ali

    Due to limited sources of fossil fuels worldwide and a large percentage wasted as heat energy, searching for efficient thermoelectric materials to convert heat to electricity has gained a great deal of attention. Most of the attempts are focused on materials with substantially lower lattice thermal conductivity and narrow band gaps. Among them, inorganic clathrates and copper-based chalcogenides possess intrinsic low thermal conductivity which makes them promising thermoelectrics. In this work, nuclear magnetic resonance (NMR), transport, and magnetic measurements were performed on clathrates and copper-based chalcogenides to investigate their vibrational and electronic charge carrier properties, as well as the unknown structures of Cu2Se and Cu 2Te at low temperatures, and the effect of rattling of guest atoms in the clathrates. The NMR results in Ba8Ga16Ge30 indicate a pseudogap in the Ga electronic density of states, superposed upon a surprisingly large Ba contribution to the conduction band. Meanwhile, the phonon contributions to the Ga relaxation rates are large and increase more rapidly with temperature than typical semiconductors due to enhanced anharmonicity of the propagative phonon modes over a wide range. Moreover, the observed NMR shifts in the Ba8Cu5Si xGe41-x clathrates change in a nonlinear way with increasing Si substitution: from x = 0 to about 20 the shifts are essentially constant, while approaching x = 41 they increase rapidly, demonstrating a significant change in hybridizations vs Si substitution. NMR studies of Cu2Se show an initial appearance of ionic hopping in a narrow temperature range above 100 K, coinciding with the recently observed low-temperature phase transition. At room temperature and above, this goes over to rapid Cu-ion hopping and a single motionally narrowed line both above and below the alpha-beta structural transition. Furthermore, the NMR results on Cu2Te and Cu 1.98Ag0.2Te demonstrate unusually large negative chemical

  1. Flow assurance intervention, hydrates remediation

    Energy Technology Data Exchange (ETDEWEB)

    Mancini, Christopher S. [Oceaneering International Inc., Houston, TX (United States)


    This paper addresses the issues of removing hydrates in sub sea flow lines and associated equipment with an Remotely Operated Vehicle (ROV) of opportunity and a multi-service-vessel (MSV). The paper is split into three topics: the equipment used with the ROV, assessing the interface points and handling fluids produced from drawing down the pressure. Each section is explained thoroughly and backed up with real world experience. The equipment section details information from actual jobs performed and why the particular components were utilized. The system is generally contained in an ROV mounted skid. Pumps are utilized to draw down the pressure inside the hydrated section of equipment, removing one of the three necessary components for hydrates formation. Once the section is pumped down, several options exist for handling the fluids pumped out of the system: pumping to surface, re-injection into the well, or injection into an operating flow line. This method of hydrates remediation is both economical and timely. Hydrate blockages form in low temperatures and high pressures. Reducing the pressure or increasing the temperature so the conditions lie to the right of the hydrate dissociation curve will slowly decompose the blockage. Depressurization and the use of MEG or methanol will give favorable conditions to remove the hydrate plug. Oceaneering has the capabilities to remove hydrates using the FRS in conjunction with an installation vessel to dispose of the gas and fluid removed from the flow line. Hydrate remediation techniques should be implemented into the initial design to reduce costs later. The cost of stopped production combined with the day rate for equipment needed for hydrate removal outweighs the costs if no technique is utilized. (author)

  2. Lattice constants and expansivities of gas hydrates from 10 K up to the stability limit

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, T. C. [Institut Laue-Langevin, 71 Avenue des Martyrs, 38000 Grenoble (France); Falenty, A.; Kuhs, W. F. [GZG, Abt. Kristallographie, Universität Göttingen, Goldschmidtstrasse 1, 37077 Göttingen (Germany)


    The lattice constants of hydrogenated and deuterated CH{sub 4}-, CO{sub 2}-, Xe- (clathrate structure type I) and N{sub 2}-hydrates (clathrate structure type II) from 10 K up to the stability limit were established in neutron- and synchrotron diffraction experiments and were used to derive the related thermal expansivities. The following results emerge from this analysis: (1) The differences of expansivities of structure type I and II hydrates are fairly small. (2) Despite the larger guest-size of CO{sub 2} as compared to methane, CO{sub 2}-hydrate has the smaller lattice constants at low temperatures, which is ascribed to the larger attractive guest-host interaction of the CO{sub 2}-water system. (3) The expansivity of CO{sub 2}-hydrate is larger than for CH{sub 4}-hydrate which leads to larger lattice constants for the former at temperatures above ∼150 K; this is likely due to the higher motional degrees of freedom of the CO{sub 2} guest molecules. (4) The cage occupancies of Xe- and CO{sub 2}-hydrates affect significantly the lattice constants. (5) Similar to ice Ih, the deuterated compounds have generally slightly larger lattice constants which can be ascribed to the somewhat weaker H-bonding. (6) Compared to ice Ih, the high temperature expansivities are about 50% larger; in contrast to ice Ih and the empty hydrate, there is no negative thermal expansion at low temperature. (7) A comparison of the experimental results with lattice dynamical work, with models based on an Einstein oscillator model, and results from inelastic neutron scattering suggest that the contribution of the guest atoms’ vibrational energy to thermal expansion is important, most prominently for CO{sub 2}- and Xe-hydrates.

  3. Geochemistry of clathrate-derived methane in Arctic Ocean waters

    Energy Technology Data Exchange (ETDEWEB)

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


    Alterations to the composition of seawater are estimated for microbial oxidation of methane from large polar clathrate destabilizations, which may arise in the coming century. Gas fluxes are taken from porous flow models of warming Arctic sediment. Plume spread parameters are then used to bracket the volume of dilution. Consumption stoichiometries for the marine methanotrophs are based on growth efficiency and elemental/enzyme composition data. The nutritional demand implied by extra CH{sub 4} removal is compared with supply in various high latitude water masses. For emissions sized to fit the shelf break, reaction potential begins at one hundred micromolar and falls to order ten a thousand kilometers downstream. Oxygen loss and carbon dioxide production are sufficient respectively to hypoxify and acidify poorly ventilated basins. Nitrogen and the monooxygenase transition metals may be depleted in some locations as well. Deprivation is implied relative to existing ecosystems, along with dispersal of the excess dissolved gas. Physical uncertainties are inherent in the clathrate abundance, patch size, outflow buoyancy and mixing rate. Microbial ecology is even less defined but may involve nutrient recycling and anaerobic oxidizers.

  4. Observed gas hydrate morphologies in marine sediment

    Energy Technology Data Exchange (ETDEWEB)

    Holland, M.; Schultheiss, P.; Roberts, J.; Druce, M. [Geotek Ltd., Daventry, Northamptonshire (United Kingdom)


    The morphology of gas hydrate in marine sediments determines the basic physical properties of the sediment-hydrate matrix and provides information regarding the formation of gas hydrate deposits, and the nature of the disruption that will occur on dissociation. Small-scale morphology is useful in estimating the concentrations of gas hydrate from geophysical data. It is also important for predicting their response to climate change or commercial production. Many remote techniques for gas hydrate detection and quantification depend on hydrate morphology. In this study, morphology of gas hydrate was examined in HYACINTH pressure cores from recent seagoing expeditions. Visual and infrared observations from non-pressurized cores were also used. The expeditions and pressure core analysis were described in detail. This paper described the difference between two types of gas hydrate morphologies, notably pore-filling and grain-displacing. Last, the paper addressed the impact of hydrate morphology. It was concluded that a detailed morphology of gas hydrate is an essential component for a full understanding of the past, present, and future of any gas hydrate environment. 14 refs., 4 figs.

  5. Skin hydration effects, film formation time, and physicochemical properties of a moisture mask containing Monostroma nitidium water-soluble mucilage. (United States)

    Chen, Rong Huei; Chen, Weei Yuu


    The objectives of the study were to explore the effects of using the water-soluble mucilage of Monostroma nitidium to replace the humectant and half of the thickening agent on the rheological properties, color, storage stability, water-holding capacity, and film formation time of moisture masks thus prepared. Results showed that moisture masks containing water-soluble mucilage were pseudoplaxtic fluids. The apparent viscosity of these moisture masks decreased with increasing shear rate but increased with increasing concentration of the aqueous extracts used. The water-holding capacity of moisture masks containing 1% aqueous extracts and 1% hydroxyethyl cellulose (HEC) were similar to those containing 2% HEC and 5% 1-3 butadiene (humectant) but better than those containing 2% methyl cellulose (MC) and 5% humectant. The film formation time of moisture masks containing different concentrations of aqueous extracts decreased with increasing concentration of the aqueous extract used. The storage stability of a moisture mask containing 1% aqueous extract and 1% HEC was similar to that containing 2% HEC and 5% humectant and better than those containing 2% MC and 5% humectant. The safety test resulted in no erythema based on the Draize score test. The pH was between 7.1 and 7.5 for all moisture masks studied.

  6. Gas hydrate inhibition of drilling fluid additives

    Energy Technology Data Exchange (ETDEWEB)

    Xiaolan, L.; Baojiang, S.; Shaoran, R. [China Univ. of Petroleum, Dongying (China). Inst. of Petroleum Engineering


    Gas hydrates that form during offshore well drilling can have adverse impacts on well operational safety. The hydrates typically form in the risers and the annulus between the casing and the drillstring, and can stop the circulation of drilling fluids. In this study, experiments were conducted to measure the effect of drilling fluid additives on hydrate inhibition. Polyalcohols, well-stability control agents, lubricating agents, and polymeric materials were investigated in a stirred tank reactor at temperatures ranging from -10 degree C to 60 degrees C. Pressure, temperature, and torque were used to detect onset points of hydrate formation and dissociation. The inhibitive effect of the additives on hydrate formation was quantified. Phase boundary shifts were measured in terms of temperature difference or sub-cooling gained when chemicals were added to pure water. Results showed that the multiple hydroxyl groups in polyalcohol chemicals significantly inhibited hydrate formation. Polymeric and polyacrylamide materials had only a small impact on hydrate formation, while sulfonated methyl tannins were found to increase hydrate formation. 6 refs., 1 tab., 4 figs.

  7. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments (United States)

    Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.


    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  8. Natural Gas Hydrates


    Ersland, Geir


    The experimental set-up with the MRI monitoring apparatus was capable of forming large quantities of methane hydrates in sandstone pores and monitor hydrate growth patterns for various initial conditions. Spontaneous conversion of methane hydrate to carbon dioxide hydrate occurred when methane hydrate, in porous media, was exposed to liquid carbon dioxide. The MRI images did not detect any significant increase in signal in the hydrate saturated cores that would indicate the presence of free w...

  9. Interplay of phase separation, tail aggregation, and micelle formation in the nanostructured organization of hydrated imidazolium ionic liquid. (United States)

    Ramya, K R; Kumar, Praveen; Kumar, Ashish; Venkatnathan, Arun


    A molecular investigation on the effect of water on structural properties of imidazolium-based ionic liquids (ILs) is essential due to its various industrial applications. In this work, we employ molecular dynamics simulations to characterize the influence of various water concentrations on nanostructural properties of the 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Hmim][NTf2] IL. An examination of molecular interactions in [Hmim][NTf2] IL-water mixtures shows the following trends: (a) At low water concentration, small regions of water molecules are surrounded by several cation-anion pairs. (b) At medium water concentration, cation tail aggregation starts, and phase separation between the IL and water is observed. (c) At high water concentration, increasing cationic tail aggregation leads to micelle formation. Further aggregates of cations and anions are solvated by large water channels. The radial distribution functions show that cation-anion, cation-cation, and anion-anion interactions decrease and water-water interaction increases with water concentration. The hydrogen bonding interactions occur between the acidic hydrogen of the positively charged imidazolium cation with the nitrogen and oxygen atoms of the anions. However, no hydrogen bonding interactions are seen between water molecules and the hydrophobic anions.

  10. Trihalomethane, haloacetonitrile, and chloral hydrate formation potentials of organic carbon fractions from sub-tropical forest soils. (United States)

    Zhang, Qian; Kuang, Wan-fang; Liu, Lu-ying; Li, Kexin; Wong, Kin-hang; Chow, Alex T; Wong, Po-keung


    Forest landscapes represent the major land-cover type for the watersheds of the East River, which is the source of water for 40 million people in South China. Forest soils with high levels of organic carbon are a potential terrestrial source of dissolved organic carbon (DOC) into the East River. DOC is of great concern, since it can form carcinogenic disinfection byproducts (DBPs) during drinking water treatment. In this study, soils from three altitudes (200, 450 and 900 m) in the Xiangtou Mountain Nature Reserve in South China, representing soils from evergreen moon forest, transitional evergreen broadleaf forest, and evergreen broadleaf forest, respectively, were evaluated for their potential contributions of DBP precursors into the East River. The water extractable organic carbon (WEOC) in three forest soils was physically and chemically fractionated into particulate organic carbon (1.2-0.45 microm), colloidal organic carbon (0.45-0.22 microm), and dissolved organic carbon (DOC) (impact of temperature effects on the availability and characteristics of WEOC. The extraction study showed that the amount of WEOC was proportional to soil organic carbon content, of which about 1% was water extractable. Regardless of soil type, DOC and HPOA were the most reactive fractions in forming THMs, CHD, and HANs. Production of DOC and HPOA in WEOC increased over 14 d incubation as incubation temperature increased, but the temperature did not alter the distribution of physical and chemical fractions and their reactivity in DBP formation. Results suggest higher inputs of DOC and DBP precursors from forest watersheds into source water may result in a warmer environment.

  11. Methane Recovery from Hydrate-bearing Sediments

    Energy Technology Data Exchange (ETDEWEB)

    J. Carlos Santamarina; Costas Tsouris


    Gas hydrates are crystalline compounds made of gas and water molecules. Methane hydrates are found in marine sediments and permafrost regions; extensive amounts of methane are trapped in the form of hydrates. Methane hydrate can be an energy resource, contribute to global warming, or cause seafloor instability. This study placed emphasis on gas recovery from hydrate bearing sediments and related phenomena. The unique behavior of hydrate-bearing sediments required the development of special research tools, including new numerical algorithms (tube- and pore-network models) and experimental devices (high pressure chambers and micromodels). Therefore, the research methodology combined experimental studies, particle-scale numerical simulations, and macro-scale analyses of coupled processes. Research conducted as part of this project started with hydrate formation in sediment pores and extended to production methods and emergent phenomena. In particular, the scope of the work addressed: (1) hydrate formation and growth in pores, the assessment of formation rate, tensile/adhesive strength and their impact on sediment-scale properties, including volume change during hydrate formation and dissociation; (2) the effect of physical properties such as gas solubility, salinity, pore size, and mixed gas conditions on hydrate formation and dissociation, and it implications such as oscillatory transient hydrate formation, dissolution within the hydrate stability field, initial hydrate lens formation, and phase boundary changes in real field situations; (3) fluid conductivity in relation to pore size distribution and spatial correlation and the emergence of phenomena such as flow focusing; (4) mixed fluid flow, with special emphasis on differences between invading gas and nucleating gas, implications on relative gas conductivity for reservoir simulations, and gas recovery efficiency; (5) identification of advantages and limitations in different gas production strategies with

  12. Thermal conductivity of hydrate-bearing sediments (United States)

    Cortes, Douglas D.; Martin, Ana I.; Yun, Tae Sup; Francisca, Franco M.; Santamarina, J. Carlos; Ruppel, Carolyn D.


    A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate–saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate–bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces.

  13. A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach (United States)

    Mehta, A.P.; Makogon, T.Y.; Burruss, R.C.; Wendlandt, R.F.; Sloan, E.D.


    A composite phase diagram is presented for Structure H (sH) clathrate hydrates. In this work, we derived the reactions occurring among the various phases along each four-phase (Ice/Liquid water, liquid hydrocarbon, vapor, and hydrate) equilibrium line. A powerful method (though seldom used in chemical engineering) for multicomponent equilibria developed by Schreinemakers is applied to determine the relative location of all quadruple (four-phase) lines emanating from three quintuple (five-phase) points. Experimental evidence validating the approximate phase diagram is also provided. The use of Schreinemakers' rules for the development of the phase diagram is novel for hydrates, but these rules may be extended to resolve the phase space of other more complex systems commonly encountered in chemical engineering.

  14. A modeling study of methane hydrate decomposition in contact with the external surface of zeolites. (United States)

    Smirnov, Konstantin S


    The behavior of methane hydrate (MH) enclosed between the (010) surfaces of the silicalite-1 zeolite was studied by means of molecular dynamics simulations at temperatures of 150 and 250 K. Calculations reveal that the interaction with the hydrophilic surface OH groups destabilizes the clathrate structure of hydrate. While MH mostly conserves the structure in the simulation at the low temperature, thermal motion at the high temperature breaks the fragilized cages of H-bonded water molecules, thus leading to the release of methane. The dissociation proceeds in a layer-by-layer manner starting from the outer parts of the MH slab until complete hydrate decomposition. The released CH 4 molecules are absorbed by the microporous solid, whereas water is retained at the surfaces of hydrophobic silicalite and forms a meniscus in the interlayer space. Methane uptake reaches 70% of the silicalite sorption capacity. The energy necessary for the endothermic MH dissociation is supplied by the exothermic methane absorption by the zeolite.

  15. Hydrate-Bearing Clayey Sediments: Morphology, Physical Properties, Production and Engineering/Geological Implications

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Sheng [Georgia Tech Research Corporation, Atlanta, GA (United States); Santamarina, J. Carlos [King Abdulaziz Univ., Jeddah (Saudi Arabia)


    Fine-grained sediments host more than 90 percent of global gas hydrate accumulation. However, hydrate formation in clay-dominated sediments is less understood and characterized than other types of hydrate occurrence. There is an inadequate understanding of hydrate formation mechanisms, segregation structures, hydrate lens topology, system connectivity, and physical macro-scale properties of clay-dominated hydrate-bearing sediments. This situation hinders further analyses of the global carbon budget as well as engineering challenges/solutions related to hydrate instability and production. This project studies hydrate-bearing clay-dominated sediments with emphasis on the enhanced fundamental understanding of hydrate formation and resulting morphology, the development laboratory techniques to emulate natural hydrate formations, the assessment of analytical tools to predict physical properties, the evaluation of engineering and geological implications, and the advanced understanding of gas production potential from finegrained sediments.

  16. Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation (United States)

    Hunt, Andrew G.; Stern, Laura; Pohlman, John W.; Ruppel, Carolyn; Moscati, Richard J.; Landis, Gary P.


    As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

  17. Gas Hydrate Storage of Natural Gas

    Energy Technology Data Exchange (ETDEWEB)

    Rudy Rogers; John Etheridge


    Environmental and economic benefits could accrue from a safe, above-ground, natural-gas storage process allowing electric power plants to utilize natural gas for peak load demands; numerous other applications of a gas storage process exist. A laboratory study conducted in 1999 to determine the feasibility of a gas-hydrates storage process looked promising. The subsequent scale-up of the process was designed to preserve important features of the laboratory apparatus: (1) symmetry of hydrate accumulation, (2) favorable surface area to volume ratio, (3) heat exchanger surfaces serving as hydrate adsorption surfaces, (4) refrigeration system to remove heat liberated from bulk hydrate formation, (5) rapid hydrate formation in a non-stirred system, (6) hydrate self-packing, and (7) heat-exchanger/adsorption plates serving dual purposes to add or extract energy for hydrate formation or decomposition. The hydrate formation/storage/decomposition Proof-of-Concept (POC) pressure vessel and supporting equipment were designed, constructed, and tested. This final report details the design of the scaled POC gas-hydrate storage process, some comments on its fabrication and installation, checkout of the equipment, procedures for conducting the experimental tests, and the test results. The design, construction, and installation of the equipment were on budget target, as was the tests that were subsequently conducted. The budget proposed was met. The primary goal of storing 5000-scf of natural gas in the gas hydrates was exceeded in the final test, as 5289-scf of gas storage was achieved in 54.33 hours. After this 54.33-hour period, as pressure in the formation vessel declined, additional gas went into the hydrates until equilibrium pressure/temperature was reached, so that ultimately more than the 5289-scf storage was achieved. The time required to store the 5000-scf (48.1 hours of operating time) was longer than designed. The lower gas hydrate formation rate is attributed to a

  18. Synthesis of polyphenylacetylene by radiation-induced polymerization in deoxycholic acid clathrate (United States)

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


    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.

  19. Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

    Energy Technology Data Exchange (ETDEWEB)

    Vlasic, Thomas M.; Servio, Phillip; Rey, Alejandro D., E-mail: [Department of Chemical Engineering, McGill University, Montreal H3A 0C5 (Canada)


    This work uses density functional theory (DFT) to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane), at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS) for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu) were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

  20. Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

    Directory of Open Access Journals (Sweden)

    Thomas M. Vlasic


    Full Text Available This work uses density functional theory (DFT to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane, at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

  1. "Self-preservation" of CO(2) gas hydrates--surface microstructure and ice perfection. (United States)

    Falenty, Andrzej; Kuhs, Werner F


    Gas hydrates can exhibit an anomalously slow decomposition outside their thermodynamic stability field; the phenomenon is called "self-preservation" and is mostly studied at ambient pressure and at temperatures between approximately 240 K and the melting point of ice. Here, we present a combination of in situ neutron diffraction studies, pVT work, and ex situ scanning electron microscopy (SEM) on CO(2) clathrates covering a much broader p-T field, stretching from 200 to 270 K and pressures between the hydrate stability limit and 0.6 kPa (6 mbar), a pressure far outside stability. The self-preservation regime above 240 K is confirmed over a broad pressure range and appears to be caused by the annealing of an ice cover formed in the initial hydrate decomposition. Another, previously unknown regime of the self-preservation exists below this temperature, extending however only over a rather narrow pressure range. In this case, the initial ice microstructure is dominated by a fast two-dimensional growth covering rapidly the clathrate surface. All observations lend strong support to the idea that the phenomenon of self-preservation is linked to the permeability of the ice cover governed by (1) the initial microstructure of ice and/or (2) the subsequent annealing of this ice coating. The interplay of the microstructure of newly formed ice and its annealing with the ongoing decomposition reaction leads to various decomposition paths and under certain conditions to a very pronounced preservation anomaly.

  2. Entrapment of Hydrate-coated Gas Bubbles into Oil and Separation of Gas and Hydrate-film; Seafloor Experiments with ROV (United States)

    Hiruta, A.; Matsumoto, R.


    We trapped gas bubbles emitted from the seafloor into oil-containing collector and observed an unique phenomena. Gas hydrate formation needs water for the crystal lattice; however, gas hydrates in some areas are associated with hydrophobic crude oil or asphalt. In order to understand gas hydrate growth in oil-bearing sediments, an experiment with cooking oil was made at gas hydrate stability condition. We collected venting gas bubbles into a collector with canola oil during ROV survey at a gas hydrate area in the eastern margin of the Sea of Japan. When the gas bubbles were trapped into collector with oil, gas phase appeared above the oil and gas hydrates, between oil and gas phase. At this study area within gas hydrate stability condition, control experiment with oil-free collector suggested that gas bubbles emitted from the seafloor were quickly covered with gas hydrate film. Therefore it is improbable that gas bubbles entered into the oil phase before hydrate skin formation. After the gas phase formation in oil-containing collector, the ROV floated outside of hydrate stability condition for gas hydrate dissociation and re-dived to the venting site. During the re-dive within hydrate stability condition, gas hydrate was not formed. The result suggests that moisture in the oil is not enough for hydrate formation. Therefore gas hydrates that appeared at the oil/gas phase boundary were already formed before bubbles enter into the oil. Hydrate film is the only possible origin. This observation suggests that hydrate film coating gas hydrate was broken at the sea water/oil boundary or inside oil. Further experiments may contribute for revealing kinetics of hydrate film and formation. This work was a part of METI (Ministry of Economy, Trade and Industry)'s project entitled "FY2014 Promoting research and development of methane hydrate". We also appreciate support of AIST (National Institute of Advanced Industrial Science and Technology).

  3. Investigations into surfactant/gas hydrate relationship

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, Rudy; Zhang, Guochang; Dearman, Jennifer; Woods, Charles [Swalm School of Chemical Engineering, Mississippi State University, Mississippi State, MS 39762 (United States)


    Gas hydrates have unique physical properties portending useful industrial applications of gas storage, gas separation, or water desalination. When gas hydrates were found in the early 1990s to occur naturally and abundantly in seafloors, three other primary interests and concerns emerged: potential new energy source, climate threat from their greenhouse gases, and seafloor instabilities. This paper presents research showing how anionic synthetic surfactants helped develop an industrial gas hydrate storage process for natural gas and how naturally-occurring in-situ anionic biosurfactants influence the formation and placement of gas hydrates in ocean sediments. The catalytic effects, mechanisms, and surface specificities imparted by synthetic surfactants in the gas storage process and imparted by biosurfactants in porous media are discussed. The Bacillus subtilis bacterium that is indigenous to gas hydrate mounds in the Gulf of Mexico was cultured in the laboratory. Its biosurfactant was separated and found to catalyze gas hydrates in porous media. The experiments indicate that seafloor-biosurfactants can be produced rapidly in-situ to achieve threshold concentrations whereby hydrates are promoted. The biosurfactants accumulate and promote hydrate formation on specific mineral surfaces such as sodium montmorillonite. (author)

  4. Gas-Phase Synthesis and Characterization of CH4-Loaded Hydroquinone Clathrates

    Energy Technology Data Exchange (ETDEWEB)

    Lee, J.; Lee, Y; Takeya, S; Kawamura, T; Yamamoto, Y; Lee, Y; Yoon, J


    A CH{sub 4}-loaded hydroquinone (HQ) clathrate was synthesized via a gas-phase reaction using the {alpha}-form of crystalline HQ and CH{sub 4} gas at 12 MPa and room temperature. Solid-state {sup 13}C cross-polarization/magic angle spinning (CP/MAS) NMR and Raman spectroscopic measurements confirm the incorporation of CH{sub 4} molecules into the cages of the HQ clathrate framework. The chemical analysis indicates that about 69% of the cages are filled by CH{sub 4} molecules, that is, 0.69 CH{sub 4} per three HQ molecules. Rietveld refinement using synchrotron X-ray powder diffraction (XRD) data shows that the CH{sub 4}-loaded HQ clathrate adopts the {beta}-form of HQ clathrate in a hexagonal space group R3 with lattice parameters of a = 16.6191 {angstrom} and c = 5.5038 {angstrom}. Time-resolved synchrotron XRD and quadrupole mass spectroscopic measurements show that the CH{sub 4}-loaded HQ clathrate is stable up to 368 K and gradually transforms to the {alpha}-form by releasing the confined CH{sub 4} gases between 368-378 K. Using solid-state {sup 13}C CP/MAS NMR, the reaction kinetics between the {alpha}-form HQ and CH{sub 4} gas is qualitatively described in terms of the particle size of the crystalline HQ.

  5. In situ study of mass transfer in aqueous solutions under high pressures via Raman spectroscopy: a new method for the determination of diffusion coefficients of methane in water near hydrate formation conditions. (United States)

    Lu, W J; Chou, I M; Burruss, R C; Yang, M Z


    A new method was developed for in situ study of the diffusive transfer of methane in aqueous solution under high pressures near hydrate formation conditions within an optical capillary cell. Time-dependent Raman spectra of the solution at several different spots along the one-dimensional diffusion path were collected and thus the varying composition profile of the solution was monitored. Diffusion coefficients were estimated by the least squares method based on the variations in methane concentration data in space and time in the cell. The measured diffusion coefficients of methane in water at the liquid (L)-vapor (V) stable region and L-V metastable region are close to previously reported values determined at lower pressure and similar temperature. This in situ monitoring method was demonstrated to be suitable for the study of mass transfer in aqueous solution under high pressure and at various temperature conditions and will be applied to the study of nucleation and dissolution kinetics of methane hydrate in a hydrate-water system where the interaction of methane and water would be more complicated than that presented here for the L-V metastable condition.

  6. Transport Properties Of Type-I Sn Clathrates (United States)

    Egbele, Peter; Joubert, Daniel; Shoko, Elvis

    The conversion of 'waste' heat into useful energy can contribute to the efficient use of available energy. This includes converting heat energy from internal combustion engines, conventional power plants and solar cells into usable energy. Thermoelectric devices can convert heat into an electric current and have immense potential for utilizing heat energy. One of the desired features of an efficient thermoelectric material is a low lattice thermal conductivity. In this study thermal transport properties of type-I Sn clathrates are investigated. We study the dynamics of the guest atoms Cs and K in the compound A8 Sn44 (A = Cs, K). We find that the guest atom are responsible for scattering of the heat in these systems, and hence responsible for the low thermal conductivity in these materials. These compounds are formed in a cubic lattice. A low thermal conductivity value of 0.17 and 0.18 W m-1 K-1 at 300 K respectively, was calculated for Cs8 Sn44 and K8 Sn44 . These are low values which makes these and similar materials attractive for further study. NRF South Africa.

  7. Modeling IR spectra of CO2 isotopologues and CH4 trapped In type I clathrate

    Directory of Open Access Journals (Sweden)

    Lakhlifi A.


    Full Text Available To test the hypothesis of atmospheric carbon dioxide or methane storage in metastable clathrate, a theoretical formalism is developed to model and simulate the spectra of the CO2 or CH4 molecule trapped in clathrates. 12-6 Lennard-Jones atomatom potentials are used to account for short and long range interactions between the atoms of the trapped molecules and atoms of H2O molecules of the cage. Effective electric charges are used for electrostatic interactions with H2O molecules. The calculations were performed on clathrates of type I, with a small and a large cage to determine equilibrium configurations for both CO2 and CH4 and vibrational shifts were determined for CO2 in an undistorted trapping nano-cage.

  8. A hydrated ion model of [UO2] 2 + in water: Structure, dynamics, and spectroscopy from classical molecular dynamics (United States)

    Pérez-Conesa, Sergio; Torrico, Francisco; Martínez, José M.; Pappalardo, Rafael R.; Sánchez Marcos, Enrique


    A new ab initio interaction potential based on the hydrated ion concept has been developed to obtain the structure, energetics, and dynamics of the hydration of uranyl in aqueous solution. It is the first force field that explicitly parameterizes the interaction of the uranyl hydrate with bulk water molecules to accurately define the second-shell behavior. The [UO2(H2O)5 ] 2 + presents a first hydration shell U-O average distance of 2.46 Å and a second hydration shell peak at 4.61 Å corresponding to 22 molecules using a coordination number definition based on a multisite solute cavity. The second shell solvent molecules have longer mean residence times than those corresponding to the divalent monatomic cations. The axial regions are relatively de-populated, lacking direct hydrogen bonding to apical oxygens. Angle-solved radial distribution functions as well as the spatial distribution functions show a strong anisotropy in the ion hydration. The [UO2(H2O)5 ] 2 + solvent structure may be regarded as a combination of a conventional second hydration shell in the equatorial and bridge regions, and a clathrate-like low density region in the axial region. Translational diffusion coefficient, hydration enthalpy, power spectra of the main vibrational modes, and the EXAFS spectrum simulated from molecular dynamics trajectories agree fairly well with the experiment.

  9. The growth of structure I methane hydrate from molecular dynamics simulations. (United States)

    Tung, Yen-Tien; Chen, Li-Jen; Chen, Yan-Ping; Lin, Shiang-Tai


    The key factors that affect the growth of methane hydrates are identified using molecular dynamics simulations. The three-phase molecular models consisting of methane gas, liquid water, and solid hydrate phase are used in this study. The melting temperatures of such a model at different pressures are found to be in good agreement with experiment. The growth rate of methane hydrate is found to be dominated by (1) the solubility of methane in the liquid phase, (2) the diffusivity of methane in water, and (3) the adsorption of methane by methane-filled incomplete water cages at the solid-liquid interface. The solubility, and hence the growth rate, increases with the partial pressure of methane in the vapor phase. The mass transport resistance from adsorption and the diffusion of methane are two competing factors, with the adsorption of methane at the interface found to be the rate-limiting step. The presence of a high concentration of incomplete clathrate hydrate cages presents strong affinity to dissolved methane at temperatures below the melting point. In addition to methane adsorption, water molecules must be expelled to form the complete clathrate cages. Both processes lead to a methane concentration minimum at 5-9 A in front of the growing interface. The methane concentration minimum provides the driving force for methane transport from the bulk to the interface. There are two types of solid layers of methane hydrate in the (1,0,0) direction. The growths of these layers are different, highly correlated, and affected by the methane concentration. A detailed mechanism of the layer growth is deduced from our simulations.

  10. 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)


    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

  11. Probing methane hydrate nucleation through the forward flux sampling method. (United States)

    Bi, Yuanfei; Li, Tianshu


    Understanding the nucleation of hydrate is the key to developing effective strategies for controlling methane hydrate formation. Here we present a computational study of methane hydrate nucleation, by combining the forward flux sampling (FFS) method and the coarse-grained water model mW. To facilitate the application of FFS in studying the formation of methane hydrate, we developed an effective order parameter λ on the basis of the topological analysis of the tetrahedral network. The order parameter capitalizes the signature of hydrate structure, i.e., polyhedral cages, and is capable of efficiently distinguishing hydrate from ice and liquid water while allowing the formation of different hydrate phases, i.e., sI, sII, and amorphous. Integration of the order parameter λ with FFS allows explicitly computing hydrate nucleation rates and obtaining an ensemble of nucleation trajectories under conditions where spontaneous hydrate nucleation becomes too slow to occur in direct simulation. The convergence of the obtained hydrate nucleation rate was found to depend crucially on the convergence of the spatial distribution for the spontaneously formed hydrate seeds obtained from the initial sampling of FFS. The validity of the approach is also verified by the agreement between the calculated nucleation rate and that inferred from the direct simulation. Analyzing the obtained large ensemble of hydrate nucleation trajectories, we show hydrate formation at 220 K and 500 bar is initiated by the nucleation events occurring in the vicinity of water-methane interface, and facilitated by a gradual transition from amorphous to crystalline structure. The latter provides the direct support to the proposed two-step nucleation mechanism of methane hydrate.

  12. Novel understanding of calcium silicate hydrate from dilute hydration

    KAUST Repository

    Zhang, Lina


    The perspective of calcium silicate hydrate (C-S-H) is still confronting various debates due to its intrinsic complicated structure and properties after decades of studies. In this study, hydration at dilute suspension of w/s equaling to 10 was conducted for tricalcium silicate (C3S) to interpret long-term hydration process and investigate the formation, structure and properties of C-S-H. Based on results from XRD, IR, SEM, NMR and so forth, loose and dense clusters of C-S-H with analogous C/S ratio were obtained along with the corresponding chemical formulae proposed as Ca5Si4O13∙6.2H2O. Crystalline structure inside C-S-H was observed by TEM, which was allocated at the foil-like proportion as well as the edge of wrinkles of the product. The long-term hydration process of C3S in dilute suspension could be sketchily described as migration of calcium hydroxide and in-situ growth of C-S-H with equilibrium silicon in aqueous solution relatively constant and calcium varied.

  13. Understanding lattice thermal conductivity in thermoelectric clathrates: A density functional theory study on binary Si-based type-I clathrates (United States)

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


    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.

  14. Pressure-induced phase transformations in the Ba8Si46 clathrate

    DEFF Research Database (Denmark)

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


    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...

  15. Comparative Assessment of Advanced Gay Hydrate Production Methods

    Energy Technology Data Exchange (ETDEWEB)

    M. D. White; B. P. McGrail; S. K. Wurstner


    Displacing natural gas and petroleum with carbon dioxide is a proven technology for producing conventional geologic hydrocarbon reservoirs, and producing additional yields from abandoned or partially produced petroleum reservoirs. Extending this concept to natural gas hydrate production offers the potential to enhance gas hydrate recovery with concomitant permanent geologic sequestration. Numerical simulation was used to assess a suite of carbon dioxide injection techniques for producing gas hydrates from a variety of geologic deposit types. Secondary hydrate formation was found to inhibit contact of the injected CO{sub 2} regardless of injectate phase state, thus diminishing the exchange rate due to pore clogging and hydrate zone bypass of the injected fluids. Additional work is needed to develop methods of artificially introducing high-permeability pathways in gas hydrate zones if injection of CO{sub 2} in either gas, liquid, or micro-emulsion form is to be more effective in enhancing gas hydrate production rates.

  16. Gas hydrates stability zone thickness map of Indian deep offshore areas - A GIS based approach

    Digital Repository Service at National Institute of Oceanography (India)

    Rastogi, A.; Deka, B.; Bhattacharya, G.C.; Ramprasad, T.; KameshRaju, K.A.; Srinivas, K.; Murty, G.P.S.; Chaubey, A.K.; Ramana, M.V.; Subrahmanyam, V.; Sarma, K.V.L.N.S.; Desa, M.; Paropkari, A.L.; Menezes, A.A.A.; Murty, V.S.N.; Antony, M.K.; SubbaRaju, L.V.; Desa, E.; Veerayya, M.

    hydrate occurrence in offshore regions and around the Indian sub-continent. This was accomplished by estimating the gas hydrate stability zone (GHSZ) thickness from the saptial analysis of the physical parameters that control the formation and stability...

  17. Pentagonal dodecahedron methane hydrate cage and methanol ...

    Indian Academy of Sciences (India)

    petroleum industry as it plugs the oil flow.12 Restric- tion of hydrate plug ... Interaction energy ( E) for cluster formation has been determined using .... Interaction energies are mentioned in table 2 for all three 1CH4@512 cage, 1CH4@512-methanol clus- ter and 1CH4@512-methanol-Na. + cluster systems. Formation of ...

  18. Methane Production and Carbon Capture by Hydrate Swapping

    DEFF Research Database (Denmark)

    Mu, Liang; von Solms, Nicolas


    gas molecules in the structural lattice. In this work, we quantitatively investigate the swapping behavior from injection of pure carbon dioxide and the (CO2 + N2) binary gas mixture through artificial hydrate-bearing sandstone samples by use of a core-flooding experimental apparatus. A total of 13...... of pure carbon dioxide in swapping methane from its hydrate phase; the methane recovery efficiency in brine water systems is enhanced relative to pure water systems. The replenishment of a fresh (CO2 + N2) gas mixture into the vapor phase can be considered as an efficient extraction method because 46...... in small hydrate cages, as long as the equilibrium formation pressure of (CO2 + N2) binary gas hydrate is below that of methane hydrate, even though adding nitrogen to carbon dioxide reduces the thermodynamic driving force for the formation of a new hydrate. When other conditions are similar, the methane...

  19. Nano-granular texture of cement hydrates

    Directory of Open Access Journals (Sweden)

    Ioannidou Katerina


    Full Text Available Mechanical behavior of concrete crucially depends on cement hydrates, the “glue” of cement. The design of high performance and more environmentally friendly cements demands a deeper understanding of the formation of the multiscale structure of cement hydrates, when they precipitate and densify. We investigate the precipitation and setting of nano-grains of cement hydrates using a combination of Monte Carlo and Molecular Dynamics numerical simulations and study their texture from nano up to the micron scale. We characterize the texture of cement hydrates using the local volume fraction distribution, the pore size distribution, the scattering intensity and the chord length distribution and we compare them with experiments. Our nano-granular model provides cement structure with realistic texture and mechanics and can be further used to investigate degradation mechanisms.

  20. Vibrational dynamics of hydration water in amylose

    CERN Document Server

    Cavatorta, F; Albanese, G; Angelini, N


    We present a study of the dynamical properties of hydration water associated with amylose helices, based on low-temperature vibrational spectra collected using the TOSCA inelastic spectrometer at ISIS. The structural constraints of the polysaccharidic chains favour the formation of a high-density structure for water, which has been suggested by Imberty and Perez on the basis of conformational analysis. According to this model, hydration water can only enter the pores formed by six adjacent helices and completely fills the pores at a hydration level of about 0.27-g water/g dry amylose. Our measurements show that the dynamical behaviour of hydration water is similar to that observed in high-density amorphous ice. (orig.)

  1. Gas hydrate in nature (United States)

    Ruppel, Carolyn D.


    Gas hydrate is a naturally occurring, ice-like substance that forms when water and gas combine under high pressure and at moderate temperatures. Methane is the most common gas present in gas hydrate, although other gases may also be included in hydrate structures, particularly in areas close to conventional oil and gas reservoirs. Gas hydrate is widespread in ocean-bottom sediments at water depths greater than 300–500 meters (m; 984–1,640 feet [ft]) and is also present in areas with permanently frozen ground (permafrost). Several countries are evaluating gas hydrate as a possible energy resource in deepwater or permafrost settings. Gas hydrate is also under investigation to determine how environmental change may affect these deposits.

  2. Exploitation of subsea gas hydrate reservoirs (United States)

    Janicki, Georg; Schlüter, Stefan; Hennig, Torsten; Deerberg, Görge


    Natural gas hydrates are considered to be a potential energy resource in the future. They occur in permafrost areas as well as in subsea sediments and are stable at high pressure and low temperature conditions. According to estimations the amount of carbon bonded in natural gas hydrates worldwide is two times larger than in all known conventional fossil fuels. Besides technical challenges that have to be overcome climate and safety issues have to be considered before a commercial exploitation of such unconventional reservoirs. The potential of producing natural gas from subsea gas hydrate deposits by various means (e.g. depressurization and/or injection of carbon dioxide) is numerically studied in the frame of the German research project »SUGAR«. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into a numerical model. The physics of the process leads to strong non-linear couplings between hydraulic fluid flow, hydrate dissociation and formation, hydraulic properties of the sediment, partial pressures and seawater solution of components and the thermal budget of the system described by the heat equation. This paper is intended to provide an overview of the recent development regarding the production of natural gas from subsea gas hydrate reservoirs. It aims at giving a broad insight into natural gas hydrates and covering relevant aspects of the exploitation process. It is focused on the thermodynamic principles and technological approaches for the exploitation. The effects occurring during natural gas production within hydrate filled sediment layers are identified and discussed by means of numerical simulation results. The behaviour of relevant process parameters such as pressure, temperature and phase saturations is described and compared for different strategies. The simulations are complemented by calculations for different safety relevant problems.

  3. The Effect of Synthetic Hydrated Calcium Aluminate Additive on the Hydration Properties of OPC


    Jolanta Doneliene; Anatolijus Eisinas; Kestutis Baltakys; Agne Bankauskaite


    The effect of synthetic CAH (130°C; 8 h; CaO/(SiO2 + Al2O3) = 0.55; Al2O3/(SiO2 + Al2O3) = 0.1, 0.15) with different crystallinity on the hydration kinetics of OPC at early stages of hydration was investigated. Also, the formation mechanism of compounds during OPC hydration was highlighted. It was determined that the synthetic CAH accelerated the initial reaction and shortened the induction period. Also, the second and third exothermic reactions begun earlier, and, during the latter reaction,...

  4. Hydration of amino acids: FTIR spectra and molecular dynamics studies. (United States)

    Panuszko, Aneta; Adamczak, Beata; Czub, Jacek; Gojło, Emilia; Stangret, Janusz


    The hydration of selected amino acids, alanine, glycine, proline, valine, isoleucine and phenylalanine, has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure and the chemometric method have been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To support interpretation of obtained spectral results, molecular dynamics simulations of amino acids were performed. The structural-energetic characteristic of these solute-affected water molecules shows that, on average, water affected by amino acids forms stronger and shorter H-bonds than those in pure water. Differences in the influence of amino acids on water structure have been noticed. The effect of the hydrophobic side chain of an amino acid on the solvent interactions seems to be enhanced because of the specific cooperative coupling of water strong H-bond chain, connecting the carboxyl and amino groups, with the clathrate-like H-bond network surrounding the hydrocarbon side chain. The parameter derived from the spectral data, which corresponds to the contributions of the population of weak hydrogen bonds of water molecules which have been substituted by the stronger ones in the hydration sphere of amino acids, correlated well with the amino acid hydrophobicity indexes.

  5. Detection of Occupancy Differences in Methane Gas Hydrates by Raman Spectroscopy

    DEFF Research Database (Denmark)

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


    Gas hydrates are solid crystalline compounds, which grow from micro crystals to bulk masses resembling ordinary slush, snow or ice. Since gas hydrates exist at elevated pressures at temperatures well above the ice point, they can cause severe problems under production and transportation...... 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....

  6. Dissociation of methane hydrate in aqueous NaCl solutions. (United States)

    Yagasaki, Takuma; Matsumoto, Masakazu; Andoh, Yoshimichi; Okazaki, Susumu; Tanaka, Hideki


    Molecular dynamics simulations of the dissociation of methane hydrate in aqueous NaCl solutions are performed. It is shown that the dissociation of the hydrate is accelerated by the formation of methane bubbles both in NaCl solutions and in pure water. We find two significant effects on the kinetics of the hydrate dissociation by NaCl. One is slowing down in an early stage before bubble formation, and another is swift bubble formation that enhances the dissociation. These effects arise from the low solubility of methane in NaCl solution, which gives rise to a nonuniform spatial distribution of solvated methane in the aqueous phase. We also demonstrate that bubbles form near the hydrate interface in dense NaCl solutions and that the hydrate dissociation proceeds inhomogeneously due to the bubbles.

  7. Carbon dioxid sequestration in natural gas hydrates: Thermodynamic considerations (United States)

    Schicks, J. M.; Beeskow-Strauch, B.; Luzi, M.; Girod, M.; Erzinger, J.


    Due to the increasing energy demands natural gas hydrates become more and more of interest. The huge amount of hydrocarbons - mainly CH4 - stored in natural hydrate reservoirs suggest the use of natural gas hydrates as an energy resource. However, the combustion of this fossil fuel results in an undesired increase of CO2 in the atmosphere. Therefore, a combination of CH4 production on the one hand and the CO2 sequestration on the other hand seems to be ideal. Several investigations regarding the exchange reaction of CH4 with CO2 using pure methane hydrates and pure CO2 or CO2-N2-mixtures have been performed as laboratory studies in the past. Some showed exchange rates up to 85% and concluded that the driving force of this exchange reaction is the higher stability of CO2 hydrates compared to methane hydrates (e.g. Park et al. 2006). However, natural conditions may differ: natural gas hydrates may contain higher hydrocarbons or H2S, which have significant impact in terms of a higher stability of the mixed hydrate phase compared to pure CH4- and CO2-hydrates. Primary results of our investigations on the exchange reaction of a mixed CH4-C3H8-hydrate with CO2 indicates that although the stability of mixed CH4-C3H8-hydrate is significantly shifted to higher temperatures and lower pressures compared to pure CH4-, mixed CH4-CO2- and pure CO2-hydrates, it changes in the presence of CO2 from a structure II hydrate phase to form a structure I CH4-CO2-hydrate which subsequently transforms to CO2-hydrate. This process starts at the interface between gas and hydrate and continues slowly into the bulk phase. These observation lead to the following conclusions: - The driving force of the exchange reaction is less the stability with respect to temperature and pressure conditions of the hydrate phase but rather the chemical equilibrium state in terms of concentration gradients between hydrate and surrounding gas phase - After the initial formation of a CO2-CH4- or CO2 hydrate layer

  8. Towards bio-silicon interfaces: Formation of an ultra-thin self-hydrated artificial membrane composed of dipalmitoylphosphatidylcholine (DPPC) and chitosan deposited in high vacuum from the gas-phase (United States)

    Retamal, María J.; Cisternas, Marcelo A.; Gutierrez-Maldonado, Sebastian E.; Perez-Acle, Tomas; Seifert, Birger; Busch, Mark; Huber, Patrick; Volkmann, Ulrich G.


    The recent combination of nanoscale developments with biological molecules for biotechnological research has opened a wide field related to the area of biosensors. In the last years, device manufacturing for medical applications adapted the so-called bottom-up approach, from nanostructures to larger devices. Preparation and characterization of artificial biological membranes is a necessary step for the formation of nano-devices or sensors. In this paper, we describe the formation and characterization of a phospholipid bilayer (dipalmitoylphosphatidylcholine, DPPC) on a mattress of a polysaccharide (Chitosan) that keeps the membrane hydrated. The deposition of Chitosan (˜25 Å) and DPPC (˜60 Å) was performed from the gas phase in high vacuum onto a substrate of Si(100) covered with its native oxide layer. The layer thickness was controlled in situ using Very High Resolution Ellipsometry (VHRE). Raman spectroscopy studies show that neither Chitosan nor DPPC molecules decompose during evaporation. With VHRE and Atomic Force Microscopy we have been able to detect phase transitions in the membrane. The presence of the Chitosan interlayer as a water reservoir is essential for both DPPC bilayer formation and stability, favoring the appearance of phase transitions. Our experiments show that the proposed sample preparation from the gas phase is reproducible and provides a natural environment for the DPPC bilayer. In future work, different Chitosan thicknesses should be studied to achieve a complete and homogeneous interlayer.

  9. Towards bio-silicon interfaces: Formation of an ultra-thin self-hydrated artificial membrane composed of dipalmitoylphosphatidylcholine (DPPC) and chitosan deposited in high vacuum from the gas-phase

    Energy Technology Data Exchange (ETDEWEB)

    Retamal, María J., E-mail:; Cisternas, Marcelo A.; Seifert, Birger; Volkmann, Ulrich G. [Instituto de Física, Pontificia Universidad Católica de Chile, Avda. Vicuña Mackenna 4860, 7820436 Santiago (Chile); Centro de Investigación en Nanotecnología y Materiales Avanzados (CIEN-UC), Pontificia Universidad Católica de Chile, Avda. Vicuña Mackenna 4860, 7820436 Santiago (Chile); Gutierrez-Maldonado, Sebastian E.; Perez-Acle, Tomas [Computational Biology Lab (DLab), Fundación Ciencia y Vida, Av. Zañartu 1482, Santiago (Chile); Centro Interdisciplinario de Neurociencias de Valparaiso (CINV), Universidad de Valparaiso, Pasaje Harrington 287, Valparaiso (Chile); Busch, Mark; Huber, Patrick [Institute of Materials Physics and Technology, Hamburg University of Technology (TUHH), D-21073 Hamburg-Harburg (Germany)


    The recent combination of nanoscale developments with biological molecules for biotechnological research has opened a wide field related to the area of biosensors. In the last years, device manufacturing for medical applications adapted the so-called bottom-up approach, from nanostructures to larger devices. Preparation and characterization of artificial biological membranes is a necessary step for the formation of nano-devices or sensors. In this paper, we describe the formation and characterization of a phospholipid bilayer (dipalmitoylphosphatidylcholine, DPPC) on a mattress of a polysaccharide (Chitosan) that keeps the membrane hydrated. The deposition of Chitosan (∼25 Å) and DPPC (∼60 Å) was performed from the gas phase in high vacuum onto a substrate of Si(100) covered with its native oxide layer. The layer thickness was controlled in situ using Very High Resolution Ellipsometry (VHRE). Raman spectroscopy studies show that neither Chitosan nor DPPC molecules decompose during evaporation. With VHRE and Atomic Force Microscopy we have been able to detect phase transitions in the membrane. The presence of the Chitosan interlayer as a water reservoir is essential for both DPPC bilayer formation and stability, favoring the appearance of phase transitions. Our experiments show that the proposed sample preparation from the gas phase is reproducible and provides a natural environment for the DPPC bilayer. In future work, different Chitosan thicknesses should be studied to achieve a complete and homogeneous interlayer.

  10. Towards bio-silicon interfaces: formation of an ultra-thin self-hydrated artificial membrane composed of dipalmitoylphosphatidylcholine (DPPC) and chitosan deposited in high vacuum from the gas-phase. (United States)

    Retamal, María J; Cisternas, Marcelo A; Gutierrez-Maldonado, Sebastian E; Perez-Acle, Tomas; Seifert, Birger; Busch, Mark; Huber, Patrick; Volkmann, Ulrich G


    The recent combination of nanoscale developments with biological molecules for biotechnological research has opened a wide field related to the area of biosensors. In the last years, device manufacturing for medical applications adapted the so-called bottom-up approach, from nanostructures to larger devices. Preparation and characterization of artificial biological membranes is a necessary step for the formation of nano-devices or sensors. In this paper, we describe the formation and characterization of a phospholipid bilayer (dipalmitoylphosphatidylcholine, DPPC) on a mattress of a polysaccharide (Chitosan) that keeps the membrane hydrated. The deposition of Chitosan (~25 Å) and DPPC (~60 Å) was performed from the gas phase in high vacuum onto a substrate of Si(100) covered with its native oxide layer. The layer thickness was controlled in situ using Very High Resolution Ellipsometry (VHRE). Raman spectroscopy studies show that neither Chitosan nor DPPC molecules decompose during evaporation. With VHRE and Atomic Force Microscopy we have been able to detect phase transitions in the membrane. The presence of the Chitosan interlayer as a water reservoir is essential for both DPPC bilayer formation and stability, favoring the appearance of phase transitions. Our experiments show that the proposed sample preparation from the gas phase is reproducible and provides a natural environment for the DPPC bilayer. In future work, different Chitosan thicknesses should be studied to achieve a complete and homogeneous interlayer.

  11. Fluid clathrate system for continuous removal of heavy noble gases from mixtures of lighter gases (United States)

    Gross, Kenneth C.; Markun, Francis; Zawadzki, Mary T.


    An apparatus and method for separation of heavy noble gas in a gas volume. An apparatus and method have been devised which includes a reservoir containing an oil exhibiting a clathrate effect for heavy noble gases with a reservoir input port and the reservoir is designed to enable the input gas volume to bubble through the oil with the heavy noble gas being absorbed by the oil exhibiting a clathrate effect. The gas having reduced amounts of heavy noble gas is output from the oil reservoir, and the oil having absorbed heavy noble gas can be treated by mechanical agitation and/or heating to desorb the heavy noble gas for analysis and/or containment and allow recycling of the oil to the reservoir.

  12. In-situ gas hydrate hydrate saturation estimated from various well logs at the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope (United States)

    Lee, M.W.; Collett, T.S.


    In 2006, the U.S. Geological Survey (USGS) completed detailed analysis and interpretation of available 2-D and 3-D seismic data and proposed a viable method for identifying sub-permafrost gas hydrate prospects within the gas hydrate stability zone in the Milne Point area of northern Alaska. To validate the predictions of the USGS and to acquire critical reservoir data needed to develop a long-term production testing program, a well was drilled at the Mount Elbert prospect in February, 2007. Numerous well log data and cores were acquired to estimate in-situ gas hydrate saturations and reservoir properties.Gas hydrate saturations were estimated from various well logs such as nuclear magnetic resonance (NMR), P- and S-wave velocity, and electrical resistivity logs along with pore-water salinity. Gas hydrate saturations from the NMR log agree well with those estimated from P- and S-wave velocity data. Because of the low salinity of the connate water and the low formation temperature, the resistivity of connate water is comparable to that of shale. Therefore, the effect of clay should be accounted for to accurately estimate gas hydrate saturations from the resistivity data. Two highly gas hydrate-saturated intervals are identified - an upper ???43 ft zone with an average gas hydrate saturation of 54% and a lower ???53 ft zone with an average gas hydrate saturation of 50%; both zones reach a maximum of about 75% saturation. ?? 2009.

  13. The U.S. Geological Survey’s Gas Hydrates Project (United States)

    Ruppel, Carolyn D.


    The Gas Hydrates Project at the U.S. Geological Survey (USGS) focuses on the study of methane hydrates in natural environments. The project is a collaboration between the USGS Energy Resources and the USGS Coastal and Marine Geology Programs and works closely with other U.S. Federal agencies, some State governments, outside research organizations, and international partners. The USGS studies the formation and distribution of gas hydrates in nature, the potential of hydrates as an energy resource, and the interaction between methane hydrates and the environment. The USGS Gas Hydrates Project carries out field programs and participates in drilling expeditions to study marine and terrestrial gas hydrates. USGS scientists also acquire new geophysical data and sample sediments, the water column, and the atmosphere in areas where gas hydrates occur. In addition, project personnel analyze datasets provided by partners and manage unique laboratories that supply state-of-the-art analytical capabilities to advance national and international priorities related to gas hydrates.

  14. Mechanism of gypsum hydration

    Directory of Open Access Journals (Sweden)

    Pacheco, G.


    Full Text Available There is an hypothesis that the mechanism o f gypsum hydration and dehydration is performed through two simultaneous phenomena. In this study we try to clear up this phenomenon using chlorides as accelerators or a mixture of ethanol-methanol as retarders to carry out the gypsum setting. Natural Mexican gypsum samples and a hemihydrate prepared in the laboratory are used. The following analytical techniques are used: MO, DRX, DTA, TG and DTG. In agreement with the obtained results, it can be concluded: that colloid formation depends on the action of accelerators or retarders and the crystals are a consequence of the quantity of hemihydrate formed.

    En el mecanismo de hidratación y deshidratación del yeso existe la hipótesis de que éste se efectúa por dos fenómenos simultáneos. Este estudio intenta esclarecer estos fenómenos, empleando: cloruros como aceleradores o mezcla etanol-metanol como retardadores para efectuar el fraguado del yeso. Se emplean muestras de yeso de origen natural mexicano y hemihydrate preparado en laboratorio; se utilizan técnicas analíticas: MO, DRX, DTA, TG y DTG. De acuerdo a los resultados obtenidos se puede deducir: que la formación del coloide depende de la acción de los agentes aceleradores o retardadores y que los cristales son consecuencia de la cantidad de hemihidrato formado.

  15. First Study of Poly(3-Methylene-2-Pyrrolidone) as a Kinetic Hydrate Inhibitor

    DEFF Research Database (Denmark)

    Abrahamsen, Eirin; Heyns, Ingrid Marié; von Solms, Nicolas


    Formation of gas hydrates is a problem in the petroleum industry where the gas hydrates can cause blockage of the flowlines. Kinetic hydrate inhibitors (KHIs) are water-soluble polymers, sometimes used in combination synergistically or with non-polymeric synergists, that are used to prevent gas...

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

    Directory of Open Access Journals (Sweden)

    Juli-Anna Dolyniuk


    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.

  17. Mechanism of concerted hydrogen bond reorientation in clathrates of Dianin's compound and hydroquinone. (United States)

    Nemkevich, Alexandra; Spackman, Mark A; Corry, Ben


    Molecular dynamics provides a means to examine the mechanism of reorientation of hydrogen bond networks that are present in a range of biological and crystalline materials. Simulations of hydroxyl reorientation in the six-membered hydrogen bonded rings in crystalline clathrates of Dianin's compound (DC) and hydroquinone (HQ) reveal that in the clathrate of Dianin's compound with ethanol (DC:ethanol), hydroxyl groups perform single independent flips, and occasionally all six hydroxyls in a ring reorient following a sequential mechanism with participation of the guest ethanol molecule. The free energy estimated for this process agrees well with experimental results. The simulations suggest that hydroxyl reorientation occurs in the empty DC lattice as well, but at a higher energy cost, from which we conclude that it is the participation of ethanol that lowers the barrier of reorientation. Single independent flips of hydroxyl groups are observed to be more frequent in the hydroquinone clathrate with methanol (HQ:methanol) than in DC:ethanol, but reorientation of all six hydroxyls does not occur. This is attributed to the larger difference in energy between the original and reoriented positions of hydroxyl hydrogen atoms in HQ:methanol compared to DC:ethanol.

  18. Measured temperature and pressure dependence of Vp and Vs in compacted, polycrystalline sI methane and sII methane-ethane hydrate (United States)

    Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.


    We report on compressional- and shear-wave-speed measurements made on compacted polycrystalline sI methane and sII methane-ethane hydrate. The gas hydrate samples are synthesized directly in the measurement apparatus by warming granulated ice to 17??C in the presence of a clathrate-forming gas at high pressure (methane for sI, 90.2% methane, 9.8% ethane for sII). Porosity is eliminated after hydrate synthesis by compacting the sample in the synthesis pressure vessel between a hydraulic ram and a fixed end-plug, both containing shear-wave transducers. Wave-speed measurements are made between -20 and 15??C and 0 to 105 MPa applied piston pressure.

  19. Measured temperature and pressure dependence of V-p and V-s in compacted, polycrystalline sI methane and sII methane-ethane hydrate (United States)

    Helgerud, M. B.; Waite, W. F.; Kirby, S. H.; Nur, A.


    We report on compressional- and shear-wave-speed measurements made on compacted polycrystalline sI methane and sII methane-ethane hydrate. The gas hydrate samples are synthesized directly in the measurement apparatus by warming granulated ice to 17degreesC in the presence of a clathrate-forming gas at high pressure (methane for sI, 90.2% methane, 9.8% ethane for sII). Porosity is eliminated after hydrate synthesis by compacting the sample in the synthesis pressure vessel between a hydraulic ram and a fixed end-plug, both containing shear-wave transducers. Wave-speed measurements are made between -20 and 15degreesC and 0 to 105 MPa applied piston pressure.

  20. Formation of stratospheric nitric acid by a hydrated ion cluster reaction: chemical and dynamical effects of energetic particle precipitation on the middle atmosphere (United States)

    Kvissel, O. K.; Orsolini, Y. J.; Stordal, F.


    In order to Improve our understanding of the effects of energetic particle precipitation upon the nitrogen family (NOy) and ozone (O3), we have modelled the chemical and dynamical middle atmosphere response to the introduction of a chemical pathway that produces nitric acid (HNO3) by conversion of dinitrogen pentoxide (N2O5) upon hydrated water clusters H+•(H2O)n. We have used an ensemble of simulations with the National Center for Atmospheric Research (NCAR) Whole-Atmosphere Community Climate Model (WACCM) chemistry-climate model. The introduced chemical pathway alters the internal partitioning of NOy during winter months in both hemispheres, and ultimately triggers statistically significant changes in the climatological distributions of constituents including: i) a cold season production of HNO3 with a corresponding loss of N2O5, and ii) a cold season decrease in NOx/NOy-ratio and an increase of O3, in polar regions. We see an improved seasonal evolution of modelled HNO3 compared to satellite observations from Microwave Limb Sounder (MLS), albeit not enough HNO3 is produced at high altitudes. Through O3 changes, both temperature and dynamics are affected, allowing for complex chemical-dynamical feedbacks beyond the cold season when the introduced pathway is active. Hence, we also find a NOx polar increase in spring-to-summer in the SH, and in spring in the NH. The springtime NOx increase arises from anomalously strong poleward transport associated with a weaker polar vortex. In the southern hemisphere, a statistical significant weakening of the stratospheric jet is altered down to the lower stratosphere, and we argue that it is caused by strengthened planetary waves induced by mid-latitude zonal asymmetries in O3 and short-wave heating.

  1. Formation of stratospheric nitric acid by a hydrated ion cluster reaction: Implications for the effect of energetic particle precipitation on the middle atmosphere (United States)

    Kvissel, O.-K.; Orsolini, Y. J.; Stordal, F.; Isaksen, I. S. A.; Santee, M. L.


    In order to improve our understanding of the effects of energetic particle precipitation on the middle atmosphere and in particular upon the nitrogen family and ozone, we have modeled the chemical and dynamical middle atmosphere response to the introduction of a chemical pathway that produces HNO3 by conversion of N2O5 upon hydrated water clusters H+·(H2O)n. We have used an ensemble of simulations with the National Center for Atmospheric Research (NCAR) Whole-Atmosphere Community Climate Model (WACCM) chemistry-climate model. The chemical pathway alters the internal partitioning of the NOy family during winter months in both hemispheres, and ultimately triggers statistically significant changes in the climatological distributions of constituents including: i) a cold season production and loss of HNO3 and N2O5, respectively, and ii) a cold season decrease and increase in NOx/NOy-ratio and O3, respectively, in the polar regions of both hemispheres. We see an improved seasonal evolution of modeled HNO3 compared to satellite observations from Microwave Limb Sounder (MLS), albeit not enough HNO3 is produced at high altitudes. Through O3changes, both temperature and dynamics are affected, allowing for complex chemical-dynamical feedbacks beyond the cold season when the pathway is active. Hence, we also find a NOxpolar increase in spring-to-summer in the southern hemisphere, and in spring in the northern hemisphere. The springtime NOxincrease arises from anomalously strong poleward transport associated with a weaker polar vortex. We argue that the weakening of zonal-mean polar winds down to the lower stratosphere, which is statistically significant at the 0.90 level in spring months in the southern hemisphere, is caused by strengthened planetary waves induced by the middle and sub-polar latitude zonal asymmetries in O3and short-wave heating.

  2. Gypsum hydration: a theoretical and experimental study

    NARCIS (Netherlands)

    Yu, Qingliang; Brouwers, Jos; de Korte, A.C.J.; Fischer, H.B; Bode, K.A.


    Calcium sulphate dihydrate (CaSO4·2H2O or gypsum) is used widely as building material because of its excellent fire resistance, aesthetics, and low price. Hemihydrate occurs in two formations of α- and β-type. Among them β-hemihydrate is mainly used to produce gypsum plasterboard since the hydration

  3. Methane Hydrates: Chapter 8 (United States)

    Boswell, Ray; Yamamoto, Koji; Lee, Sung-Rock; Collett, Timothy S.; Kumar, Pushpendra; Dallimore, Scott


    Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be

  4. Simulating the effect of hydrate dissociation on wellhead stability during oil and gas development in deepwater (United States)

    Li, Qingchao; Cheng, Yuanfang; Zhang, Huaiwen; Yan, Chuanliang; Liu, Yuwen


    It is well known that methane hydrate has been identified as an alternative resource due to its massive reserves and clean property. However, hydrate dissociation during oil and gas development (OGD) process in deep water can affect the stability of subsea equipment and formation. Currently, there is a serious lack of studies over quantitative assessment on the effects of hydrate dissociation on wellhead stability. In order to solve this problem, ABAQUS finite element software was used to develop a model and to evaluate the behavior of wellhead caused by hydrate dissociation. The factors that affect the wellhead stability include dissociation range, depth of hydrate formation and mechanical properties of dissociated hydrate region. Based on these, series of simulations were carried out to determine the wellhead displacement. The results revealed that, continuous dissociation of hydrate in homogeneous and isotropic formations can causes the non-linear increment in vertical displacement of wellhead. The displacement of wellhead showed good agreement with the settlement of overlying formations under the same conditions. In addition, the shallower and thicker hydrate formation can aggravate the influence of hydrate dissociation on the wellhead stability. Further, it was observed that with the declining elastic modulus and Poisson's ratio, the wellhead displacement increases. Hence, these findings not only confirm the effect of hydrate dissociation on the wellhead stability, but also lend support to the actions, such as cooling the drilling fluid, which can reduce the hydrate dissociation range and further make deepwater operations safer and more efficient.


    Energy Technology Data Exchange (ETDEWEB)

    Richard Sigal; Kent Newsham; Thomas Williams; Barry Freifeld; Timothy Kneafsey; Carl Sondergeld; Shandra Rai; Jonathan Kwan; Stephen Kirby; Robert Kleinberg; Doug Griffin


    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. The work scope drilled and cored a well The Hot Ice No. 1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report. The Hot Ice No. 1 well was drilled from the surface to a measured depth of 2300 ft. There was almost 100% core recovery from the bottom of surface casing at 107 ft to total depth. Based on the best estimate of the bottom of the methane hydrate stability zone (which used new data obtained from Hot Ice No. 1 and new analysis of data from adjacent wells), core was recovered over its complete range. Approximately 580 ft of porous, mostly frozen, sandstone and 155 of conglomerate were recovered in the Ugnu Formation and approximately 215 ft of porous sandstone were recovered in the West Sak Formation. There were gas shows in the bottom

  6. Geomechanical Performance of Hydrate-Bearing Sediment in Offshore Environments

    Energy Technology Data Exchange (ETDEWEB)

    Stephen Holditch; Tad Patzek; Jonny Rutqvist; George Moridis; Richard Plumb


    The objective of this multi-year, multi-institutional research project was to develop the knowledge base and quantitative predictive capability for the description of geomechanical performance of hydrate-bearing sediments (hereafter referred to as HBS) in oceanic environments. The focus was on the determination of the envelope of hydrate stability under conditions typical of those related to the construction and operation of offshore platforms. We have developed a robust numerical simulator of hydrate behavior in geologic media by coupling a reservoir model with a commercial geomechanical code. We also investigated the geomechanical behavior of oceanic HBS using pore-scale models (conceptual and mathematical) of fluid flow, stress analysis, and damage propagation. The objective of the UC Berkeley work was to develop a grain-scale model of hydrate-bearing sediments. Hydrate dissociation alters the strength of HBS. In particular, transformation of hydrate clusters into gas and liquid water weakens the skeleton and, simultaneously, reduces the effective stress by increasing the pore pressure. The large-scale objective of the study is evaluation of geomechanical stability of offshore oil and gas production infrastructure. At Lawrence Berkeley National Laboratory (LBNL), we have developed the numerical model TOUGH + Hydrate + FLAC3D to evaluate how the formation and disassociation of hydrates in seafloor sediments affects seafloor stability. Several technical papers were published using results from this model. LBNL also developed laboratory equipment and methods to produce realistic laboratory samples of sediments containing gas hydrates so that mechanical properties could be measured in the laboratory. These properties are required to run TOUGH + Hydrate + FLAC3D to evaluate seafloor stability issues. At Texas A&M University we performed a detailed literature review to determine what gas hydrate formation properties had been measured and reported in the literature. We

  7. Hydration testing of athletes. (United States)

    Oppliger, Robert A; Bartok, Cynthia


    Dehydration not only reduces athletic performance, but also places athletes at risk of health problems and even death. For athletes, monitoring hydration has significant value in maximising performance during training and competition. It also offers medical personnel the opportunity to reduce health risks in situations where athletes engage in intentional weight loss. Simple non-invasive techniques, including weight monitoring and urine tests, can provide useful information. Bioimpedance methods tend to be easy to use and fairly inexpensive, but generally lack the precision and accuracy necessary for hydration monitoring. Blood tests appear to be the most accurate monitoring method, but are impractical because of cost and invasiveness. Although future research is needed to determine which hydration tests are the most accurate, we encourage sports teams to develop and implement hydration monitoring protocols based on the currently available methods. Medical personnel can use this information to maximise their team's athletic performance and minimise heat- and dehydration-related health risks to athletes.

  8. Hydrate morphology: Physical properties of sands with patchy hydrate saturation (United States)

    Dai, S.; Santamarina, J.C.; Waite, William F.; Kneafsey, T.J.


    The physical properties of gas hydrate-bearing sediments depend on the volume fraction and spatial distribution of the hydrate phase. The host sediment grain size and the state of effective stress determine the hydrate morphology in sediments; this information can be used to significantly constrain estimates of the physical properties of hydrate-bearing sediments, including the coarse-grained sands subjected to high effective stress that are of interest as potential energy resources. Reported data and physical analyses suggest hydrate-bearing sands contain a heterogeneous, patchy hydrate distribution, whereby zones with 100% pore-space hydrate saturation are embedded in hydrate-free sand. Accounting for patchy rather than homogeneous hydrate distribution yields more tightly constrained estimates of physical properties in hydrate-bearing sands and captures observed physical-property dependencies on hydrate saturation. For example, numerical modeling results of sands with patchy saturation agree with experimental observation, showing a transition in stiffness starting near the series bound at low hydrate saturations but moving toward the parallel bound at high hydrate saturations. The hydrate-patch size itself impacts the physical properties of hydrate-bearing sediments; for example, at constant hydrate saturation, we find that conductivity (electrical, hydraulic and thermal) increases as the number of hydrate-saturated patches increases. This increase reflects the larger number of conductive flow paths that exist in specimens with many small hydrate-saturated patches in comparison to specimens in which a few large hydrate saturated patches can block flow over a significant cross-section of the specimen.

  9. Well log characterization of natural gas-hydrates (United States)

    Collett, Timothy S.; Lee, Myung W.


    In the last 25 years there have been significant advancements in the use of well-logging tools to acquire detailed information on the occurrence of gas hydrates in nature: whereas wireline electrical resistivity and acoustic logs were formerly used to identify gas-hydrate occurrences in wells drilled in Arctic permafrost environments, more advanced wireline and logging-while-drilling (LWD) tools are now routinely used to examine the petrophysical nature of gas-hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. Resistivity- and acoustic-logging tools are the most widely used for estimating the gas-hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. Recent integrated sediment coring and well-log studies have confirmed that electrical-resistivity and acoustic-velocity data can yield accurate gas-hydrate saturations in sediment grain-supported (isotropic) systems such as sand reservoirs, but more advanced log-analysis models are required to characterize gas hydrate in fractured (anisotropic) reservoir systems. New well-logging tools designed to make directionally oriented acoustic and propagation-resistivity log measurements provide the data needed to analyze the acoustic and electrical anisotropic properties of both highly interbedded and fracture-dominated gas-hydrate reservoirs. Advancements in nuclear magnetic resonance (NMR) logging and wireline formation testing (WFT) also allow for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids(i.e., free water along with clay- and capillary-bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms

  10. 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)


    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.

  11. Hydrate pingoes at Nyegga: some characteristic features (United States)

    Hovland, M.


    from above. It is, therefore, expected that hydrate pingoes continually accrete from below and ablate from above, processes which cause a continuous change of size and shape over time, as long as fluid migration is active. These active (mainly inorganic) processes also stimulate organic life, by the continuous release of: a) dissolved methane and other reduced chemical species, and b) low-salinity and/or high-salinity water, released by active hydrate formation and dissociation.

  12. Methane gas hydrate effect on sediment acoustic and strength properties (United States)

    Winters, W.J.; Waite, W.F.; Mason, D.H.; Gilbert, L.Y.; Pecher, I.A.


    To improve our understanding of the interaction of methane gas hydrate with host sediment, we studied: (1) the effects of gas hydrate and ice on acoustic velocity in different sediment types, (2) effect of different hydrate formation mechanisms on measured acoustic properties (3) dependence of shear strength on pore space contents, and (4) pore pressure effects during undrained shear.A wide range in acoustic p-wave velocities (Vp) were measured in coarse-grained sediment for different pore space occupants. Vp ranged from less than 1 km/s for gas-charged sediment to 1.77–1.94 km/s for water-saturated sediment, 2.91–4.00 km/s for sediment with varying degrees of hydrate saturation, and 3.88–4.33 km/s for frozen sediment. Vp measured in fine-grained sediment containing gas hydrate was substantially lower (1.97 km/s). Acoustic models based on measured Vp indicate that hydrate which formed in high gas flux environments can cement coarse-grained sediment, whereas hydrate formed from methane dissolved in the pore fluid may not.The presence of gas hydrate and other solid pore-filling material, such as ice, increased the sediment shear strength. The magnitude of that increase is related to the amount of hydrate in the pore space and cementation characteristics between the hydrate and sediment grains. We have found, that for consolidation stresses associated with the upper several hundred meters of sub-bottom depth, pore pressures decreased during shear in coarse-grained sediment containing gas hydrate, whereas pore pressure in fine-grained sediment typically increased during shear. The presence of free gas in pore spaces damped pore pressure response during shear and reduced the strengthening effect of gas hydrate in sands.

  13. Prospects of gas hydrate presence in the Chukchi sea

    Directory of Open Access Journals (Sweden)

    Т. В. Матвеева


    Full Text Available The purpose of this study is to forecast the scale and distribution character of gas hydrate stability zone in the Chukchi Sea under simulated natural conditions and basing on these results to estimate resource potential of gas hydrates within this area. Three types of stability zone have been identified. A forecast map of gas hydrate environment and potentially gas hydrate-bearing water areas in the Chukchi Sea has been plotted to a scale of 1:5 000 000. Mapping of gas hydrate stability zone allowed to give a justified forecast based on currently available data on geologic, fluid dynamic, cryogenic, geothermal and pressure-temperature conditions of gas hydrate formation in the Chukchi Sea. It is the first forecast of such kind that focuses on formation conditions for hydrates of various types and compositions in the Arctic seas offshore Russia. Potential amount of gas, stored beneath the Chukchi Sea in the form of hydrates, is estimated based on mapping of their stability zone and falls into the interval of 7·1011-11.8·1013 m3.

  14. Natural gas hydrates : development and test of innovative methods for gas production from hydrate-bearing sediments

    Energy Technology Data Exchange (ETDEWEB)

    Schicks, J.M.; Spangenberg, E.; Steinhauer, B.; Klump, J.; Giese, R.; Erzinger, J. [German Research Centre for Geosciences, Potsdam (Germany). Helmholtz Centre; Haeckel, M.; Bigalke, N.; Savy, J.P.; Kossel, E.; Deusner, C.; Wallmann, K. [Leibniz Inst. of Marine Sciences (Germany)


    This paper discussed a German project conducted to determine the stability of natural gas hydrates during methane production activities. The Submarine Gas Hydrate Reservoirs (SUGAR) project was established to determine depressurization, thermal stimulation, and chemical addition reaction routes for gas hydrates. A heat exchange reactor was used to test for the catalytic oxidation of methane. A large-scale reservoir simulator was used to model hydrates in sediments in natural conditions and to investigate the efficiency of the reactors. Thermocouples were used to collect data related to the expansion of the heat front. The data were then used to upscale the simulations for field conditions. Nuclear magnetic resonance (NMR) spectroscopy, confocal Raman spectroscopy, and X-ray diffraction techniques were used to investigate the effects of carbon dioxide (CO{sub 2}) injection on methane production from pure hydrate phases. Results of the study indicated that the exposure of CH{sub 4} hydrates to CO{sub 2} initiates the decomposition of methane hydrates with the subsequent formation of a CO{sub 2} hydrate. The hydrate structure was destroyed and then rebuilt. 28 refs., 9 figs.

  15. Mechanical and electromagnetic properties of northern Gulf of Mexico sediments with and without THF hydrates (United States)

    Lee, J.Y.; Santamarina, J.C.; Ruppel, C.


    Using an oedometer cell instrumented to measure the evolution of electromagnetic properties, small strain stiffness, and temperature, we conducted consolidation tests on sediments recovered during drilling in the northern Gulf of Mexico at the Atwater Valley and Keathley Canyon sites as part of the 2005 Chevron Joint Industry Project on Methane Hydrates. The tested specimens include both unremolded specimens (as recovered from the original core liner) and remolded sediments both without gas hydrate and with pore fluid exchanged to attain 100% synthetic (tetrahydrofuran) hydrate saturation at any stage of loading. Test results demonstrate the extent to which the electromagnetic and mechanical properties of hydrate-bearing marine sediments are governed by the vertical effective stress, stress history, porosity, hydrate saturation, fabric, ionic concentration of the pore fluid, and temperature. We also show how permittivity and electrical conductivity data can be used to estimate the evolution of hydrate volume fraction during formation. The gradual evolution of geophysical properties during hydrate formation probably reflects the slow increase in ionic concentration in the pore fluid due to ion exclusion in closed systems and the gradual decrease in average pore size in which the hydrate forms. During hydrate formation, the increase in S-wave velocity is delayed with respect to the decrease in permittivity, consistent with hydrate formation on mineral surfaces and subsequent crystal growth toward the pore space. No significant decementation/debonding occurred in 100% THF hydrate-saturated sediments during unloading, hence the probability of sampling hydrate-bearing sediments without disturbing the original sediment fabric is greatest for samples in which the gas hydrate is primarily responsible for maintaining the sediment fabric and for which the time between core retrieval and restoration of in situ effective stress in the laboratory is minimized. In evaluating the

  16. Temporal constraints on hydrate-controlled methane seepage off Svalbard. (United States)

    Berndt, C; Feseker, T; Treude, T; Krastel, S; Liebetrau, V; Niemann, H; Bertics, V J; Dumke, I; Dünnbier, K; Ferré, B; Graves, C; Gross, F; Hissmann, K; Hühnerbach, V; Krause, S; Lieser, K; Schauer, J; Steinle, L


    Methane hydrate is an icelike substance that is stable at high pressure and low temperature in continental margin sediments. Since the discovery of a large number of gas flares at the landward termination of the gas hydrate stability zone off Svalbard, there has been concern that warming bottom waters have started to dissociate large amounts of gas hydrate and that the resulting methane release may possibly accelerate global warming. Here, we corroborate that hydrates play a role in the observed seepage of gas, but we present evidence that seepage off Svalbard has been ongoing for at least 3000 years and that seasonal fluctuations of 1° to 2°C in the bottom-water temperature cause periodic gas hydrate formation and dissociation, which focus seepage at the observed sites.

  17. A density functional theory study of the hydrates of NH{sub 3}{center_dot}H{sub 2}SO{sub 4} and its implications for the formation of new atmospheric particles

    Energy Technology Data Exchange (ETDEWEB)

    Ianni, J.C.; Bandy, A.R. [Drexel Univ., Philadelphia, PA (United States). Dept. of Chemistry


    The interest in tropospheric and stratospheric aerosols has risen in past years. This is primarily due to the fact that aerosols in the troposphere and stratosphere are altering the earth`s climate by scattering radiation directly or indirectly by changing the reflectivity of clouds. They have also been involved in indirectly depleting the Antarctic stratospheric ozone layer by converting relatively inert chlorine species to photochemically reactive species which are well-known ozone-destroying species. Density functional molecular orbital theory was used at the B3LYP/6-311++G(2d,2p)//B3LYP/6-311++G(2d,2p) level of theory to study the hydrates of NH{sub 3}{center_dot}H{sub 2}SO{sub 4}{center_dot}nH{sub 2}O for n = 0--5 and NH{sub 3}{center_dot}(H{sub 2}SO{sub 4}){sub 2}{center_dot}H{sub 2}O. Neutrals of the first four NH{sub 3}{center_dot}H{sub 2}SO{sub 4}{center_dot}nH{sub 2}O clusters (n = 0--4) spontaneously formed and were determined to be hydrogen-bonded molecular complexes of H{sub 2}SO{sub 4}, H{sub 2}O, and NH{sub 3}. Double ions (clusters containing a NH{sub 4}{sup +} cation and a HSO{sub 4}{sup {minus}} anion) spontaneously formed in clusters of NH{sub 3}{center_dot}{approximately}H{sub 2}SO{sub 4}{center_dot}nH{sub 2}O where n = 1--5. The energetics of the hydration and isomerization reactions also were calculated. Double ions are not energetically favorable until NH{sub 3}{center_dot}H{sub 2}SO{sub 4}{center_dot}4H{sub 2}O. The free energy of formation from free NH{sub 3} and H{sub 2}SO{sub 4}{center_dot}nH{sub 2}O had a maximum at n = 3 at room temperature with {Delta}G {approx} {minus}3 kcal/mol. NH{sub 3}{center_dot}(H{sub 2}SO{sub 4}){sub 2}{center_dot}H{sub 2}O was studied to see if NH{sub 3} can initiate new atmospheric particle growth. It has been shown that NH{sub 3} has no role in the initialization of new atmospheric particles.

  18. Isotopic fractionation of hydrate-bound hydrocarbons in the sub-bottom sediments of Lake Baikal (United States)

    Hachikubo, A.; Khlystov, O.; Sakagami, H.; Minami, H.; Yamashita, S.; Takahashi, N.; Shoji, H.; Kalmychkov, G.; Poort, J.


    We investigated the molecular and stable isotope composition of hydrate-bound and dissolved hydrocarbons in pore water in subsurface sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved at southern and central Baikal basins in 2002-2009. Gas hydrates exist at the mud volcanoes at Malenky, Bolshoy, Malyutka and Peschanka in the southern Baikal basin and Kukuy in the central Baikal basin. The Goloustnoye seepage site in the southern Baikal basin seems active and gas plumes are ascending from the lake bottom. Delta 13C of hydrate-bound methane is several permil lower than that of dissolved methane in pore water at most places, however, delta 13C values of hydrate-bound and dissolved methane are almost the same each other and delta D values of hydrate-bound methane was about 5 permil lower than that of dissolved methane at Goloustnoye. Hachikubo et al. [2007] revealed in their laboratory experiments that delta D of hydrate-bound methane and ethane becomes several permil lower than that of the original gases at a formation of gas hydrate, whereas delta 13C of hydrate-bound and original gases remains almost constant. Based on their results, the current gas dissolved in pore water is not the source of the gas hydrates at most hydrate-bearing sites in Lake Baikal. On the contrary, the gas hydrate at Goloustnoye seems to be rather new crystal. Although isotopic fractionation of ethane also occurs at the formation of gas hydrate in the laboratory experiments, isotopic differences between hydrate-bound and dissolved ethane differ from each other according to the sediment cores. Hachikubo, A., T. Kosaka, M. Kida, A. Krylov, H. Sakagami, H. Minami, N. Takahashi, and H. Shoji (2007), Isotopic fractionation of methane and ethane hydrates between gas and hydrate phases, Geophys. Res. Lett., 34, L21502, doi:10.1029/2007GL030557.

  19. N-Acetylcysteine plus Saline Hydration versus Saline Hydration

    African Journals Online (AJOL)

    ) in patients undergoing coronary angiography pretreated with N-acetylcysteine NAC plus saline hydration or saline hydration alone and to determine the association between various risk factors and RCIN. Methods: Patients were ...

  20. Guest-cage atomic interactions in a clathrate-based phase-change material. (United States)

    Loke, Desmond; Skelton, Jonathan M; Law, Leong-Tat; Wang, Wei-Jie; Li, Ming-Hua; Song, Wen-Dong; Lee, Tae-Hoon; Elliott, Stephen R


    New clathrate-based phase-change materials with cage-like structures incorporating Cs and Ba guest atoms, are reported as a means of altering crystallization and amorphization behavior by controlling 'guest-cage' interactions via intra-complex guest vibrational effects. Both a high resistance to spontaneous crystallization, and long retention of the amorphous phase are achieved, as well as a low melting energy. This approach provides a route for achieving cage-controlled semiconductor devices. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


    Directory of Open Access Journals (Sweden)

    Milan Drabik


    Full Text Available Essential focus of the study has been to acquire thermoanalytical events, incl. enthalpies of decompositions - ΔH, of technological materials based on two types of Portland cements. The values of thermoanalytical events and also ΔH of probes of technological compositions, if related with the data of a choice of minerals of calcium-silicate-sulfate-aluminate hydrates, served as a valued input for the assessment of phases present and phase changes due to the topical hydraulic processes. The results indicate mainly the effects of "standard humidity" or "wet storage" of the entire hydration/hydraulic treatment, but also the presence of cement residues alongside calcium-silicate-sulfate-aluminate hydrates (during the tested period of treatment. "A diluting" effect of unhydrated cement residues upon the values of decomposition enthalpies in the studied multiphase system is postulated and discussed

  2. Molecular potential energies in dodecahedron cell of methane hydrate and dispersion correction for DFT. (United States)

    Du, Qi-Shi; Li, Da-Peng; Liu, Peng-Jun; Huang, Ri-Bo


    The interaction potential energies of water-water and water-methane in structure-I unit cell of methane hydrate are calculated from 2.1 to 8.0A using density functional theory (DFT) B3LYP/TZVP. The curves of potential energies are corrected for basis set superposition error (BSSE) and dispersion interaction using a 4-term L-J (4,6-8,12) correction equation, which is derived from CCSD(T)/cc-pVTZ calculations of water-water and water-methane molecular pairs, using least squares curve-fitting. The methane hydrate unit cell is a regular water dodecahedron cell consisting of 20 water molecules with a methane molecule in the center. The geometries of water and methane are optimized at CCSD(T)/cc-pVTZ level. The BSSE-corrections are calculated for water-water and water-methane interaction energies as functions of the side length, l, of the dodecahedron cell at B3LYP/TZVP level in the range from 2.1 to 8.0A. The BSSE CP-corrected and dispersion-corrected potential energy surfaces (PES) of water-water and water-methane are useful for molecular dynamics simulation of gas clathrate-hydrates.

  3. Investigation of Kinetic Hydrate Inhibition Using a High Pressure Micro Differential Scanning Calorimeter

    DEFF Research Database (Denmark)

    Daraboina, Nagu; Malmos, Christine; von Solms, Nicolas


    . These investigations were performed using small samples in four different capillary tubes in the calorimeter cell. When the isothermal method was employed, it was found that Luvicap EG significantly delays the hydrate nucleation time as compared to water. The results obtained from the ramping method demonstrated...... of hydrate growth. Additionally, hydrate formed in the presence of inhibitor decomposed at higher temperatures compared to pure water, indicating that while hydrate formation is initially inhibited; once hydrates form, they are more stable in the presence of inhibitor. Overall, this method proved a viable...

  4. A DFT-based comparative equilibrium study of thermal dehydration and hydrolysis of CaCl₂ hydrates and MgCl₂ hydrates for seasonal heat storage. (United States)

    Pathak, Amar Deep; Nedea, Silvia; Zondag, Herbert; Rindt, Camilo; Smeulders, David


    Salt hydrates store solar energy in chemical form via a reversible dehydration-hydration reaction. However, as a side reaction to dehydration, hydrolysis (HCl formation) may occur in chloride based salt hydrates (specially in MgCl2 hydrates), affecting the durability of the storage system. The mixture of CaCl2 and MgCl2 hydrates has been shown experimentally to have exceptional cycle stability and improved kinetics. However, the optimal operating conditions for the mixture are unknown. To understand the appropriate balance between dehydration and hydrolysis kinetics in the mixtures, it is essential to gain in-depth insight into the mixture components. We present a GGA-DFT level study to investigate the various gaseous structures of CaCl2 hydrates and to understand the relative stability of their conformers. The hydration strength and relative stability of conformers are dominated by electrostatic interactions. A wide network of intramolecular homonuclear and heteronuclear hydrogen bonds is observed in CaCl2 hydrates. Equilibrium product concentrations are obtained during dehydration and hydrolysis reactions under various temperature and pressure conditions. The trend of the dehydration curve with temperature in CaCl2 hydrates is similar to the experiments. Comparing these results to those of MgCl2 hydrates, we find that CaCl2 hydrates are more resistant towards hydrolysis in the temperature range of 273-800 K. Specifically, the present study reveals that the onset temperatures of HCl formation, a crucial design parameter for MgCl2 hydrates, are lower than for CaCl2 hydrates except for the mono-hydrate.

  5. Evaluation of Gas Hydrate at Alaminos Canyon 810, Northern Gulf of Mexico Slope (United States)

    Yang, C.; Cook, A.; Sawyer, D.; Hillman, J. I. T.


    We characterize the gas hydrate reservoir in Alaminos Canyon Block 810 (AC810) on the northern Gulf of Mexico slope, approximately 400 km southeast of Houston, Texas, USA. Three-dimensional seismic data shows a bottom-simulating-reflection (BSR), over 30 km2, which suggests that a significant gas hydrate accumulation may occur at AC810. Furthermore, logging while drilling (LWD) data acquired from a Statoil well located that penetrated the BSR near the crest of the regional anticline indicates two possible gas hydrate units (Hydrate Unit A and Hydrate Unit B). LWD data in this interval are limited to gamma ray and resistivity only. Resistivity curve separations are observed in Hydrate Unit A (131 to 253 mbsf) suggesting hydrate-filled fractures in marine mud. A spiky high resistivity response in Hydrate Unit B (308 to 354 mbsf) could either be a marine mud or a sand-prone interval. The abrupt decrease (from 7 to 1 Ωm) in resistivity logs at 357 mbsf generally corresponds with the interpreted base of hydrate stability, as the BSR is observed near 350 mbsf on the seismic data. To further investigate the formation characteristics, we generate synthetic traces using general velocity and density trends for marine sediments to match the seismic trace extracted at the Statoil well. We consider models with 1) free gas and 2) water only below the base of hydrate stability. In our free gas-below models, we find the velocity of Hydrate Unit A and Hydrate Unit B is generally low and does not deviate significantly from the general velocity trends, suggesting that gas hydrate is present in a marine mud. In the water-below model, the compressional velocity of Hydrate Unit B ranges from 2450 m/s to 3150 m/s. This velocity is similar to the velocity of high hydrate saturation in sand; typically greater than 2500 m/s. This may indicate that Hydrate Unit B is sand with high hydrate saturation; however, to achieve a suitable match between the water-below synthetic seismogram and the

  6. Experimental study on 2-D acoustic characteristics and hydrate distribution in sand (United States)

    Bu, Qingtao; Hu, Gaowei; Ye, Yuguang; Liu, Changling; Li, Chengfeng; Wang, Jiasheng


    An experimental system was developed to measure the acoustic velocity of hydrate-bearing sands and to infer their 2-D velocity structure and hydrate content during hydrate formation. For this purpose, sands of two different grain sizes were chosen and arranged in alternating layers in a pressure vessel before saturating them with a solution of dissolved methane gas in a sodium dodecyl sulphate solution. During cooling and subsequent hydrate formation, acoustic velocities were measured with ultrasonic probes along the vessel wall. Hydrate formation was measured by time domain reflectometry. A straight ray-tracing method and an iterative algorithm based on the simultaneous iterative reconstruction technique algorithm were used to perform forward modelling and inversion of the ultrasonic tomography. The tomography results were used to obtain acoustic velocity profile distribution images of hydrate formation in loose sediments. The results show that the acoustic velocity in each layer increases rapidly when the hydrate saturation is less than 20 per cent. In contrast, the acoustic velocity increases slowly when the hydrate saturation is greater than 20 per cent. The effective medium theory was used to describe the changes of velocities with hydrate saturation. The empirical formula of P and S-wave velocity in hydrate-bearing sediments as well as the correlation between the wave velocity ratio and the hydrate saturation are also obtained. In the first stage of hydrate formation, the acoustic velocity is larger in the coarse sediment than in the fine sediment. At the end of hydrate formation, the acoustic velocities in different layers differ little and the hydrates are nearly homogeneously distributed in the reservoir. The 2-D velocity structure and inferred hydrate distribution indicate that in the longitudinal direction, the hydrate preferentially forms close to the gas source, thus the acoustic velocity is large in this area. In the transverse direction, the hydrate

  7. Aluminum Sulfate 18 Hydrate (United States)

    Young, Jay A.


    A chemical laboratory information profile (CLIP) of the chemical, aluminum sulfate 18 hydrate, is presented. The profile lists physical and harmful properties, exposure limits, reactivity risks, and symptoms of major exposure for the benefit of teachers and students using the chemical in the laboratory.


    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  9. Characterization of un-hydrated and hydrated BioAggregate™ and MTA Angelus™. (United States)

    Camilleri, J; Sorrentino, F; Damidot, D


    high calcium ion release early, which was maintained over the 28-day period as opposed to MTA Angelus, which demonstrated low early calcium ion release which increased as the material aged. The mineralogical composition of BioAggregate was different to MTA Angelus. As opposed to MTA Angelus, BioAggregate did not contain aluminium and contained additives such as calcium phosphate and silicon dioxide. As a consequence, BioAggregate reacted more slowly and formation of calcium hydroxide and leaching of calcium ions in solution were not evident as the material aged. The additives in BioAggregate modify the kinetics and the end products of hydration. Although newer generation tricalcium silicate-based materials contain similar constituents to MTA, they do not undergo the same setting reactions, and thus, their clinical performance will not be comparable to that of MTA.

  10. Inferred gas hydrate and permafrost stability history models linked to climate change in the Beaufort-Mackenzie Basin, Arctic Canada

    Directory of Open Access Journals (Sweden)

    J. Majorowicz


    Full Text Available Atmospheric methane from episodic gas hydrate (GH destabilization, the "clathrate gun" hypothesis, is proposed to affect past climates, possibly since the Phanerozoic began or earlier. In the terrestrial Beaufort-Mackenzie Basin (BMB, GHs occur commonly below thick ice-bearing permafrost (IBP, but they are rare within it. Two end-member GH models, where gas is either trapped conventionally (Case 1 or where it is trapped dynamically by GH formation (Case 2, were simulated using profile (1-D models and a 14 Myr ground surface temperature (GST history based on marine isotopic data, adjusted to the study setting, constrained by deep heat flow, sedimentary succession conductivity, and observed IBP and Type I GH contacts in Mallik wells. Models consider latent heat effects throughout the IBP and GH intervals. Case 1 GHs formed at ~0.9 km depth only ~1 Myr ago by in situ transformation of conventionally trapped natural gas. Case 2 GHs begin to form at ~290–300 m ~6 Myr ago in the absence of lithological migration barriers. During glacial intervals Case 2 GH layers expand both downward and upward as the permafrost grows downward through and intercalated with GHs. The distinctive model results suggest that most BMB GHs resemble Case 1 models, based on the observed distinct and separate occurrences of GHs and IBP and the lack of observed GH intercalations in IBP. Case 2 GHs formed >255 m, below a persistent ice-filled permafrost layer that is as effective a seal to upward methane migration as are Case 1 lithological seals. All models respond to GST variations, but in a delayed and muted manner such that GH layers continue to grow even as the GST begins to increase. The models show that the GH stability zone history is buffered strongly by IBP during the interglacials. Thick IBP and GHs could have persisted since ~1.0 Myr ago and ~4.0 Myr ago for Cases 1 and 2, respectively. Offshore BMB IBP and GHs formed terrestrially during Pleistocene sea level low

  11. Rheological properties of methane hydrate slurries formed from AOT + water + oil microemulsions. (United States)

    Webb, Eric B; Koh, Carolyn A; Liberatore, Matthew W


    The in situ formation and flow properties of methane hydrates formed from water-in-oil microemulsions composed of water, dodecane, and aerosol OT surfactant (AOT) were studied using a unique high pressure rheometer. AOT microemulsions have high stability (order of months), well-characterized composition, and yield reproducible results compared to hydrate studies in water-in-crude oil emulsions. Viscosity increases on the order of minutes upon hydrate formation, and then decreases on the order of hours. If significant unconverted water remained after the initial formation event, then viscosity increases for a time as methane slowly dissolves and converts additional water to hydrate. In addition to transient formation measurements, yield stresses and flow curves are measured for a set of experimental conditions. Hydrate slurry viscosity and yield stress increase with increasing water volume fraction, increasing initial pressure, decreasing temperature, and decreasing formation shear rate.

  12. Serrano charged up for hydrates battle

    Energy Technology Data Exchange (ETDEWEB)

    Flatern, R. von


    The plugging of pipelines by paraffin and hydrate formations is an obstacle still to be overcome in the transportation of gases in deep cold water. However, a new flow assurance technique is soon to be installed in Shell's Serrano and Oregano fields in the Gulf of Mexico and this is expected to eventually impact on the entire offshore industry: it is this development which is discussed. The system uses electricity to heat the pipelines.

  13. The German gas hydrate initiative sugar : innovative exploitation techniques, numerical modelling, and laboratory experiments

    Energy Technology Data Exchange (ETDEWEB)

    Haeckel, M. [IFM-GEOMAR, Kiel (Germany)


    The German gas hydrate initiative and innovative exploitation techniques, numerical modelling, and laboratory experiments were discussed in this presentation. The main objectives of the sugar project are to model spatial and temporal distribution of sub-seafloor gas hydrates; to constrain major control parameters of hydrate formation; and to develop a new tool for three-dimensional prediction of gas hydrate deposits. The overall purpose is to predict exploitable gas hydrate deposits. Several illustrations were offered, including basin/geological modelling; properties of gas hydrate layers; and nested model/local grid refinement. The future of basin modeling was also discussed with particular reference to testing and calibration of software packages. Options for carbon dioxide storage and methane hydrate exploitation as well as critical issues that needed to be addressed were also outlined. Several reservoir modelling projects were presented. Scenarios and technical concepts were discussed. The presentation concluded with a summary of international co-operation efforts in this area. tabs., figs.

  14. Hydration of Blended Portland Cements Containing Calcium-Aluminosilicate Glass Powder and Limestone

    DEFF Research Database (Denmark)

    Moesgaard, Mette; Poulsen, S.L.; Herfort, D.


    This work investigates the hydration of blended Portland cement containing 30 wt.% Na2O-CaO-Al2O3-SiO2 (NCAS) glass particles either as the only supplementary cementitious material (SCM) or in combination with limestone, using 29Si MAS NMR, powder XRD, and thermal analyses. The NCAS glass...... represents a potential alternative to traditional SCMs, used for reduction of the CO2 emission associated with cement production. It is found that the NCAS glass takes part in the hydration reactions after about two weeks of hydration and a degree of reaction of approx. 50 % is observed after 90 days...... of hydration. The hydrated glass contributes to the formation of the calcium-silicate-hydrate (C-S-H) phase, consuming a part of the Portlandite (Ca(OH)2) formed during hydration of the Portland cement. Furthermore, the presence of the glass and limestone particles, alone or in combination, results...

  15. Formats

    Directory of Open Access Journals (Sweden)

    Gehmann, Ulrich


    Full Text Available In the following, a new conceptual framework for investigating nowadays’ “technical” phenomena shall be introduced, that of formats. The thesis is that processes of formatting account for our recent conditions of life, and will do so in the very next future. It are processes whose foundations have been laid in modernity and which will further unfold for the time being. These processes are embedded in the format of the value chain, a circumstance making them resilient to change. In addition, they are resilient in themselves since forming interconnected systems of reciprocal causal circuits.Which leads to an overall situation that our entire “Lebenswelt” became formatted to an extent we don’t fully realize, even influencing our very percep-tion of it.

  16. The effect of hydrate promoters on gas uptake. (United States)

    Xu, Chun-Gang; Yu, Yi-Song; Ding, Ya-Long; Cai, Jing; Li, Xiao-Sen


    Gas hydrate technology is considered as a promising technology in the fields of gas storage and transportation, gas separation and purification, seawater desalination, and phase-change thermal energy storage. However, to date, the technology is still not commercially used mainly due to the low gas hydrate formation rate and the low gas uptake. In this study, the effect of hydrate promoters on gas uptake was systematically studied and analyzed based on hydrate-based CH4 storage and CO2 capture from CO2/H2 gas mixture experiments. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and gas chromatography (GC) were employed to analyze the microstructures and gas compositions. The results indicate that the effect of the hydrate promoter on the gas uptake depends on the physical and chemical properties of the promoter and gas. A strong polar ionic promoter is not helpful towards obtaining the ideal gas uptake because a dense hydrate layer is easily formed at the gas-liquid interface, which hinders gas diffusion from the gas phase to the bulk solution. For a weak polar or non-polar promoter, the gas uptake depends on the dissolution characteristics among the different substances in the system. The lower the mutual solubility among the substances co-existing in the system, the higher the independence among the substances in the system; this is so that each phase has an equal chance to occupy the hydrate cages without or with small interactions, finally leading to a relatively high gas uptake.

  17. Effects of ensembles on methane hydrate nucleation kinetics. (United States)

    Zhang, Zhengcai; Liu, Chan-Juan; Walsh, Matthew R; Guo, Guang-Jun


    By performing molecular dynamics simulations to form a hydrate with a methane nano-bubble in liquid water at 250 K and 50 MPa, we report how different ensembles, such as the NPT, NVT, and NVE ensembles, affect the nucleation kinetics of the methane hydrate. The nucleation trajectories are monitored using the face-saturated incomplete cage analysis (FSICA) and the mutually coordinated guest (MCG) order parameter (OP). The nucleation rate and the critical nucleus are obtained using the mean first-passage time (MFPT) method based on the FS cages and the MCG-1 OPs, respectively. The fitting results of MFPT show that hydrate nucleation and growth are coupled together, consistent with the cage adsorption hypothesis which emphasizes that the cage adsorption of methane is a mechanism for both hydrate nucleation and growth. For the three different ensembles, the hydrate nucleation rate is quantitatively ordered as follows: NPT > NVT > NVE, while the sequence of hydrate crystallinity is exactly reversed. However, the largest size of the critical nucleus appears in the NVT ensemble, rather than in the NVE ensemble. These results are helpful for choosing a suitable ensemble when to study hydrate formation via computer simulations, and emphasize the importance of the order degree of the critical nucleus.

  18. Rheological properties of hydrate suspensions in asphaltenic crude oils; Proprietes rheologiques de suspensions d'hydrate dans des bruts asphalteniques

    Energy Technology Data Exchange (ETDEWEB)

    Marques de Toledo Camargo, R.


    The development of offshore oil exploitation under increasing water depths has forced oil companies to increase their understanding of gas hydrate formation and transportation in multiphase flow lines in which a liquid hydrocarbon phase is present. This work deals with the flow behaviour of hydrate suspensions in which a liquid hydrocarbon is the continuous phase. Three different liquid hydrocarbons are used: an asphaltenic crude oil, a condensate completely free of asphaltenes and a mixture between the asphaltenic oil and heptane. The rheological characterisation of hydrate suspensions is the main tool employed. Two original experimental devices are used: a PVT cell adapted to operate as a Couette type rheometer and a semi-industrial flow loop. Hydrate suspensions using the asphaltenic oil showed shear-thinning behaviour and thixotropy. This behaviour is typically found in flocculated systems, in which the particles attract each other forming flocs of aggregated particles at low shear rates. The suspensions using the condensate showed Newtonian behaviour. Their relative viscosities were high, which suggests that an aggregation process between hydrate particles takes. place during hydrate formation. Finally, hydrate suspensions using the mixture asphaltenic oil-heptane showed shear-thinning behaviour, thixotropy and high relative viscosity. From these results it can be inferred that, after the achievement of the hydrate formation process, the attractive forces between hydrate particles are weak. making unlikely pipeline obstruction by an aggregation process. Nevertheless, during the hydrate formation, these attractive forces can be sufficiently high. It seems that the hydrate surface wettability is an important parameter in this phenomena. (author)

  19. 3D pore-type digital rock modeling of natural gas hydrate for permafrost and numerical simulation of electrical properties (United States)

    Dong, Huaimin; Sun, Jianmeng; Lin, Zhenzhou; Fang, Hui; Li, Yafen; Cui, Likai; Yan, Weichao


    Natural gas hydrate is being considered as an alternative energy source for sustainable development and has become a focus of research throughout the world. In this paper, based on CT scanning images of hydrate reservoir rocks, combined with the microscopic distribution of hydrate, a diffusion limited aggregation (DLA) model was used to construct 3D hydrate digital rocks of different distribution types, and the finite-element method was used to simulate their electrical characteristics in order to study the influence of different hydrate distribution types, hydrate saturation and formation of water salinity on electrical properties. The results show that the hydrate digital rocks constructed using the DLA model can be used to characterize the microscopic distribution of different types of hydrates. Under the same conditions, the resistivity of the adhesive hydrate digital rock is higher than the cemented and scattered type digital rocks, and the resistivity of the scattered hydrate digital rock is the smallest among the three types. Besides, the difference in the resistivity of the different types of hydrate digital rocks increases with an increase in hydrate saturation, especially when the saturation is larger than 55%, and the rate of increase of each of the hydrate types is quite different. Similarly, the resistivity of the three hydrate types decreases with an increase in the formation of water salinity. The single distribution hydrate digital rock constructed, combined with the law of microscopic distribution and influence of saturation on the electrical properties, can effectively improve the accuracy of logging identification of hydrate reservoirs and is of great significance for the estimation of hydrate reserves.


    Energy Technology Data Exchange (ETDEWEB)



    Results from simulated experiments in several laboratories show that host sediments influence hydrate formation in accord with known heterogeneity of host sediments at sites of gas hydrate occurrence (1). For example, in Mackenzie Delta, NWT Canada (Mallik 2L-38 well), coarser-grained units (pore-filling model) are found whereas in the Gulf of Mexico, the found hydrate samples do not appear to be lithologically controlled. We have initiated a systematic study of sediments, initially focusing on samples from various depths at a specific site, to establish a correlation with hydrate occurrence (or variations thereof) to establish differences in their microstructure, porosity, and other associated properties. The synchrotron computed microtomography (CMT) set-up at the X-27A tomography beam line at the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory was used as a tool to study sediments from Blake Ridge at three sub bottom depths of 0.2, 50, and 667 meters. Results from the tomographic analysis of the deepest sample (667 m) are presented here to illustrate how tomography can be used to obtain new insights into the structures of methane hydrate host sediments. The investigation shows the internal grain/pore space resolution in the microstructure and a 3-D visualization of the connecting pathways obtained following data segmentation into pore space and grains within the sediment sample. The analysis gives the sample porosity, specific surface area, mean particle size, and tortuosity, as well. An earlier report on the experimental program has been given by Mahajan et al. (2).

  1. Molecular modeling of the dissociation of methane hydrate in contact with a silica surface. (United States)

    Bagherzadeh, S Alireza; Englezos, Peter; Alavi, Saman; Ripmeester, John A


    We use constant energy, constant volume (NVE) molecular dynamics simulations to study the dissociation of the fully occupied structure I methane hydrate in a confined geometry between two hydroxylated silica surfaces between 36 and 41 Å apart, at initial temperatures of 283, 293, and 303 K. Simulations of the two-phase hydrate/water system are performed in the presence of silica, with and without a 3 Å thick buffering water layer between the hydrate phase and silica surfaces. Faster decomposition is observed in the presence of silica, where the hydrate phase is prone to decomposition from four surfaces, as compared to only two sides in the case of the hydrate/water simulations. The existence of the water layer between the hydrate phase and the silica surface stabilizes the hydrate phase relative to the case where the hydrate is in direct contact with silica. Hydrates bound between the silica surfaces dissociate layer-by-layer in a shrinking core manner with a curved decomposition front which extends over a 5-8 Å thickness. Labeling water molecules shows that there is exchange of water molecules between the surrounding liquid and intact cages in the methane hydrate phase. In all cases, decomposition of the methane hydrate phase led to the formation of methane nanobubbles in the liquid water phase. © 2012 American Chemical Society

  2. Preliminary discussion on gas hydrate reservoir system of Shenhu Area, North Slope of South China Sea

    Energy Technology Data Exchange (ETDEWEB)

    Wu, N.; Yang, S.; Liang, J.; Wang, H.; Fu, S. [Guangzhou Marine Geological Survey, Guangzhou (China); Zhang, H. [China Geological Survey, Beijing (China); Su, X. [China Univ. of Geosciences, Beijing (China)


    Gas hydrate is a type of ice-like solid substance formed by the combination of certain low-molecular-weight gases such as methane, ethane, and carbon dioxide with water. Gas hydrate primarily occurs naturally in sediments beneath the permafrost and the sediments of the continental slope with the water depth greater than 300 m. Marine gas hydrate geological systems are important because they may be sufficiently concentrated in certain locations to be an economically viable fossil fuel resource. However, gas hydrates can cause geo-hazards through large-scale slope destabilization and can release methane, a potential greenhouse gas, into the environment. This paper discussed the hydrate drilling results from a geological and geophysical investigation of the gas hydrate reservoir system of the Shenhu Area, located in the north slope of South China Sea. The paper identified the basic formation conditions, and discussed the pore-water geochemical features of shallow sediments and their inflected gas sources, gas hydrate distribution and seismic characteristics. It was concluded that the gas hydrate was heterogeneously distributed in space, and mainly distributed in certain ranges above the bottom of the gas hydrate stability zone. It was also concluded that methane gas that formed hydrate was likely from in-situ micro-biogenic methane. Last, it was found that distributed and in-situ micro-biogenic methane resulted in low methane flux, and formed the distributed pattern of gas hydrate system with the features of differential distribution and saturation. 34 refs., 2 tabs., 3 figs.

  3. Experimental verification of methane-carbon dioxide replacement in natural gas hydrates using a differential scanning calorimeter. (United States)

    Lee, Seungmin; Lee, Yohan; Lee, Jaehyoung; Lee, Huen; Seo, Yongwon


    The methane (CH4) - carbon dioxide (CO2) swapping phenomenon in naturally occurring gas hydrates is regarded as an attractive method of CO2 sequestration and CH4 recovery. In this study, a high pressure microdifferential scanning calorimeter (HP μ-DSC) was used to monitor and quantify the CH4 - CO2 replacement in the gas hydrate structure. The HP μ-DSC provided reliable measurements of the hydrate dissociation equilibrium and hydrate heat of dissociation for the pure and mixed gas hydrates. The hydrate dissociation equilibrium data obtained from the endothermic thermograms of the replaced gas hydrates indicate that at least 60% of CH4 is recoverable after reaction with CO2, which is consistent with the result obtained via direct dissociation of the replaced gas hydrates. The heat of dissociation values of the CH4 + CO2 hydrates were between that of the pure CH4 hydrate and that of the pure CO2 hydrate, and the values increased as the CO2 compositions in the hydrate phase increased. By monitoring the heat flows from the HP μ-DSC, it was found that the noticeable dissociation or formation of a gas hydrate was not detected during the CH4 - CO2 replacement process, which indicates that a substantial portion of CH4 hydrate does not dissociate into liquid water or ice and then forms the CH4 + CO2 hydrate. This study provides the first experimental evidence using a DSC to reveal that the conversion of the CH4 hydrate to the CH4 + CO2 hydrate occurs without significant hydrate dissociation.

  4. Gas Hydrate Stability and Sampling: The Future as Related to the Phase Diagram

    Directory of Open Access Journals (Sweden)

    E. Dendy Sloan


    Full Text Available The phase diagram for methane + water is explained, in relation to hydrate applications, such as in flow assurance and in nature. For natural applications, the phase diagram determines the regions for hydrate formation for two- and three-phase conditions. Impacts are presented for sample preparation and recovery. We discuss an international study for “Round Robin” hydrate sample preparation protocols and testing.

  5. Synthesis of hydrogen-carbon clathrate material and hydrogen evolution therefrom at moderate temperatures and pressures (United States)

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


    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.

  6. Methane Hydrates: More Than a Viable Aviation Fuel Feedstock Option (United States)

    Hendricks, Robert C.


    Demand for hydrocarbon fuels is steadily increasing, and greenhouse gas emissions continue to rise unabated with the energy demand. Alternate fuels will be coming on line to meet that demand. This report examines the recovering of methane from methane hydrates for fuel to meet this demand rather than permitting its natural release into the environment, which will be detrimental to the planet. Some background on the nature, vast sizes, and stability of sedimentary and permafrost formations of hydrates are discussed. A few examples of the severe problems associated with methane recovery from these hydrates are presented along with the potential impact on the environment and coastal waters. Future availability of methane from hydrates may become an attractive option for aviation fueling, and so future aircraft design associated with methane fueling is considered.

  7. Homogeneous Nucleation of Methane Hydrate in Microsecond Molecular Dynamics Simulations. (United States)

    Sarupria, Sapna; Debenedetti, Pablo G


    We report atomistically detailed molecular dynamics simulations of homogeneous nucleation of methane hydrate in bulk aqueous phase in the absence of any interface. Subcritical clusters of water and methane molecules are formed in the initial segment of the simulations, which then aggregate to give the critical hydrate nucleus. This occurs over time scales of several hundred nanoseconds, indicating that the formation and aggregation of subcritical clusters can contribute significantly to the overall rate of hydrate nucleation. The clusters have elements of sI hydrate structure, such as 5(12) and 5(12)6(2) cages as well as other uncommon 5(12)6(3) and 5(12)6(4) cages, but do not possess long-range order. Clusters are dynamic in nature and undergo continuous structural rearrangements.

  8. X-ray CT Observations of Methane Hydrate Distribution Changes over Time in a Natural Sediment Core from the BPX-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well

    Energy Technology Data Exchange (ETDEWEB)

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


    When maintained under hydrate-stable conditions, methane hydrate in laboratory samples is often considered a stable and immobile solid material. Currently, there do not appear to be any studies in which the long-term redistribution of hydrates in sediments has been investigated in the laboratory. These observations are important because if the location of hydrate in a sample were to change over time (e.g. by dissociating at one location and reforming at another), the properties of the sample that depend on hydrate saturation and pore space occupancy would also change. Observations of hydrate redistribution under stable conditions are also important in understanding natural hydrate deposits, as these may also change over time. The processes by which solid hydrate can move include dissociation, hydrate-former and water migration in the gas and liquid phases, and hydrate formation. Chemical potential gradients induced by temperature, pressure, and pore water or host sediment chemistry can drive these processes. A series of tests were performed on a formerly natural methane-hydrate-bearing core sample from the BPX-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well, in order to observe hydrate formation and morphology within this natural sediment, and changes over time using X-ray computed tomography (CT). Long-term observations (over several weeks) of methane hydrate in natural sediments were made to investigate spatial changes in hydrate saturation in the core. During the test sequence, mild buffered thermal and pressure oscillations occurred within the sample in response to laboratory temperature changes. These oscillations were small in magnitude, and conditions were maintained well within the hydrate stability zone.

  9. Numerical modeling of gas recovery from methane hydrate reservoirs (United States)

    Silpngarmlert, Suntichai

    Class 1 hydrate deposits are characterized by a hydrate bearing layer underlain by a two phase, free-gas and water, zone. A Class 1 hydrate reservoir is more preferable than class 2 and class 3 hydrate accumulations because a small change of pressure and temperature can induce hydrate dissociation. In this study, production characteristics from class 1 methane-hydrate reservoirs by means of conventional depressurization technique are studied. In this work, the production characteristics and efficiency from different production strategies (mainly focused on a constant bottom-hole pressure production scheme) such as well-completion locations, well spacing, and production scheduling are investigated. In the production of conventional gas reservoirs using a constant bottom-hole pressure production scheme, both gas and water production rates exponentially decrease with time. However, for methane-hydrate reservoirs, gas production rate exponentially declines with time whereas water production rate increases with time because methane hydrate dissociation increases water saturation of the reservoir. The effects of well-completion locations on the production performances are examined. The simulation results indicate that the moving well completion location strategy provides better gas production performance than the fixed completion location strategy. The optimum well-completion location (using a moving completion location strategy) is at the middle of free-gas zone. Due to the effects of hydrate saturation on formation permeability, one should not complete a well in the hydrate zone. The effect of well spacing on the production efficiency is also investigated. As expected, smaller well-spacing system yields more total gas production and it can dissociate gas-hydrate more rapidly than the larger well-spacing system. However, the number of wells increases when the well-spacing decreases resulting in the increase of the capital investment of the project. Based on this study

  10. Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions (United States)

    Bindeman, Ilya N.; Lowenstern, Jacob B.


    Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant “onion-skin” fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2–3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched “hydration fronts” where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between ~110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at hydration at temperatures as low as 60 °C; prolonged exposure to high temperature of 175°–225° during water addition is less likely as the glass would lose alkalies and should alter to clays within days. A compilation of low-temperature hydration diffusion coefficients suggests ~2 orders of magnitude higher rates of diffusion at 60–110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites, measuring


    Ning, F.; Wu, N.; Jiang, G.; Zhang, L.


    Under the condition of over-pressure drilling, the solid-phase and liquid-phase in drilling fluids immediately penetrate into the oceanic gas hydrates-bearing sediment, which causes the water content surrounding the borehole to increase largely. At the same time, the hydrates surrounding borehole maybe quickly decompose into water and gas because of the rapid change of temperature and pressure. The drilling practices prove that this two factors may change the rock characteristics of wellbore, such as rock strength, pore pressure, resistivity, etc., and then affect the logging response and evaluation, wellbore stability and well safty. The invasion of filtrate can lower the angle of friction and weaken the cohesion of hydrates-bearing sediment,which is same to the effect of invading into conventional oil and gas formation on borehole mechnical properties. The difference is that temperature isn’t considered in the invasion process of conventional formations while in hydrates-bearing sediments, it is a factor that can not be ignored. Temperature changes can result in hydrates dissociating, which has a great effect on mechanical properties of borehole. With the application of numerical simulation method, we studied the changes of pore pressure and variation of water content in the gas hydrates-bearing sediment caused by drilling fluid invasion under pressure differential and gas hydrate dissociation under temperature differential and analyzed their influence on borehole stability.The result of simulation indicated that the temperature near borehole increased quickly and changed hardly any after 6 min later. About 1m away from the borehole, the temperature of formation wasn’t affected by the temperature change of borehole. At the place near borehole, as gas hydrate dissociated dramatically and drilling fluid invaded quickly, the pore pressure increased promptly. The degree of increase depends on the permeability and speed of temperature rise of formation around

  12. Parametric study of the physical properties of hydrate-bearing sand, silt, and clay sediments: 2. Small-strain mechanical properties (United States)

    Lee, J.Y.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.


    The small-strain mechanical properties (e.g., seismic velocities) of hydrate-bearing sediments measured under laboratory conditions provide reference values for calibration of logging and seismic exploration results acquired in hydrate-bearing formations. Instrumented cells were designed for measuring the compressional (P) and shear (S) velocities of sand, silts, and clay with and without hydrate and subject to vertical effective stresses of 0.01 to 2 MPa. Tetrahydrofuran (THF), which is fully miscible in water, was used as the hydrate former to permit close control over the hydrate saturation Shyd and to produce hydrate from dissolved phase, as methane hydrate forms in most natural marine settings. The results demonstrate that laboratory hydrate formation technique controls the pattern of P and S velocity changes with increasing Shyd and that the small-strain properties of hydrate-bearing sediments are governed by effective stress, δ'v and sediment specific surface. The S velocity increases with hydrate saturation owing to an increase in skeletal shear stiffness, particularly when hydrate saturation exceeds Shyd≈ 0.4. At very high hydrate saturations, the small strain shear stiffness is determined by the presence of hydrates and becomes insensitive to changes in effective stress. The P velocity increases with hydrate saturation due to the increases in both the shear modulus of the skeleton and the bulk modulus of pore-filling phases during fluid-to-hydrate conversion. Small-strain Poisson's ratio varies from 0.5 in soft sediments lacking hydrates to 0.25 in stiff sediments (i.e., subject to high vertical effective stress or having high Shyd). At Shyd ≥ 0.5, hydrate hinders expansion and the loss of sediment stiffness during reduction of vertical effective stress, meaning that hydrate-rich natural sediments obtained through pressure coring should retain their in situ fabric for some time after core retrieval if the cores are maintained within the hydrate

  13. Natural Gas Hydrate as a Storage Mechanism for Safe, Sustainable and Economical Production from Offshore Petroleum Reserves

    Directory of Open Access Journals (Sweden)

    Michael T. Kezirian


    Full Text Available Century Fathom presents an innovative process to utilize clathrate hydrates for the production, storage and transportation of natural gas from off-shore energy reserves in deep ocean environments. The production scheme was developed by considering the preferred state of natural gas in the deep ocean and addressing the hazards associated with conventional techniques to transport natural gas. It also is designed to mitigate the significant shipping cost inherent with all methods. The resulting proposed scheme restrains transport in the hydrate form to the ocean and does not attempt to supply energy to the residential consumer. Instead; the target recipients are industrial operations. The resulting operational concept is intrinsically safer by design; environmentally sustainable and significantly cost-effective compared with currently proposed schemes for the use of natural gas hydrates and has the potential to be the optimal solution for new production of reserves; depending on the distance to shore and capacity of the petroleum reserve. A potential additional benefit is the byproduct of desalinated water.

  14. DFT calculation of the potential energy landscape topology and Raman spectra of type I CH4 and CO2 hydrates. (United States)

    Vidal-Vidal, Ángel; Pérez-Rodríguez, Martín; Torré, Jean-Philippe; Piñeiro, Manuel M


    CO2 and CH4 clathrate hydrates of type I were studied by means of DFT and QTAIM, in order to better understand their properties at the molecular level. Sub-cells of type I hydrates were modeled as independent rigid cages, both empty and containing guest molecules. Interaction potentials of guest molecules inside each cage, and moving from a cell to the adjacent one, were calculated using the DFT approximation B3LYP/6-311+g(d,p), considering the cases with and without long range Coulombic corrections. The selected theory level was validated by comparison of the simulated Raman spectra with the experimental ones, for the case of type I lattice at full occupation of CO2 and CH4, respectively. For this comparison, Fermi resonances of CO2 were taken into account by transforming experimental bands to the corresponding theoretical non-mixed states. On the one hand, our results confirm the validity of the theory level selected for the model. We have shown the high anisotropy of the guest-cell interaction potential of the molecules analyzed, which has implications in the formulation and use of equations of state, and in the study of transport properties as well. On the other hand, our results suggest that the concentration of guest species inside type I hydrates could be computed from the comparison of experimental and predicted Raman spectra, although there are non-trivial experimental limitations to get over for that purpose.

  15. Systematic Studies on Anharmonicity of Rattling Phonons in Type I Clathrates by Low Temperature Heat Capacity Measurements (United States)

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


    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.

  16. Diurnally-Varying Lunar Hydration (United States)

    Hendrix, A. R.; Hurley, D.; Retherford, K. D.; Mandt, K.; Greathouse, T. K.; Farrell, W. M.; Vilas, F.


    Dayside, non-polar lunar hydration signatures have been observed by a handful of instruments and present insights into the lunar water cycle. In this study, we utilize the unique measurements from the current Lunar Reconnaissance Orbiter (LRO) mission to study the phenomenon of diurnally-varying dayside lunar hydration. The Lyman Alpha Mapping Project (LAMP) onboard LRO senses a strong far-ultraviolet water absorption edge indicating hydration in small abundances in the permanently shadowed regions as well as on the lunar dayside. We report on diurnal variability in hydration in different terrain types. We investigate the importance of different sources of hydration, including solar wind bombardment and meteoroid bombardment, by observing trends during magnetotail and meteor stream crossings.

  17. TOUGH+Hydrate v1.0 User's Manual: A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media

    Energy Technology Data Exchange (ETDEWEB)

    Moridis, George; Moridis, George J.; Kowalsky, Michael B.; Pruess, Karsten


    TOUGH+HYDRATE v1.0 is a new code for the simulation of the behavior of hydrate-bearing geologic systems. By solving the coupled equations of mass and heat balance, TOUGH+HYDRATE can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH{sub 4}-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy's law is valid. TOUGH+HYDRATE v1.0 includes both an equilibrium and a kinetic model of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH{sub 4}, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects. TOUGH+HYDRATE is the first member of TOUGH+, the successor to the TOUGH2 [Pruess et al., 1991] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. It is written in standard FORTRAN 95, and can be run on any computational platform (workstation, PC, Macintosh) for which such compilers are available.

  18. Postglacial response of Arctic Ocean gas hydrates to climatic amelioration (United States)

    Serov, Pavel; Mienert, Jürgen; Patton, Henry; Portnov, Alexey; Silyakova, Anna; Panieri, Giuliana; Carroll, Michael L.; Carroll, JoLynn; Andreassen, Karin; Hubbard, Alun


    Seafloor methane release due to the thermal dissociation of gas hydrates is pervasive across the continental margins of the Arctic Ocean. Furthermore, there is increasing awareness that shallow hydrate-related methane seeps have appeared due to enhanced warming of Arctic Ocean bottom water during the last century. Although it has been argued that a gas hydrate gun could trigger abrupt climate change, the processes and rates of subsurface/atmospheric natural gas exchange remain uncertain. Here we investigate the dynamics between gas hydrate stability and environmental changes from the height of the last glaciation through to the present day. Using geophysical observations from offshore Svalbard to constrain a coupled ice sheet/gas hydrate model, we identify distinct phases of subglacial methane sequestration and subsequent release on ice sheet retreat that led to the formation of a suite of seafloor domes. Reconstructing the evolution of this dome field, we find that incursions of warm Atlantic bottom water forced rapid gas hydrate dissociation and enhanced methane emissions during the penultimate Heinrich event, the Bølling and Allerød interstadials, and the Holocene optimum. Our results highlight the complex interplay between the cryosphere, geosphere, and atmosphere over the last 30,000 y that led to extensive changes in subseafloor carbon storage that forced distinct episodes of methane release due to natural climate variability well before recent anthropogenic warming. PMID:28584081

  19. Postglacial response of Arctic Ocean gas hydrates to climatic amelioration (United States)

    Serov, Pavel; Vadakkepuliyambatta, Sunil; Mienert, Jürgen; Patton, Henry; Portnov, Alexey; Silyakova, Anna; Panieri, Giuliana; Carroll, Michael L.; Carroll, JoLynn; Andreassen, Karin; Hubbard, Alun


    Seafloor methane release due to the thermal dissociation of gas hydrates is pervasive across the continental margins of the Arctic Ocean. Furthermore, there is increasing awareness that shallow hydrate-related methane seeps have appeared due to enhanced warming of Arctic Ocean bottom water during the last century. Although it has been argued that a gas hydrate gun could trigger abrupt climate change, the processes and rates of subsurface/atmospheric natural gas exchange remain uncertain. Here we investigate the dynamics between gas hydrate stability and environmental changes from the height of the last glaciation through to the present day. Using geophysical observations from offshore Svalbard to constrain a coupled ice sheet/gas hydrate model, we identify distinct phases of subglacial methane sequestration and subsequent release on ice sheet retreat that led to the formation of a suite of seafloor domes. Reconstructing the evolution of this dome field, we find that incursions of warm Atlantic bottom water forced rapid gas hydrate dissociation and enhanced methane emissions during the penultimate Heinrich event, the Bølling and Allerød interstadials, and the Holocene optimum. Our results highlight the complex interplay between the cryosphere, geosphere, and atmosphere over the last 30,000 y that led to extensive changes in subseafloor carbon storage that forced distinct episodes of methane release due to natural climate variability well before recent anthropogenic warming.

  20. Sources of biogenic methane to form marine gas hydrates: In situ production or upward migration?

    Energy Technology Data Exchange (ETDEWEB)

    Paull, C.K.; Ussler, W. III; Borowski, W.S.


    Potential sources of biogenic methane in the Carolina Continental Rise -- Blake Ridge sediments have been examined. Two models were used to estimate the potential for biogenic methane production: (1) construction of sedimentary organic carbon budgets, and (2) depth extrapolation of modern microbial production rates. While closed-system estimates predict some gas hydrate formation, it is unlikely that >3% of the sediment volume could be filled by hydrate from methane produced in situ. Formation of greater amounts requires migration of methane from the underlying continental rise sediment prism. Methane may be recycled from below the base of the gas hydrate stability zone by gas hydrate decomposition, upward migration of the methane gas, and recrystallization of gas hydrate within the overlying stability zone. Methane bubbles may also form in the sediment column below the depth of gas hydrate stability because the methane saturation concentration of the pore fluids decreases with increasing depth. Upward migration of methane bubbles from these deeper sediments can add methane to the hydrate stability zone. From these models it appears that recycling and upward migration of methane is essential in forming significant gas hydrate concentrations. In addition, the depth distribution profiles of methane hydrate will differ if the majority of the methane has migrated upward rather than having been produced in situ.

  1. A Sea Floor Methane Hydrate Displacement Experiment Using N2 Gas (United States)

    Brewer, P. G.; Peltzer, E. T.; Walz, P. M.; Zhang, X.; Hester, K.


    The production of free methane gas from solid methane hydrate accumulations presents a considerable challenge. The presently preferred procedure is pressure reduction whereby the relief of pressure to a condition outside the hydrate phase boundary creates a gas phase. The reaction is endothermic and thus a problematic water ice phase can form if the extraction of gas is too rapid, limiting the applicability of this procedure. Additionally, the removal of the formation water in contact with the hydrate phase is required before meaningful pressure reduction can be attained -- and this can take time. An alternate approach that has been suggested is the injection of liquid CO2 into the formation, thereby displacing the formation water. Formation of a solid CO2 hydrate is thermodynamically favored under these conditions. Competition between CH4 and CO2 for the hydrate host water molecules can occur displacing CH4 from the solid to the gas phase with formation of a solid CO2 hydrate. We have investigated another alternate approach with displacement of the surrounding bulk water phase by N2 gas, resulting in rapid release of CH4 gas and complete loss of the solid hydrate phase. Our experiment was carried out at the Southern Summit of Hydrate Ridge, offshore Oregon, at 780m depth. There we harvested hydrate fragments from surficial sediments using the robotic arm of the ROV Doc Ricketts. Specimens of the hydrate were collected about 1m above the sediment surface in an inverted funnel with a mesh covered neck as they floated upwards. The accumulated hydrate was transferred to an inverted glass cylinder, and N2 gas was carefully injected into this container. Displacement of the water phase occurred and when the floating hydrate material approached the lower rim the gas injection was stopped and the cylinder placed upon a flat metal plate effectively sealing the system. We returned to this site after 7 days to measure progress, and observed complete loss of the hydrate phase

  2. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates (United States)

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; d'Espinose de Lacaillerie, Jean-Baptiste


    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured. PMID:27009966

  3. Calcium Aluminate Cement Hydration Model

    Directory of Open Access Journals (Sweden)

    Matusinović, T.


    Full Text Available Calcium aluminate cement (AC is a very versatile special cement used for specific applications. As the hydration of AC is highly temperature dependent, yielding structurally different hydration products that continuously alter material properties, a good knowledge of thermal properties at early stages of hydration is essential. The kinetics of AC hydration is a complex process and the use of single mechanisms models cannot describe the rate of hydration during the whole stage.This paper examines the influence of temperature (ϑ=5–20 °C and water-to-cement mass ratio (mH /mAC = 0.4; 0.5 and 1.0 on hydration of commercial iron-rich AC ISTRA 40 (producer: Istra Cement, Pula, Croatia, which is a part of CALUCEM group, Figs 1–3. The flow rate of heat generation of cement pastes as a result of the hydration reactions was measured with differential microcalorimeter. Chemically bonded water in the hydrated cement samples was determined by thermo-gravimetry.Far less heat is liberated when cement and water come in contact for the first time, Fig. 1, than in the case for portland cement (PC. Higher water-to-cement ratio increases the heat evolved at later ages (Fig. 3 due to higher quantity of water available for hydration. A significant effect of the water-to-cement ratio on the hydration rate and hydration degree showed the importance of water as being the limiting reactant that slows down the reaction early. A simplified stoichiometric model of early age AC hydration (eq. (8 based on reaction schemes of principal minerals, nominally CA, C12A7 and C4AF (Table 1, was employed. Hydration kinetics after the induction period (ϑ < 20 °C had been successfully described (Fig. 4 and Table 2 by a proposed model (eq. (23 which simultaneously comprised three main mechanisms: nucleation and growth, interaction at phase boundary, and mass transfer. In the proposed kinetic model the nucleation and growth is proportional to the amount of reacted minerals (eq

  4. Life Origination and Development Hydrate theory (LOH-Theory): new approaches to the problems of the optimal nutrition and life prolongation (United States)

    Kadyshevich, E. A.; Ostrovskii, V. E.


    Life Origination Hydrate Theory (LOH-Theory) and Mitosis and Replication Hydrate Theory (MRHTheory), both grounded on the notion of honeycomb gas-hydrate structures formation/destruction as the physicochemical phenomenon governing the DNA origination and replication, allow new approaches to the optimal nutrition and life prolongation problems.

  5. Shifting Focus: From Hydration for Performance to Hydration for Health. (United States)

    Perrier, Erica T


    Over the past 10 years, literature on hydration biomarkers has evolved considerably - from (de)hydration assessment towards a more global definition of biomarkers of hydration in daily life. This shift in thinking about hydration markers was largely driven by investigating the differences that existed between otherwise healthy individuals whose habitual, ad-libitum drinking habits differ, and by identifying physiological changes in low-volume drinkers who subsequently increase their water intake. Aside from obvious differences in urinary volume and concentration, a growing body of evidence is emerging that links differences in fluid intake with small, but biologically significant, differences in vasopressin (copeptin), glomerular filtration rate, and markers of metabolic dysfunction or disease. Taken together, these pieces of the puzzle begin to form a picture of how much water intake should be considered adequate for health, and represent a shifting focus from hydration for performance, toward hydration for health outcomes. This narrative review outlines the key areas of research in which the global hydration process - including water intake, urinary hydration markers, and vasopressin - has been associated with health outcomes, focusing on kidney and metabolic endpoints. It will also provide a commentary on how various hydration biomarkers may be used in hydration for health assessment. Finally, if adequate water intake can play a role in maintaining health, how might we tell if we are drinking enough? Urine output is easily measured, and can take into account differences in daily physical activity, climate, dietary solute load, and other factors that influence daily water needs. Today, targets have been proposed for urine osmolality, specific gravity, and color that may be used by researchers, clinicians, and individuals as simple indicators of optimal hydration. However, there remain a large number of incomplete or unanswered research questions regarding the

  6. Grain-scale imaging and compositional characterization of cryo-preserved India NGHP 01 gas-hydrate-bearing cores (United States)

    Stern, Laura A.; Lorenson, T.D.


    We report on grain-scale characteristics and gas analyses of gas-hydrate-bearing samples retrieved by NGHP Expedition 01 as part of a large-scale effort to study gas hydrate occurrences off the eastern-Indian Peninsula and along the Andaman convergent margin. Using cryogenic scanning electron microscopy, X-ray spectroscopy, and gas chromatography, we investigated gas hydrate grain morphology and distribution within sediments, gas hydrate composition, and methane isotopic composition of samples from Krishna–Godavari (KG) basin and Andaman back-arc basin borehole sites from depths ranging 26 to 525 mbsf. Gas hydrate in KG-basin samples commonly occurs as nodules or coarse veins with typical hydrate grain size of 30–80 μm, as small pods or thin veins 50 to several hundred microns in width, or disseminated in sediment. Nodules contain abundant and commonly isolated macropores, in some places suggesting the original presence of a free gas phase. Gas hydrate also occurs as faceted crystals lining the interiors of cavities. While these vug-like structures constitute a relatively minor mode of gas hydrate occurrence, they were observed in near-seafloor KG-basin samples as well as in those of deeper origin (>100 mbsf) and may be original formation features. Other samples exhibit gas hydrate grains rimmed by NaCl-bearing material, presumably produced by salt exclusion during original hydrate formation. Well-preserved microfossil and other biogenic detritus are also found within several samples, most abundantly in Andaman core material where gas hydrate fills microfossil crevices. The range of gas hydrate modes of occurrence observed in the full suite of samples suggests a range of formation processes were involved, as influenced by local in situconditions. The hydrate-forming gas is predominantly methane with trace quantities of higher molecular weight hydrocarbons of primarily microbial origin. The composition indicates the gas hydrate is Structure I.

  7. The temperature hydration kinetics

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    Mircea Oroian


    Full Text Available The aim of this study is to evaluate the hydration kinetics of lentil seeds (Lens culinaris in water at different temperatures (25, 32.5, 40, 55, 70 and 80 °C for assessing the adequacy of models for describing the absorption phenomena during soaking. The diffusion coefficient values were calculated using Fick’s model for spherical and hemispherical geometries and the values were in the range of 10−6 m2/s. The experimental data were fitted to Peleg, Sigmoidal, Weibull and Exponential models. The models adequacy was determined using regression coefficients (R2, root mean square error (RMSE and reduced chi-square (χ2. The Peleg model is the suitable one for predicting the experimental data. Temperature had a positive and significant effect on the water absorption capacities and absorption was an endothermic process.

  8. Comparison of the physical and geotechnical properties of gas-hydrate-bearing sediments from offshore India and other gas-hydrate-reservoir systems (United States)

    Winters, William J.; Wilcox-Cline, R.W.; Long, P.; Dewri, S.K.; Kumar, P.; Stern, Laura A.; Kerr, Laura A.


    The sediment characteristics of hydrate-bearing reservoirs profoundly affect the formation, distribution, and morphology of gas hydrate. The presence and type of gas, porewater chemistry, fluid migration, and subbottom temperature may govern the hydrate formation process, but it is the host sediment that commonly dictates final hydrate habit, and whether hydrate may be economically developed.In this paper, the physical properties of hydrate-bearing regions offshore eastern India (Krishna-Godavari and Mahanadi Basins) and the Andaman Islands, determined from Expedition NGHP-01 cores, are compared to each other, well logs, and published results of other hydrate reservoirs. Properties from the hydrate-free Kerala-Konkan basin off the west coast of India are also presented. Coarser-grained reservoirs (permafrost-related and marine) may contain high gas-hydrate-pore saturations, while finer-grained reservoirs may contain low-saturation disseminated or more complex gas-hydrates, including nodules, layers, and high-angle planar and rotational veins. However, even in these fine-grained sediments, gas hydrate preferentially forms in coarser sediment or fractures, when present. The presence of hydrate in conjunction with other geologic processes may be responsible for sediment porosity being nearly uniform for almost 500 m off the Andaman Islands.Properties of individual NGHP-01 wells and regional trends are discussed in detail. However, comparison of marine and permafrost-related Arctic reservoirs provides insight into the inter-relationships and common traits between physical properties and the morphology of gas-hydrate reservoirs regardless of location. Extrapolation of properties from one location to another also enhances our understanding of gas-hydrate reservoir systems. Grain size and porosity effects on permeability are critical, both locally to trap gas and regionally to provide fluid flow to hydrate reservoirs. Index properties corroborate more advanced

  9. Catalysis of gas hydrates by biosurfactants in seawater-saturated sand/clay

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, R. E.; Kothapalli, C.; Lee, M.S. [Mississippi State University, Swalm School of Chemical Engineering, MS (United States); Woolsey, J. R. [University of Mississippi, Centre of Marine Resources and Environmental Technology, MS (United States)


    Large gas hydrate mounds have been photographed in the seabed of the Gulf of Mexico and elsewhere. According to industry experts, the carbon trapped within gas hydrates is two or three times greater than all known crude oil, natural gas and coal reserves in the world. Gas hydrates, which are ice-like solids formed from the hydrogen bonding of water as water temperature is lowered under pressure to entrap a suitable molecular-size gas in cavities of the developing crystal structure, are found below the ocean floor to depths exhibiting temperature and pressure combinations within the appropriate limits. The experiments described in this study attempt to ascertain whether biosurfactant byproducts of microbial activity in seabeds could catalyze gas hydrate formation. Samples of five possible biosurfactants classifications were used in the experiments. Results showed that biosurfactants enhanced hydrate formation rate between 96 per cent and 288 percent, and reduced hydrate induction time 20 per cent to 71 per cent relative to the control. The critical micellar concentration of rhamnolipid/seawater solution was found to be 13 ppm at hydrate-forming conditions. On the basis of these results it was concluded that minimal microbial activity in sea floor sands could achieve the threshold concentration of biosurfactant that would greatly promote hydrate formation. 28 refs., 2 tabs., 4 figs.

  10. Unravelling the progressive role of rattlers in thermoelectric clathrate and strategies for performance improvement: Concurrently enhancing electronic transport and blocking phononic transport (United States)

    Yang, Jia-Yue; Cheng, Long; Hu, Ming


    Intermetallic clathrates, one class of guest-host systems with perfectly crystalline structures, hold great potential to be the "phonon glass - electron crystal" thermoelectric materials. Previous studies focus on revealing the atomistic origins of blocked phononic transport, yet little attention is drawn to the enhanced electronic transport. In this work, we investigate the binary type-I M8Si46 (M = Sr, Ba, Tl, and Pb) clathrates and unravel how rattlers concurrently block phononic transport and enhance electronic transport from first-principles. By comparing the empty and filled clathrates, the lattice thermal conductivity is greatly reduced by a factor of 21 due to the decrease in phonon relaxation time for propagative phonons over 0-6 THz by 1.5 orders of magnitude. On the other hand, rattlers bridge charge gaps among cages by donating electrons and thus drastically increase electrical conductivity. The concurrent realization of blocked phononic transport and enhanced electronic transport boosts the figure-of-merit (ZT) of empty clathrate by 4 orders of magnitude. Furthermore, by manipulating metallic rattlers and n-type doping, the power factor is markedly improved and ZT can reach 0.55 at 800 K. These results provide a quantitative description of the guest-host interaction and coupling dynamics from first-principles. The proposed strategy of manipulating ratting atoms and in-situ doping offers important guidance to engineer clathrates with high thermoelectric performance.

  11. Inhibited phase behavior of gas hydrates in graphene oxide: influences of surface and geometric constraints. (United States)

    Kim, Daeok; Kim, Dae Woo; Lim, Hyung-Kyu; Jeon, Jiwon; Kim, Hyungjun; Jung, Hee-Tae; Lee, Huen


    Porous materials have provided us unprecedented opportunities to develop emerging technologies such as molecular storage systems and separation mechanisms. Pores have also been used as supports to contain gas hydrates for the application in gas treatments. Necessarily, an exact understanding of the properties of gas hydrates in confining pores is important. Here, we investigated the formation of CO2, CH4 and N2 hydrates in non-interlamellar voids in graphene oxide (GO), and their thermodynamic behaviors. For that, low temperature XRD and P-T traces were conducted to analyze the water structure and confirm hydrate formation, respectively, in GO after its exposure to gaseous molecules. Confinement and strong interaction of water with the hydrophilic surface of graphene oxide reduce water activity, which leads to the inhibited phase behavior of gas hydrates.

  12. Gas hydrates in gas storage caverns; Gashydrate bei der Gaskavernenspeicherung

    Energy Technology Data Exchange (ETDEWEB)

    Groenefeld, P. [Kavernen Bau- und Betriebs-GmbH, Hannover (Germany)


    Given appropriate pressure and temperature conditions the storage of natural gas in salt caverns can lead to the formation of gas hydrates in the producing well or aboveground operating facilities. This is attributable to the stored gas becoming more or less saturated with water vapour. The present contribution describes the humidity, pressure, and temperature conditions conducive to gas hydrate formation. It also deals with the reduction of the gas removal capacity resulting from gas hydrate formation, and possible measures for preventing hydrate formation such as injection of glycol, the reduction of water vapour absorption from the cavern sump, and dewatering of the cavern sump. (MSK) [Deutsch] Bei der Speicherung von Erdgas in Salzkavernen kann es unter entsprechenden Druck- und Temperaturverhaeltnissen zur Gashydratbildung in den Foerdersonden oder obertaegigen Betriebseinrichtungen kommen, weil sich das eingelagerte Gas mehr oder weniger mit Wasserdampf aufsaettigt. Im Folgenden werden die Feuchtigkeits-, Druck- und Temperaturbedingungen, die zur Hydratbildung fuehren erlaeutert. Ebenso werden die Verringerung der Auslagerungskapazitaet durch die Hydratbildung, Massnahmen zur Verhinderung der Hydratbildung wie die Injektion von Glykol, die Verringerung der Wasserdampfaufnahme aus dem Kavernensumpf und die Entwaesserung der Kavernensumpfs selbst beschrieben.

  13. Historical methane hydrate project review (United States)

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


    In 1995, U.S. Geological Survey made the first systematic assessment of the volume of natural gas stored in the hydrate accumulations of the United States. That study, along with numerous other studies, has shown that the amount of gas stored as methane hydrates in the world greatly exceeds the volume of known conventional gas resources. However, gas 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 gas hydrates in nature, (2) assessing the volume of natural gas stored within various gas 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 gas hydrates, and (5) analyzing the effects of methane hydrate on drilling safety.Methane hydrates are naturally occurring crystalline substances composed of water and gas, in which a solid water-­‐lattice holds gas molecules in a cage-­‐like structure. The gas and water becomes a solid under specific temperature and pressure conditions within the Earth, called the hydrate stability zone. Other factors that control the presence of methane hydrate in nature include the source of the gas included within the hydrates, the physical and chemical controls on the migration of gas with a sedimentary basin containing methane hydrates, the availability of the water also included in the hydrate structure, and the presence of a suitable host sediment or “reservoir”. The geologic controls on the occurrence of gas hydrates have become collectively known as the “methane hydrate petroleum system”, which has become the focus of numerous hydrate research programs.Recognizing the importance of methane hydrate research and the need for a coordinated

  14. Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions (United States)

    Bindeman, Ilya N.; Lowenstern, Jacob B.


    Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant "onion-skin" fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2-3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched "hydration fronts" where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between 110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at 400 °C) experimental data. The thick hydration rinds in perlites, measuring hundreds of microns, preserve the original D/H values of hydrating water as a recorder of paleoclimate conditions. Measured δD values in perlitic lavas are -150 to -191 or 20-40 ‰ lower than glass hydrated by modern Yellowstone waters. This suggests that Yellowstone perlites record the low-δD signature of glacial ice. Cooling calculations, combined with the observed high water diffusion coefficients noted for 60-150 °C, suggest that if sufficient hot

  15. Solvent Clathrate Driven Dynamic Stereomutation of a Supramolecular Polymer with Molecular Pockets. (United States)

    Kulkarni, Chidambar; Korevaar, Peter A; Bejagam, Karteek K; Palmans, Anja R A; Meijer, E W; George, Subi J


    Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3,5-dialkoxy substitution on the imide phenyl groups (CBI-35CH), leading to "molecular pockets" in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of CBI-35CH at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of self-assembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly.

  16. Thermoelectric properties of Cu/Ag doped type-III Ba24Ge100 clathrates (United States)

    Fu, Jiefei; Su, Xianli; Yan, Yonggao; Liu, Wei; Zhang, Zhengkai; She, Xiaoyu; Uher, Ctirad; Tang, Xinfeng


    Type-III Ba24Ge100 clathrates possess low thermal conductivity and high electrical conductivity at room temperature and, as such, have a great potential as thermoelectric materials for power generation. However, the Seebeck coefficient is very low due to the intrinsically high carrier concentration. In this paper, a series of Ba24CuxGe100-x and Ba24AgyGe100-y specimens were prepared by vacuum melting combined with the subsequent spark plasma sintering (SPS) process. Doping Cu or Ag on the Ge site not only suppresses the concentration of electrons but it also decreases the thermal conductivity. In addition, the carrier mobility and the Seebeck coefficient increase due to the decrease in the carrier concentration. Thus, the power factor is greatly improved, leading to an improvement in the dimensionless figure of merit ZT. Cu-doped Ba24Cu6Ge94 reaches the maximum ZT value of about 0.17 at 873 K, while Ag-doped Ba24Ag6Ge94 attains the dimensionless figure of merit ZT of 0.31 at 873 K, more than 2 times higher value compared to un-doped Ba24Ge100.

  17. TOUGH+HYDRATE v1.2 User's Manual: A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media

    Energy Technology Data Exchange (ETDEWEB)

    Moridis, George J. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kowalsky, Michael B. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pruess, Karsten [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)


    TOUGH+HYDRATE v1.2 is a code for the simulation of the behavior of hydratebearing geologic systems, and represents the second update of the code since its first release [Moridis et al., 2008]. By solving the coupled equations of mass and heat balance, TOUGH+HYDRATE can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH4-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy’s law is valid. TOUGH+HYDRATE v1.2 includes both an equilibrium and a kinetic model of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH4, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects. TOUGH+HYDRATE is a member of TOUGH+, the successor to the TOUGH2 [Pruess et al., 1991] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. It is written in standard FORTRAN 95/2003, and can be run on any computational platform (workstation, PC, Macintosh) for which such compilers are available.

  18. Proton affinities of hydrated molecules (United States)

    Valadbeigi, Younes


    Proton affinities (PA) of non-hydrated, M, and hydrated forms, M(H2O)1,2,3, of 20 organic molecules including alcohols, ethers, aldehydes, ketones and amines were calculated by the B3LYP/6-311++G(d,p) method. For homogeneous families, linear correlations were observed between PAs of the M(H2O)1,2,3 and the PAs of the non-hydrated molecules. Also, the absolute values of the hydration enthalpies of the protonated molecules decreased linearly with the PAs. The correlation functions predicted that for an amine with PA amine with PA > 1100 kJ/mol the PA(M(H2O)) is smaller than the PA.

  19. Elevated gas hydrate saturation within silt and silty clay sediments in the Shenhu area, South China Sea (United States)

    Wang, Xiujuan; Hutchinson, Deborah R.; Wu, Shiguo; Yang, Shengxiong; Guo, Yiqun


    Gas hydrate saturations were estimated using five different methods in silt and silty clay foraminiferous sediments from drill hole SH2 in the South China Sea. Gas hydrate saturations derived from observed pore water chloride values in core samples range from 10 to 45% of the pore space at 190–221 m below seafloor (mbsf). Gas hydrate saturations estimated from resistivity (Rt) using wireline logging results are similar and range from 10 to 40.5% in the pore space. Gas hydrate saturations were also estimated by P wave velocity obtained during wireline logging by using a simplified three-phase equation (STPE) and effective medium theory (EMT) models. Gas hydrate saturations obtained from the STPE velocity model (41.0% maximum) are slightly higher than those calculated with the EMT velocity model (38.5% maximum). Methane analysis from a 69 cm long depressurized core from the hydrate-bearing sediment zone indicates that gas hydrate saturation is about 27.08% of the pore space at 197.5 mbsf. Results from the five methods show similar values and nearly identical trends in gas hydrate saturations above the base of the gas hydrate stability zone at depths of 190 to 221 mbsf. Gas hydrate occurs within units of clayey slit and silt containing abundant calcareous nannofossils and foraminifer, which increase the porosities of the fine-grained sediments and provide space for enhanced gas hydrate formation. In addition, gas chimneys, faults, and fractures identified from three-dimensional (3-D) and high-resolution two-dimensional (2-D) seismic data provide pathways for fluids migrating into the gas hydrate stability zone which transport methane for the formation of gas hydrate. Sedimentation and local canyon migration may contribute to higher gas hydrate saturations near the base of the stability zone.

  20. Hydration in soccer: a review


    Monteiro Cristiano Ralo; Guerra Isabela; Barros Turíbio Leite de


    Hydration should be considered before, during and after the exercise. This review intends to approach the main points of hydration process in soccer. The replacement of fluids during exercise is proportional to some factors, such as: exercise intensity; climatic conditions; the athlete's acclimatization; the athlete's physical conditioning; physiologic individual characteristics and the player's biomechanics. Performance is improved when players ingest not only water but also carbohydrate. Th...

  1. Distribution and Characters of Gas Hydrate Offshore of Southwestern Taiwan

    Directory of Open Access Journals (Sweden)

    Char-Shine Liu


    Full Text Available Bottom simulating reflector (BSR is a key indicator for the presence of gas hydrate beneath the sea floor. Widely distributed BSRs have been observed in the area offshore of southwestern Taiwan where the active accretionary complex meets with the passive China continental margin. In order to better understand the distribution and characters of the gas hydrate in the region, closely spaced (1.86-km line spacing multichannel seismic reflection surveys have been conducted in recent years under the support of the Central Geological Survey, ROC. Over 10000 km of multichannel seismic reflection profiles have been collected that cover an area of about 10000 km2 offshore of southwestern Taiwan. BSRs can be identified along 50% of the seismic profiles that we collected. A newly compiled BSR distribution map suggests that gas hydrates are distributed both in the passive margin of the China continental slope as well as in the submarine Taiwan accretionary wedge, from water depths of 500 to over 3000 m. Gas hydrates are most concentrated underneath anticlinal ridges in the accretionary wedge, and underneath the slope ridges of the passive continental margin that were formed due to sedimentary processes. Active fluid activities are evident from various features observed on seismic reflection and chirp sonar profiles, such as mud volcanoes, gas plumes and gas charged shallow sedimentary layers. Fluid migration model has been established from a set of pseudo 3D seismic reflection data. The predicted locations of high fluid flux correlate well with those interpreted from geochemical analyses that show very high methane concentrations and very shallow sulfate-methane interfaces (SMI. This demonstrates the importance of structural control over gas hydrate emplacement. From the observed gas hydrate distribution and characters, the area offshore of southwestern Taiwan provides an ideal place to study and compare the formation and migration of gas hydrates under

  2. Stages of Gas-Hydrate Evolution on the Northern Cascadia Margin

    Directory of Open Access Journals (Sweden)

    the IODP Expedition 311 Scientists


    Full Text Available Natural gas hydrate occurs beneath many continental slopes and in arctic permafrost areas. Recent studies have indicated that the largest deposits of gas hydrate might lie in nearly horizontal layers several hundred meters beneath the seafloor of continental slopes, especially in the large, accretionary sedimentary prisms of subduction zones. Expedition 311 of the Integrated Ocean Drilling Program (IODP investigated the formation of gas hydrate in the accretionary prism of the Cascadia subduction zone (Fig. 1. The primary objectives of Expedition 311 were to test and constraingeological models of gas hydrate formation by upward fluidand methane transport in accretionary prisms. We specifi -cally sought to (a determine the mechanisms that controlthe nature, magnitude, and distribution of the gas hydrate,(b find the pathways of the fluid migration required to formlarge concentrations of gas hydrate, (c examine the effectsof gas hydrate on the physical properties of the host sediment,and (d investigate the microbiology and geochemistryassociated with the occurrence of gas hydrate. Furthermore,we concentrated on the contrast between methane transportby focused fl ow in fault zones and by dispersed pervasiveupward flow at various scales of permeability.

  3. Hydration characteristics and compressive strength of hardened cement pastes containing nano-metakaolin

    Directory of Open Access Journals (Sweden)

    S.M.A. El-Gamal


    Full Text Available In this study the effect of inclusion of nano-metakaolin (NMK to ordinary Portland cement (OPC on the hydration characteristics and microstructure of hardened OPC–NMK pastes was studied. The OPC–NMK blends were prepared by the partial substitution of OPC by NMK (4, 6, 10 and 15 weight %. The fresh pastes were made using an initial water/solid (W/S ratio of 0.27 by weight and then hydrated for various time intervals. At the end of each hydration time, the hardened blended cement pastes were tested for compressive strength, free lime content, combined water content, X-ray diffraction (XRD analysis, differential scanning calorimetry (DSC and scanning electron microscopy (SEM. The compressive strength results revealed that the inclusion of nano-metakaolin into OPC improved the mechanical properties of NMK–OPC pastes during almost all ages of hydration, especially with the paste containing 10 wt% NMK. The compressive strength values obtained for OPC paste blended with 4% silica fume (SF and 6% NMK are comparable to those of the neat OPC paste. The DSC thermograms and XRD diffractograms obtained for some selected hardened pastes indicated the formation of amorphous calcium silicate hydrates, calcium sulfoaluminate hydrates, calcium aluminate hydrate and calcium hydroxide. SEM micrographs showed the formation of a dense microstructure for the hardened OPC–NMK and OPC–NMK-SF pastes as compared to the neat OPC paste after 90 days of hydration.

  4. Time of Formation and Chemical Alteration of Small Icy Objects in the Outer Solar System (United States)

    Castillo-Rogez, Julie; Haw, M.; Vance, S.; Matson, D.; Johnson, T.


    We consider scenarios for the early chronology of outer solar system icy objects (e.g. satellites, dwarf planets) depending on the time at which these objects formed with respect to the production of calcium-aluminum inclusions. Recent models and observations indicate that the outer Solar system could have formed within a few My after the beginning of the Solar system. In such conditions meteorite parent bodies and icy objects (from planetesimals to large icy objects) could have had a similar early history. We investigate conditions that may drive hydrothermal activity in icy planetesimals, and the consequences of such activity for the early history of bigger objects. Early melting can be accompanied by hydrothermal circulation, resulting in aqueous alteration of the silicate interior and redistribution of major elements between the rock and volatile phases, as well as the destabilization of clathrates. These processes could have consequences on the long-term evolution of the larger bodies. For example, salts affect the melting temperature of icy shells and hydrated silicates affect heat transfer through a rocky core. We identify several classes of planetesimals based on size, time of formation, initial rock mass fraction and volatile composition. The smallest ones are not affected by short-lived radioisotope decay. The medium-sized planetesimals (in the 5-20 km range) are affected by partial melting while planetesimals several tens of km in radius could be fully differentiated before they accreted into larger objects. We explore the consequences of the potential diversity of early outer solar system planetesimal composition on the evolution of icy satellites and dwarf planets. Acknowledgements: This work has been conducted at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration. Copyright 2008 California Institute of Technology. Government sponsorship acknowledged.

  5. Numerical modelling of hydration reactions (United States)

    Vrijmoed, Johannes C.; John, Timm


    Mineral reactions are generally accompanied by volume changes. Observations in rocks and thin section indicate that this often occurred by replacement reactions involving a fluid phase. Frequently, the volume of the original rock or mineral seems to be conserved. If the density of the solid reaction products is higher than the reactants, the associated solid volume decrease generates space for a fluid phase. In other words, porosity is created. The opposite is true for an increase in solid volume during reaction, which leads to a porosity reduction. This slows down and may even stop the reaction if it needs fluid as a reactant. Understanding the progress of reactions and their rates is important because reaction generally changes geophysical and rock mechanical properties which will therefore affect geodynamical processes and seismic properties. We studied the case of hydration of eclogite to blueschist in a subduction zone setting. Eclogitized pillow basalt structures from the Tian-Shan orogeny are transformed to blueschist on the rims of the pillow (van der Straaten et al., 2008). Fluid pathways existed between the pillow structures. The preferred hypothesis of blueschist formation is to supply the fluid for hydration from the pillow margins progressing inward. Using numerical modelling we simulate this coupled reaction-diffusion process. Porosity and fluid pressure evolution are coupled to local thermodynamic equilibrium and density changes. The first rim of blueschist that forms around the eclogite pillow increases volume to such a degree that the system is clogged and the reaction stops. Nevertheless, the field evidence suggests the blueschist formation continued. To prevent the system from clogging, a high incoming pore fluid pressure on the pillow boundaries is needed along with removal of mass from the system to accommodate the volume changes. The only other possibility is to form blueschist from any remaining fluid stored in the core of the pillow

  6. Natural gas hydrates and the mystery of the Bermuda Triangle

    Energy Technology Data Exchange (ETDEWEB)

    Gruy, H.J.


    Natural gas hydrates occur on the ocean floor in such great volumes that they contain twice as much carbon as all known coal, oil and conventional natural gas deposits. Releases of this gas caused by sediment slides and other natural causes have resulted in huge slugs of gas saturated water with density too low to float a ship, and enough localized atmospheric contamination to choke air aspirated aircraft engines. The unexplained disappearances of ships and aircraft along with their crews and passengers in the Bermuda Triangle may be tied to the natural venting of gas hydrates. The paper describes what gas hydrates are, their formation and release, and their possible link to the mystery of the Bermuda Triangle.

  7. Behavior of gas seep bubbles below the hydrate stability zone (United States)

    Wang, B.; Jun, I.; Hutschenreuter, K.; Socolofsky, S. A.; Kessler, J. D.; Lavery, A.; Breier, J. A., Jr.; Seewald, J.


    Two research cruises (GISR G07 and G08) have been carried out during 2014-2015 to study the behavior of natural gas seep plumes escaping on the seafloor below the hydrate stability zone at MC 118 and GC 600 in the Gulf of Mexico. Quantitative image measurements suggest both temporal and spatial variation of the bubble size and gas flow rate. Hydrate formation on the natural gas seep bubbles was a very fast process in the deep sea environment (890 and 1200 m depth), where the measured methane concentration in water close to the source was also saturated. The measured rise velocities of the bubbles differed significantly from the predicted terminal velocities using empirical equations in Clift et al. (1978). The measured bubble characteristics (size distribution and flow rate) were provided as input to a bubble dissolution model, which accounts for the effect of hydrate on the mass transfer coefficient. The model shows results consistent with the measurements.

  8. Characterization of CO2 and mixed methane/CO2 hydrates intercalated in smectites by means of atomistic calculations. (United States)

    Martos-Villa, Rubén; Mata, M Pilar; Sainz-Díaz, C Ignacio


    The recent increase in anthropogenic CO2 gas released to the atmosphere and its contribution to global warming make necessary to investigate new ways of CO2 storage. Injecting CO2 into subsurface CH4 hydrate reservoirs would displace some of the CH4 in the hydrate crystal lattice, converting simple CH4 hydrates into either simple CO2 hydrates or mixed CH4CO2 hydrates. Molecular simulations were performed to determine the structure and behavior of CO2 and mixed hydrate complexes in the interlayer of Na-rich montmorillonite and beidellite smectite. Molecular Dynamics (MD) simulations used NPT ensembles in a 4×4×1 supercell comprised of montmorillonite or beidellite with CO2 or mixed CH4/CO2 hydrate complexes in the interlayer. The smectite 2:1 layer surface helps provide a stabilizing influence on the formation of gas hydrate complexes. The type of smectite affects the stability of the smectite-hydrate complexes, where high charge located on the tetrahedral layer of the smectites disfavor the formation of hydrate complexes. Copyright © 2014 Elsevier Inc. All rights reserved.

  9. Microcanonical molecular simulations of methane hydrate nucleation and growth: evidence that direct nucleation to sI hydrate is among the multiple nucleation pathways. (United States)

    Zhang, Zhengcai; Walsh, Matthew R; Guo, Guang-Jun


    The results of six high-precision constant energy molecular dynamics (MD) simulations initiated from methane-water systems equilibrated at 80 MPa and 250 K indicate that methane hydrates can nucleate via multiple pathways. Five trajectories nucleate to an amorphous solid. One trajectory nucleates to a structure-I hydrate template with long-range order which spans the simulation box across periodic boundaries despite the presence of several defects. While experimental and simulation data for hydrate nucleation with different time- and length-scales suggest that there may exist multiple pathways for nucleation, including metastable intermediates and the direct formation of the globally-stable phase, this work provides the most compelling evidence that direct formation to the globally stable crystalline phase is one of the multiple pathways available for hydrate nucleation.

  10. Non-equilibrium Simulation of CO­2-hydrate Phase Transitions from Mixtures of CO2 and N2 Gases (United States)

    Qorbani Nashaqi, K.


    Storage of CO2 in aquifers is one of several options for reducing the emissions of CO2 to the atmosphere. Generally this option requires sealing integrity through layers of clay or shale. Many reservoirs have regions of temperature and pressure inside hydrate formation conditions. Whether hydrate formation can provide long term extra sealing still remains unverified in view of all co-existing phases that affect hydrate stability. Yet another storage option for CO2 is in the form of hydrate through exchange of in situ CH4 hydrate. Injection of CO2 into hydrate filled sediments is challenging due to the partial filling of pores with hydrate which results in low porosity and low permeability. Formation of new hydrate from injected CO2 will enhance these problems, Mixing N2 gas with the CO2 will increase permeability and will reduce driving forces for formation of new hydrate from pore water and injection gas. Hydrate can generally not reach thermodynamic equilibrium due to Gibbs' phase rule and the combined first and second laws of thermodynamics. These thermodynamic constraints on distribution of masses over co-existing phases are dynamically coupled to local mass- and heat-transport. Reservoir simulations are one possible method for investigation of possible scenarios related to injection of CO2 with N2 into aquifers containing CH4 hydrate. In this work we have developed prevoiusly modified RetrasoCodeBrite (RCB) simulator to handle injection of CO2/N2 gas mixtures. Hydrate formation and dissociation were determined by investigating Gibbs free energy differences between hydrate and hydrate formers. Gibbs free energy differences were calculated from changes in chemical potentials, which were obtained using non-equilibrium thermodynamic approach. Further extension of RCB has been implemented in this work through adding on-the-fly thermodynamic calculations. Correspondingly, hydrate phase transitions are calculated directly inside the code as a result of super

  11. Integrating Natural Gas Hydrates in the Global Carbon Cycle

    Energy Technology Data Exchange (ETDEWEB)

    David Archer; Bruce Buffett


    We produced a two-dimensional geological time- and basin-scale model of the sedimentary margin in passive and active settings, for the simulation of the deep sedimentary methane cycle including hydrate formation. Simulation of geochemical data required development of parameterizations for bubble transport in the sediment column, and for the impact of the heterogeneity in the sediment pore fluid flow field, which represent new directions in modeling methane hydrates. The model is somewhat less sensitive to changes in ocean temperature than our previous 1-D model, due to the different methane transport mechanisms in the two codes (pore fluid flow vs. bubble migration). The model is very sensitive to reasonable changes in organic carbon deposition through geologic time, and to details of how the bubbles migrate, in particular how efficiently they are trapped as they rise through undersaturated or oxidizing chemical conditions and the hydrate stability zone. The active margin configuration reproduces the elevated hydrate saturations observed in accretionary wedges such as the Cascadia Margin, but predicts a decrease in the methane inventory per meter of coastline relative to a comparable passive margin case, and a decrease in the hydrate inventory with an increase in the plate subduction rate.

  12. 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


    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.

  13. Natural gas hydrates from different marine environments. Physical and geochemical characterization. (United States)

    Charlou, J.; Donval, J.; Ruffine, L.; Bourry, C.; Jean-Baptiste, P.; Chazallon, B.


    During the last past decade, IFREMER has participated to numerous surface/diving oceanographic cruises to investigate fluid circulation, cold seep discharges and gas hydrate formation on continental margins. The development of sampling tools, instrumentations and laboratory apparatuses related to gas hydrate study is shown. The instrumentation path has then been widen to investigate on a variety of natural gas hydrate properties as well as the associated pore waters and gas bubbles. The field deployable instrumentations include PEGAZ for sampling of gas bubbles, chemical tracers measurement like methane concentration for determining anomalies in the seawater column above mud volcanoes and pockmarks. Besides, laboratory development was mainly focused on Raman Spectroscopy, high resolution powder X-ray synchrotron diffraction, gas chromatographic techniques, Inductive coupled plasma mass-spectometry. Now we are enlarging our expertise by modeling. During those research activities, emphasis was given to the understanding of the geochemical processes related to the formation, stability and migration of marine gas hydrates. A lot of various gas hydrate specimens have been collected and studied at both sea and laboratory for their origin, formation and stability in different environments at different temperature/pressure conditions. High-resolution powder X-ray synchrotron diffraction and UV-Raman spectroscopy techniques are shown to be efficient and powerful tools to determine the hydrate structures (I, II, H). Gas and isotopic composition of gas hydrates is important for determining the gas origin (thermogenic, bacterial or mixing). The chemical signature of the hydrate waters help to understand the influence of pore waters on the hydrate composition. In areas where gas bubbles are present, stability field of natural gas hydrates may be obtained from bubble composition, providing information on the thickness of the hydrate layer in the sediment. This work will most

  14. High concentration hydrate in disseminated forms obtained in Shenhu area, north slope of South China Sea

    Energy Technology Data Exchange (ETDEWEB)

    Yang, S.; Wu, N.; Zhang, G.; Liang, J.; Lu, J. [Guangzhou Marine Geology Survey, Guangzhou (China); Zhang, H. [China Geological Survey, Beijing (China); Su, X. [China Univ. of Geosciences, Beijing (China); Schultheiss, P.; Holland, M. [Geotek, Daventry (United Kingdom); Rose, K. [National Energy Technology Laboratory, Morgantown, WV (United States)


    The geological and tectonic settings, the temperature and pressure regimes, and the methane-generating potential from the thick organic-rich sediments of the north slope of the South China Seas are all favorable properties for gas hydrate formation. The Guangzhou Marine Geological Survey (GMGS) has been performing geological, geophysical and geochemical investigations for gas hydrate in the northern South China Sea since 2001. In order to determine the nature and distribution of gas hydrates, a gas hydrate drilling expedition was initiated in the Shenhu area of the north slope of the South China Sea in April and June of 2007. The purpose of the expedition was to detect gas hydrates and quantify its nature, distribution and concentration. The study involved the use of different observation and measurement techniques to provide multiple lines of evidence for gas hydrate. Pressure cores provided benchmark spot measurements of actual methane concentration, gas hydrate concentration, and background chlorinity. In order to detect the presence of dissociating/dissociated gas hydrate throughout the hole, infrared imaging of non-pressurized cores were utilized. Porewater freshening analysis from chlorinity variations was employed to quantify the gas hydrate at the centimeter scale. Gas hydrate saturations from the pressure and non-pressurized cores within the cored intervals were then compared to the resistivity, acoustic, and other well logs for a complete hydrate picture of the borehole. The expedition also involved the collection of samples from both non-pressure and pressure cores that were likely to contain gas hydrate and preserved them in liquid nitrogen. The paper discussed the general operations and strategy; coring plan; preservation of gas hydrate samples in liquid nitrogen; core temperature measurement; porewater sampling, porewater analysis, and gas hydrate from porewater freshening. Other procedures that were discussed included gas sampling and analyses

  15. Clinker mineral hydration at reduced relative humidities

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede; Hansen, Per Freiesleben; Lachowski, Eric E.


    Vapour phase hydration of purl cement clinker minerals at reduced relative humidities is described. This is relevant to modern high performance concrete that may self-desiccate during hydration and is also relevant to the quality of the cement during storage. Both the oretical considerations...... and experimental data are presented showing that C(3)A can hydrate at lower humidities than either C3S or C2S. It is suggested that the initiation of hydration during exposure to water vapour is nucleation controlled. When C(3)A hydrates at low humidity, the characteristic hydration product is C(3)AH(6...

  16. Life Origination Hydrate Hypothesis (LOH-Hypothesis

    Directory of Open Access Journals (Sweden)

    Victor Ostrovskii


    Full Text Available The paper develops the Life Origination Hydrate Hypothesis (LOH-hypothesis, according to which living-matter simplest elements (LMSEs, which are N-bases, riboses, nucleosides, nucleotides, DNA- and RNA-like molecules, amino-acids, and proto-cells repeatedly originated on the basis of thermodynamically controlled, natural, and inevitable processes governed by universal physical and chemical laws from CH4, niters, and phosphates under the Earth's surface or seabed within the crystal cavities of the honeycomb methane-hydrate structure at low temperatures; the chemical processes passed slowly through all successive chemical steps in the direction that is determined by a gradual decrease in the Gibbs free energy of reacting systems. The hypothesis formulation method is based on the thermodynamic directedness of natural movement and consists ofan attempt to mentally backtrack on the progression of nature and thus reveal principal milestones alongits route. The changes in Gibbs free energy are estimated for different steps of the living-matter origination process; special attention is paid to the processes of proto-cell formation. Just the occurrence of the gas-hydrate periodic honeycomb matrix filled with LMSEs almost completely in its final state accounts for size limitation in the DNA functional groups and the nonrandom location of N-bases in the DNA chains. The slowness of the low-temperature chemical transformations and their “thermodynamic front” guide the gross process of living matter origination and its successive steps. It is shown that the hypothesis is thermodynamically justified and testable and that many observed natural phenomena count in its favor.

  17. Life Origination Hydrate Hypothesis (LOH-Hypothesis) (United States)

    Ostrovskii, Victor; Kadyshevich, Elena


    The paper develops the Life Origination Hydrate Hypothesis (LOH-hypothesis), according to which living-matter simplest elements (LMSEs, which are N-bases, riboses, nucleosides, nucleotides), DNA- and RNA-like molecules, amino-acids, and proto-cells repeatedly originated on the basis of thermodynamically controlled, natural, and inevitable processes governed by universal physical and chemical laws from CH4, niters, and phosphates under the Earth's surface or seabed within the crystal cavities of the honeycomb methane-hydrate structure at low temperatures; the chemical processes passed slowly through all successive chemical steps in the direction that is determined by a gradual decrease in the Gibbs free energy of reacting systems. The hypothesis formulation method is based on the thermodynamic directedness of natural movement and consists ofan attempt to mentally backtrack on the progression of nature and thus reveal principal milestones alongits route. The changes in Gibbs free energy are estimated for different steps of the living-matter origination process; special attention is paid to the processes of proto-cell formation. Just the occurrence of the gas-hydrate periodic honeycomb matrix filled with LMSEs almost completely in its final state accounts for size limitation in the DNA functional groups and the nonrandom location of N-bases in the DNA chains. The slowness of the low-temperature chemical transformations and their “thermodynamic front” guide the gross process of living matter origination and its successive steps. It is shown that the hypothesis is thermodynamically justified and testable and that many observed natural phenomena count in its favor. PMID:25382120

  18. Dry heat treatment affects wheat bran surface properties and hydration kinetics. (United States)

    Jacobs, Pieter J; Hemdane, Sami; Delcour, Jan A; Courtin, Christophe M


    Heat stabilization of wheat bran aims at inactivation of enzymes which may cause rancidity and processability issues. Such treatments may however cause additional unanticipated phenomena which may affect wheat bran technological properties. In this work, the impact of toasting on wheat bran hydration capacity and hydration kinetics was studied. Hydration properties were assessed using the Enslin-Neff and drainage centrifugation water retention capacity methods, thermogravimetric analysis and contact angle goniometry, next to more traditional methods. While equilibrium hydration properties of bran were not affected by the heat treatment, the rate at which the heat treated bran hydrated was, however, very significantly reduced compared to the untreated bran. This phenomenon was found to originate from the formation of a lipid coating during the treatment rendering the bran surface hydrophobic. These insights help to understand and partially account for the modified processability of heat treated bran in food applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Pressurized laboratory experiments show no stable carbon isotope fractionation of methane during gas hydrate dissolution and dissociation. (United States)

    Lapham, Laura L; Wilson, Rachel M; Chanton, Jeffrey P


    The stable carbon isotopic ratio of methane (δ(13)C-CH(4)) recovered from marine sediments containing gas hydrate is often used to infer the gas source and associated microbial processes. This is a powerful approach because of distinct isotopic fractionation patterns associated with methane production by biogenic and thermogenic pathways and microbial oxidation. However, isotope fractionations due to physical processes, such as hydrate dissolution, have not been fully evaluated. We have conducted experiments to determine if hydrate dissolution or dissociation (two distinct physical processes) results in isotopic fractionation. In a pressure chamber, hydrate was formed from a methane gas source at 2.5 MPa and 4 °C, well within the hydrate stability field. Following formation, the methane source was removed while maintaining the hydrate at the same pressure and temperature which stimulated hydrate dissolution. Over the duration of two dissolution experiments (each ~20-30 days), water and headspace samples were periodically collected and measured for methane concentrations and δ(13)C-CH(4) while the hydrate dissolved. For both experiments, the methane concentrations in the pressure chamber water and headspace increased over time, indicating that the hydrate was dissolving, but the δ(13)C-CH(4) values showed no significant trend and remained constant, within 0.5‰. This lack of isotope change over time indicates that there is no fractionation during hydrate dissolution. We also investigated previous findings that little isotopic fractionation occurs when the gas hydrate dissociates into gas bubbles and water due to the release of pressure. Over a 2.5 MPa pressure drop, the difference in the δ(13)C-CH(4) was hydrate dissociates and demonstrated that there is no fractionation when the hydrate dissolves. Therefore, measured δ(13)C-CH(4) values near gas hydrates are not affected by physical processes, and can thus be interpreted to result from either the gas source

  20. Molecular Dynamics Simulation of the Crystal Nucleation and Growth Behavior of Methane Hydrate in the Presence of the Surface and Nanopores of Porous Sediment. (United States)

    Yan, Ke-Feng; Li, Xiao-Sen; Chen, Zhao-Yang; Xia, Zhi-Ming; Xu, Chun-Gang; Zhang, Zhiqiang


    The behavior of hydrate formation in porous sediment has been widely studied because of its importance in the investigation of reservoirs and in the drilling of natural gas hydrate. However, it is difficult to understand the hydrate nucleation and growth mechanism on the surface and in the nanopores of porous media by experimental and numerical simulation methods. In this work, molecular dynamics simulations of the nucleation and growth of CH4 hydrate in the presence of the surface and nanopores of clay are carried out. The molecular configurations and microstructure properties are analyzed for systems containing one H2O hydrate layer (System A), three H2O hydrate layers (System B), and six H2O hydrate layers (System C) in both clay and the bulk solution. It is found that hydrate formation is more complex in porous media than in the pure bulk solution and that there is cooperativity between hydrate growth and molecular diffusion in clay nanopores. The hydroxylated edge sites of the clay surface could serve as a source of CH4 molecules to facilitate hydrate nucleation. The diffusion velocity of molecules is influenced by the growth of the hydrate that forms a block in the throats of the clay nanopore. Comparing hydrate growth in different clay pore sizes reveals that the pore size plays an important role in hydrate growth and molecular diffusion in clay. This simulation study provides the microscopic mechanism of hydrate nucleation and growth in porous media, which can be favorable for the investigation of the formation of natural gas hydrate in sediments.


    Energy Technology Data Exchange (ETDEWEB)

    R.E. Rogers


    DOE Contract DE-AC26-97FT33203 studied feasibility of utilizing the natural-gas storage property of gas hydrates, so abundantly demonstrated in nature, as an economical industrial process to allow expanded use of the clean-burning fuel in power plants. The laboratory work achieved breakthroughs: (1) Gas hydrates were found to form orders of magnitude faster in an unstirred system with surfactant-water micellar solutions. (2) Hydrate particles were found to self-pack by adsorption on cold metal surfaces from the micellar solutions. (3) Interstitial micellar-water of the packed particles were found to continue forming hydrates. (4) Aluminum surfaces were found to most actively collect the hydrate particles. These laboratory developments were the bases of a conceptual design for a large-scale process where simplification enhances economy. In the design, hydrates form, store, and decompose in the same tank in which gas is pressurized to 550 psi above unstirred micellar solution, chilled by a brine circulating through a bank of aluminum tubing in the tank employing gas-fired refrigeration. Hydrates form on aluminum plates suspended in the chilled micellar solution. A low-grade heat source, such as 110 F water of a power plant, circulates through the tubing bank to release stored gas. The design allows a formation/storage/decomposition cycle in a 24-hour period of 2,254,000 scf of natural gas; the capability of multiple cycles is an advantage of the process. The development costs and the user costs of storing natural gas in a scaled hydrate process were estimated to be competitive with conventional storage means if multiple cycles of hydrate storage were used. If more than 54 cycles/year were used, hydrate development costs per Mscf would be better than development costs of depleted reservoir storage; above 125 cycles/year, hydrate user costs would be lower than user costs of depleted reservoir storage.

  2. Gas hydrate saturation and distribution in the Kumano Forearc Basin of the Nankai Trough (United States)

    Jia, Jihui; Tsuji, Takeshi; Matsuoka, Toshifumi


    The Kumano Forearc Basin is located to the south-east of the Kii Peninsula, Japan, overlying the accretionary prism in the Nankai Trough. The presence of gas hydrate in submarine sediments of the forearc basin has resulted in the widespread occurrence of bottom simulating reflectors (BSRs) on seismic profiles, and has caused distinct anomalies in logging data in the region. We estimated the in situ gas hydrate saturation from logging data by using three methods: effective rock physics models, Archie's equation, and empirical relationships between acoustic impedance (AI) and water-filled porosity. The results derived from rock physics models demonstrate that gas hydrates are attached to the grain surfaces of the rock matrix and are not floating in pore space. By applying the empirical relationships to the AI distribution derived from model-based AI inversion of the three-dimensional (3D) seismic data, we mapped the spatial distribution of hydrate saturation within the Kumano Basin and characterised locally concentrated gas hydrates. Based on the results, we propose two different mechanisms of free gas supply to explain the process of gas hydrate formation in the basin: (1) migration along inclined strata that dip landwards, and (2) migration through the faults or cracks generated by intensive tectonic movements of the accretionary prism. The dipping strata with relatively low AI in the forearc basin could indicate the presence of hydrate formation due to gas migration along the dipping strata. However, high hydrate concentration is observed at fault zones with high pore pressures, thus the second mechanism likely plays an important role in the genesis of gas hydrates in the Kumano Basin. Therefore, the tectonic activities in the accretionary wedge significantly influence the hydrate saturation and distribution in the Kumano Forearc Basin.

  3. Mechanical instability of monocrystalline and polycrystalline methane hydrates

    NARCIS (Netherlands)

    Wu, J.; Ning, F.; Trinh, T.T.; Kjelstrup, S.; Vlugt, T.J.H.; He, J.; Skallerud, B.H.; Zhang, Z.


    Despite observations of massive methane release and geohazards associated with gas hydrate instability in nature, as well as ductile flow accompanying hydrate dissociation in artificial polycrystalline methane hydrates in the laboratory, the destabilising mechanisms of gas hydrates under deformation

  4. Hydrated interfacial ions and electrons. (United States)

    Abel, Bernd


    Charged particles such as hydrated ions and transient hydrated electrons, the simplest anionic reducing agents in water, and the special hydronium and hydroxide ions at water interfaces play an important role in many fields of science, such as atmospheric chemistry, radiation chemistry, and biology, as well as biochemistry. This article focuses on these species near hydrophobic interfaces of water, such as the air or vacuum interface of water or water protein/membrane interfaces. Ions at interfaces as well as solvated electrons have been reviewed frequently during the past decade. Although all species have been known for some time with seemingly familiar features, recently the picture in all cases became increasingly diffuse rather than clearer. The current account gives a critical state-of-the art overview of what is known and what remains to be understood and investigated about hydrated interfacial ions and electrons.

  5. Protocol for Measuring the Thermal Properties of a Supercooled Synthetic Sand-water-gas-methane Hydrate Sample. (United States)

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


    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.

  6. Oil and gas pipelines with hydrophobic surfaces better equipped to deal with gas hydrate flow assurance issues

    DEFF Research Database (Denmark)

    Perfeldt, Christine Malmos; Sharifi, Hassan; von Solms, Nicolas


    Gas hydrate deposition can cause plugging in oil and gas pipelines with resultant flow assurance challenges. Presently, the energy industry uses chemical additives in order to manage hydrate formation, however these chemicals are expensive and may be associated with safety and environmental...

  7. [NMF and cosmetology of cutaneous hydration]. (United States)

    Marty, J-P


    In the stratum corneum, the water binds to the intracellular hygroscopic and hydrosoluble substances called "natural moisturizing factors" or NMF. These "natural moisturizing factors" contained in the corneocytes are formed during epidermal differentiation and may represent up to 10 p. cent of the corneocyte mass. They are principally amino acids, carboxylic pyrrolidone acid, lactic acid, urea, glucose and mineral ions. Keratinization plays an important part in the formation of NMF that exhibit strong osmotic potential attracting the water molecules. The binding of water to NMF is the static aspect of cutaneous hydration. The second, dynamic, aspect is related to the selective permeability of the stratum corneum and to its lipid barrier properties, the permeability of which depends on the integrity and nature of the inter-corneocyte lipids and their lamellar organization between the cells. In these conditions, hydration cosmetics rely on two concepts that can be isolated or associated: the supply of hydrophilic substances to the stratum corneum, capable of attracting and retaining water (moisturizer) or capable of restoring the barrier in order to restore normal water loss or of protecting it against aggression (occlusive).

  8. Monoclinic 122-Type BaIr2Ge2 with a Channel Framework: A Structural Connection between Clathrate and Layered Compounds

    Directory of Open Access Journals (Sweden)

    Xin Gui


    Full Text Available A new 122-type phase, monoclinic BaIr2Ge2 is successfully synthesized by arc melting; X-ray diffraction and scanning electron microscopy are used to purify the phase and determine its crystal structure. BaIr2Ge2 adopts a clathrate-like channel framework structure of the monoclinic BaRh2Si2-type, with space group P21/c. Structural comparisons of clathrate, ThCr2Si2, CaBe2Ge2, and BaRh2Si2 structure types indicate that BaIr2Ge2 can be considered as an intermediate between clathrate and layered compounds. Magnetic measurements show it to be diamagnetic and non-superconducting down to 1.8 K. Different from many layered or clathrate compounds, monoclinic BaIr2Ge2 displays a metallic resistivity. Electronic structure calculations performed for BaIr2Ge2 support its observed structural stability and physical properties.

  9. Microbial community structure in methane hydrate-bearing sediments of freshwater Lake Baikal. (United States)

    Kadnikov, Vitaly V; Mardanov, Andrey V; Beletsky, Alexey V; Shubenkova, Olga V; Pogodaeva, Tatiana V; Zemskaya, Tamara I; Ravin, Nikolai V; Skryabin, Konstantin G


    Gas hydrates in marine sediments have been known for many years but recently hydrates were found in the sediments of Lake Baikal, the largest freshwater basin in the world. Marine gas hydrates are associated with complex microbial communities involved in methanogenesis, methane oxidation, sulfate reduction and other biotransformations. However, the contribution of microorganisms to the formation of gas hydrates remains poorly understood. We examined the microbial communities in the hydrate-bearing sediments and water column of Lake Baikal using pyrosequencing of 16S rRNA genes. Aerobic methanotrophic bacteria dominated the water sample collected at the lake floor in the hydrate-bearing site. The shallow sediments were dominated by Archaea. Methanogens of the orders Methanomicrobiales and Methanosarcinales were abundant, whereas representatives of archaeal lineages known to perform anaerobic oxidation of methane, as well as sulfate-reducing bacteria, were not found. Affiliation of archaea to methanogenic rather than methane-oxidizing lineages was supported by analysis of the sequences of the methyl coenzyme M reductase gene. The deeper sediments located at 85-90 cm depth close to the hydrate were dominated by Bacteria, mostly assigned to Chloroflexi, candidate division JS1 and Caldiserica. Overall, our results are consistent with the biological origin of methane hydrates in Lake Baikal. © 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

  10. Permafrost-associated gas hydrate: is it really approximately 1% of the global system? (United States)

    Ruppel, Carolyn


    Permafrost-associated gas hydrates are often assumed to contain ∼1 % of the global gas-in-place in gas hydrates based on a study26 published over three decades ago. As knowledge of permafrost-associated gas hydrates has grown, it has become clear that many permafrost-associated gas hydrates are inextricably linked to an associated conventional petroleum system, and that their formation history (trapping of migrated gas in situ during Pleistocene cooling) is consistent with having been sourced at least partially in nearby thermogenic gas deposits. Using modern data sets that constrain the distribution of continuous permafrost onshore5 and subsea permafrost on circum-Arctic Ocean continental shelves offshore and that estimate undiscovered conventional gas within arctic assessment units,16 the done here reveals where permafrost-associated gas hydrates are most likely to occur, concluding that Arctic Alaska and the West Siberian Basin are the best prospects. A conservative estimate is that 20 Gt C (2.7·1013 kg CH4) may be sequestered in permafrost-associated gas hydrates if methane were the only hydrate-former. This value is slightly more than 1 % of modern estimates (corresponding to 1600 Gt C to 1800 Gt C2,22) for global gas-in-place in methane hydrates and about double the absolute estimate (11.2 Gt C) made in 1981.26

  11. Dissociation of methane hydrate granules (United States)

    Misyura, S. Y.; Donskoy, I. G.; Morozov, V. S.


    The methane hydrate dissociation at negative temperatures and under external pressure of 1 bar is studied experimentally. It is shown that the dissociation rate of the gas hydrate depends on the granule diameter and heat transfer. The dissociation curve has an extremum. The dissociation rate initially increases due to the temperature increase and reaches the maximum value and then sharply falls due to the curvature of the granules. When describing dissociation kinetics of the spherical granules, it is important to take into account the granule size and their composition.

  12. Numerical research of the gas hydrate dissociation to gas and Ice in a reservoir during the gas extraction

    Directory of Open Access Journals (Sweden)

    Musakaev Nail


    Full Text Available The peculiarities of the gas hydrate decomposition to gas and ice during the gas extraction from the porous medium initially saturated with methane and its hydrate are studied. It is shown that at a negative initial reservoir temperature, the gas hydrate decomposition always occurs with the formation of ice either on the frontal surface or in the extended region. It is established that the extended region of hydrate dissociation is characteristic for large values of the mass flow rate of the gas extraction.

  13. Methods to determine hydration states of minerals and cement hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Baquerizo, Luis G., E-mail: [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Matschei, Thomas [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Scrivener, Karen L. [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)


    This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na{sub 2}SO{sub 4}–H{sub 2}O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions.

  14. 3-D basin-scale reconstruction of natural gas hydrate system of the Green Canyon, Gulf of Mexico (United States)

    Burwicz, Ewa; Reichel, Thomas; Wallmann, Klaus; Rottke, Wolf; Haeckel, Matthias; Hensen, Christian


    Our study presents a basin-scale 3-D modeling solution, quantifying and exploring gas hydrate accumulations in the marine environment around the Green Canyon (GC955) area, Gulf of Mexico. It is the first modeling study that considers the full complexity of gas hydrate formation in a natural geological system. Overall, it comprises a comprehensive basin reconstruction, accounting for depositional and transient thermal history of the basin, source rock maturation, petroleum components generation, expulsion and migration, salt tectonics, and associated multistage fault development. The resulting 3-D gas hydrate distribution in the Green Canyon area is consistent with independent borehole observations. An important mechanism identified in this study and leading to high gas hydrate saturation (>80 vol %) at the base of the gas hydrate stability zone (GHSZ) is the recycling of gas hydrate and free gas enhanced by high Neogene sedimentation rates in the region. Our model predicts the rapid development of secondary intrasalt minibasins situated on top of the allochthonous salt deposits which leads to significant sediment subsidence and an ensuing dislocation of the lower GHSZ boundary. Consequently, large amounts of gas hydrates located in the deepest parts of the basin dissociate and the released free methane gas migrates upward to recharge the GHSZ. In total, we have predicted the gas hydrate budget for the Green Canyon area that amounts to ˜3256 Mt of gas hydrate, which is equivalent to ˜340 Mt of carbon (˜7 × 1011 m3 of CH4 at STP conditions), and consists mostly of biogenic hydrates.

  15. Effect of Propane and NaCl-SDS Solution on Nucleation Process of Mine Gas Hydrate

    Directory of Open Access Journals (Sweden)

    Qiang Zhang


    Full Text Available In order to explore the method of accelerating hydration separation process to recover methane from mine gas, propane hydrate phase equilibrium was used to measure the equilibrium points of three kinds of mine gas in NaCl solution. Driving force was set as 1 MPa on this basis and high-pressure experimental apparatus of mine gas hydrate was used to carry out the nucleation kinetics experiments of mine gas hydrate for three gas samples in different concentrations of sodium chloride (NaCl and sodium dodecyl sulfate (SDS compound systems, which was to study the effect of propane and NaCl-SDS solution on nucleation process of mine gas hydrate. The results showed that induction time of multicomponent mine gas hydrate formation was shortened with the decrease of methane concentration and increase of propane concentration. The induction time of mine gas hydrate formation was shortened with the reduction of NaCl concentration and the increase of SDS concentration. It was found that methane and propane in multicomponent mine gas nucleated collaboratively, which simplified its nucleation process compared with the single component. NaCl has two kinds of functions.

  16. Simultaneous determination of thermal conductivity, thermal diffusivity and specific heat in sI methane hydrate (United States)

    Waite, W.F.; Stern, L.A.; Kirby, S.H.; Winters, W.J.; Mason, D.H.


    Thermal conductivity, thermal diffusivity and specific heat of sI methane hydrate were measured as functions of temperature and pressure using a needle probe technique. The temperature dependence was measured between −20°C and 17°C at 31.5 MPa. The pressure dependence was measured between 31.5 and 102 MPa at 14.4°C. Only weak temperature and pressure dependencies were observed. Methane hydrate thermal conductivity differs from that of water by less than 10 per cent, too little to provide a sensitive measure of hydrate content in water-saturated systems. Thermal diffusivity of methane hydrate is more than twice that of water, however, and its specific heat is about half that of water. Thus, when drilling into or through hydrate-rich sediment, heat from the borehole can raise the formation temperature more than 20 per cent faster than if the formation's pore space contains only water. Thermal properties of methane hydrate should be considered in safety and economic assessments of hydrate-bearing sediment.

  17. 77 FR 40032 - Methane Hydrate Advisory Committee (United States)


    ... Methane Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee.... SUPPLEMENTARY INFORMATION: Purpose of the Committee: The purpose of the Methane Hydrate Advisory Committee is to...

  18. 78 FR 37536 - Methane Hydrate Advisory Committee (United States)


    ... meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of methane... Department of Energy's Methane Hydrate Research and Development Program. Tentative Agenda: The agenda will...

  19. Hydrate pingoes at Nyegga - natural small-scale carbon capture laboratories? (United States)

    Hovland, M. T.; Rueslaatten, H.


    methane clathrates into CO2 hydrates by segregation. A ‘Chinese hat’ (steel cone) could for example be put over one of the most accessible pingoes, to collect fluids emitting from it. After a year or so of fluid type and flux monitoring, the next research step could for example be to inject a known volume of CO2 into the base of the pingo and monitor what happens to the flux and fluid type emitting from it. Such pioneering experiments will call for a high degree of international cooperation and probably also the involvement of industry partners, especially with respect to offshore multi-purpose vessel support. References Hovland, M., Svensen, H., 2006. Marine Geology 228, 15-23 Ivanov et al., 2007. EOS 88 (19), 209, 212 Westbrook et al., 2008. ICGH Conf. Proc., Vancouver, July 6-10

  20. Hydration modelling of calcium sulphates

    NARCIS (Netherlands)

    de Korte, A.C.J.; Eligehausen, R.; Gehlen, C.


    The CEMHYD3D model has been extended at the University of Twente in last ten years1,2. At present the cement hydration model is extended for the use of gypsum. Although gypsum was present in the model already, the model was not suitable for high contents of gypsum and did not include the transitions

  1. Hydrated-electron population dynamics

    NARCIS (Netherlands)

    Pshenichnikov, MS; Baltuska, A; Wiersma, DA; Pshenichnikov, Maxim S.; Baltuška, Andrius


    A detailed frequency-resolved pump-probe study of hydrated electron dynamics, performed with 5-fs pulses, is presented. We show that the experimental data can be successfully described with a model in which the excited state lifetime is similar to50 fs in regular water and similar to70 A in heavy

  2. In-Situ Sampling and Characterization of Naturally Occurring Marine Methane Hydrate Using the D/V JOIDES Resolution

    Energy Technology Data Exchange (ETDEWEB)

    Rack, Frank; Bohrmann, Gerhard; Trehu, Anne; Storms, Michael; Schroeder, Derryl


    The primary accomplishment of the JOI Cooperative Agreement with DOE/NETL in this quarter was the deployment of tools and measurement systems on ODP Leg 204 to study hydrate deposits on Hydrate Ridge, offshore Oregon from July through September, 2002. During Leg 204, we cored and logged 9 sites on the Oregon continental margin to determine the distribution and concentration of gas hydrates in an accretionary ridge and adjacent slope basin, investigate the mechanisms that transport methane and other gases into the gas hydrate stability zone (GHSZ), and obtain constraints on physical properties of hydrates in situ. A 3D seismic survey conducted in 2000 provided images of potential subsurface fluid conduits and indicated the position of the GHSZ throughout the survey region. After coring the first site, we acquired Logging-While-Drilling (LWD) data at all but one site to provide an overview of downhole physical properties. The LWD data confirmed the general position of key seismic stratigraphic horizons and yielded an initial estimate of hydrate concentration through the proxy of in situ electrical resistivity. These records proved to be of great value in planning subsequent coring. The second new hydrate proxy to be tested was infrared thermal imaging of cores on the catwalk as rapidly as possible after retrieval. The thermal images were used to identify hydrate samples and to map estimate the distribution and texture of hydrate within the cores. Geochemical analyses of interstitial waters and of headspace and void gases provide additional information on the distribution and concentration of hydrate within the stability zone, the origin and pathway of fluids into and through the GHSZ, and the rates at which the process of gas hydrate formation is occurring. Bio- and lithostratigraphic description of cores, measurement of physical properties, and in situ pressure core sampling and thermal measurements complement the data set, providing ground-truth tests of inferred

  3. Gas hydrate drilling transect across northern Cascadia margin - IODP Expedition 311 (United States)

    Riedel, M.; Collett, T.; Malone, M.J.; Collett, T.S.; Mitchell, M.; Guerin, G.; Akiba, F.; Blanc-Valleron, M.; Ellis, M.; Hashimoto, Y.; Heuer, V.; Higashi, Y.; Holland, M.; Jackson, P.D.; Kaneko, M.; Kastner, M.; Kim, J.-H.; Kitajima, H.; Long, P.E.; Malinverno, A.; Myers, Gwen E.; Palekar, L.D.; Pohlman, J.; Schultheiss, P.; Teichert, B.; Torres, M.E.; Trehu, A.M.; Wang, Jingyuan; Worthmann, U.G.; Yoshioka, H.


    A transect of four sites (U1325, U1326, U1327 and U1329) across the northern Cascadia margin was established during Integrated Ocean Drilling Program Expedition 311 to study the occurrence and formation of gas hydrate in accretionary complexes. In addition to the transect sites, a fifth site (U1328) was established at a cold vent with active fluid flow. The four transect sites represent different typical geological environments of gas hydrate occurrence across the northern Cascadia margin from the earliest occurrence on the westernmost first accreted ridge (Site U1326) to the eastward limit of the gas hydrate occurrence in shallower water (Site U1329). Expedition 311 complements previous gas hydrate studies along the Cascadia accretionary complex, especially ODP Leg 146 and Leg 204 by extending the aperture of the transect sampled and introducing new tools to systematically quantify the gas hydrate content of the sediments. Among the most significant findings of the expedition was the occurrence of up to 20 m thick sand-rich turbidite intervals with gas hydrate concentrations locally exceeding 50% of the pore space at Sites U1326 and U1327. Moreover, these anomalous gas hydrate intervals occur at unexpectedly shallow depths of 50-120 metres below seafloor, which is the opposite of what was expected from previous models of gas hydrate formation in accretionary complexes, where gas hydrate was predicted to be more concentrated near the base of the gas hydrate stability zone just above the bottom-simulating reflector. Gas hydrate appears to be mainly concentrated in turbidite sand layers. During Expedition 311, the visual correlation of gas hydrate with sand layers was clearly and repeatedly documented, strongly supporting the importance of grain size in controlling gas hydrate occurrence. The results from the transect sites provide evidence for a structurally complex, lithology-controlled gas hydrate environment on the northern Cascadia margin. Local shallow

  4. Hydration mechanisms of mineral trioxide aggregate. (United States)

    Camilleri, J


    To report the hydration mechanism of white mineral trioxide aggregate (White MTA, Dentsply, Tulsa Dental Products, Tulsa, OK, USA). The chemical constitution of white MTA was studied by viewing the powder in polished sections under the scanning electron microscope (SEM). The hydration of both white MTA and white Portland cement (PC) was studied by characterizing cement hydrates viewed under the SEM, plotting atomic ratios, performing quantitative energy dispersive analyses with X-ray (EDAX) and by calculation of the amount of anhydrous clinker minerals using the Bogue calculation. Un-hydrated MTA was composed of impure tri-calcium and di-calcium silicate and bismuth oxide. The aluminate phase was scarce. On hydration the white PC produced a dense structure made up of calcium silicate hydrate, calcium hydroxide, monosulphate and ettringite as the main hydration products. The un-reacted cement grain was coated with a layer of hydrated cement. In contrast MTA produced a porous structure on hydration. Levels of ettringite and monosulphate were low. Bismuth oxide was present as un-reacted powder but also incorporated with the calcium silicate hydrate. White MTA was deficient in alumina suggesting that the material was not prepared in a rotary kiln. On hydration this affected the production of ettringite and monosulphate usually formed on hydration of PC. The bismuth affected the hydration mechanism of MTA; it formed part of the structure of C-S-H and also affected the precipitation of calcium hydroxide in the hydrated paste. The microstructure of hydrated MTA would likely be weaker when compared with that of PC.

  5. Thermal properties of methane gas hydrates (United States)

    Waite, William F.


    Gas hydrates are crystalline solids in which molecules of a “guest” species occupy and stabilize cages formed by water molecules. Similar to ice in appearance (fig. 1), gas hydrates are stable at high pressures and temperatures above freezing (0°C). Methane is the most common naturally occurring hydrate guest species. Methane hydrates, also called simply “gas hydrates,” are extremely concentrated stores of methane and are found in shallow permafrost and continental margin sediments worldwide. Brought to sea-level conditions, methane hydrate breaks down and releases up to 160 times its own volume in methane gas. The methane stored in gas hydrates is of interest and concern to policy makers as a potential alternative energy resource and as a potent greenhouse gas that could be released from sediments to the atmosphere and ocean during global warming. In continental margin settings, methane release from gas hydrates also is a potential geohazard and could cause submarine landslides that endanger offshore infrastructure. Gas hydrate stability is sensitive to temperature changes. To understand methane release from gas hydrate, the U.S. Geological Survey (USGS) conducted a laboratory investigation of pure methane hydrate thermal properties at conditions relevant to accumulations of naturally occurring methane hydrate. Prior to this work, thermal properties for gas hydrates generally were measured on analog systems such as ice and non-methane hydrates or at temperatures below freezing; these conditions limit direct comparisons to methane hydrates in marine and permafrost sediment. Three thermal properties, defined succinctly by Briaud and Chaouch (1997), are estimated from the experiments described here: - Thermal conductivity, λ: if λ is high, heat travels easily through the material. - Thermal diffusivity, κ: if κ is high, it takes little time for the temperature to rise in the material. - Specific heat, cp: if cp is high, it takes a great deal of heat to

  6. Experimental validation of kinetic inhibitor strength on natural gas hydrate nucleation

    DEFF Research Database (Denmark)

    Daraboina, Nagu; Pachitsas, Stylianos; von Solms, Nicolas


    The kinetics of natural gas hydrate formation in the presence of dissolved salts (NaCl) and crude oil ( a middle east crude with density 851.5 kg/m3 were investigated by using a standard rocking cell (RC-5) apparatus. The hydrate nucleation temperature was reduced in the presence of NaCl and oil...... management in oil and gas facilities. (C) 2014 Elsevier Ltd. All rights reserved....

  7. X-ray computed-tomography observations of water flow through anisotropic methane hydrate-bearing sand

    Energy Technology Data Exchange (ETDEWEB)

    Seol, Yongkoo; Kneafsey, Timothy J.


    We used X-ray computed tomography (CT) to image and quantify the effect of a heterogeneous sand grain-size distribution on the formation and dissociation of methane hydrate, as well as the effect on water flow through the heterogeneous hydrate-bearing sand. A 28 cm long sand column was packed with several segments having vertical and horizontal layers with sands of different grain-size distributions. During the hydrate formation, water redistribution occurred. Observations of water flow through the hydrate-bearing sands showed that water was imbibed more readily into the fine sand, and that higher hydrate saturation increased water imbibition in the coarse sand due to increased capillary strength. Hydrate dissociation induced by depressurization resulted in different flow patterns with the different grain sizes and hydrate saturations, but the relationships between dissociation rates and the grain sizes could not be identified using the CT images. The formation, presence, and dissociation of hydrate in the pore space dramatically impact water saturation and flow in the system.

  8. Geophysical evidence for gas hydrates in the deep water of the South Caspian Basin, Azerbaijan

    Energy Technology Data Exchange (ETDEWEB)

    Diaconescu, C.C. [Cornell University, Ithaca, NY (United States). Dept. of Geological Sciences; National Institute for Earth Physics, Bucharest (Romania); Kieckhefer, R.M. [Chevron Overseas Petroluem Inc., San Ramon, CA (United States); Knapp, J.H. [Cornell University, Ithaca, NY (United States). Dept. of Geological Sciences; University of South Carolina, Columbia, SC (United States). Dept. of Geological Sciences


    New 2-D seismic reflection data from the South Caspian Sea, offshore Azerbaijan, document for the first time in the deep water (up to 650m) of this area, the presence of gas hydrates. Geophysical evidence for gas hydrates consists of a shallow (300-500m below seafloor) zone of pronounced high velocity ({approx}2,100m/s) as compared with the surrounding sediments (1550-1600m/s). This zone appears on the seismic data as a depth-limited ({approx}200m thick) layer extending down the flank of an elongated structural high, and displays seismic blanking effects on the sedimentary section. A strong positive-polarity (R{sub c}{approx}0.123) reflector marks the top of this velocity anomaly, and is interpreted as the top of the gas hydrate layer. Similarly, a high-amplitude (R{sub c}{approx}0.11), negative polarity reflector coincides with the base of the high velocity layer, and is interpreted as the base of the hydrate zone. Both the top and bottom of the hydrate layer approximately parallel the seafloor bathymetry, and cut discordantly across the stratigraphic section, suggesting that the two reflectors are thermobaric and not stratigraphic interfaces. Decreasing amplitude with offset at the base of the gas hydrate layer may indicate the accumulation of free gas beneath this interface. These gas hydrates fall within the hydrate stability field predicted from thermobaric modelling for the South Caspian Basin, but typically in thinner layers than would be expected from theoretical calculations. The minimum predicted water depth that allows hydrate formation is {approx}150m, and the maximum predicted thickness of the gas hydrate stability field is {approx}1350m. (Author)

  9. Terahertz Time Domain Spectroscopy for Structure-II Gas Hydrates

    DEFF Research Database (Denmark)

    Takeya, Kei; Zhang, Caihong; Kawayama, Iwao


    For the nondestructive inspection of gas hydrates, terahertz (THz) time-domain spectroscopy (TDS) was applied to tetrahydrofuran (THF) hydrate and propane hydrate. The absorption of propane hydrate monotonically increases with frequency, similar to the case of ice, while THF hydrate has a charact......For the nondestructive inspection of gas hydrates, terahertz (THz) time-domain spectroscopy (TDS) was applied to tetrahydrofuran (THF) hydrate and propane hydrate. The absorption of propane hydrate monotonically increases with frequency, similar to the case of ice, while THF hydrate has...

  10. Seismic reflections associated with submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Andreassen, K.


    Gas hydrates are often suggested as a future energy resource. This doctoral thesis improves the understanding of the concentration and distribution of natural submarine gas hydrates. The presence of these hydrates are commonly inferred from strong bottom simulating reflection (BSR). To investigate the nature of BSR, this work uses seismic studies of hydrate-related BSRs at two different locations, one where gas hydrates are accepted to exist and interpreted to be very extensive (in the Beaufort Sea), the other with good velocity data and downhole logs available (offshore Oregon). To ascertain the presence of free gas under the BSR, prestack offset data must supplement near-vertical incidence seismic data. A tentative model for physical properties of sediments partially saturated with gas hydrate and free gas is presented. This model, together with drilling information and seismic data containing the BSR beneath the Oregon margin and the Beaufort Sea, made it possible to better understand when to apply the amplitude-versus-offset (AVO) method to constrain BSR gas hydrate and gas models. Distribution of natural gas hydrates offshore Norway and Svalbard is discussed and interpreted as reflections from the base of gas hydrate-bearing sediments, overlying sediments containing free gas. Gas hydrates inferred to exist at the Norwegian-Svalbard continental margin correlate well with Cenozoic depocenters, and the associated gas is assumed to be mainly biogenic. Parts of that margin have a high potential for natural gas hydrates of both biogenic and thermogenic origin. 235 refs., 86 figs., 4 tabs.

  11. Handbook of gas hydrate properties and occurrence

    Energy Technology Data Exchange (ETDEWEB)

    Kuustraa, V.A.; Hammershaimb, E.C.


    This handbook provides data on the resource potential of naturally occurring hydrates, the properties that are needed to evaluate their recovery, and their production potential. The first two chapters give data on the naturally occurring hydrate potential by reviewing published resource estimates and the known and inferred occurrences. The third and fourth chapters review the physical and thermodynamic properties of hydrates, respectively. The thermodynamic properties of hydrates that are discussed include dissociation energies and a simplified method to calculate them; phase diagrams for simple and multi-component gases; the thermal conductivity; and the kinetics of hydrate dissociation. The final chapter evaluates the net energy balance of recovering hydrates and shows that a substantial positive energy balance can theoretically be achieved. The Appendices of the Handbook summarize physical and thermodynamic properties of gases, liquids and solids that can be used in designing and evaluating recovery processes of hydrates. 158 references, 67 figures, 47 tables.

  12. A new class of kinetic hydrate inhibitor with good biodegradability

    Energy Technology Data Exchange (ETDEWEB)

    Del Villano, L.; Kommedal, R.; Kelland, M.A. [Stavanger Univ., Stavanger (Norway). Dept. of Mathematics and Natural Sciences


    Kinetic hydrate inhibitors (KHIs) are often used to prevent gas hydrate formation in oil and gas production lines by preventing the growth and nucleation of hydrate crystals. However, very few KHIs are used in offshore drilling processes due to their high biodegradability rates. This paper discussed a KHI developed for use in offshore drilling processes. Performance tests were conducted using stirred autoclaves with a natural gas blend and saline water. Structure 2 hydrates were formed. The KHIs were synthesized using a range of polyaspartamides formed from polysuccinimide (PSI) dissolved in a polar solvent. Oxygen demand during degradation was measured and compared with theoretical oxygen demand calculated from the literature. Biodegradation (BOD) time lag was monitored. Results of the study showed that polymers with a 3:1 ratio of isobutyl:methyl pendant groups performed as well as the commercial KHI polymer Luvicap 55W. Closed bottle tests showed that the polymer had biodegradation levels greater than 20 per cent after a 28 day period. It was concluded that biodegradation rates increased to between 57 and 60 per cent when growth assimilation was accounted for. 25 refs., 6 tabs., 9 figs.

  13. Improvement of gas hydrate preservation by increasing compression pressure to simple hydrates of methane, ethane, and propane (United States)

    Kida, Masato; Jin, Yusuke; Watanabe, Mizuho; Murayama, Tetsuro; Nagao, Jiro


    In this report, we describe the dissociation behavior of gas hydrate grains pressed at 1 and 6 MPa. Certain simple gas hydrates in powder form show anomalous preservation phenomenon under their thermodynamic unstable condition. Investigation of simple hydrates of methane, ethane, and propane reveals that high pressure applied to the gas hydrate particles enhances their preservation effects. Application of high pressure increases the dissociation temperature of methane hydrate and has a restrictive effect against the dissociation of ethane and propane hydrate grains. These improvements of gas hydrate preservation by increasing pressure to the initial gas hydrate particles imply that appropriate pressure applied to gas hydrate particles enhances gas hydrate preservation effects.

  14. Lithological controls on gas hydrate saturation: Insights from signal classification of NMR downhole data (United States)

    Bauer, Klaus; Kulenkampff, Johannes; Henninges, Jan; Spangenberg, Erik


    Nuclear magnetic resonance (NMR) downhole data are analyzed with a new strategy to study gas hydrate-bearing sediments in the Mackenzie Delta (NW Canada). NMR logging is a powerful tool to study geological reservoir formations. The measurements are based on interactions between the magnetic moments of protons in geological formation water and an external magnetic field. Inversion of the measured raw data provides so-called transverse relaxation time (T2) distribution curves or spectra. Different parts of the T2 curve are related with distinct pore radii and corresponding fluid components. A common practice in the analysis of T2 distribution curves is to extract single-valued parameters such as apparent total porosity. Moreover, the derived total NMR apparent porosity and the gamma-gamma density log apparent porosity can be combined to estimate gas hydrate saturation in hydrate-bearing sediments. To avoid potential loss of information, in our new approach we analyze the entire T2 distribution curves as quasi-continuous signals to characterize the rock formation. The approach is applied to NMR data measured in gas hydrate research well Mallik 5L-38. We use self-organizing maps, a neural network clustering technique, to subdivide the data set of NMR T2 distribution curves into classes with a similar and distinctive signal shape. The method includes (1) preparation of data vectors, (2) unsupervised learning, (3) cluster definition, and (4) classification and depth mapping of all NMR signals. Each signal class thus represents a specific pore size distribution which can be interpreted in terms of distinct lithologies and reservoir types. A key step in the interpretation strategy is to reconcile the NMR classes with other log data not considered in the clustering analysis, such as gamma ray, photo-electric factor, hydrate saturation, and other logs. Our results defined six main lithologies within the target zone. Gas hydrate layers were recognized by their low signal

  15. Nature of the guest-host interactions for dibromine in the T, P, and H clathrate cages (United States)

    Batista-Romero, Fidel A.; Pajón-Suárez, Pedro; Roncero, Octavio; Hernández-Lamoneda, Ramón


    The guest-host intermolecular potentials for the ground states of Br2 in the tetrakaidecahedral (T), pentakaidecahedral (P), and hexakaidecahedral clathrate (H) cages have been calculated using ab initio local correlation methods. Applying the local correlation energy partitioning analysis together with first-order symmetry adapted perturbation theory, we obtain a detailed understanding of the nature of the interactions. In particular, the debated question concerning the possible presence of halogen bonding (XB) is carefully analyzed. In the case of the T cage, given its smaller size, the Br-O distance is too short leading to a larger exchange-repulsion for XB orientations which therefore do not represent minima. For the other two cages, the Br-O distance is too large leading to little orbital overlap effects and thus weaker donor-acceptor interactions; however, these orientations coincide with the global minima.

  16. Geochemical anomaly of pore waters and implications for gas hydrate occurrence in the South China Sea

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, S.Y.; Yang, T.; Ge, L.; Yang, J.H. [Nanjing Univ., State Key Laboratory for Mineral Deposits Research and Center for Marine Geochemistry Research, Nanjing (China). Dept. of Earth Sciences; Wu, N.Y.; Liu, J.; Zhang, G.X.; Chen, D.H. [China Geological Survey, Guangzhou (China). Guangzhou Marine Geological Survey


    Gas hydrate is an ice-like solid substance primarily composed of water and methane, which commonly occurs in deep-water marine sediments under appropriate pressure, temperature, and salinity conditions. Gas hydrate deposits have been found in oceans around the world and in permafrost regions. With the exception of direct drilling and sampling of marine gas hydrates, the occurrence of gas hydrates has been identified mainly by indirect evidence determined from geological, geophysical, and geochemical data. This paper discussed the geochemical anomalies of pore waters and their implications for gas hydrate occurrence in the northern continental slope of the South China Sea. The paper provided background on the northern continental slope of the South China Sea as it contains many sedimentary basins with large sources of oil and natural gas which is a favourable place for the formation of gas hydrates. It also discussed gas compositions; sulphate gradients and sulphate-methane interface depths; chlorinity; ammonia and phosphate concentrations; cations; bromine and iodine concentrations; oxygen and hydrogen isotopes; dissolved inorganic carbon and carbon isotopes; and seep carbonates and their carbon and oxygen isotopes. It was concluded that geochemical anomalies occurred in three prospecting target areas including the Xisha Trough, Shenhu and Dongsha areas. The geochemical evidence indicated that the Dongsha area was also one of the most promising target areas for gas hydrate occurrence in the South China Sea. 29 refs., 1 fig.

  17. Methods of thermoelectric enhancement in silicon-germanium alloy type I clathrates and in nanostructured lead chalcogenides (United States)

    Martin, Joshua

    The rapid increase in thermoelectric (TE) materials R&D is a consequence of the growing need to increase energy efficiency and independence through waste heat recovery. TE materials enable the direct solid-state conversion of heat into electricity, with little maintenance, noise, or cost. In addition, these compact devices can be incorporated into existing technologies to increase the overall operating efficiency. High efficiency TE materials would enable the practical solid-state conversion of thermal to electrical energy. Optimizing the interdependent physical parameters to achieve acceptable efficiencies requires materials exhibiting a unique combination of properties. This research reports two methods of thermoelectric enhancement: lattice strain effects in silicon-germanium alloy type I clathrates and the nanostructured enhancement of lead chalcogenides. The synthesis and chemical, structural, and transport properties characterization of Ba8Ga16SixGe30-x type I clathrates with similar Ga-to-group IV element ratios but with increasing Si substitution (4 effective mass on Si substitution level, may imply a modified band structure with Si substitution. These materials were then further optimized by adjusting the Ga-to-group IV element ratios. Recent progress in a number of higher efficiency TE materials can be attributed to nanoscale enhancement. Many of these materials demonstrate increased Seebeck coefficient and decreased thermal conductivity due to the phenomenological properties of nanometer length scales. To satisfy the demands of bulk industrial applications requires additional synthesis techniques to incorporate nanostructure directly within a bulk matrix. This research investigates, for the first time, dense dimensional nanocomposites prepared by densifying nanocrystals synthesized employing a solution-phase reaction. Furthermore, the carrier concentration of the PbTe nanocomposites can be adjusted by directly doping the nanocrystals, necessary for power

  18. Dipolar response of hydrated proteins


    Matyushov, Dmitry V.


    The paper presents an analytical theory and numerical simulations of the dipolar response of hydrated proteins. The effective dielectric constant of the solvated protein, representing the average dipole moment induced at the protein by a uniform external field, shows a remarkable variation among the proteins studied by numerical simulations. It changes from 0.5 for ubiquitin to 640 for cytochrome c. The former value implies a negative dipolar susceptibility of ubiquitin, that is a dia-electri...


    Directory of Open Access Journals (Sweden)

    Goran Vasić


    Full Text Available Importance of hydration is detrmined by importance of functions of water in the human organism: i.e. regulation of body temperature, transport, excretion of waste materials through urine, digestion of food which is facilititated by saliva and gastric juices, maintenance of flexibility of organs and tissues About 60 % body mass of an adult person (males: 61 %, females: 54 % is made up of water. Water content of a newly born baby reaches 77 %, and it is up to 50 % in adults. It is very important for sportsmen to provide adequate hydration during and after the time of bodily activities. A symptom of water shortage is thirst. However, thirst is a late response of an organism and it occurs when dehydration has already taken place. Minimum in take of fluids in humans should range between one-and-half to two liters. It has been known for a long time that there is no success in sport without proper hydration in a sportsman.

  20. Gas hydrates: Technology status report

    Energy Technology Data Exchange (ETDEWEB)


    In 1983, the US Department of Energy (DOE) assumed the responsibility for expanding the knowledge base and for developing methods to recover gas from hydrates. These are ice-like mixtures of gas and water where gas molecules are trapped within a framework of water molecules. This research is part of the Unconventional Gas Recovery (UGR) program, a multidisciplinary effort that focuses on developing the technology to produce natural gas from resources that have been classified as unconventional because of their unique geologies and production mechanisms. Current work on gas hydrates emphasizes geological studies; characterization of the resource; and generic research, including modeling of reservoir conditions, production concepts, and predictive strategies for stimulated wells. Complementing this work is research on in situ detection of hydrates and field tests to verify extraction methods. Thus, current research will provide a comprehensive technology base from which estimates of reserve potential can be made, and from which industry can develop recovery strategies. 7 refs., 3 figs., 6 tabs.

  1. Field Data and the Gas Hydrate Markup Language

    Directory of Open Access Journals (Sweden)

    Ralf Löwner


    Full Text Available Data and information exchange are crucial for any kind of scientific research activities and are becoming more and more important. The comparison between different data sets and different disciplines creates new data, adds value, and finally accumulates knowledge. Also the distribution and accessibility of research results is an important factor for international work. The gas hydrate research community is dispersed across the globe and therefore, a common technical communication language or format is strongly demanded. The CODATA Gas Hydrate Data Task Group is creating the Gas Hydrate Markup Language (GHML, a standard based on the Extensible Markup Language (XML to enable the transport, modeling, and storage of all manner of objects related to gas hydrate research. GHML initially offers an easily deducible content because of the text-based encoding of information, which does not use binary data. The result of these investigations is a custom-designed application schema, which describes the features, elements, and their properties, defining all aspects of Gas Hydrates. One of the components of GHML is the "Field Data" module, which is used for all data and information coming from the field. It considers international standards, particularly the standards defined by the W3C (World Wide Web Consortium and the OGC (Open Geospatial Consortium. Various related standards were analyzed and compared with our requirements (in particular the Geographic Markup Language (ISO19136, GML and the whole ISO19000 series. However, the requirements demanded a quick solution and an XML application schema readable for any scientist without a background in information technology. Therefore, ideas, concepts and definitions have been used to build up the modules of GHML without importing any of these Markup languages. This enables a comprehensive schema and simple use.

  2. Identification of the hydrate gel phases present in phosphate-modified calcium aluminate binders

    Energy Technology Data Exchange (ETDEWEB)

    Chavda, Mehul A.; Bernal, Susan A. [Department of Materials Science and Engineering, The University of Sheffield, Sheffield S1 3JD (United Kingdom); Apperley, David C. [Solid-State NMR Group, Department of Chemistry, Durham University, Durham DH1 3LE (United Kingdom); Kinoshita, Hajime [Department of Materials Science and Engineering, The University of Sheffield, Sheffield S1 3JD (United Kingdom); Provis, John L., E-mail: [Department of Materials Science and Engineering, The University of Sheffield, Sheffield S1 3JD (United Kingdom)


    The conversion of hexagonal calcium aluminate hydrates to cubic phases in hydrated calcium aluminate cements (CAC) can involve undesirable porosity changes and loss of strength. Modification of CAC by phosphate addition avoids conversion, by altering the nature of the reaction products, yielding a stable amorphous gel instead of the usual crystalline hydrate products. Here, details of the environments of aluminium and phosphorus in this gel were elucidated using solid-state NMR and complementary techniques. Aluminium is identified in both octahedral and tetrahedral coordination states, and phosphorus is present in hydrous environments with varying, but mostly low, degrees of crosslinking. A {sup 31}P/{sup 27}Al rotational echo adiabatic passage double resonance (REAPDOR) experiment showed the existence of aluminium–phosphorus interactions, confirming the formation of a hydrated calcium aluminophosphate gel as a key component of the binding phase. This resolves previous disagreements in the literature regarding the nature of the disordered products forming in this system.

  3. Direct Visualization of the Hydration Layer on Alumina Nanoparticles with the Fluid Cell STEM in situ (United States)

    Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya


    Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions. We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. Our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles. PMID:25996055

  4. Effect of G