WorldWideScience

Sample records for situ hydrate conditions

  1. An in situ synchrotron energy-dispersive diffraction study of the hydration of oilwell cement systems under high temperature/autoclave conditions up to 130 deg. C

    International Nuclear Information System (INIS)

    Colston, Sally L.; Barnes, Paul; Jupe, Andrew C.; Jacques, Simon D.M.; Hall, Christopher; Livesey, Paul; Dransfield, John; Meller, Nicola; Maitland, Geoffrey C.

    2005-01-01

    The technique of synchrotron energy dispersive diffraction has been developed for in situ studies of cement hydration under autoclave conditions. This has been applied to oilwell cements hydrating at typical oilwell temperatures up to 130 deg. C. The results show clearly the detailed interplay between 11 detectable phases, from which a phase transformation scheme has been derived; this illustrates the progression of hydration up to 130 deg. C for two extreme cases, with and without conservation of water content and autoclave pressure. The monosulphate hydrate phases are found to exhibit different stability bounds, with a surprising sequence of the 14-water, 10-water then 12-water monosulphate as temperature/time increases; the latter form is particularly associated with conditions of water/pressure loss. The effect of retarders on C 3 S dissolution and CH formation is negligible above 70 deg. C, whereas the effect on the calcium sulphoaluminate hydrates is more complex, and possible reasons for this are discussed

  2. Gas hydrates forming and decomposition conditions analysis

    Directory of Open Access Journals (Sweden)

    А. М. Павленко

    2017-07-01

    Full Text Available The concept of gas hydrates has been defined; their brief description has been given; factors that affect the formation and decomposition of the hydrates have been reported; their distribution, structure and thermodynamic conditions determining the gas hydrates formation disposition in gas pipelines have been considered. Advantages and disadvantages of the known methods for removing gas hydrate plugs in the pipeline have been analyzed, the necessity of their further studies has been proved. In addition to the negative impact on the process of gas extraction, the hydrates properties make it possible to outline the following possible fields of their industrial use: obtaining ultrahigh pressures in confined spaces at the hydrate decomposition; separating hydrocarbon mixtures by successive transfer of individual components through the hydrate given the mode; obtaining cold due to heat absorption at the hydrate decomposition; elimination of the open gas fountain by means of hydrate plugs in the bore hole of the gushing gasser; seawater desalination, based on the hydrate ability to only bind water molecules into the solid state; wastewater purification; gas storage in the hydrate state; dispersion of high temperature fog and clouds by means of hydrates; water-hydrates emulsion injection into the productive strata to raise the oil recovery factor; obtaining cold in the gas processing to cool the gas, etc.

  3. In Situ Raman Analyses of Natural Gas and Gas Hydrates at Hydrate Ridge, Oregon

    Science.gov (United States)

    Peltzer, E. T.; White, S. N.; Dunk, R. M.; Brewer, P. G.; Sherman, A. D.; Schmidt, K.; Hester, K. C.; Sloan, E. D.

    2004-12-01

    During a July 2004 cruise to Hydrate Ridge, Oregon, MBARI's sea-going laser Raman spectrometer was used to obtain in situ Raman spectra of natural gas hydrates and natural gas venting from the seafloor. This was the first in situ analysis of gas hydrates on the seafloor. The hydrate spectra were compared to laboratory analyses performed at the Center for Hydrate Research, Colorado School of Mines. The natural gas spectra were compared to MBARI gas chromatography (GC) analyses of gas samples collected at the same site. DORISS (Deep Ocean Raman In Situ Spectrometer) is a laboratory model laser Raman spectrometer from Kaiser Optical Systems, Inc modified at MBARI for deployment in the deep ocean. It has been successfully deployed to depths as great as 3600 m. Different sampling optics provide flexibility in adapting the instrument to a particular target of interest. An immersion optic was used to analyze natural gas venting from the seafloor at South Hydrate Ridge ( ˜780 m depth). An open-bottomed cube was placed over the vent to collect the gas. The immersion optic penetrated the side of the cube as did a small heater used to dissociate any hydrate formed during sample collection. To analyze solid hydrates at both South and North Hydrate Ridge ( ˜590 m depth), chunks of hydrate were excavated from the seafloor and collected in a glass cylinder with a mesh top. A stand-off optic was used to analyze the hydrate inside the cylinder. Due to the partial opacity of the hydrate and the small focal volume of the sampling optic, a precision underwater positioner (PUP) was used to focus the laser spot onto the hydrate. PUP is a stand-alone system with three degrees-of-freedom, capable of moving the DORISS probe head with a precision of 0.1 mm. In situ Raman analyses of the gas indicate that it is primarily methane. This is verified by GC analyses of samples collected from the same site. Other minor constituents (such as CO2 and higher hydrocarbons) are present but may be in

  4. In-situ membrane hydration measurement of proton exchange membrane fuel cells

    Science.gov (United States)

    Lai, Yeh-Hung; Fly, Gerald W.; Clapham, Shawn

    2015-01-01

    Achieving proper membrane hydration control is one of the most critical aspects of PEM fuel cell development. This article describes the development and application of a novel 50 cm2 fuel cell device to study the in-situ membrane hydration by measuring the through-thickness membrane swelling via an array of linear variable differential transducers. Using this setup either as an air/air (dummy) cell or as a hydrogen/air (operating) cell, we performed a series of hydration and dehydration experiments by cycling the RH of the inlet gas streams at 80 °C. From the linear relationship between the under-the-land swelling and the over-the-channel water content, the mechanical constraint within the fuel cell assembly can suppress the membrane water uptake by 11%-18%. The results from the air/air humidity cycling test show that the membrane can equilibrate within 120 s for all RH conditions and that membrane can reach full hydration at a RH higher than 140% in spite of the use of a liquid water impermeable Carbel MP30Z microporous layer. This result confirms that the U.S. DOE's humidity cycling mechanical durability protocol induces sufficient humidity swings to maximize hygrothermal mechanical stresses. This study shows that the novel experimental technique can provide a robust and accurate means to study the in-situ hydration of thin membranes subject to a wide range of fuel cell conditions.

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

    Science.gov (United States)

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

    2011-01-01

    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.

  6. Hydration of refractory cements, with spinel phase generated in-situ

    International Nuclear Information System (INIS)

    Lavat, A.E; Grasselli, M.C; Giuliodori Lovecchio, E

    2008-01-01

    High alumina refractory materials with additions of synthetic spinel (MgAl 2 O 4 ) have good thermo mechanical and attack from slag properties, which are useful in many technological applications. The spinel phase generated in-situ, MA, has proven to be a suitable and economic alternative to the use of sintered or electrocast spinels. Prior studies have established synthesis conditions for refractory cements with the spinel phase generated in-situ (CCAMA) starting with alumina mixtures and Buenos Aires dolomites. The binding properties of the aluminous cements depend on the hydrated calcium aluminates that form in the setting and hardening stages of the pastes. To avoid breaks, the refractory material must undergo programmed heating before reaching the serviceable temperature. It should also include the present phases and the transformations that occur at different temperatures. In this context knowledge about the green mineral composition and its response to an increase in temperature is especially important. This work presents studies to define the composition of CCAMA cement mortars at different hydration ages, and to estimate phase proportions and behavior during dehydration. DRX and FTIR techniques are applied in order to follow the structural changes that take place during the hydration process. The evolution of the dehydration is also studied, mostly using FTIR. The mortars were prepared with a water/cement ration of 0.5, recommended for this kind of work. The hydration was carried out at room temperature and samples were analyzed at the following ages: 15 min.; 1 h.; 1, 3, 7, 14, 28, 60 and 90 days. With the results the evolution of the phases as a function of the age of the hydration were studied. The main hydrate that was formed was CAH 10 , with a significantly increased proportion during the first 14 days of hydration. Its carbonation was also observed by the presence of calcium carboaluminates and the formation of gibbsite. The MA phase is also

  7. Methane and carbon dioxide hydrates on Mars: Potential origins, distribution, detection, and implications for future in situ resource utilization

    Science.gov (United States)

    Pellenbarg, Robert E.; Max, Michael D.; Clifford, Stephen M.

    2003-04-01

    There is high probability for the long-term crustal accumulation of methane and carbon dioxide on Mars. These gases can arise from a variety of processes, including deep biosphere activity and abiotic mechanisms, or, like water, they could exist as remnants of planetary formation and by-products of internal differentiation. CH4 and CO2 would tend to rise buoyantly toward the planet's surface, condensing with water under appropriate conditions of temperature and pressure to form gas hydrate. Gas hydrates are a class of materials created when gas molecules are trapped within a crystalline lattice of water-ice. The hydrate stability fields of both CH4 and CO2 encompass a portion of the Martian crust that extends from within the water-ice cryosphere, from a depth as shallow as ~10-20 m to as great as a kilometer or more below the base of the Martian cryosphere. The presence and distribution of methane and carbon dioxide hydrates may be of critical importance in understanding the geomorphic evolution of Mars and the geophysical identification of water and other volatiles stored in the hydrates. Of critical importance, Martian gas hydrates would ensure the availability of key in situ resources for sustaining future robotic and human exploration, and the eventual colonization, of Mars.

  8. Magnetic Resonance Microscopy for Assessment of Morphological Changes in Hydrating Hydroxypropylmethyl Cellulose Matrix Tablets In Situ

    OpenAIRE

    Kulinowski, Piotr; Młynarczyk, Anna; Dorożyński, Przemysław; Jasiński, Krzysztof; Gruwel, Marco L. H.; Tomanek, Bogusław; Węglarz, Władysław P.

    2012-01-01

    ABSTRACT Purpose To resolve contradictions found in morphology of hydrating hydroxypropylmethyl cellulose (HPMC) matrix as studied using Magnetic Resonance Imaging (MRI) techniques. Until now, two approaches were used in the literature: either two or three regions that differ in physicochemical properties were identified. Methods Multiparametric, spatially and temporally resolved T2 MR relaxometry in situ was applied to study the hydration progress in HPMC matrix tablets using a 11.7 T MRI sy...

  9. In Situ Soft X-ray Spectromicroscopy of Early Tricalcium Silicate Hydration

    Directory of Open Access Journals (Sweden)

    Sungchul Bae

    2016-12-01

    Full Text Available The understanding and control of early hydration of tricalcium silicate (C3S is of great importance to cement science and concrete technology. However, traditional characterization methods are incapable of providing morphological and spectroscopic information about in situ hydration at the nanoscale. Using soft X-ray spectromicroscopy, we report the changes in morphology and molecular structure of C3S at an early stage of hydration. In situ C3S hydration in a wet cell, beginning with induction (~1 h and acceleration (~4 h periods of up to ~8 h, was studied and compared with ex situ measurements in the deceleration period after 15 h of curing. Analysis of the near-edge X-ray absorption fine structure showed that the Ca binding energy and energy splitting of C3S changed rapidly in the early age of hydration and exhibited values similar to calcium silicate hydrate (C–S–H. The formation of C–S–H nanoseeds in the C3S solution and the development of a fibrillar C–S–H morphology on the C3S surface were visualized. Following this, silicate polymerization accompanied by C–S–H precipitation produced chemical shifts in the peaks of the main Si K edge and in multiple scattering. However, the silicate polymerization process did not significantly affect the Ca binding energy of C–S–H.

  10. Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study; Hydratation des argiles gonflantes et influence des bacteries. Etude experimentale de reaction in situ

    Energy Technology Data Exchange (ETDEWEB)

    Berger, J

    2008-01-15

    This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour

  11. Steam hydration-reactivation of FBC ashes for enhanced in situ desulphurization

    Energy Technology Data Exchange (ETDEWEB)

    Fabio Montagnaro; Marianna Nobili; Antonio Telesca; Gian Lorenz Valenti; Edward J. Anthony; Piero Salatino [Universita degli Studi di Napoli Federico II, Napoli (Italy). Dipartimento di Chimica

    2009-06-15

    Bed and fly ashes originating from industrial-scale fluidized bed combustors (FBCs) were steam hydrated to produce sorbents suitable for further in situ desulphurization. Samples of the hydrated ash were characterized by X-ray diffraction analysis, scanning electron microscopy and porosimetry. Bed ashes were hydrated in a pressure bomb for 30 and 60 min at 200{sup o}C and 250{sup o}C. Fly ash was hydrated in an electrically heated tubular reactor for 10 and 60 min at 200{sup o}C and 300{sup o}C. The results were interpreted by considering the hydration process and the related development of accessible porosity suitable for resulphation. The performance of the reactivated bed ash as sulphur sorbent improved with a decrease of both the hydration temperature and time. For reactivated fly ash, more favourable porosimetric features were observed at longer treatment times and lower hydration temperatures. Finally, it was shown that an ashing treatment (at 850{sup o}C for 20 min) promoted a speeding up of the hydration process and an increase in the accessible porosity. 36 refs., 6 figs., 2 tabs.

  12. Direct Visualization of the Hydration Layer on Alumina Nanoparticles with the Fluid Cell STEM in situ.

    Science.gov (United States)

    Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya

    2015-05-21

    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.

  13. In-situ study of the thermal properties of hydrate slurry by high pressure DSC

    Energy Technology Data Exchange (ETDEWEB)

    Sari, O.; Hu, J.; Brun, F.; Erbeau, N. [Institute of Thermal Engineering, University of Applied Sciences of Western Switzerland, Yverdon-les-Bains (Switzerland); Homsy, P. [Nestec, Vevey (Switzerland); Logel, J.-C. [Axima Refrigeration, Bischheim (France)

    2008-07-01

    Knowing the enthalpy of hydrate slurry is very essential for energy balance and industrial applications. No direct measurement processes had been developed in this field in the past time. A new experimental method with special device has been developed to carry out on-line measurement of the thermal properties for hydrate slurry under dynamic conditions. With this special device, it is possible to deliver the hydrate slurry to the high pressure DSC (Differential Scanning Calorimetry) directly from the production tank or pipes. Thermal data acquisition will be performed afterwards by DSC. The investigated conditions were at pressure of 30 bar and temperature of {approx}+7 {sup o}C. The dissociation enthalpy of CO{sub 2} hydrate slurry was about 54 kJ/kg, corresponding 10.8% of solid fraction. The on-line measurement results for CO{sub 2} hydrate slurry give a good tendency to apply this phase change slurry to the industrial refrigeration process. (author)

  14. Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study

    International Nuclear Information System (INIS)

    Berger, J.

    2008-01-01

    This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour observed

  15. In situ monitoring of the hydration process of K-PS geopolymer cement with ESEM

    International Nuclear Information System (INIS)

    Sun Wei; Zhang Yunsheng; Lin Wei; Liu Zhiyong

    2004-01-01

    Environmental scanning electron microscope (ESEM) was used to in situ quantitatively study the hydration process of K-PS geopolymer cement under an 80% RH environment. An energy dispersion X-ray analysis (EDXA) was also employed to distinguish the chemical composition of hydration product. The ESEM micrographs showed that metakaolin particles pack loosely at 10 min after mixing, resulting in the existence of many large voids. As hydration proceeds, a lot of gels were seen and gradually precipitated on the surfaces of these particles. At later stage, these particles were wrapped by thick gel layers and their interspaces were almost completely filled. The corresponding EDXA results illustrated that the molar ratios of K/Al increase while Si/Al decrease with the development of hydration. As a result, the molar ratios of K/Al and Si/Al of hydration products at an age of 4 h amounted to 0.99 and 1.49, respectively, which were close to the theoretical values (K/Al=1.0, Si/Al=1.0 for K-PS geopolymer cement paste). In addition, well-developed crystals could not been found at any ages; instead, spongelike amorphous gels were always been observed

  16. Magnetic resonance microscopy for assessment of morphological changes in hydrating hydroxypropylmethyl cellulose matrix tablets in situ.

    Science.gov (United States)

    Kulinowski, Piotr; Młynarczyk, Anna; Dorożyński, Przemysław; Jasiński, Krzysztof; Gruwel, Marco L H; Tomanek, Bogusław; Węglarz, Władysław P

    2012-12-01

    To resolve contradictions found in morphology of hydrating hydroxypropylmethyl cellulose (HPMC) matrix as studied using Magnetic Resonance Imaging (MRI) techniques. Until now, two approaches were used in the literature: either two or three regions that differ in physicochemical properties were identified. Multiparametric, spatially and temporally resolved T(2) MR relaxometry in situ was applied to study the hydration progress in HPMC matrix tablets using a 11.7 T MRI system. Two spin-echo based pulse sequences-one of them designed to specifically study short T(2) signals-were used. Two components in the T(2) decay envelope were estimated and spatial distributions of their parameters, i.e. amplitudes and T(2) values, were obtained. Based on the data, five different regions and their temporal evolution were identified: dry glassy, hydrated solid like, two interface layers and gel layer. The regions were found to be separated by four evolving fronts identified as penetration, full hydration, total gelification and apparent erosion. The MRI results showed morphological details of the hydrating HPMC matrices matching compound theoretical models. The proposed method will allow for adequate evaluation of controlled release polymeric matrix systems loaded with drug substances of different solubility.

  17. Computational Recreation of Carbon Dioxide Hydrates at Habitable Planetary Conditions

    Science.gov (United States)

    Recio, J. M.; Izquierdo-Ruiz, F.; Prieto-Ballesteros, O.

    2017-12-01

    Gas clathrate hydrates are proposed as constituents of the icy moons of the giant planets in the Solar System [1]. Carbon dioxide has been detected on the surface of the moons of Jupiter, supposedly originated by internal degasification. In Ganymede, an aqueous ocean is proposed to exist under a thick ice crust in coexistence with several forms of ice, with pressure reaching up to 1.3 GPa [2]. Due to the limited available data on these systems under these conditions, we propose a combination of computational and experimental studies to describe microscopically and macroscopically the structural and chemical behavior of CO2@H2O polymorphs. This will allow us to understand how their presence affects the geophysical structure and activity and their impact on the habitability of the icy moon. A transition from the sI cubic structure to a high pressure phase at around 0.7 GPa has been found for CO2@H2O. In spite of different attempts to characterize the new structure, a definite answer has not been provided yet. A MH-III Filled Ice Structure type was proposed after neutron diffraction experiments in contrast with an alternative structure similar to the hexagonal C0 type for H2 hydrates [3]. It has an estimated hydration level ratio up to 2H2O:1CO2 and 6 water molecules per unit cell. In the figure below, our optimized unit cell based on this hexagonal C0 structure is displayed. Ab initio calculations using the XDM approximation to include van der Waals effects are performed in our search for the pressure evolution of the equilibrium geometries of the C0-CO2@H2O phase and those of a close related structure to this one called Ih-C0, with 8 water molecules per unit cell. We obtain occupation energies at different hydration ratios, densities, equations of state parameters, and stability energies with respect to decomposition. Raman and IR frequencies are also computed in the 0-2 GPa range. High pressure experiments are also being done in a newly designed chamber able to

  18. Temporal Characterization of Hydrates System Dynamics beneath Seafloor Mounds. Integrating Time-Lapse Electrical Resistivity Methods and In Situ Observations of Multiple Oceanographic Parameters

    Energy Technology Data Exchange (ETDEWEB)

    Lutken, Carol [Univ. of Mississippi, Oxford, MS (United States); Macelloni, Leonardo [Univ. of Mississippi, Oxford, MS (United States); D' Emidio, Marco [Univ. of Mississippi, Oxford, MS (United States); Dunbar, John [Univ. of Mississippi, Oxford, MS (United States); Higley, Paul [Univ. of Mississippi, Oxford, MS (United States)

    2015-01-31

    This study was designed to investigate temporal variations in hydrate system dynamics by measuring changes in volumes of hydrate beneath hydrate-bearing mounds on the continental slope of the northern Gulf of Mexico, the landward extreme of hydrate occurrence in this region. Direct Current Resistivity (DCR) measurements were made contemporaneously with measurements of oceanographic parameters at Woolsey Mound, a carbonate-hydrate complex on the mid-continental slope, where formation and dissociation of hydrates are most vulnerable to variations in oceanographic parameters affected by climate change, and where changes in hydrate stability can readily translate to loss of seafloor stability, impacts to benthic ecosystems, and venting of greenhouse gases to the water-column, and eventually, the atmosphere. We focused our study on hydrate within seafloor mounds because the structurally-focused methane flux at these sites likely causes hydrate formation and dissociation processes to occur at higher rates than at sites where the methane flux is less concentrated and we wanted to maximize our chances of witnessing association/dissociation of hydrates. We selected a particularly well-studied hydrate-bearing seafloor mound near the landward extent of the hydrate stability zone, Woolsey Mound (MC118). This mid-slope site has been studied extensively and the project was able to leverage considerable resources from the team’s research experience at MC118. The site exhibits seafloor features associated with gas expulsion, hydrates have been documented at the seafloor, and changes in the outcropping hydrates have been documented, photographically, to have occurred over a period of months. We conducted observatory-based, in situ measurements to 1) characterize, geophysically, the sub-bottom distribution of hydrate and its temporal variability, and 2) contemporaneously record relevant environmental parameters (temperature, pressure, salinity, turbidity, bottom currents) to

  19. Investigation of the mechanical behaviour of gas-hydrate bearing clayey sediments from the Gulf of Guinea using in-situ geotechnical measurements

    Science.gov (United States)

    Taleb, F.; Garziglia, S.; Sultan, N.

    2017-12-01

    Expanding needs for energy resources and concerns about climate change have moved industrial and academic interests towards regions where specific thermobaric conditions allow the formation of gas hydrates (GH). While significant advances have been made to characterize the fabric and structure of these metastable geo-compounds, considerable uncertainty remains regarding the impact of their mechanical properties on the seafloor morphology and stability. This is particularly true for gas hydrates-bearing fine-grained sediments, which remain challenging to preserve or synthesise prior to laboratory testing. As a step towards understanding the mechanical consequences of the concentration and distribution of GH in this type of sediments, this work uses acoustic and geotechnical in situ measurements collected in a high gas flux system offshore Nigeria. Acoustic measurements of compressional wave velocity were shown to be convenient means of both detecting and quantifying gas hydrates in marine sediments. Geotechnical data derived from piezocone readings and their distribution in normalised soil classification charts allowed identifying distinct features of gas hydrates-bearing clayey sediments; such as a mechanical behaviour sharing similarities with that of cemented clays. Correlations between acoustic and piezocone data showed that the stiffness and strength tend to generally increase with increasing GH concentrations. However, several sediment intervals sharing the same hydrates concentration have revealed different features of mechanical behaviour. This was linked to the presence of various GH morphologies within the marine sediments such as groups of hydrate veins or massive hydrate nodules. This in-situ approach allowing both understanding the heterogeneous distribution of GH and characterising their host sediment seems key to assess the potential link between seafloor stability and GH dissociation/dissolution caused by human activities or by natural environmental

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

    Energy Technology Data Exchange (ETDEWEB)

    Herri, J M

    1996-02-02

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

  1. Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions

    Science.gov (United States)

    Bindeman, Ilya N.; Lowenstern, Jacob B.

    2016-01-01

    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 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 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

  2. Phase equilibrium condition of marine carbon dioxide hydrate

    International Nuclear Information System (INIS)

    Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang

    2013-01-01

    Highlights: ► CO 2 hydrate phase equilibrium was studied in simulated marine sediments. ► CO 2 hydrate equilibrium temperature in NaCl and submarine pore water was depressed. ► Coarse-grained silica sand does not affect CO 2 hydrate phase equilibrium. ► The relationship between equilibrium temperature and freezing point was discussed. - Abstract: The phase equilibrium of ocean carbon dioxide hydrate should be understood for ocean storage of carbon dioxide. In this paper, the isochoric multi-step heating dissociation method was employed to investigate the phase equilibrium of carbon dioxide hydrate in a variety of systems (NaCl solution, submarine pore water, silica sand + NaCl solution mixture). The experimental results show that the depression in the phase equilibrium temperature of carbon dioxide hydrate in NaCl solution is caused mainly by Cl − ion. The relationship between the equilibrium temperature and freezing point in NaCl solution was discussed. The phase equilibrium temperature of carbon dioxide hydrate in submarine pore water is shifted by −1.1 K to lower temperature region than that in pure water. However, the phase equilibrium temperature of carbon dioxide hydrate in mixture samples of coarsed-grained silica sand and NaCl solution is in agreement with that in NaCl solution with corresponding concentrations. The relationship between the equilibrium temperature and freezing point in mixture samples was also discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  4. Hysteresis of methane hydrate formation/decomposition at subsea geological conditions

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  5. Investigation on the effect of THF on Nitrogen Hydrate formation under isobaric condition

    Science.gov (United States)

    Jamil, N.; Husin, H.; Aman, Z.; Hassan, Z.

    2018-03-01

    In this paper, we studied nitrogen (N2) hydrate formation in the presence of tetrahydrofuran (THF) under 3 different conditions; different concentration of THF (0, 3 and 30 %(v/v), different temperature setting (room temperature and induced temperature) and different water content (15, 35 and 55 mL) in an isobaric condition. We found that in the presence of THF which acting as an enhancer, hydrate formation kinetic is highly influenced by these parameters. We observed a striking contrast in hydrate formation behaviour observed at room temperature (RT) and induced temperature (IT) with and without the presence of THF under similar operating conditions. At the presence of 30 %(v/v) of THF in 15 mL water, it can be seen that, hydrate tend to form faster than other samples. Visual observation of N2hydrates are also conducted at 30 %(v/v) of THF in 15 mL water.

  6. In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

    Science.gov (United States)

    Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

    2017-12-01

    Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and

  7. BACCHUS 2: an in situ backfill hydration experiment for model validation

    International Nuclear Information System (INIS)

    Volckaert, G.; Bernier, F.; Alonso, E.; Gens, A.

    1995-01-01

    The BACCHUS 2 experiment is an in situ backfill hydration test performed in the HADES underground research facility situated in the plastic Boom clay layer at 220 m depth. The experiment aims at the optimization and demonstration of an installation procedure for a clay based backfill material. The instrumentation has been optimized in such a way that the results of the experiments can be used for the validation of hydro-mechanical codes such a NOSAT developed at the University of Catalunya Spain (UPC). The experimental set-up consists in a bottom flange and a central filter around which the backfill material was applied. The backfill material consist of a mixture of high density clay pellets and clay powder. The experimental set-up and its instrumentation are described in detail. The results of the hydro-mechanical characterization of the backfill material is summarized. (authors). 8 refs., 16 figs., 1 tab

  8. Coupled numerical modeling of gas hydrates bearing sediments from laboratory to field-scale conditions

    Science.gov (United States)

    Sanchez, M. J.; Santamarina, C.; Gai, X., Sr.; Teymouri, M., Sr.

    2017-12-01

    Stability and behavior of Hydrate Bearing Sediments (HBS) are characterized by the metastable character of the gas hydrate structure which strongly depends on thermo-hydro-chemo-mechanical (THCM) actions. Hydrate formation, dissociation and methane production from hydrate bearing sediments are coupled THCM processes that involve, amongst other, exothermic formation and endothermic dissociation of hydrate and ice phases, mixed fluid flow and large changes in fluid pressure. The analysis of available data from past field and laboratory experiments, and the optimization of future field production studies require a formal and robust numerical framework able to capture the very complex behavior of this type of soil. A comprehensive fully coupled THCM formulation has been developed and implemented into a finite element code to tackle problems involving gas hydrates sediments. Special attention is paid to the geomechanical behavior of HBS, and particularly to their response upon hydrate dissociation under loading. The numerical framework has been validated against recent experiments conducted under controlled conditions in the laboratory that challenge the proposed approach and highlight the complex interaction among THCM processes in HBS. The performance of the models in these case studies is highly satisfactory. Finally, the numerical code is applied to analyze the behavior of gas hydrate soils under field-scale conditions exploring different features of material behavior under possible reservoir conditions.

  9. On the conditions of preparation of hydrated rare earth orthovanadates

    Energy Technology Data Exchange (ETDEWEB)

    Nakhodnova, A P; Belousova, E E; Shuba, Yu I; Zaslavskij, L V

    1988-10-01

    The properties of Ln(NO/sub 3/)/sub 3/-Na/sub 3/VO/sub 4/-H/sub 2/O solution series, where Ln is Er, Ho, Eu are investigated by the methods of residual concentrations, conductometry and potentiometry. It is found that at equivalent ratios of the initial components LnVO/sub 4/xmH/sub 2/O hydrated orthovanadates are formed. Deviations towards excess of rare earths or vanadium result in contamination of the compounds by products of side reactions. According to the data on X-ray phase analysis, hydrated erbium, holmium, europium orthovanadates have the zirconium crystal structure typical for anhydrous compounds. It is shown that hydrate water, being a component of orthovanadates, can be referred to adsorbed and interlayer water.

  10. On the conditions of preparation of hydrated rare earth orthovanadates

    International Nuclear Information System (INIS)

    Nakhodnova, A.P.; Belousova, E.E.; Shuba, Yu.I.; Zaslavskij, L.V.

    1988-01-01

    The properties of Ln(NO 3 ) 3 -Na 3 VO 4 -H 2 O solution series, where Ln is Er, Ho, Eu are investigated by the methods of residual concentrations, conductometry and potentiometry. It is found that at equivalent ratios of the initial components LnVO 4 xmH 2 O hydrated orthovanadates are formed. Deviations towards excess of rare earths or vanadium result in contamination of the compounds by products of side reactions. According to the data on X-ray phase analysis, hydrated erbium, holmium, europium orthovanadates have the zirconium crystal structure typical for anhydrous compounds. It is shown that hydrate water, being a component of orthovanadates, can be referred to adsorbed and interlayer water

  11. Hydration of the Atlantis Massif: Halogen, Noble Gas and In-Situ δ18O Constraints

    Science.gov (United States)

    Williams, M. J.; Kendrick, M. A.; Rubatto, D.

    2017-12-01

    A combination of halogen (Cl, Br, I), noble gases (He, Ne, Ar, Kr and Xe) and in situ oxygen isotope analysis have been utilized to investigate the fluid-mobile element record of hydration and alteration processes at the Atlantis Massif (30°N on the Mid-Atlantic Ridge). The sample suite investigated includes serpentinite, talc-amphibole ± chlorite schist and hydrated gabbro recovered by seafloor drilling undertaken at sites on a transect across the Atlantis Massif during IODP Expedition 357. Serpentine mesh and veins analysed in-situ by SHRIMP SI exhibit δ18O from 6‰ down to ≈0‰, suggesting serpentinization temperatures of 150 to >280°C and water/rock ratios >5. Differences of 1.5-2.5‰ are observed between adjacent generations of serpentine, but the δ18O range is similar at each investigated drilling site. Halogen and noble gas abundances in serpentinites, talc-amphibole schist and hydrated gabbro have been measured by noble gas mass spectrometry of both irradiated and non-irradiated samples. Serpentinites contain low abundances of halogens and noble gases (e.g. 70-430 ppm Cl, 4.7-12.2 x 10-14 mol/g 36Ar) relative to other seafloor serpentinites. The samples have systematically different Br/Cl and I/Cl ratios related to their mineralogy. Serpentinites retain mantle-like Br/Cl with a wide variation in I/Cl that stretches toward seawater values. Talc-amphibole schists exhibit depletion of Br and I relative to Cl with increasing Cl abundances, suggesting tremolite exerts strong control on halogen abundance ratios. Serpentinites show no evidence of interaction with halogen-rich sedimentary pore fluids. Iodine abundances are variable across serpentinites, and are decoupled from Br and Cl; iodine enrichment (up to 530 ppb) is observed within relatively oxidised and clay-bearing samples. Serpentinized harzburgites exhibit distinct depletion of Kr and Xe relative to atmospheric 36Ar in seawater. Oxygen isotope compositions and low abundances of both halogens

  12. Effect of cement/wood ratios and wood storage conditions on hydration temperature, hydration time, and compressive strength of wood-cement mixtures

    Science.gov (United States)

    Andy W.C. Lee; Zhongli Hong; Douglas R. Phillips; Chung-Yun Hse

    1987-01-01

    This study investigated the effect of cement/wood ratios and wood storage conditions on hydration temperature, hydration time, and compressive strength of wood-cement mixtures made from six wood species: southern pine, white oak, southern red oak, yellow-poplar, sweetgum, and hickory. Cement/wood ratios varied from 13/1 to 4/1. Wood storage conditions consisted of air-...

  13. Determination of appropriate condition on replacing methane from hydrate with carbon dioxide

    International Nuclear Information System (INIS)

    Zhou Xitang; Fan Shuanshi; Liang Deqing; Du Jianwei

    2008-01-01

    This paper is intended to determine the appropriate conditions for replacing CH 4 from NGH with CO 2 . By analyzing the hydration equilibrium graphs and geotherms, the HSZs of NGH and CO 2 hydrate, both in permafrost and under deep sea, were determined. Based on the above analysis and experimental results, it is found that to replace CH 4 from NGH with gaseous CO 2 , the appropriate experimental condition should be in the area surrounded by four curves: the geotherm, (H-V) CO2 , (L-V) CO2 and (H-V) CH4 , and to replace CH 4 from NGH with liquid CO 2 , the condition should be in the area surrounded by three curves: (L-V) CO2 , (H-L) CO2 and (H-V) CH4 . For conditions in other areas, either CO 2 can not form a hydrate or CH 4 can release little from its hydrate, which are not desirable results

  14. A Numerical Model for the Thermomechanical Conditions During Hydration of Early-age Concrete

    DEFF Research Database (Denmark)

    Hattel, Jesper; Thorborg, Jesper

    2003-01-01

    In the present study, a macroscopic numerical model for the thermomechanical conditions during hydration of early-age concrete is presented. The formulation is based on a semi-coupled, incremental thermomechanical model where the heat production from the hydration process is expressed in terms...... of the maturity and the thermal activation is expressed by the Arrhenius principle. The material properties are assumed to depend on the hydration process via the maturity. The discretization of the governing equations is accomplished by a control volume formulation involving a time-splitting scheme for the heat...

  15. Calculation of the eroei coefficient for natural gas hydrates in laboratory conditions

    Science.gov (United States)

    Siažik, Ján; Malcho, Milan; Čaja, Alexander

    2017-09-01

    In the 1960s, scientists discovered that methane hydrate existed in the gas field in Siberia. Gas hydrates are known to be stable under conditions of high pressure and low temperature that have been recognized in polar regions and in the uppermost part of deep -water sediments below the sea floor. The article deals with the determination of the EROEI coefficient to generate the natural gas hydrate in the device under specific temperature and pressure conditions. Energy returned on energy invested expresses ratio of the amount of usable energy delivered from a particular energy resource to the amount of exergy used to obtain that energy resource. Gas hydrates have been also discussed before decades like potential source mainly for regions with restricted access to conventional hydrocarbons also tactic interest in establishing alternative gas reserves.

  16. Modelling a deep water oil/gas spill under conditions of gas hydrate formation and decomposition

    International Nuclear Information System (INIS)

    Zheng, L.; Yapa, P.D.

    2000-01-01

    A model for the behavior of oil and gas spills at deepwater locations was presented. Such spills are subjected to pressures and temperatures that can convert gases to gas hydrates which are lighter than water. Knowing the state of gases as they rise with the plume is important in predicting the fate of an oil or gas plume released in deepwater. The objective of this paper was to develop a comprehensive jet/plume model which includes computational modules that simulate the gas hydrate formation/decomposition of gas bubbles. This newly developed model is based on the kinetics of hydrate formation and decomposition coupled with mass and heat transfer phenomena. The numerical model was successfully tested using results of experimental data from the Gulf of Mexico. Hydrate formation and decomposition are integrated with an earlier model by Yapa and Zheng for underwater oil or gas jets and plumes. The effects of hydrate on the behavior of an oil or gas plume was simulated to demonstrate the models capabilities. The model results indicate that in addition to thermodynamics, the kinetics of hydrate formation/decomposition should be considered when studying the behavior of oil and gas spills. It was shown that plume behavior changes significantly depending on whether or not the local conditions force the gases to form hydrates. 25 refs., 4 tabs., 12 figs

  17. A pressure core ultrasonic test system for on-board analysis of gas hydrate-bearing sediments under in situ pressures.

    Science.gov (United States)

    Yang, Lei; Zhou, Weihua; Xue, Kaihua; Wei, Rupeng; Ling, Zheng

    2018-05-01

    The enormous potential as an alternative energy resource has made natural gas hydrates a material of intense research interest. Their exploration and sample characterization require a quick and effective analysis of the hydrate-bearing cores recovered under in situ pressures. Here a novel Pressure Core Ultrasonic Test System (PCUTS) for on-board analysis of sediment cores containing gas hydrates at in situ pressures is presented. The PCUTS is designed to be compatible with an on-board pressure core transfer device and a long gravity-piston pressure-retained corer. It provides several advantages over laboratory core analysis including quick and non-destructive detection, in situ and successive acoustic property acquisition, and remission of sample storage and transportation. The design of the unique assembly units to ensure the in situ detection is demonstrated, involving the U-type protecting jackets, transducer precession device, and pressure stabilization system. The in situ P-wave velocity measurements make the detection of gas hydrate existence in the sediments possible on-board. Performance tests have verified the feasibility and sensitivity of the ultrasonic test unit, showing the dependence of P-wave velocity on gas hydrate saturation. The PCUTS has been successfully applied for analysis of natural samples containing gas hydrates recovered from the South China Sea. It is indicated that on-board P-wave measurements could provide a quick and effective understanding of the hydrate occurrence in natural samples, which can assist further resource exploration, assessment, and subsequent detailed core analysis.

  18. A pressure core ultrasonic test system for on-board analysis of gas hydrate-bearing sediments under in situ pressures

    Science.gov (United States)

    Yang, Lei; Zhou, Weihua; Xue, Kaihua; Wei, Rupeng; Ling, Zheng

    2018-05-01

    The enormous potential as an alternative energy resource has made natural gas hydrates a material of intense research interest. Their exploration and sample characterization require a quick and effective analysis of the hydrate-bearing cores recovered under in situ pressures. Here a novel Pressure Core Ultrasonic Test System (PCUTS) for on-board analysis of sediment cores containing gas hydrates at in situ pressures is presented. The PCUTS is designed to be compatible with an on-board pressure core transfer device and a long gravity-piston pressure-retained corer. It provides several advantages over laboratory core analysis including quick and non-destructive detection, in situ and successive acoustic property acquisition, and remission of sample storage and transportation. The design of the unique assembly units to ensure the in situ detection is demonstrated, involving the U-type protecting jackets, transducer precession device, and pressure stabilization system. The in situ P-wave velocity measurements make the detection of gas hydrate existence in the sediments possible on-board. Performance tests have verified the feasibility and sensitivity of the ultrasonic test unit, showing the dependence of P-wave velocity on gas hydrate saturation. The PCUTS has been successfully applied for analysis of natural samples containing gas hydrates recovered from the South China Sea. It is indicated that on-board P-wave measurements could provide a quick and effective understanding of the hydrate occurrence in natural samples, which can assist further resource exploration, assessment, and subsequent detailed core analysis.

  19. Trichloroethylene decomposition and in-situ dry sorption of Cl-products by calcium oxides prepared from hydrated limes.

    Science.gov (United States)

    Gotoh, Yoshimi; Iwata, Goichi; Choh, Kyaw; Kubota, Mitsuhiro; Matsuda, Hitoki

    2011-10-01

    A comparison of CaOs produced by calcining two types of hydrated lime and calcium carbonate was made for decomposition of trichloroethylene and in-situ dry sorption of the decomposed Cl-products using a lab-scale gas flow type tubular packed bed reactor. About 20 mg of CaO sample was mixed with about 2 g of Al2O3 particles and packed in the reactor and allowed to react with a flowing standard gas containing 500 ppm of C2HCl3 (N2 balance) at 673 and 873 K, under the condition that the reaction of CaO with C2HCl3 might be completed within a few hours. It was found that no thermal decomposition of C2HCl3 at or below 673 K was observed in a reactor packed only with Al2O3 particles. However, a considerable amount of decomposition of C2HCl3 was obtained in a reactor packed with CaO and Al2O3, even at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)2 at 673 K, decomposition of 0.42 mol of C2HCl3 and in-situ absorption product of 0.53 mol of CaCl2 were obtained. At 873 K, about 46% of C2HCl3 was thermally decomposed. The total amount of C2HCl3 decomposed in CaO-Al2O3 particle bed at 873 K became nearly twice larger than that at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)2 at 873 K, decomposition of 0.59 mol of C2HCl3 and in-situ absorption product of 0.67 mol of CaCl2 were obtained. Small amounts of C2Cl2, C2Cl4, CCl4, etc. were detected during decomposition of C2HCl3 at 673 and 873 K. It was recognized that the data on decomposition of C2HCl3 as well as in-situ dry sorption of Cl-products in CaO particle bed were correlated with specific surface area of the CaO employed. Copyright © 2011 Elsevier Ltd. All rights reserved.

  20. Assessing the conditions favorable for the occurrence of gas hydrate in the Tuonamu area Qiangtang basin, Qinghai–Tibetan, China

    International Nuclear Information System (INIS)

    He Jianglin; Wang Jian; Fu Xiugen; Zheng Chenggang; Chen Yanting

    2012-01-01

    Highlights: ► This is a pioneer research on the exploration of gas hydrate in Qiangtang basin. ► The factors influencing the stable of gas hydrate in Tuonamu area were studied. ► Simulation shows that gas hydrate stable zone is about 300 m thick in target area. ► Source condition is the key factor for the formation of gas hydrate in this area. ► The areas around the deeper faults are favorable targets for gas hydrate. - Abstract: Qiangtang basin, which is located in the largest continuous permafrost area in Qinghai–Tibetan Plateau, is expected to be a strategic area of gas hydrate exploitation in China. However, relatively little work has been done on the exploration of gas hydrate in this area. In this work, we evaluated the factors controlling the formation of gas hydrate in the Tuonamu area and provided a preliminary insight into gas hydrate distribution in it on the basis of the core samples, seismic data and laboratory analysis. It can be concluded that the source rock in the deeper formation would be dominant thermogenic source for the formation of gas hydrate in Tuonamu area. The thickness of gas hydrate stable zone in this area is about 300 m. The gas hydrate in the area most probably is in the form of gas-hydrate-water. The source condition is the key factor for the formation of gas hydrate and the gas hydrate layer would be mainly present in the form of interlayer in this area. The areas around the deeper faults are the favorable targets for the exploration of gas hydrate in the Tuonamu area.

  1. Hydrogen Storage Capacity of Tetrahydrofuran and Tetra-N-Butylammonium Bromide Hydrates Under Favorable Thermodynamic Conditions

    Directory of Open Access Journals (Sweden)

    Joshua T. Weissman

    2017-08-01

    Full Text Available An experimental study was conducted to evaluate the feasibility of employing binary hydrates as a medium for H2 storage. Two reagents, tetrahydrofuran (THF and tetra-n-butylammonium bromide (TBAB, which had been reported previously to have potential to form binary hydrates with H2 under favorable conditions (i.e., low pressures and high temperatures, were investigated using differential scanning calorimetry and Raman spectroscopy. A scale-up facility was employed to quantify the hydrogen storage capacity of THF binary hydrate. Gas chromatography (GC and pressure drop analyses indicated that the weight percentages of H2 in hydrate were less than 0.1%. The major conclusions of this investigation were: (1 H2 can be stored in binary hydrates at relatively modest pressures and temperatures which are probably feasible for transportation applications; and (2 the storage capacity of H2 in binary hydrate formed from aqueous solutions of THF over a concentration range extending from 2.78 to 8.34 mol % and at temperatures above 263 K and pressures below 11 MPa was <0.1 wt %.

  2. Phase equilibrium conditions of semi-calthrate hydrates of (tetra-n-butyl ammonium chloride + carbon dioxide)

    International Nuclear Information System (INIS)

    Sun, Zhi-Gao; Jiao, Li-Jun; Zhao, Zhi-Gui; Wang, Gong-Liang; Huang, Hai-Feng

    2014-01-01

    Highlights: • Carbon dioxide hydrate stability zone was enlarged with the help of TBAC. • Carbon dioxide uptake into TBAC semi-clathrate hydrates is confirmed. • Equilibrium pressure of hydrate decreased with the increase of TBAC mass concentration. • The addition of TBAC reduces the formation pressures of carbon dioxide hydrate by 2.5 MPa. - Abstract: In the present work, hydrate equilibrium conditions for (tetra-n-butyl ammonium chloride (TBAC) + carbon dioxide + water) mixtures were investigated. Tetra-n-butyl ammonium chloride was reported to form a semi-clathrate hydrate. The experiments were carried out within the TBAC mass fraction range of (0.05 to 0.3). The experimental results showed that the presence of TBAC decreased the formation pressure of carbon dioxide double hydrate within the experimental temperature range. Moreover, pressure reduction was dependent on the TBAC concentration

  3. 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.

    Science.gov (United States)

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

    2015-05-01

    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

  4. Self-preservation and structural transition of gas hydrates during dissociation below the ice point: an in situ study using Raman spectroscopy

    OpenAIRE

    Jin-Rong Zhong; Xin-Yang Zeng; Feng-He Zhou; Qi-Dong Ran; Chang-Yu Sun; Rui-Qin Zhong; Lan-Ying Yang; Guang-Jin Chen; Carolyn A. Koh

    2016-01-01

    The hydrate structure type and dissociation behavior for pure methane and methane-ethane hydrates at temperatures below the ice point and atmospheric pressure were investigated using in situ Raman spectroscopic analysis. The self-preservation effect of sI methane hydrate is significant at lower temperatures (268.15 to 270.15?K), as determined by the stable C-H region Raman peaks and A L/A S value (Ratio of total peak area corresponding to occupancies of guest molecules in large cavities to sm...

  5. In situ bioremediation under high saline conditions

    International Nuclear Information System (INIS)

    Bosshard, B.; Raumin, J.; Saurohan, B.

    1995-01-01

    An in situ bioremediation treatability study is in progress at the Salton Sea Test Base (SSTB) under the NAVY CLEAN 2 contract. The site is located in the vicinity of the Salon Sea with expected groundwater saline levels of up to 50,000 ppm. The site is contaminated with diesel, gasoline and fuel oils. The treatability study is assessing the use of indigenous heterotrophic bacteria to remediate petroleum hydrocarbons. Low levels of significant macro nutrients indicate that nutrient addition of metabolic nitrogen and Orthophosphate are necessary to promote the process, requiring unique nutrient addition schemes. Groundwater major ion chemistry indicates that precipitation of calcium phosphorus compounds may be stimulated by air-sparging operations and nutrient addition, which has mandated the remedial system to include pneumatic fracturing as an option. This presentation is tailored at an introductory level to in situ bioremediation technologies, with some emphasize on innovations in sparge air delivery, dissolved oxygen uptake rates, nutrient delivery, and pneumatic fracturing that should keep the expert's interest

  6. Molecular dynamics simulations of a fully hydrated dipalmitoyl phosphatidylcholine bilayer with different macroscopic boundary conditions and parameters

    NARCIS (Netherlands)

    Tieleman, D.P; Berendsen, H.J.C.

    1996-01-01

    We compared molecular dynamics simulations of a bilayer of 128 fully hydrated phospholipid (DPPC) molecules, using different parameters and macroscopic boundary conditions. The same system was studied under constant pressure, constant volume, and constant surface tension boundary conditions, with

  7. Study of belite calcium sulfo-aluminate cement potential for zinc conditioning: From hydration to durability

    International Nuclear Information System (INIS)

    Berger, St.

    2009-12-01

    Calcium silicate cements are widely used for low- and intermediate-level radioactive waste conditioning. However, wastes produced by nuclear activities are very diverse and some of their components may chemically react with cement phases. For instance, ashes resulting from the incineration of technological wastes including neoprene and polyvinylchloride may contain substantial amounts of soluble zinc chloride. This compound is known to strongly delay or inhibit Portland cement setting. One approach to limit adverse cement-waste interactions is to select a binder showing a better compatibility with the waste while keeping cement matrix advantages (low cost, simple process, hydration with water provided by the waste...). This work thus investigates the potential of calcium sulfo-aluminate cement for zinc Zn(II) immobilization. Four aspects were considered: hydration (kinetics and products formed), properties of hydrated binders, mechanisms of zinc retention and durability of the cement pastes (based on leaching experiments and modelling). The influence of three main parameters was assessed: the gypsum content of the cement, the concentration of ZnCl 2 and the thermal evolution at early age. It follows that materials based on a calcium sulfo-aluminate cement containing 20% gypsum are interesting candidates for zinc Zn(II) stabilization/solidification: there is no delay in hydration, mineralogy of the hydrated phases is slightly dependent on thermal history, mechanical strength is high, dimensional changes are limited and zinc Zn(II) is well immobilized, even if the cement paste is leached by pure water during a long period (90 d). (author)

  8. A Long Gravity-Piston Corer Developed for Seafloor Gas Hydrate Coring Utilizing an In Situ Pressure-Retained Method

    Directory of Open Access Journals (Sweden)

    Lin-Yi Gu

    2013-07-01

    Full Text Available A corer, which can obtain long in situ pressure-retained sediments of up to 30 m core containing gas hydrates, has been applied in the South China Sea (SCS dozens of times. The corer presented in this paper is a convenient, efficient and economical long in situ pressure-retained coring and research tool for submarine sediments, that can applied to completely cope with all sediments close to the seafloor ranging from shallow waters to the deep sea depths of 6000 m. This article mainly presents the overall structure, working principles, key pressure-retained components, coring mechanism, sea trials and outlook of the corer. The analyses found that the coring ability was affected by formation characteristics, the outer diameter of the core barrels and inner diameter of the core liners, the shapes of the cutter and the dead weight of the corer. This study can provide the practical basis for the structural optimization of this type of corer and designs for corers with greater penetrability. Sea trials showed that the developed corer presented in this paper can support the in situ pressure of the seafloor sediment core, which is an improvement over the conventional piston corer.

  9. Development of salt hydrate eutectics as latent heat storage for air conditioning and cooling

    International Nuclear Information System (INIS)

    Efimova, Anastasia; Pinnau, Sebastian; Mischke, Matthias; Breitkopf, Cornelia; Ruck, Michael; Schmidt, Peer

    2014-01-01

    Graphical abstract: - Highlights: • Inorganic salt hydrates. • Latent heat thermal energy storage. • Thermal behavior of melting and crystallization. • Cycling stability. • Nucleation. - Abstract: Sustainable air conditioning systems require heat reservoirs that operate between 4 and 20 °C. A systematic search for binary and ternary eutectics of inorganic salts and salt hydrates with melting temperatures in this temperature regime and with high enthalpies of fusion has been performed by means of differential scanning calorimetry (DSC). Promising results were obtained for the pseudo-ternary system Zn(NO 3 ) 2 ·6H 2 O, Mn(NO 3 ) 2 ·4H 2 O, and KNO 3 with the melting temperature range 18–21 °C and the enthalpy of fusion of about 110 kJ kg −1 . Suitable nucleating and thickening agents have been found and tested to prevent the mixture from supercooling and phase separation

  10. Modeling hydrate formation conditions in the presence of electrolytes and polar inhibitor solutions

    International Nuclear Information System (INIS)

    Osfouri, Shahriar; Azin, Reza; Gholami, Reza; Izadpanah, Amir Abbas

    2015-01-01

    Highlights: • A new predictive model is proposed for prediction of hydrate formation pressures. • A new local composition model was used to evaluate water activity in the presence of electrolyte. • MEG, DEG and TEG were used to test ability of the proposed model in the presence of polar inhibitors. • Cage occupancies by methane for the small cage were higher than carbon dioxide for gas mixtures. • The proposed model gives better match with experimental data in mixed electrolyte solutions. - Abstract: In this paper, a new predictive model is proposed for prediction of gas hydrate formation conditions in the presence of single and mixed electrolytes and solutions containing both electrolyte and a polar inhibitor such as monoethylene glycol (MEG), diethylene glycol (DEG) and triethylene glycol (TEG). The proposed model is based on the γ–φ approach, which uses modified Patel–Teja equation of state (VPT EOS) for characterizing the vapor phase, the solid solution theory by van der Waals and Platteeuw for modeling the hydrate phase, the non-electrolyte NRTL-NRF local composition model and Pitzer–Debye–Huckel equation as short-range and long-range contributions to calculate water activity in single electrolyte solutions. Also, the Margules equation was used to determine the activity of water in solutions containing polar inhibitor (glycols). The model predictions are in acceptable agreement with experimental data. For single electrolyte solutions, the model predictions are similar to available models, while for mixtures of electrolytes and mixtures of electrolytes and inhibitors, the proposed model gives significantly better predictions. In addition, the absolute average deviation of hydrate formation pressures (AADP) for 144 experimental data in solutions containing single electrolyte is 5.86% and for 190 experimental data in mixed electrolytes solutions is 5.23%. Furthermore, the proposed model has an AADP of 14.13%, 5.82% and 5.28% in solutions

  11. Custom AFM for X-ray beamlines: in situ biological investigations under physiological conditions

    Energy Technology Data Exchange (ETDEWEB)

    Gumí-Audenis, B. [ESRF, The European Synchrotron, Grenoble (France); Institute for Bioengineering of Catalonia (IBEC), Barcelona (Spain); Physical Chemistry Department, Universitat de Barcelona, Barcelona (Spain); Networking Biomedical Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), Madrid (Spain); Carlà, F. [ESRF, The European Synchrotron, Grenoble (France); Vitorino, M. V. [University of Lisboa, Falculty of Science, Biosystems and Integrative Sciences Institute - BIOISI, Lisbon (Portugal); Panzarella, A. [ESRF, The European Synchrotron, Grenoble (France); Porcar, L. [Institut Laue-Langevin, Grenoble (France); Boilot, M. [ORTEC, Marseille (France); Guerber, S. [CEA, LETI Grenoble (France); Bernard, P. [ESRF, The European Synchrotron, Grenoble (France); Rodrigues, M. S. [University of Lisboa, Falculty of Science, Biosystems and Integrative Sciences Institute - BIOISI, Lisbon (Portugal); Sanz, F.; Giannotti, M. I. [Institute for Bioengineering of Catalonia (IBEC), Barcelona (Spain); Physical Chemistry Department, Universitat de Barcelona, Barcelona (Spain); Networking Biomedical Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), Madrid (Spain); Costa, L., E-mail: luca.costa@esrf.fr [ESRF, The European Synchrotron, Grenoble (France)

    2015-09-30

    The performance of a custom atomic force microscope for grazing-incidence X-ray experiments on hydrated soft and biological samples is presented. A fast atomic force microscope (AFM) has been developed that can be installed as a sample holder for grazing-incidence X-ray experiments at solid/gas or solid/liquid interfaces. It allows a wide range of possible investigations, including soft and biological samples under physiological conditions (hydrated specimens). The structural information obtained using the X-rays is combined with the data gathered with the AFM (morphology and mechanical properties), providing a unique characterization of the specimen and its dynamics in situ during an experiment. In this work, lipid monolayers and bilayers in air or liquid environment have been investigated by means of AFM, both with imaging and force spectroscopy, and X-ray reflectivity. In addition, this combination allows the radiation damage induced by the beam on the sample to be studied, as has been observed on DOPC and DPPC supported lipid bilayers under physiological conditions.

  12. Correlations between skin hydration parameters and corneocyte-derived parameters to characterize skin conditions.

    Science.gov (United States)

    Masaki, Hitoshi; Yamashita, Yuki; Kyotani, Daiki; Honda, Tatsuya; Takano, Kenichi; Tamura, Toshiyasu; Mizutani, Taeko; Okano, Yuri

    2018-03-30

    Skin hydration is generally assessed using the parameters of skin surface water content (SWC) and trans-epidermal water loss (TEWL). To date, few studies have characterized skin conditions using correlations between skin hydration parameters and corneocyte parameters. The parameters SWC and TEWL allow the classification of skin conditions into four distinct Groups. The purpose of this study was to assess the characteristics of skin conditions classified by SWC and TEWL for correlations with parameters from corneocytes. A human volunteer test was conducted that measured SWC and TEWL. As corneocyte-derived parameters, the size and thick abrasion ratios, the ratio of sulfhydryl groups and disulfide bonds (SH/SS) and CP levels were analyzed. Volunteers were classified by their median SWC and TEWL values into 4 Groups: Group I (high SWC/low TEWL), Group II (high SWC/high TEWL), Group III (low SWC/low TEWL), and Group IV (low SWC/high TEWL). Group IV showed a significantly smaller size of corneocytes. Groups III and IV had significantly higher thick abrasion ratios and CP levels. Group I had a significantly lower SH/SS value. The SWC/TEWL value showed a decline in order from Group I to Group IV. Groups classified by their SWC and TEWL values showed characteristic skin conditions. We propose that the SWC and TEWL ratio is a comprehensive parameter to assess skin conditions. © 2018 Wiley Periodicals, Inc.

  13. Magnetic resonance microscopy for assessment of morphological changes in hydrating hydroxypropylmethylcellulose matrix tablets in situ-is it possible to detect phenomena related to drug dissolution within the hydrated matrices?

    Science.gov (United States)

    Kulinowski, Piotr; Młynarczyk, Anna; Jasiński, Krzysztof; Talik, Przemysław; Gruwel, Marco L H; Tomanek, Bogusław; Węglarz, Władysław P; Dorożyński, Przemysław

    2014-09-01

    So far, the hydrated part of the HPMC matrix has commonly been denoted as a "gel" or "pseudogel" layer. No MRI-based results have been published regarding observation of internal phenomena related to drug dissolution inside swelling polymeric matrices during hydration. The purpose of the study was to detect such phenomena. Multiparametric, spatially and temporally resolved T2 MR relaxometry, in situ, was applied to study formation of the hydration progress in HPMC matrix tablets loaded with L-dopa and ketoprofen using a 11.7 T MRI system. Two spin-echo based pulse sequences were used, one of them specifically designed to study short T2 signals. Two components in the T2 decay envelope were estimated and spatial distributions of their parameters, i.e. amplitudes and T2 values, were obtained. Based on the data, different region formation patterns (i.e. multilayer structure) were registered depending on drug presence and solubility. Inside the matrix with incorporated sparingly soluble drug a specific layer formation due to drug dissolution was detected, whereas a matrix with very slightly soluble drug does not form distinct external "gel-like" layer. We have introduced a new paradigm in the characterization of hydrating matrices using (1)H MRI methods. It reflects molecular mobility and concentration of water inside the hydrated matrix. For the first time, drug dissolution related phenomena, i.e. particular front and region formation, were observed by MRI methods.

  14. Phase equilibrium condition measurements in nitrogen and air clathrate hydrate forming systems at temperatures below freezing point of water

    International Nuclear Information System (INIS)

    Yasuda, Keita; Oto, Yuya; Shen, Renkai; Uchida, Tsutomu; Ohmura, Ryo

    2013-01-01

    Highlights: • Phase equilibrium conditions in the nitrogen and modelled air hydrate forming systems are measured. • Measurements are conducted at temperatures below the freezing point of water. • Results have relevance to the air hydrate formation in the ice sheets. • Measured data are quantitatively compared with the previously reported values. • Range of the equilibrium measurements was from (242 to 268) K. -- Abstract: Contained in this paper are the three phase equilibrium conditions of the (ice + clathrate hydrate + guest-rich) vapour in the (nitrogen + water) and the modelled (air + water) systems at temperatures below the freezing point of water. The precise determination of the equilibrium conditions in those systems are of importance for the analysis of the past climate change using the cored samples from the ice sheets at Antarctica and Greenland because the air hydrates keep the ancient climate signals. The mole ratio of the modelled air composed of nitrogen and oxygen is 0.790:0.210. The equilibrium conditions were measured by the batch, isochoric procedure. The temperature range of the measurements in the nitrogen hydrate forming system is (244.05 < T < 266.55) K and the corresponding equilibrium pressure range is (7.151 < p < 12.613) MPa. The temperature range of the measurements in the modelled air hydrate forming system is (242.55 < T < 267.85) K, and the corresponding equilibrium pressure range is (6.294 < p < 12.144) MPa. The data obtained quantitatively compared with the previously reported data

  15. In Situ Distribution And Speciation Of Toxic Copper, Nickel, And Zinc In Hydrated Roots Of Cowpea

    Science.gov (United States)

    The phytotoxicity of trace metals is of global concern due to contamination of the landscape by human activities. Using synchrotron-based X-ray fluorescence microscopy and X-ray absorption spectroscopy, the distribution and speciation of Cu, Ni, and Zn was examined in situ

  16. Historical methane hydrate project review

    Science.gov (United States)

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

    2013-01-01

    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

  17. Glycerol and urea can be used to increase skin permeability in reduced hydration conditions.

    Science.gov (United States)

    Björklund, Sebastian; Engblom, Johan; Thuresson, Krister; Sparr, Emma

    2013-12-18

    The natural moisturizing factor (NMF) is a group of hygroscopic molecules that is naturally present in skin and protects from severe drying. Glycerol and urea are two examples of NMF components that are also used in skin care applications. In the present study, we investigate the influence of glycerol and urea on the permeability of a model drug (metronidazole, Mz) across excised pig skin membranes at different hydrating conditions. The degree of skin hydration is regulated by the gradient in water activity across the membrane, which in turn depends on the water activity of the formulation in contact with the skin membrane. Here, we determine the water activity of all formulations employed using an isothermal calorimetric method. Thus, the gradient in water activity is controlled by a novel experimental set-up with well-defined boundary conditions on both sides of the skin membrane. The results demonstrate that glycerol and urea can retain high steady state flux of Mz across skin membranes at dehydrating conditions, which otherwise would decrease the permeability due to dehydration. X-ray diffraction measurements are performed to give insight into the effects of glycerol and urea on SC molecular organization. The novel steady state flux results can be related to the observation that water, glycerol, and urea all affect the structural features of the SC molecular components in a similar manner. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

  18. Application of conditional simulation of heterogeneous rock properties to seismic scattering and attenuation analysis in gas hydrate reservoirs

    Science.gov (United States)

    Huang, Jun-Wei; Bellefleur, Gilles; Milkereit, Bernd

    2012-02-01

    We present a conditional simulation algorithm to parameterize three-dimensional heterogeneities and construct heterogeneous petrophysical reservoir models. The models match the data at borehole locations, simulate heterogeneities at the same resolution as borehole logging data elsewhere in the model space, and simultaneously honor the correlations among multiple rock properties. The model provides a heterogeneous environment in which a variety of geophysical experiments can be simulated. This includes the estimation of petrophysical properties and the study of geophysical response to the heterogeneities. As an example, we model the elastic properties of a gas hydrate accumulation located at Mallik, Northwest Territories, Canada. The modeled properties include compressional and shear-wave velocities that primarily depend on the saturation of hydrate in the pore space of the subsurface lithologies. We introduce the conditional heterogeneous petrophysical models into a finite difference modeling program to study seismic scattering and attenuation due to multi-scale heterogeneity. Similarities between resonance scattering analysis of synthetic and field Vertical Seismic Profile data reveal heterogeneity with a horizontal-scale of approximately 50 m in the shallow part of the gas hydrate interval. A cross-borehole numerical experiment demonstrates that apparent seismic energy loss can occur in a pure elastic medium without any intrinsic attenuation of hydrate-bearing sediments. This apparent attenuation is largely attributed to attenuative leaky mode propagation of seismic waves through large-scale gas hydrate occurrence as well as scattering from patchy distribution of gas hydrate.

  19. The structure of hydrate bearing fine grained marine sediments

    Energy Technology Data Exchange (ETDEWEB)

    Priest, J.; Kingston, E.; Clayton, C. [Southampton Univ., Highfield (United Kingdom). School of Civil Engineering and the Environment; Schultheiss, P.; Druce, M. [Geotek Ltd., Daventry (United Kingdom)

    2008-07-01

    This paper discussed the structure of naturally occurring methane gas hydrates in fine-grained sediments from core samples recovered using in situ pressures from the eastern margin of the Indian Ocean. High resolution X-ray computed tomography (CT) images were taken of gas hydrate cores. The hydrate structure was examined and comparisons were made between low resolution X-ray images obtained on the cores prior to sub-sectioning and depressurization procedures. The X-ray images showed the presence of high-angle, sub-parallel veins within the recovered sediments. The scans indicated that the hydrates occurred as fracture filing veins throughout the core. Fracture orientation was predominantly sub-vertical. Thick millimetric hydrate veins were composed of sub-millimetric veins with variations in fracture angle. The analysis indicated that hydrate formation was episodic in nature and subject to changes in the stress regime. Results of the study showed that depressurization and subsequent freezing alter the structure of the sediment even when the gas hydrate has not been altered. A large proportion of the hydrate survived when outside of its stability region. The self-preserving behaviour of the hydrate was attributed to the endothermic nature of gas hydrate dissociation. It was concluded that the accurate physical characterization of gas hydrates can only be conducted when the core section remains under in situ stress conditions. 13 refs., 9 figs.

  20. Differential gene expression in Pyropia columbina (Bangiales, Rhodophyta under natural hydration and desiccation conditions

    Directory of Open Access Journals (Sweden)

    Loretto Contreras-Porcia

    2013-11-01

    Full Text Available In rocky shores, desiccation is triggered by daily tide changes, and experimental evidence suggests that local distribution of algal species across the intertidal rocky zone is related to their capacity to tolerate desiccation. In this context, the permanence of Pyropia columbina in the high intertidal rocky zone is explained by its exceptional physiological tolerance to desiccation. This study explored the metabolic pathways involved in tolerance to desiccation in the Chilean P. columbina, by characterizing its transcriptome under contrasting conditions of hydration. We obtained 1,410 ESTs from two subtracted cDNA libraries in naturally hydrated and desiccated fronds. Results indicate that transcriptome from both libraries contain transcripts from diverse metabolic pathways related to tolerance. Among the transcripts differentially expressed, 15% appears involved in protein synthesis, processing and degradation, 14.4% are related to photosynthesis and chloroplast, 13.1% to respiration and mitochondrial function (NADH dehydrogenase and cytochrome c oxidase proteins, 10.6% to cell wall metabolism, and 7.5% are involved in antioxidant activity, chaperone and defense factors (catalase, thioredoxin, heat shock proteins, cytochrome P450. Both libraries highlight the presence of genes/proteins never described before in algae. This information provides the first molecular work regarding desiccation tolerance in P. columbina, and helps, to some extent, explaining the classical patterns of ecological distribution described for algae across the intertidal zone.

  1. Development of salt hydrate eutectics as latent heat storage for air conditioning and cooling

    Energy Technology Data Exchange (ETDEWEB)

    Efimova, Anastasia [Brandenburgische Technische Universität (BTU) Cottbus – Senftenberg, Chair of Inorganic Chemistry, Großenhainer Str. 57, 01968 Senftenberg (Germany); Pinnau, Sebastian; Mischke, Matthias; Breitkopf, Cornelia [Technische Universität Dresden, Chair of Technical Thermodynamics, Helmholtzstr. 14, 01069 Dresden (Germany); Ruck, Michael [Technische Universität Dresden, Chair of Inorganic Chemistry, Bergstr. 66, 01062 Dresden (Germany); Schmidt, Peer, E-mail: peer.schmidt@hs-lausitz.de [Brandenburgische Technische Universität (BTU) Cottbus – Senftenberg, Chair of Inorganic Chemistry, Großenhainer Str. 57, 01968 Senftenberg (Germany)

    2014-01-10

    Graphical abstract: - Highlights: • Inorganic salt hydrates. • Latent heat thermal energy storage. • Thermal behavior of melting and crystallization. • Cycling stability. • Nucleation. - Abstract: Sustainable air conditioning systems require heat reservoirs that operate between 4 and 20 °C. A systematic search for binary and ternary eutectics of inorganic salts and salt hydrates with melting temperatures in this temperature regime and with high enthalpies of fusion has been performed by means of differential scanning calorimetry (DSC). Promising results were obtained for the pseudo-ternary system Zn(NO{sub 3}){sub 2}·6H{sub 2}O, Mn(NO{sub 3}){sub 2}·4H{sub 2}O, and KNO{sub 3} with the melting temperature range 18–21 °C and the enthalpy of fusion of about 110 kJ kg{sup −1}. Suitable nucleating and thickening agents have been found and tested to prevent the mixture from supercooling and phase separation.

  2. 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.

    2004-10-15

    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)

  3. Insights into the dynamics of in situ gas hydrate formation and dissociation at the Bush Hill gas hydrate field, Gulf of Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Solomon, Evan A.; Kastner, Miriam; Robertson, Gretchen; Jannasch, Hans; Weinstein, Yishai

    2005-07-01

    Four newly designed flux meters called the MOSQUITO (Multiple Orifice Sampler and Quantitative Injection Tracer Observer), capable of measuring fluid flow rates and sampling pore fluid chemistry simultaneously, and two temperature loggers were deployed for 430 days adjacent to the Bush Hill hydrate mound in the northern Gulf of Mexico (GC 185). The main objective of the deployment was to understand how chemistry, temperature, and subsurface hydrology dynamically influence the growth and dissociation of the gas hydrate mound. The flux meters were deployed in a mussel field, in bacterial mats, in a tubeworm field, and at a background site approximately 100 m southwest of the hydrate mound. Results from the longterm chemical monitoring suggest that this system is not in dynamic equilibrium. Gas hydrate actively formed within the mussel field adjacent to the most active gas vent, in the tubeworm field, and at the background site. The hydrology is variable with upward flow rates ranging from 1-90 cm/yr and downward flow rates from 3-130 cm/yr. Two distinct hydrologic pulsing events were sampled across the three mound sites, which advect a fluid from depth that further stabilizes the gas hydrate deposit. The hydrogeochemistry at Bush Hill seems to be influenced by multiple mechanisms such as active formation of gas hydrate, fluid influx and outflux due to active venting of CH4 at transient methane seeps at and near the mound, local salt tectonics, and density driven convection. The fluxes of fluid, solutes, and methane may have a significant impact on the seafloor biochemical environment and the water column chemistry at Bush Hill. (Author)

  4. Novel method reveals a narrow phylogenetic distribution of bacterial dispersers in environmental communities exposed to low hydration conditions

    DEFF Research Database (Denmark)

    Krüger, U. S.; Bak, F.; Aamand, J.

    2018-01-01

    In this study, we developed a method that provides community-level surface dispersal profiles under controlled hydration conditions from environmental samples and enables us to isolate and uncover the diversity of the fastest bacterial dispersers. The method expands on the Porous Surface Model (PSM...... Pseudomonas putida and Flavobacterium johnsoniae strains from their non-motile mutants. Applying the method to soil and lake water bacterial communities showed that community-scale dispersal declined as conditions became drier. However, for both communities, dispersal was detected even under low hydration...... dispersers were substantially less diverse than the total communities. The dispersing fraction of the soil microbial community was dominated by Pseudomonas which increased in abundance at low hydration conditions, while the dispersing fraction of the lake community was dominated by Aeromonas and, under wet...

  5. Rapid hydrogen hydrate growth from non-stoichiometric tuning mixtures during liquid nitrogen quenching.

    Science.gov (United States)

    Grim, R Gary; Kerkar, Prasad B; Sloan, E Dendy; Koh, Carolyn A; Sum, Amadeu K

    2012-06-21

    In this study the rapid growth of sII H(2) hydrate within 20 min of post formation quenching towards liquid nitrogen (LN(2)) temperature is presented. Initially at 72 MPa and 258 K, hydrate samples would cool to the conditions of ~60 MPa and ~90 K after quenching. Although within the stability region for H(2) hydrate, new hydrate growth only occurred under LN(2) quenching of the samples when preformed hydrate "seeds" of THF + H(2) were in the presence of unconverted ice. The characterization of hydrate seeds and the post-quenched samples was performed with confocal Raman spectroscopy. These results suggest that quenching to LN(2) temperature, a common preservation technique for ex situ hydrate analysis, can lead to rapid unintended hydrate growth. Specifically, guest such as H(2) that may otherwise need sufficiently long induction periods to nucleate, may still experience rapid growth through an increased kinetic effect from a preformed hydrate template.

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

    NARCIS (Netherlands)

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

    2012-01-01

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

  7. In situ conditioning for proton storage ring vacuum systems

    International Nuclear Information System (INIS)

    Blechschmidt, D.

    1978-01-01

    Average pressure and vacuum-stability limit as expected in the presence of a proton beam were measured after in situ treatments such as bakeout under various conditions, argon glow-discharge cleaning and sputter deposition of titanium. Measurements were carried out for test pipes made of stainless steel (untreated, electropolished, or cooled to 77 K), pure titanium and aluminum alloy. The measurement method used to obtain the vacuum-stability limit in the laboratory and in a prototype system is described. The results can be applied also to other systems of different geometry by use of scaling laws. In situ conditioning generally has a stronger influence on vacuum performance than a particular choice of material. Bakeout gives low average pressures and rather good vacuum stability. Glow discharges also increase the vacuum stability but have only a small effect on the static pressure. Coating the beam-pipe wall with titanium by in situ sputtering provides large linear pumping, thus a lower pressure and an extremely good vacuum stability

  8. In situ thermal conductivity of gas-hydrate-bearing sediments of the Mallik 5L-38 well

    Science.gov (United States)

    Henninges, J.; Huenges, E.; Burkhardt, H.

    2005-11-01

    Detailed knowledge about thermal properties of rocks containing gas hydrate is required in order to quantify processes involving gas hydrate formation and decomposition in nature. In the framework of the Mallik 2002 program, three wells penetrating a continental gas hydrate occurrence under permafrost were successfully equipped with permanent fiber-optic distributed temperature sensing cables. Temperature data were collected over a 21-month period after completing the wells. Thermal conductivity profiles were calculated from the geothermal data as well as from a petrophysical model derived from the available logging data and application of mixing law models. Results indicate that thermal conductivity variations are mainly lithologically controlled with a minor influence from hydrate saturation. Average thermal conductivity values of the hydrate-bearing sediments range between 2.35 and 2.77 W m-1 K-1. Maximum gas hydrate saturations can reach up to about 90% at an average porosity of 0.3.

  9. Physical Properties of Gas Hydrates: A Review

    Energy Technology Data Exchange (ETDEWEB)

    Gabitto, Jorge [Prairie View A& M University; Tsouris, Costas [ORNL

    2010-01-01

    Methane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 1016?m3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.

  10. [Laser Raman Spectroscopy and Its Application in Gas Hydrate Studies].

    Science.gov (United States)

    Fu, Juan; Wu, Neng-you; Lu, Hai-long; Wu, Dai-dai; Su, Qiu-cheng

    2015-11-01

    Gas hydrates are important potential energy resources. Microstructural characterization of gas hydrate can provide information to study the mechanism of gas hydrate formation and to support the exploitation and application of gas hydrate technology. This article systemly introduces the basic principle of laser Raman spectroscopy and summarizes its application in gas hydrate studies. Based on Raman results, not only can the information about gas composition and structural type be deduced, but also the occupancies of large and small cages and even hydration number can be calculated from the relative intensities of Raman peaks. By using the in-situ analytical technology, laser Raman specstropy can be applied to characterize the formation and decomposition processes of gas hydrate at microscale, for example the enclathration and leaving of gas molecules into/from its cages, to monitor the changes in gas concentration and gas solubility during hydrate formation and decomposition, and to identify phase changes in the study system. Laser Raman in-situ analytical technology has also been used in determination of hydrate structure and understanding its changing process under the conditions of ultra high pressure. Deep-sea in-situ Raman spectrometer can be employed for the in-situ analysis of the structures of natural gas hydrate and their formation environment. Raman imaging technology can be applied to specify the characteristics of crystallization and gas distribution over hydrate surface. With the development of laser Raman technology and its combination with other instruments, it will become more powerful and play a more significant role in the microscopic study of gas hydrate.

  11. Methane Production and Carbon Capture by Hydrate Swapping

    DEFF Research Database (Denmark)

    Mu, Liang; von Solms, Nicolas

    2017-01-01

    There are essentially two different approaches to producing methane from natural gas hydrate reservoirs, either bring the hydrate out of its thermodynamic stability region or expose the hydrate to a substance that will form a more stable hydrate structure, forcing an in situ swapping of the trapped...... experimental runs were performed to examine the influence of operating conditions on methane production by CO2/(CO2 + N2) injection in the temperature range of 274.15–277.15 K and 7.039–10.107 MPa pressure. Our results show that the use of the (CO2 + N2) binary gas mixture is advantageous compared to the use...

  12. Hydrate dissociation conditions for gas mixtures containing carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons using SAFT

    International Nuclear Information System (INIS)

    Li Xiaosen; Wu Huijie; Li Yigui; Feng Ziping; Tang Liangguang; Fan Shuanshi

    2007-01-01

    A new method, a molecular thermodynamic model based on statistical mechanics, is employed to predict the hydrate dissociation conditions for binary gas mixtures with carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons in the presence of aqueous solutions. The statistical associating fluid theory (SAFT) equation of state is employed to characterize the vapor and liquid phases and the statistical model of van der Waals and Platteeuw for the hydrate phase. The predictions of the proposed model were found to be in satisfactory to excellent agreement with the experimental data

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

    DEFF Research Database (Denmark)

    Zuo, You-Xiang; Stenby, Erling Halfdan

    1997-01-01

    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...... employs the Barkan and Sheinin hydrate model for the description of the hydrate phase, the original Patel-Teja equation of state for the vapor phase fugacities, and the MPT EOS (instead of the activity coefficient model) for the activity of water in the aqueous phase. The new method has succesfully...

  14. A consistent and verifiable macroscopic model for the dissolution of liquid CO2 in water under hydrate forming conditions

    International Nuclear Information System (INIS)

    Radhakrishnan, R.; Demurov, A.; Trout, B.L.; Herzog, H.

    2003-01-01

    Direct injection of liquid CO 2 into the ocean has been proposed as one method to reduce the emission levels of CO 2 into the atmosphere. When liquid CO 2 is injected (normally as droplets) at ocean depths >500 m, a solid interfacial region between the CO 2 and the water is observed to form. This region consists of hydrate clathrates and hinders the rate of dissolution of CO 2 . It is, therefore, expected to have a significant impact on the injection of liquid CO 2 into the ocean. Up until now, no consistent and predictive model for the shrinking of droplets of CO 2 under hydrate forming conditions has been proposed. This is because all models proposed to date have had too many unknowns. By computing rates of the physical and chemical processes in hydrates via molecular dynamics simulations, we have been able to determine independently some of these unknowns. We then propose the most reasonable model and use it to make independent predictions of the rates of mass transfer and thickness of the hydrate region. These predictions are compared to measurements, and implications to the rates of shrinkage of CO 2 droplets under varying flow conditions are discussed. (author)

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

    Science.gov (United States)

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

    2016-01-19

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

  16. Can hydrate dissolution experiments predict the fate of a natural hydrate system?

    Energy Technology Data Exchange (ETDEWEB)

    Hester, K.C.; Peltzer, E.T.; Dunk, R.M.; Walz, P.M.; Brewer, P.G. [Monterey Bay Aquarium Research Inst., Moss Landing, CA (United States); Dendy Sloan, E. [Colorado School of Mines, Golden, CO (United States). Center for Hydrate Research

    2008-07-01

    Gas hydrates are naturally occurring compounds found in permafrost regions and in oceans. In the natural environment, sufficient temperature and pressure conditions for hydrate formation exist over a significant portion of the ocean. However, in addition to pressure and temperature, the chemical potential of the gas in the hydrate must be equal to the surrounding waters. If the concentration of the gas in surrounding water is under-saturated with respect to the gas in the hydrate, the hydrate will dissolve to drive the system towards chemical equilibrium. This paper presented a dissolution study of exposed hydrate from outcrops at Barkley Canyon, located off Vancouver Island, British Columbia. A previous field experiment on synthetic methane hydrate samples had demonstrated that mass transfer controlled dissolution in under-saturated seawater. However, seafloor hydrate outcrops have been shown to have significant longevity compared to expected dissolution rates based upon convective boundary layer diffusion calculations. An in-situ dissolution experiment was performed on two distinct natural hydrate fabrics in order to help resolve this apparent disconnect between the dissolution rates of synthetic and natural hydrate. The paper presented a map of Barkley Canyon and discussed the field measurements and methods for the study. Exposed outcrops of gas hydrates were cored using a specially constructed stainless steel coring device and a hydraulic ram was located inside the corer. Hydrate samples were cored directly using the a manipulator arm and then injected into a sampling cell. The hydrate was then added to an open mesh exposure container, which allowed for exposure to ambient benthic currents with minimal disturbance. As well, in order to observe the slow dissolution of the hydrate in seawater at Barkley Canyon, time-lapse photography was employed. Last, the paper presented the results of the hydrate fabric porosities and hydrate dissolution rates. It was

  17. An Examination of the Prediction of Hydrate Formation Conditions in the Presence of Thermodynamic Inhibitors

    Directory of Open Access Journals (Sweden)

    Carollina de M. Molinari O. Antunes

    Full Text Available Abstract Gas hydrates are crystalline compounds, solid structures where water traps small guest molecules, typically light gases, in cages formed by hydrogen bonds. They are notorious for causing problems in oil and gas production, transportation and processing. Gas hydrates may form at pressures and temperatures commonly found in natural gas and oil production pipelines, thus causing partial or complete pipe blockages. In order to inhibit hydrate formation, chemicals such as alcohols (e.g., ethanol, methanol, mono-ethylene glycol and salts (sodium, magnesium or potassium chloride are injected into the produced stream. The purpose of this work is to briefly review the literature on hydrate formation in mixtures containing light gases (hydrocarbons and carbon dioxide and water in the presence of thermodynamic inhibitors. Four calculation methods to predict hydrate formation in those systems were examined and compared. Three commercial packages (Multiflash®, PVTSim® and CSMGem and a hydrate prediction routine in Fortran90 using the van der Waals and Platteeuw theory and the Peng-Robinson equation of state were tested. Predictions given by the four methods were compared to independent experimental data from the literature. In general, the four methods were found to be reasonably accurate. CSMGem and Multiflash® showed the best results.

  18. Experimental solid state NMR of gas hydrates : problems and solutions

    Energy Technology Data Exchange (ETDEWEB)

    Moudrakovski, I.; Lu, H.; Ripmeester, J. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences; Kumar, R.; Susilo, R. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering; Luzi, M. [GeoForschungsZentrum Potsdam, Potsdam (Germany)

    2008-07-01

    Solid State NMR is a suitable spectroscopic technique for hydrate research for several reasons, including its capability to distinguish between different structural types of hydrates, its quantitative nature and potential for both in-situ and time resolved experiments. This study illustrated the applications of solid state NMR for compositional and structural studies of clathrate hydrates, with particular emphasis on experimental techniques and potential ways to overcome technical difficulties. In order to use the method to its full capacity, some instrumental developments are needed to adapt it to the specific experimental requirements of hydrate studies, such as very low temperatures and high pressures. This presentation discussed the quantification of the Carbon-13 spectra with examples from natural and synthetic hydrates prepared from multi-component mixtures of hydrocarbons. The main approach used for the first two examples was Carbon-13 NMR with Magic Angle Spinning (MAS) at -100 degrees C. The detailed characterization of mixed hydrogen hydrates required low temperature hydrogen MAS. The quantification problems encountered during these experiments were also discussed. The purpose of these recent experimental developments was to prompt wider application of Solid State NMR in hydrate research. NMR proved to be a viable method for analyzing the composition and structure of multi-component mixed gas hydrates; characterizing natural gas hydrates; and, evaluating the formation conditions and properties of mixed hydrogen hydrates. The limitations of the method were highlighted and sensible choices of experimental conditions and techniques that ensure accurate results were discussed. 34 refs., 10 figs.

  19. Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations

    Science.gov (United States)

    Yuhara, Daisuke; Brumby, Paul E.; Wu, David T.; Sum, Amadeu K.; Yasuoka, Kenji

    2018-05-01

    To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

  20. Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations.

    Science.gov (United States)

    Yuhara, Daisuke; Brumby, Paul E; Wu, David T; Sum, Amadeu K; Yasuoka, Kenji

    2018-05-14

    To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

  1. Dissolution of methane bubbles with hydrate armoring in deep ocean conditions

    Science.gov (United States)

    Kovalchuk, Margarita; Socolofsky, Scott

    2017-11-01

    The deep ocean is a storehouse of natural gas. Methane bubble moving upwards from marine sediments may become trapped in gas hydrates. It is uncertain precisely how hydrate armoring affects dissolution, or mass transfer from the bubble to the surrounding water column. The Texas A&M Oilspill Calculator was used to simulate a series of gas bubble dissolution experiments conducted in the United States Department of Energy National Energy Technology Laboratory High Pressure Water Tunnel. Several variations of the mass transfer coefficient were calculated based on gas or hydrate phase solubility and clean or dirty bubble correlations. Results suggest the mass transfer coefficient may be most closely modeled with gas phase solubility and dirty bubble correlation equations. Further investigation of hydrate bubble dissolution behavior will refine current numeric models which aid in understanding gas flux to the atmosphere and plumes such as oil spills. Research funded in part by the Texas A&M University 2017 Undergraduate Summer Research Grant and a Grant from the Methane Gas Hydrates Program of the US DOE National Energy Technology Laboratory.

  2. Seismic-Scale Rock Physics of Methane Hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Amos Nur

    2009-01-08

    We quantify natural methane hydrate reservoirs by generating synthetic seismic traces and comparing them to real seismic data: if the synthetic matches the observed data, then the reservoir properties and conditions used in synthetic modeling might be the same as the actual, in-situ reservoir conditions. This approach is model-based: it uses rock physics equations that link the porosity and mineralogy of the host sediment, pressure, and hydrate saturation, and the resulting elastic-wave velocity and density. One result of such seismic forward modeling is a catalogue of seismic reflections of methane hydrate which can serve as a field guide to hydrate identification from real seismic data. We verify this approach using field data from known hydrate deposits.

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

    Science.gov (United States)

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

    2018-06-01

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

  4. In-Situ Sampling and Characterization of Naturally Occurring Marine Methane Hydrate Using the D/V JOIDES Resolution

    Energy Technology Data Exchange (ETDEWEB)

    Frank R. Rack

    2006-09-20

    Cooperative Agreement DE-FC26-01NT41329 between Joint Oceanographic Institutions and DOE-NETL was divided into two phases based on successive proposals and negotiated statements of work pertaining to activities to sample and characterize methane hydrates on ODP Leg 204 (Phase 1) and on IODP Expedition 311 (Phase 2). The Phase 1 Final Report was submitted to DOE-NETL in April 2004. This report is the Phase 2 Final Report to DOE-NETL. The primary objectives of Phase 2 were to sample and characterize methane hydrates using the systems and capabilities of the D/V JOIDES Resolution during IODP Expedition 311, to enable scientists the opportunity to establish the mass and distribution of naturally occurring gas and gas hydrate at all relevant spatial and temporal scales, and to contribute to the DOE methane hydrate research and development effort. The goal of the work was to provide expanded measurement capabilities on the JOIDES Resolution for a dedicated hydrate cruise to the Cascadia continental margin off Vancouver Island, British Columbia, Canada (IODP Expedition 311) so that hydrate deposits in this region would be well characterized and technology development continued for hydrate research. IODP Expedition 311 shipboard activities on the JOIDES Resolution began on August 28 and were concluded on October 28, 2005. The statement of work for this project included three primary tasks: (1) research management oversight, provided by JOI; (2) mobilization, deployment and demobilization of pressure coring and core logging systems, through a subcontract with Geotek Ltd.; and, (3) mobilization, deployment and demobilization of a refrigerated container van that will be used for degassing of the Pressure Core Sampler and density logging of these pressure cores, through a subcontract with the Texas A&M Research Foundation (TAMRF). Additional small tasks that arose during the course of the research were included under these three primary tasks in consultation with the DOE

  5. Experimental study on neptunium migration under in situ geochemical conditions

    Science.gov (United States)

    Kumata, M.; Vandergraaf, T. T.

    1998-12-01

    Results are reported for migration experiments performed with Np under in situ geochemical conditions over a range of groundwater flow rates in columns of crushed rock in a specially designed facility at the 240-level of the Underground Research Laboratory (URL) near Pinawa, Manitoba, Canada. This laboratory is situated in an intrusive granitic rock formation, the Lac du Bonnet batholith. Highly altered granitic rock and groundwater were obtained from a major subhorizontal fracture zone at a depth of 250 m in the URL. The granite was wet-crushed and wet-sieved with groundwater from this fracture zone. The 180-850-μm size fraction was selected and packed in 20-cm long, 2.54-cm in diameter Teflon™-lined stainless steel columns. Approximately 30-ml vols of groundwater containing 3HHO and 237Np were injected into the columns at flow rates of 0.3, 1, and 3 ml/h, followed by elution with groundwater, obtained from the subhorizontal fracture, at the same flow rates, for a period of 95 days. Elution profiles for 3HHO were obtained, but no 237Np was detected in the eluted groundwater. After terminating the migration experiments, the columns were frozen, the column material was removed and cut into twenty 1-cm thick sections and each section was analyzed by gamma spectrometry. Profiles of 237Np were obtained for the three columns. A one-dimensional transport model was fitted to the 3HHO breakthrough curves to obtain flow parameters for this experiment. These flow parameters were in turn applied to the 237Np concentration profiles in the columns to produce sorption and dispersion coefficients for Np. The results show a strong dependence of retardation factors ( Rf) on flow rate. The decrease in the retarded velocity of the neptunium ( Vn) varied over one order of magnitude under the geochemical conditions for these experiments.

  6. Magnetic susceptibility and magnetic resonance measurements of the moisture content and hydration condition of a magnetic mixture material

    International Nuclear Information System (INIS)

    Tsukada, K.; Kusaka, T.; Saari, M. M.; Takagi, R.; Sakai, K.; Kiwa, T.; Bito, Y.

    2014-01-01

    We developed a magnetic measurement method to measure the moisture content and hydration condition of mortar as a magnetic mixture material. Mortar is a mixture of Portland cement, sand, and water, and these materials exhibit different magnetic properties. The magnetization–magnetic field curves of these components and of mortars with different moisture contents were measured, using a specially developed high-temperature-superconductor superconducting quantum interference device. Using the differences in magnetic characteristics, the moisture content of mortar was measured at the ferromagnetic saturation region over 250 mT. A correlation between magnetic susceptibility and moisture content was successfully established. After Portland cement and water are mixed, hydration begins. At the early stage of the hydration/gel, magnetization strength increased over time. To investigate the magnetization change, we measured the distribution between bound and free water in the mortar in the early stage by magnetic resonance imaging (MRI). The MRI results suggest that the amount of free water in mortar correlates with the change in magnetic susceptibility

  7. Spatial resolution of gas hydrate and permeability changes from ERT data in LARS simulating the Mallik gas hydrate production test

    Science.gov (United States)

    Priegnitz, Mike; Thaler, Jan; Spangenberg, Erik; Schicks, Judith M.; Abendroth, Sven

    2014-05-01

    The German gas hydrate project SUGAR studies innovative methods and approaches to be applied in the production of methane from hydrate-bearing reservoirs. To enable laboratory studies in pilot scale, a large reservoir simulator (LARS) was realized allowing for the formation and dissociation of gas hydrates under simulated in-situ conditions. LARS is equipped with a series of sensors. This includes a cylindrical electrical resistance tomography (ERT) array composed of 25 electrode rings featuring 15 electrodes each. The high-resolution ERT array is used to monitor the spatial distribution of the electrical resistivity during hydrate formation and dissociation experiments over time. As the present phases of poorly conducting sediment, well conducting pore fluid, non-conducting hydrates, and isolating free gas cover a wide range of electrical properties, ERT measurements enable us to monitor the spatial distribution of these phases during the experiments. In order to investigate the hydrate dissociation and the resulting fluid flow, we simulated a hydrate production test in LARS that was based on the Mallik gas hydrate production test (see abstract Heeschen et al., this volume). At first, a hydrate phase was produced from methane saturated saline water. During the two months of gas hydrate production we measured the electrical properties within the sediment sample every four hours. These data were used to establish a routine estimating both the local degrees of hydrate saturation and the resulting local permeabilities in the sediment's pore space from the measured resistivity data. The final gas hydrate saturation filled 89.5% of the total pore space. During hydrate dissociation, ERT data do not allow for a quantitative determination of free gas and remaining gas hydrates since both phases are electrically isolating. However, changes are resolved in the spatial distribution of the conducting liquid and the isolating phase with gas being the only mobile isolating phase

  8. Evaluation and analysis of geological condition of in-situ fragmentation leaching uranium

    International Nuclear Information System (INIS)

    Yang Jianming; Tan Kaixuan; Huang Xiaonai

    2003-01-01

    The ore geological condition, hydrogeological condition, engineering geological condition and technological mineralogical character of in-situ fragmentation leaching uranium are analyzed, and it is considered that the implementation of in-situ fragmentation leaching uranium technology is decided by different geological factor. Previously prospecting and geological condition evaluation of uranium ore is based on traditional mining method. If in-situ fragmentation leaching uranium method is adopted, one must re-evaluate previously prospected deposits before they are mined, or one must evaluate new prospecting deposits according to geological conditions of in-situ fragmentation leaching uranium method. The feasibility evaluation method of uranium deposit by in-situ fragmentation leaching uranium put forward by B. N. Mociniets is introducd, and it is considered that B. N. Mociniets method has guidable significance for geological condition evaluation before uranium deposits are mined. A feasibility study is done by applying B. N. Mociniets method to a uranium deposit. (authors)

  9. [Skin hydration and hydrating products].

    Science.gov (United States)

    Duplan, H; Nocera, T

    2018-05-01

    One of the skin's principal functions is to protect the body against its environment by maintaining an effective epidermal barrier, not only against external factors, but also to prevent water loss from the body. Indeed, water homeostasis is vital for the normal physiological functioning of skin. Hydration levels affect not only visible microscopic parameters such as the suppleness and softness of skin, but also molecular parameters, enzyme activities and cellular signalling within the epidermis. The body is continually losing some of its water, but this phenomenon is limited and the optimal hydration gradient in skin is ensured via a set of sophisticated regulatory processes that rely on the functional and dynamic properties of the uppermost level of the skin consisting of the stratum corneum. The present article brings together data recently acquired in the fields of skin hydration and the characterisation of dehydrated or dry skin, whether through study of the regulatory processes involved or as a result of changes in the techniques used for in situ measurement, and thus in optimisation of management. Copyright © 2018. Published by Elsevier Masson SAS.

  10. Hydration forces between aligned DNA helices undergoing B to A conformational change: In-situ X-ray fiber diffraction studies in a humidity and temperature controlled environment.

    Science.gov (United States)

    Case, Ryan; Schollmeyer, Hauke; Kohl, Phillip; Sirota, Eric B; Pynn, Roger; Ewert, Kai E; Safinya, Cyrus R; Li, Youli

    2017-12-01

    Hydration forces between DNA molecules in the A- and B-Form were studied using a newly developed technique enabling simultaneous in situ control of temperature and relative humidity. X-ray diffraction data were collected from oriented calf-thymus DNA fibers in the relative humidity range of 98%-70%, during which DNA undergoes the B- to A-form transition. Coexistence of both forms was observed over a finite humidity range at the transition. The change in DNA separation in response to variation in humidity, i.e. change of chemical potential, led to the derivation of a force-distance curve with a characteristic exponential decay constant of∼2Å for both A- and B-DNA. While previous osmotic stress measurements had yielded similar force-decay constants, they were limited to B-DNA with a surface separation (wall-to-wall distance) typically>5Å. The current investigation confirms that the hydration force remains dominant even in the dry A-DNA state and at surface separation down to∼1.5Å, within the first hydration shell. It is shown that the observed chemical potential difference between the A and B states could be attributed to the water layer inside the major and minor grooves of the A-DNA double helices, which can partially interpenetrate each other in the tightly packed A phase. The humidity-controlled X-ray diffraction method described here can be employed to perform direct force measurements on a broad range of biological structures such as membranes and filamentous protein networks. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Impact of Isotonic Beverage on the Hydration Status of Healthy Chinese Adults in Air-Conditioned Environment

    Directory of Open Access Journals (Sweden)

    Phei Ching Siow

    2017-03-01

    Full Text Available People living in tropical climates spend much of their time in confined air-conditioned spaces, performing normal daily activities. This study investigated the effect of distilled water (W or isotonic beverage (IB on the hydration status in subjects living under these conditions. In a randomized crossover design, forty-nine healthy male subjects either consumed beverage or IB over a period of 8 h (8 h in a controlled air-conditioned environment. Blood, urine, and saliva samples were collected at baseline and after 8 h. Hydration status was assessed by body mass, urine output, blood and plasma volume, fluid retention, osmolality, electrolyte concentration and salivary flow rate. In the IB group, urine output (1862 ± 86 mL vs. 2104 ± 98 mL was significantly lower and more fluids were retained (17% ± 3% vs. 7% ± 3% as compared to W (p < 0.05 after 8 h. IB also resulted in body mass gain (0.14 ± 0.06 kg, while W led to body mass loss (−0.04 ± 0.05 kg (p = 0.01. A significantly smaller drop in blood volume and lower free water clearance was observed in IB (−1.18% ± 0.43%; 0.55 ± 0.26 mL/min compared to W (−2.11% ± 0.41%; 1.35 ± 0.24 mL/min (p < 0.05. IB increased salivary flow rate (0.54 ± 0.05 g/min 0.62 ± 0.04 g/min. In indoor environments, performing routine activities and even without excessive sweating, isotonic beverages may be more effective at retaining fluids and maintaining hydration status by up to 10% compared to distilled water.

  12. Halogen systematics in the Mallik 5L-38 gas hydrate production research well, Northwest Territories, Canada: Implications for the origin of gas hydrates under terrestrial permafrost conditions

    International Nuclear Information System (INIS)

    Tomaru, Hitoshi; Fehn, Udo; Lu, Zunli; Matsumoto, Ryo

    2007-01-01

    The authors report here halogen concentrations in pore waters and sediments collected from the Mallik 5L-38 gas hydrate production research well, a permafrost location in the Mackenzie Delta, Northwest Territories, Canada. Iodine and Br are commonly enriched in waters associated with CH 4 , reflecting the close association between these halogens and source organic materials. Pore waters collected from the Mallik well show I enrichment, by one order of magnitude above that of seawater, particularly in sandy layers below the gas hydrate stability zone (GHSZ). Although Cl and Br concentrations increase with depth similar to the I profile, they remain below seawater values. The increase in I concentrations observed below the GHSZ suggests that I-rich fluids responsible for the accumulation of CH 4 in gas hydrates are preferentially transported through the sandy permeable layers below the GHSZ. The Br and I concentrations and I/Br ratios in Mallik are considerably lower than those in marine gas hydrate locations, demonstrating a terrestrial nature for the organic materials responsible for the CH 4 at the Mallik site. Halogen systematics in Mallik suggest that they are the result of mixing between seawater, freshwater and an I-rich source fluid. The comparison between I/Br ratios in pore waters and sediments speaks against the origin of the source fluids within the host formations of gas hydrates, a finding compatible with the results from a limited set of 129 I/I ratios determined in pore waters, which gives a minimum age of 29 Ma for the source material, i.e. at the lower end of the age range of the host formations. The likely scenario for the gas hydrate formation in Mallik is the derivation of CH 4 together with I from the terrestrial source materials in formations other than the host layers through sandy permeable layers into the present gas hydrate zones

  13. Experimental Simulation of Methane Hydrate Extraction at High Pressure Conditions: Influence of the Sediment Bed

    Science.gov (United States)

    Agudo, J. R.; Park, J.; Luzi, G.; Williams, M.; Rauh, C.; Wierschem, A.; Delgado, A.

    2017-10-01

    Being a clean alternative to other fossil fuels, Methane Hydrate (MH) is currently considered as one of the most important potential sources for hydrocarbon fuels [1]. In addition, the high energy density of MH and its stability at higher temperatures as compared to LNG (Liquefied Natural Gas) makes MH a potential greener method for energy transportation. At the same time, the low thermodynamic stability of MH strongly questions the future exploitation of gas hydrate deposits, turning its extraction into a possible geohazard [2]. Fluctuations in pressure, temperature, salinity, degree of saturation or sediment bed properties may cause methane gas release from the water lattice. We experimentally study the influence of the sediment bed geometry during formation-dissociation of MH. For this purpose, MH is synthesized within regular substrates in a 93 cm3 high pressure vessel. The regular substrates are triangular and quadratic arrangements of identical glass spheres with a diameter of 2 and 5 mm, respectively. MH formation within regular substrate reduces the possibility of spontaneous nucleation to a unique geometrical configuration. This fact permits us to characterize the kinetics of MH formation-dissociation as a function of the sediment bed geometry. Preliminary experimental results reveal a strong dependence of MH formation on the geometry of the regular substrate. For instance, under the same pressure and temperature, the kinetics of MH production is found to change by a factor 3 solely depending on the substrate symmetry, i.e. triangular or quadratic.

  14. In-Situ Sampling and Characterization of Naturally Occurring Marine Methane Hydrate Using the D/V JOIDES Resolution

    Energy Technology Data Exchange (ETDEWEB)

    Frank Rack

    2005-06-30

    The primary accomplishments of the JOI Cooperative Agreement with DOE/NETL in this quarter were to refine budgets and operational plans for Phase 2 of this cooperative agreement based on the scheduling of a scientific ocean drilling expedition to study marine methane hydrates along the Cascadia margin, in the NE Pacific as part of the Integrated Ocean Drilling Program (IODP) using the R/V JOIDES Resolution. The proposed statement of work for Phase 2 will include three primary tasks: (1) research management oversight, provided by JOI; (2) mobilization, deployment and demobilization of pressure coring and core logging systems, through a subcontract with Geotek Ltd., who will work with Fugro and Lawrence Berkeley National Laboratory to accomplish some of the subtasks; and, (3) mobilization, deployment and demobilization of a refrigerated container van that will be used for degassing of the Pressure Core Sampler and density logging of these pressure cores, through a subcontract with the Texas A&M Research Foundation (TAMRF). More details about these tasks are provided in the following sections of this report. The appendices to this report contain a copy of the scientific prospectus for the upcoming IODP Expedition 311 (Cascadia Margin Hydrates), which provides details of operational and scientific planning for this expedition.

  15. Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

    Science.gov (United States)

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

    2005-01-01

    The composition of methane hydrate, namely nW for CH 4??nWH2O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but nW may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n W = 5.81-6.10 H2O describes the entire range of measured values, with an average composition of CH4??5.99(??0.07) H2O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence. ?? 2005 American Chemical Society.

  16. Class H cement hydration at 180 deg. C and high pressure in the presence of added silica

    International Nuclear Information System (INIS)

    Jupe, Andrew C.; Wilkinson, Angus P.; Luke, Karen; Funkhouser, Gary P.

    2008-01-01

    Under deep oil-well conditions of elevated temperature and pressure, crystalline calcium silicate hydrates are formed during Portland cement hydration. The use of silica rich mineral additives leads to the formation of crystalline hydrates with better mechanical properties than those formed without the additive. The effects of silica flour, silica fume (amorphous silica), and a natural zeolite mixture on the hydration of Class H cement slurries at 180 deg. C under externally applied pressures of 7 and 52 MPa are examined in real time using in-situ synchrotron X-ray diffraction. For some compositions examined, but not all, pressure was found to have a large effect on the kinetics of crystalline hydrate formation. The use of silica fume delayed both C 3 S hydration and the formation of crystalline silicate hydrates compared to what was seen with other silica sources

  17. Stability conditions and guest distribution of the methane + ethane + propane hydrates or semiclathrates in the presence of tetrahydrofuran or quaternary ammonium salts

    International Nuclear Information System (INIS)

    Lee, Seungmin; Lee, Youngjun; Park, Sungwon; Kim, Yunju; Cha, Inuk; Seo, Yongwon

    2013-01-01

    Highlights: • We examined the stability conditions and guest distributions of natural gas hydrates. • THF, TBAB, and TBAF could remarkably stabilize the hydrate dissociation conditions. • Preferential occupation of CH 4 molecules was observed at the stoichiometric concentrations. -- Abstract: In this study, the stability conditions and guest distributions of methane (CH 4 ) + ethane (C 2 H 6 ) + propane (C 3 H 8 ) hydrates or semiclathrates are examined in the presence of tetrahydrofuran (THF) and quaternary ammonium salts such as tetra-n-butylammonium bromide (TBAB) and tetra-n-butylammonium fluoride (TBAF) through thermodynamic and spectroscopic analyses. The three-phase equilibria of hydrate or semiclathrate (H), liquid water (L W ), and vapor (V) for the quinary CH 4 + C 2 H 6 + C 3 H 8 + THF + water, CH 4 + C 2 H 6 + C 3 H 8 + TBAB + water, and CH 4 + C 2 H 6 + C 3 H 8 + TBAF + water mixtures with various concentrations were experimentally measured in order to determine the hydrate or semiclathrate stability conditions. The experimental results demonstrated that all thermodynamic promoters such as THF, TBAB, and TBAF used in this study could remarkably stabilize the hydrate dissociation conditions even though the degree of stabilization was dependent on the type of promoters and on the concentrations of each promoter used. From the 13 C NMR analysis, preferential occupation of CH 4 molecules in the hydrate or semiclathrate lattices was observed at the stoichiometric concentrations of each hydrate or semiclathrate structure. However, at the THF mole fraction lower than 0.056, the large cages of structure II were shared by CH 4 , C 2 H 6 , C 3 H 8 , and THF molecules, whereas the small cages were occupied by only CH 4 molecules. The results given in this study are very useful in understanding the thermodynamic stability, structural characteristics, and guest distribution of the hydrates or semiclathrates with multi-components in the presence of

  18. 3Wave propagation in rock samples under medium and low temperature conditions. Characteristics of methane hydrate-BSR phenomena; Chu teion ryoiki ni okeru ganseki shiryo no hado denpa tokusei. 1. Methane hydrate BSR gensho no kosatsu suitei

    Energy Technology Data Exchange (ETDEWEB)

    Rokugawa, S; Kato, Y; Matsushima, J; Sano, A [The University of Tokyo, Tokyo (Japan). Faculty of Engineering

    1997-10-22

    In relation to sea-bottom pseudo reflection face and methane hydrate in seismic exploration records, fundamental experimental studies have been made. In order to get a handhold to elucidate phenomena accompanying methane hydrate, the studies have investigated wave propagation behavior of rock samples and sandy sediments under medium and low temperature conditions. The experiments have used a constant-temperature cooling water circulating equipment to control temperatures of each sample. The samples were placed in a cooler box with the vibration transmitter and receiver fixedly installed, and changes of the waves against temperature change were measured. Sand-stones and two kinds of tuffs were used as rock samples for the measurement. Artificial sand sample soaked in water was used as a substitute for a methane hydrate layer. As a result of the experiments, the relation between the hydrate layer and the gas layer was comprehended. In addition, the blanking phenomenon was thought occurring as a result of the nearly whole substance presenting the speed of ice due to freezing of the sediments, rather than by what is described in the ground homogeneousness theory. 5 refs., 9 figs.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-11-01

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

  20. Situ leaching uranium mining conditions of the pilot phase of the safety management

    International Nuclear Information System (INIS)

    Liu Wenyuan

    2014-01-01

    With China's large, very large sandstone type uranium deposits have been discovered in the Ordos Basin, Inner Mongolia and its surrounding for uranium mining in the region has been carried out. Sandstone-type uranium mining, mainly used in China is 'to dip' and the technology is relatively mature. Situ leaching mining process, the deposit conditions Test conditions pilot phase, however, limited by cost control and field conditions, equipment shabby, out in the conditions of the pilot phase of security issues in the larger securityrisks. This will be Ordos ongoing test conditions situ leaching uranium mines, for example, raised situ leaching uranium mining conditions of the pilot phase a few safety measures recommended. (author)

  1. Detection of gas hydrate with downhole logs and assessment of gas hydrate concentrations (saturations) and gas volumes on the Blake Ridge with electrical resistivity log data

    Science.gov (United States)

    Collett, T.S.; Ladd, J.

    2000-01-01

    Let 164 of the Ocean Drilling Program was designed to investigate the occurrence of gas hydrate in the sedimentary section beneath the Blake Ridge on the southeastern continental margin of North America. Site 994, and 997 were drilled on the Blake Ridge to refine our understanding of the in situ characteristics of natural gas hydrate. Because gas hydrate is unstable at surface pressure and temperature conditions, a major emphasis was placed on the downhole logging program to determine the in situ physical properties of the gas hydrate-bearing sediments. Downhole logging tool strings deployed on Leg 164 included the Schlumberger quad-combination tool (NGT, LSS/SDT, DIT, CNT-G, HLDT), the Formation MicroScanner (FMS), and the Geochemical Combination Tool (GST). Electrical resistivity (DIT) and acoustic transit-time (LSS/SDT) downhole logs from Sites 994, 995, and 997 indicate the presence of gas hydrate in the depth interval between 185 and 450 mbsf on the Blake Ridge. Electrical resistivity log calculations suggest that the gas hydrate-bearing sedimentary section on the Blake Ridge may contain between 2 and 11 percent bulk volume (vol%) gas hydrate. We have determined that the log-inferred gas hydrates and underlying free-gas accumulations on the Blake Ridge may contain as much as 57 trillion m3 of gas.

  2. Study on tertiary in-situ leachable uranium mineralization conditions in South Songliao basin

    International Nuclear Information System (INIS)

    Zhang Zhenqiang; Li Guokuan; Zhao Zonghua; Zhang Jingxun

    2001-01-01

    Tertiary in-situ leachable mineralization in Songliao Basin was analyzed in theory in the past. Since 1998, regional investigation at 1:200000 scale has been done with about 120 holes drilled. Based on drill holes recording, section compiling and sample analysis, the authors investigate into the Tertiary in-situ leachable conditions including rock character, sedimentary facies, rock chemistry, organic substances, uranium content, sandstone porosity, sandstone bodies, interlayer oxidation, and hydro-dynamic value. The study would play important role in prospecting for in-situ leachable uranium in South Songliao basin

  3. Clathrate hydrate dissociation conditions of refrigerants R404A, R406A, R408A and R427A: Experimental measurements and thermodynamic modeling

    International Nuclear Information System (INIS)

    Hashemi, Hamed; Babaee, Saeedeh; Mohammadi, Amir H.; Naidoo, Paramespri; Ramjugernath, Deresh

    2015-01-01

    Highlights: • The application of refrigerant hydrates in cold storage systems is investigated. • Hydrate dissociation conditions of various refrigerants have been measured. • A correlative thermodynamic model was applied to the data. • Enthalpy of dissociation for the refrigerants studied calculated. • Experimental measurements performed over a wide range of pressures. - Abstract: Clathrate hydrate dissociation conditions were measured for four “alternative” refrigerants, viz. R404A, R406A, R408A and R427A. The experimental measurements were performed within the pressure range of (0.079 to 9.995) MPa and temperatures ranging from (272.7 to 288.7) K. An isochoric pressure-search method was used to perform the measurements. A thermodynamic model based on the van der Waals–Platteeuw (vdW–P) model was applied for the prediction of the dissociation conditions which were compared to the experimental measurements. The fluid phase was modeled using the MHV2 G E -EoS mixing rule along with the UNIFAC (original) activity model. The van der Waals–Platteeuw (vdW–P) model was used for the modeling of the hydrate phase. There was reasonable agreement between the experimental and predicted values

  4. Effect of the ensiling time of hydrated ground corn on silage composition and in situ starch degradability

    Directory of Open Access Journals (Sweden)

    Marcos André Arcari

    2016-04-01

    Full Text Available O objetivo deste estudo foi avaliar o efeito do tempo de ensilagem sobre a composição química e a degradabilidade in situ do amido do milho moído hidratado (MMH em grãos de média vitreosidade. Os grãos de milho foram colhidos com 83% de matéria seca (MS e vitreosidade de 67% ± 3, e foram secos até atingirem 87% de MS. Os grãos foram moídos a dois milímetros, sendo posteriormente reconstituídos, 67% MS, e ensilados (densidade de 880 kg / m³ para até 330 dias. Uma amostra MMH foi coletado mensalmente para a determinação da composição, produtos finais da fermentação e para degradabilidade in situ do amido de milho. O tempo de ensilagem não afetou o teor de MS e proteína bruta (PB. No entanto, a concentração de amido foi reduzido em 2,4 pontos percentuais em comparação de 3 com 330 dias de ensilagem. Foram observados o aumento das concentrações de N-NH3 (8,5 vezes, ácidos láctico (3,45 vezes, acético (4,1 vezes, propionico (1,7 vezes, butírico (2,8 vezes e álcool (2,4 vezes, durante o período de ensilagem. A fracção rapidamente degradável (fração A e a taxa de degradação da fracção lentamente degradável (fração C do amido do MMH foram aumentadas 3,51 e 2,21 vezes, respectivamente, durante o período de ensilagem. Por outro lado, a fração lentamente degradável (fração B do amido do MMH foi diminuída em 1,93 vezes durante o período de ensilagem. A degradabilidade efetiva do amido do MMH foi aumentado para as taxas de passagem de 0,02 / h (79,9% vs. 94,5%; 0,05 / h (65,9% vs 90,01% e de 0,08/h (56,98% vs. 86,52% quando foi comparada o período de 3 vs 330 dias de ensilagem, respectivamente. Em conclusão, o tempo de ensilagem afetou a composição química e aumentou a degradabilidade ruminal do amido do MMH de grãos com média vitreosidade.

  5. The effects of silica fume and hydrated lime on the strength development and durability characteristics of concrete under hot water curing condition

    Directory of Open Access Journals (Sweden)

    Hamza Ali

    2017-01-01

    Full Text Available Sustainability is considered to be highly important for preserving continued industrial growth and human development. Concrete, being the world’s largest manufacturing material comprises cement as an essential binding component for strength development. However, excessive production of cement due to high degree of construction practices around the world frames cement as a leading pollutant of releasing significant amounts of CO2 in the atmosphere. To overcome this environmental degradation, silica fume and hydrated lime are used as partial replacements to cement. This paper begins with the examination of the partial replacement levels of hydrated lime and silica fume in concrete and their influence on the mechanical properties and durability characteristics of concrete. The effect of hot water curing on concrete incorporated with both silica fume and hydrated lime is also investigated in this paper. The results reported in this paper show that the use of silica fume as a partial replacement material improved both the mechanical properties and durability characteristics of concrete due to the formation of calcium silica hydrate crystals through the pozzolanic reaction. Although the hydrated lime did not significantly contribute in the development of strength, its presence enhanced the durability of concrete especially at long-term. The results also showed that hot water curing enhanced the strength development of concrete incorporated with silica fume due to the accelerated rate of both the hydration and pozzolanic reaction that takes place between silica fume and calcium hydroxide of the cement matrix particularly at early times. The results reported in this paper have significant contribution in the development of sustainable concrete. The paper does not only address the use of alternative binders as a partial replacement material in concrete but also suggest proper curing conditions for the proposed replacement materials. These practices

  6. Electrochemical cell for in situ x-ray diffraction under ultrapure conditions

    DEFF Research Database (Denmark)

    Koop, T.; Schindler, W.; Kazimirov, A.

    1998-01-01

    within a few seconds. The oxygen level in the electrolyte is reduced by continuous N(2) flow to less than 0.2% compared to that of a fresh electrolyte. This can be done while rotating the cell by 360 degrees about the surface normal. The electrode potential is accurately measured at the position......An electrochemical cell has been developed for in situ x-ray diffraction from a working electrode under clean conditions equivalent to ultrahigh vacuum conditions of 5 x 10(-10) mbar. The substrate crystals can be prepared ex situ and transferred into the cell under protection of ultrapure water...... of the crystal using a Luggin capillary and a standard reference electrode. We demonstrate the performance of our cell by in situ synchrotron x-ray diffraction measurements on ultrathin Co layers electrodeposited on Cu(001) in an aqueous H(2)SO(4)/CoSO(4) solution. (C) 1998 American Institute of Physics....

  7. Detailed evaluation of gas hydrate reservoir properties using JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well downhole well-log displays

    Science.gov (United States)

    Collett, T.S.

    1999-01-01

    The JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well project was designed to investigate the occurrence of in situ natural gas hydrate in the Mallik area of the Mackenzie Delta of Canada. Because gas hydrate is unstable at surface pressure and temperature conditions, a major emphasis was placed on the downhole logging program to determine the in situ physical properties of the gas-hydrate-bearing sediments. Downhole logging tool strings deployed in the Mallik 2L-38 well included the Schlumberger Platform Express with a high resolution laterolog, Array Induction Imager Tool, Dipole Shear Sonic Imager, and a Fullbore Formation Microlmager. The downhole log data obtained from the log- and core-inferred gas-hydrate-bearing sedimentary interval (897.25-1109.5 m log depth) in the Mallik 2L-38 well is depicted in a series of well displays. Also shown are numerous reservoir parameters, including gas hydrate saturation and sediment porosity log traces, calculated from available downhole well-log and core data. The gas hydrate accumulation delineated by the Mallik 2L-38 well has been determined to contain as much as 4.15109 m3 of gas in the 1 km2 area surrounding the drill site.

  8. Conditioning of the vacuum system of the TPS storage ring without baking in situ

    Energy Technology Data Exchange (ETDEWEB)

    Chan, C.K., E-mail: ckchan@nsrrc.org.tw; Chang, C.C.; Shueh, C.; Yang, I.C.; Wu, L.H.; Chen, B.Y.; Cheng, C.M.; Huang, Y.T.; Chuang, J.Y.; Cheng, Y.T.; Hsiao, Y.M.; Sheng, Albert

    2017-04-11

    To shorten the machine downtime, a maintenance procedure without baking in situ has been developed and applied to maintain and to upgrade the vacuum system of the TPS storage ring. The data of photon-stimulated desorption (PSD) reveal no obvious discrepancy between baking and not baking the vacuum system in situ. A beam-conditioning dose of extent only 11.8 A h is required to recover quickly the dynamic pressure of an unbaked vacuum system to its pre-intervention value according to the TPS maintenance experience.

  9. Conditioning of the vacuum system of the TPS storage ring without baking in situ

    Science.gov (United States)

    Chan, C. K.; Chang, C. C.; Shueh, C.; Yang, I. C.; Wu, L. H.; Chen, B. Y.; Cheng, C. M.; Huang, Y. T.; Chuang, J. Y.; Cheng, Y. T.; Hsiao, Y. M.; Sheng, Albert

    2017-04-01

    To shorten the machine downtime, a maintenance procedure without baking in situ has been developed and applied to maintain and to upgrade the vacuum system of the TPS storage ring. The data of photon-stimulated desorption (PSD) reveal no obvious discrepancy between baking and not baking the vacuum system in situ. A beam-conditioning dose of extent only 11.8 A h is required to recover quickly the dynamic pressure of an unbaked vacuum system to its pre-intervention value according to the TPS maintenance experience.

  10. Conditioning of the vacuum system of the TPS storage ring without baking in situ

    International Nuclear Information System (INIS)

    Chan, C.K.; Chang, C.C.; Shueh, C.; Yang, I.C.; Wu, L.H.; Chen, B.Y.; Cheng, C.M.; Huang, Y.T.; Chuang, J.Y.; Cheng, Y.T.; Hsiao, Y.M.; Sheng, Albert

    2017-01-01

    To shorten the machine downtime, a maintenance procedure without baking in situ has been developed and applied to maintain and to upgrade the vacuum system of the TPS storage ring. The data of photon-stimulated desorption (PSD) reveal no obvious discrepancy between baking and not baking the vacuum system in situ. A beam-conditioning dose of extent only 11.8 A h is required to recover quickly the dynamic pressure of an unbaked vacuum system to its pre-intervention value according to the TPS maintenance experience.

  11. Gas hydrates

    Digital Repository Service at National Institute of Oceanography (India)

    Ramprasad, T.

    , not all of them are white like snow. Some hydrates from the deep Gulf of Mexico are richly colored in shades of yellow, orange, or even red. The ice-like masses are beautiful, and contrast with the dull gray of deep sea muds. Hydrates from the Blake... volcanoes and associated gas hydrates: Marine Geology, v. 167, p. 29-42. Milkov, A.V. and R. Sassen, 2001a, Estimate of gas hydrate resource, northwestern Gulf of Mexico continental slope: Marine Geology, v. 179, pp. 71-83. Milkov, A.V., Sassen, R...

  12. Estimation of In-Situ Groundwater Conditions Based on Geochemical Equilibrium Simulations

    Directory of Open Access Journals (Sweden)

    Toshiyuki Hokari

    2014-03-01

    Full Text Available This paper presents a means of estimating in-situ groundwater pH and oxidation-redox potential (ORP, two very important parameters for species migration analysis in safety assessments for radioactive waste disposal or carbon dioxide sequestration. The method was applied to a pumping test in a deep borehole drilled in a tertiary formation in Japan for validation. The following application examples are presented: when applied to several other pumping tests at the same site, it could estimate distributions of the in-situ groundwater pH and ORP; applied to multiple points selected in the groundwater database of Japan, it could help estimate the in-situ redox reaction governing the groundwater conditions in some areas.

  13. Methane Hydrates: Chapter 8

    Science.gov (United States)

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

    2008-01-01

    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

  14. Assessing the permafrost temperature and thickness conditions favorable for the occurrence of gas hydrate in the Qinghai-Tibet Plateau

    International Nuclear Information System (INIS)

    Wu Qingbai; Jiang Guanli; Zhang Peng

    2010-01-01

    Permafrost accounts for about 52% of the total area of the Qinghai-Tibet Plateau, and the permafrost area is about 140 x 10 4 km 2 . The mean annual ground temperature of permafrost ranges from -0.1 to -5 deg. C, and lower than -5 deg. C at extreme high-mountains. Permafrost thickness ranges from 10 to 139.4 m by borehole data, and more than 200 m by geothermal gradients. The permafrost geothermal gradient ranges from 1.1 deg. C/100 m to 8.0 deg. C/100 m with an average of 2.9 deg. C/100 m, and the geothermal gradient of the soil beneath permafrost is about 2.8-8.5 deg. C/100 m with an average of 6.0 deg. C/100 m in the Qinghai-Tibet Plateau. For a minimum of permafrost geothermal gradients of 1.1 deg. C/100 m, the areas of the potential occurrence of methane hydrate (sI) is approximately estimated to be about 27.5% of the total area of permafrost regions in the Qinghai-Tibet Plateau. For an average of permafrost geothermal gradients of 2.9 deg. C/100 m, the areas of the potential occurrence of methane hydrate (sI) is approximately estimated about 14% of the total area of permafrost regions in the Qinghai-Tibet Plateau. For the sII hydrate, the areas of the potential occurrence of sII hydrate are more than that of sI methane hydrate.

  15. In-situ transmission electron microscopy growth of nanoparticles under extreme conditions

    International Nuclear Information System (INIS)

    Luce, F. P.; Azevedo, G. de M.; Baptista, D. L.; Zawislak, F. C.; Oliviero, E.; Fichtner, P. F. P.

    2016-01-01

    The formation and time resolved behavior of individual Pb nanoparticles embedded in silica have been studied by in-situ transmission electron microscopy observations at high temperatures (400–1100 °C) and under 200 keV electron irradiation. It is shown that under such extreme conditions, nanoparticles can migrate at long distances presenting a Brownian-like behavior and eventually coalesce. The particle migration phenomenon is discussed considering the influence of the thermal energy and the electron irradiation effects on the atomic diffusion process which is shown to control particle migration. These results and comparison with ex-situ experiments tackle the stability and the microstructure evolution of nanoparticles systems under extreme conditions. It elucidates on the effects of energetic particle irradiation-annealing treatments either as a tool or as a detrimental issue that could hamper their long-term applications in radiation-harsh environments such as in space or nuclear sectors

  16. Ptychographic X-ray Tomography of Silk Fiber Hydration

    DEFF Research Database (Denmark)

    Esmaeili, Morteza; Fløystad, Jostein B.; Diaz, Ana

    2013-01-01

    Studying noninvasively the internal nanoporous structure of a single Tussah silk fiber under different humidity conditions, we demonstrate for the first time the feasibility of in-situ ptychographic tomography. The resulting 3D images of the silk fiber interior, obtained at both dry and humid con...... normal to the fiber axis. Exploiting quantitative information on the fiber’s electron density, hydration was found to proceed through interaction with the silk protein rather than filling of pores....

  17. Influence of lithium and boron ions on calcium sulfo-aluminate cement hydration: application for the conditioning of boron ion exchange resins

    International Nuclear Information System (INIS)

    Dhoury, Melanie

    2015-01-01

    down. When sodium borate and lithium hydroxide are simultaneously introduced in the mixing solution, these two mechanisms are superimposed. With a gypsum-free cement, a third process is additionally observed: lithium promotes the initial precipitation of a borated AFm phase which is later converted into a borated AFt phase when hydration accelerates.Finally, based on the achieved results, a cement-based formulation is designed for the encapsulation of borated resins. Its properties fulfill the requirements for a conditioning matrix over the duration of the study. (author) [fr

  18. Instrumented Pressure Testing Chamber (IPTC) Characterization of Methane Gas Hydrate-Bearing Pressure Cores Collected from the Methane Production Test Site in the Eastern Nankai Trough, Offshore Japan

    Science.gov (United States)

    Waite, W. F.; Santamarina, J. C.; Dai, S.; Winters, W. J.; Yoneda, J.; Konno, Y.; Nagao, J.; Suzuki, K.; Fujii, T.; Mason, D. H.; Bergeron, E.

    2014-12-01

    Pressure cores obtained at the Daini-Atsumi Knoll in the eastern Nankai Trough, the site of the methane hydrate production test completed by the Methane Hydrate Resources in Japan (MH21) project in March 2013, were recovered from ~300 meters beneath the sea floor at close to in situ pressure. Cores were subsequently stored at ~20 MPa and ~5°C, which maintained hydrate in the cores within stability conditions. Pressure core physical properties were measured at 10 MPa and ~6°C, also within the methane hydrate stability field, using the IPTC and other Pressure Core Characterization Tools (PCCTs). Discrete IPTC measurements were carried out in strata ranging from silty sands to clayey silts within the turbidite sequences recovered in the cores. As expected, hydrate saturations were greatest in more permeable coarser-grained layers. Key results include: 1) Where hydrate saturation exceeded 40% in sandy sediments, the gas hydrate binds sediment grains within the matrix. The pressure core analyses yielded nearly in situ mechanical properties despite the absence of effective stress in the IPTC. 2) In adjacent fine-grained sediment (hydrate saturation < 15%), hydrate did not significantly bind the sediment. IPTC results in these locations were consistent with the zero effective-stress limit of comparable measurements made in PCCT devices that are designed to restore the specimen's in situ effective stress. In sand-rich intervals with high gas hydrate saturations, the measured compressional and shear wave velocities suggest that hydrate acts as a homogeneously-distributed, load-bearing member of the bulk sediment. The sands with high gas hydrate saturations were prone to fracturing (brittle failure) during insertion of the cone penetrometer and electrical conductivity probes. Authors would like to express their sincere appreciation to MH21 and the Ministry of Economy, Trade and Industry for permitting this work to be disclosed at the 2014 Fall AGU meeting.

  19. Development of new ultrafiltration techniques maintaining in-situ hydrochemical conditions for colloidal study

    International Nuclear Information System (INIS)

    Aosai, Daisuke; Yamamoto, Yuhei; Mizuno, Takashi

    2011-01-01

    Chemical state of elements in groundwater is one of the most important information for understanding behavior of elements in underground environment. Chemical state of elements controlled mainly by groundwater physico-chemical parameters. Because the change of physico-chemical parameters of groundwater, due to pressure release and oxidation during sampling, causes changes in chemical state of elements, systematic methodologies for understanding in situ chemical state is required. In this study, in order to understand chemical state of elements in groundwater, an ultrafiltration instrument for maintaining in-situ pressure and anaerobic conditions was developed. The instrument developed in this study for ultrafiltration made of passivated Stainless Used Steel (SUS) materials, was designed to keep groundwater samples maintaining in-situ pressure/anaerobic conditions. Ultrafiltration of groundwater was conducted at a borehole drilled from the 200 mbGL (meters below ground level) Sub-stage at a depth of 200 m at the Mizunami Underground Research Laboratory. Chemical analyses of groundwater were also conducted using samples filtered under both pressurized/anaerobic and atmospheric conditions and passivated SUS materials with different elapsed times after passivation. The results indicate that our ultrafiltration method is suitable for collection of filtered groundwater and passivation is an essential treatment before ultrafiltration. (author)

  20. Permeability of sediment cores from methane hydrate deposit in the Eastern Nankai Trough, Japan

    Science.gov (United States)

    Konno, Y.; Yoneda, J.; Egawa, K.; Ito, T.; Jin, Y.; Kida, M.; Suzuki, K.; Nakatsuka, Y.; Nagao, J.

    2013-12-01

    Effective and absolute permeability are key parameters for gas production from methane-hydrate-bearing sandy sediments. Effective and/or absolute permeability have been measured using methane-hydrate-bearing sandy cores and clayey and silty cores recovered from Daini Atsumi Knoll in the Eastern Nankai Trough during the 2012 JOGMEC/JAPEX Pressure coring operation. Liquid-nitrogen-immersed cores were prepared by rapid depressurization of pressure cores recovered by a pressure coring system referred to as the Hybrid PCS. Cores were shaped cylindrically on a lathe with spraying of liquid nitrogen to prevent hydrate dissociation. Permeability was measured by a flooding test or a pressure relaxation method under near in-situ pressure and temperature conditions. Measured effective permeability of hydrate-bearing sediments is less than tens of md, which are order of magnitude less than absolute permeability. Absolute permeability of clayey cores is approximately tens of μd, which would perform a sealing function as cap rocks. Permeability reduction due to a swelling effect was observed for a silty core during flooding test of pure water mimicking hydrate-dissociation-water. Swelling effect may cause production formation damage especially at a later stage of gas production from methane hydrate deposits. This study was financially supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) that carries out Japan's Methane Hydrate R&D Program conducted by the Ministry of Economy, Trade and Industry (METI).

  1. Formation of submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Soloviev, V.; Ginsburg, G.D. (Reserch Institute of Geology and Mineral Resources of the Ocean ' ' VNII Okeangeologia' ' , St. Petersburg (Russian Federation))

    1994-03-01

    Submarine gas hydrates have been discoverd in the course of deep-sea drilling (DSDP and ODP) and bottom sampling in many offshore regions. This paper reports on expeditions carried out in the Black, Caspian and Okhotsk Seas. Gas hydrate accumulations were discovered and investigated in all these areas. The data and an analysis of the results of the deep-sea drilling programme suggest that the infiltration of gas-bearing fluids is a necessary condition for gas hydrate accumulation. This is confirmed by geological observations at three scale levels. Firstly, hydrates in cores are usually associated with comparatively coarse-grained, permeable sediments as well as voids and fractures. Secondly, hydrate accumulations are controlled by permeable geological structures, i.e. faults, diapirs, mud volcanos as well as layered sequences. Thirdly, in the worldwide scale, hydrate accumulations are characteristic of continental slopes and rises and intra-continental seas where submarine seepages also are widespread. Both biogenic and catagenic gas may occur, and the gas sources may be located at various distances from the accumulation. Gas hydrates presumably originate from water-dissolved gas. The possibility of a transition from dissolved gas into hydrate is confirmed by experimental data. Shallow gas hydrate accumulations associated with gas-bearing fluid plumes are the most convenient features for the study of submarine hydrate formation in general. These accumulations are known from the Black, Caspian and Okhotsk Seas, the Gulf of Mexico and off northern California. (au) (24 refs.)

  2. Chloral Hydrate

    Science.gov (United States)

    ... if you are allergic to chloral hydrate, aspirin, tartrazine (a yellow dye in some processed foods and ... in, tightly closed, and out of reach of children. Store it at room temperature, away from excess ...

  3. Ice nucleation activity of diesel soot particles at cirrus relevant temperature conditions: Effects of hydration, secondary organics coating, soot morphology, and coagulation

    Science.gov (United States)

    Kulkarni, Gourihar; China, Swarup; Liu, Shang; Nandasiri, Manjula; Sharma, Noopur; Wilson, Jacqueline; Aiken, Allison C.; Chand, Duli; Laskin, Alexander; Mazzoleni, Claudio; Pekour, Mikhail; Shilling, John; Shutthanandan, Vaithiyalingam; Zelenyuk, Alla; Zaveri, Rahul A.

    2016-04-01

    Ice formation by diesel soot particles was investigated at temperatures ranging from -40 to -50°C. Size-selected soot particles were physically and chemically aged in an environmental chamber, and their ice nucleating properties were determined using a continuous flow diffusion type ice nucleation chamber. Bare (freshly formed), hydrated, and compacted soot particles, as well as α-pinene secondary organic aerosol (SOA)-coated soot particles at high relative humidity conditions, showed ice formation activity at subsaturation conditions with respect to water but below the homogeneous freezing threshold conditions. However, SOA-coated soot particles at dry conditions were observed to freeze at homogeneous freezing threshold conditions. Overall, our results suggest that heterogeneous ice nucleation activity of freshly emitted diesel soot particles are sensitive to some of the aging processes that soot can undergo in the atmosphere.

  4. Modeling the kinetics of hydrates formation using phase field method under similar conditions of petroleum pipelines; Modelagem da cinetica de formacao de hidratos utilizando o Modelo do Campo de Fase em condicoes similares a dutos de petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Mabelle Biancardi; Castro, Jose Adilson de; Silva, Alexandre Jose da [Universidade Federal Fluminense (UFF), Volta Redonda, RJ (Brazil). Programa de Pos-Graduacao em Engenharia Metalurgica], e-mails: mabelle@metal.eeimvr.uff.br; adilson@metal.eeimvr.uff.br; ajs@metal.eeimvr.uff.br

    2008-10-15

    Natural hydrates are crystalline compounds that are ice-like formed under oil extraction transportation and processing. This paper deals with the kinetics of hydrate formation by using the phase field approach coupled with the transport equation of energy. The kinetic parameters of the hydrate formation were obtained by adjusting the proposed model to experimental results in similar conditions of oil extraction. The effect of thermal and nucleation conditions were investigated while the rate of formation and morphology were obtained by numerical computation. Model results of kinetics growth and morphology presented good agreement with the experimental ones. Simulation results indicated that super-cooling and pressure were decisive parameters for hydrates growth, morphology and interface thickness. (author)

  5. [Incidence of vitreoretinal pathologic conditions in myopic eyes after laser in situ keratomileusis].

    Science.gov (United States)

    Lin, Jijian; Xie, Xin; Du, Xinhua; Yang, Yabo; Yao, Ke

    2002-09-01

    To determine the incidence of vitreoretinal pathologic conditions in myopic eyes after laser in situ keratomileusis. Vitreoretinal pathologic conditions of 1981 consecutive eyes (995 patients) having undergone laser-assisted in situ keratomileusis for the correction of myopia were studied. Preoperative and postoperative basic examinations included visual acuity, manifest and cycloplegic refraction, slit-lamp microscope examination, applanation tonometry and a fundus examination after pupil dilatation by indirect ophthalmoscopy and biomicroscopy with spherical lens of + 90 diopters. Before laser in situ keratomileusis, preventive treatment was carried out for predisposing lesion of retinal detachment in 8 eyes: 6 eyes for lattice degeneration and 2 eyes for atrophic holes. Postoperative examinations were conducted at 1, 3 and 12 months and once a year thereafter. All eyes were followed up for >/= 12 months. Eyes were followed for a mean of (18.40 +/- 4.50) months (range 12 - 28) after the surgery. Sixteen eyes of 13 patients (0.81%) developed vitreoretinopathy after LASIK, including 6 eyes with lattice degeneration (0.30%) in which one of them had previous laser treatment, 2 with posterior vitreous detachment (0.10%), 2 with macular hemorrhage (0.10%), 4 with rhegmatogenous retinal detachment (0.20%), and 2 with retinal tear without retinal detachment (0.10%) in which one of them had previous laser treatment for lattice degeneration. Five patients were males (5 eyes involved). Others were females. Mean age of the group with vitreoretinal pathologic conditions was 31.80 +/- 5.85 years (range 22 to 43). The interval between refractive surgery and development of vitreoretinal complication was (10.38 +/- 6.20) months (range 1 to 24). The eyes that developed vitreoretinopathy had myopia -4.75 to -15.00 diopters (mean -9.45 +/- 2.61 D) before LASIK. The comparison of incidences of vitreoretinopathy after LASIK between the group of >/= -6.00 D and lattice degeneration and

  6. Extraction of compositional and hydration information of sulfates from laser-induced plasma spectra recorded under Mars atmospheric conditions - Implications for ChemCam investigations on Curiosity rover

    Energy Technology Data Exchange (ETDEWEB)

    Sobron, Pablo, E-mail: pablo.sobron@asc-csa.gc.ca [Department of Earth and Planetary Sciences and McDonnell Center for the Space Sciences, Washington University, St. Louis, MO 63130 (United States); Wang, Alian [Department of Earth and Planetary Sciences and McDonnell Center for the Space Sciences, Washington University, St. Louis, MO 63130 (United States); Sobron, Francisco [Unidad Asociada UVa-CSIC a traves del Centro de Astrobiologia, Parque Tecnologico de Boecillo, Parcela 203, Boecillo (Valladolid), 47151 (Spain)

    2012-02-15

    Given the volume of spectral data required for providing accurate compositional information and thereby insight in mineralogy and petrology from laser-induced breakdown spectroscopy (LIBS) measurements, fast data processing tools are a must. This is particularly true during the tactical operations of rover-based planetary exploration missions such as the Mars Science Laboratory rover, Curiosity, which will carry a remote LIBS spectrometer in its science payload. We have developed: an automated fast pre-processing sequence of algorithms for converting a series of LIBS spectra (typically 125) recorded from a single target into a reliable SNR-enhanced spectrum; a dedicated routine to quantify its spectral features; and a set of calibration curves using standard hydrous and multi-cation sulfates. These calibration curves allow deriving the elemental compositions and the degrees of hydration of various hydrous sulfates, one of the two major types of secondary minerals found on Mars. Our quantitative tools are built upon calibration-curve modeling, through the correlation of the elemental concentrations and the peak areas of the atomic emission lines observed in the LIBS spectra of standard samples. At present, we can derive the elemental concentrations of K, Na, Ca, Mg, Fe, Al, S, O, and H in sulfates, as well as the hydration degrees of Ca- and Mg-sulfates, from LIBS spectra obtained in both Earth atmosphere and Mars atmospheric conditions in a Planetary Environment and Analysis Chamber (PEACh). In addition, structural information can be potentially obtained for various Fe-sulfates. - Highlights: Black-Right-Pointing-Pointer Routines for LIBS spectral data fast automated processing. Black-Right-Pointing-Pointer Identification of elements and determination of the elemental composition. Black-Right-Pointing-Pointer Calibration curves for sulfate samples in Earth and Mars atmospheric conditions. Black-Right-Pointing-Pointer Fe curves probably related to the crystalline

  7. Thermodynamic model for predicting equilibrium conditions of clathrate hydrates of noble gases + light hydrocarbons: Combination of Van der Waals–Platteeuw model and sPC-SAFT EoS

    International Nuclear Information System (INIS)

    Abolala, Mostafa; Varaminian, Farshad

    2015-01-01

    Highlights: • Applying sPC-SAFT for phase equilibrium calculations. • Determining Kihara potential parameters for hydrate formers. • Successful usage of the model for systems with hydrate azeotropes. - Abstract: In this communication, equilibrium conditions of clathrate hydrates containing mixtures of noble gases (Argon, Krypton and Xenon) and light hydrocarbons (C 1 –C 3 ), which form structure I and II, are modeled. The thermodynamic model is based on the solid solution theory of Van der Waals–Platteeuw combined with the simplified Perturbed-Chain Statistical Association Fluid Theory equation of state (sPC-SAFT EoS). In dispersion term of sPC-SAFT EoS, the temperature dependent binary interaction parameters (k ij ) are adjusted; taking advantage of the well described (vapor + liquid) phase equilibria. Furthermore, the Kihara potential parameters are optimized based on the P–T data of pure hydrate former. Subsequently, these obtained parameters are used to predict the binary gas hydrate dissociation conditions. The equilibrium conditions of the binary gas hydrates predicted by this model agree well with experimental data (overall AAD P ∼ 2.17)

  8. PETher - Physical Properties of Thermal Water under In-situ-Conditions

    Science.gov (United States)

    Herfurth, Sarah; Schröder, Elisabeth

    2016-04-01

    The objective of PETher, a research project funded by the German Federal Ministry for Economic Affairs and Energy (BMWi), is to experimentally determine thermo-physical properties (specific isobaric heat capacity, kinematic viscosity, density and thermal conductivity) of geothermal water in-situ-conditions (pressure, temperature, chemical composition including gas content of the brine) present in geothermal applications. Knowing these thermo-physical properties reduces the uncertainties with respect to estimating the thermal output and therefore the economic viability of the power plant. Up to now, only a limited number of measurements of selected physical properties have been made, usually under laboratory conditions and for individual geothermal plants. In-situ measured parameters, especially in the temperature range of 120°C and higher, at pressures of 20 bar and higher, as well as with a salinity of up to 250 g/l, are sparse to non-existing. Therefore, pure water properties are often used as reference data and for designing the power plant and its components. Currently available numerical models describing the thermo-physical properties are typically not valid for the conditions in geothermal applications and do not consider the substantial influence of the chemical composition of the thermal water. Also, actual geothermal waters have not been subject of detailed measurements systematically performed under operational conditions on a large-scale basis. Owing to the lack of reliable data, a validation of numerical models for investigating geothermal systems is not possible. In order to determine the dependency of the thermo-physical properties of geothermal water on temperature, pressure and salinity in-situ measurements are conducted. The measurements are taking place directly at several geothermal applications located in Germany's hydrogeothermal key regions. In order to do this, a mobile testing unit was developed and refined with instruments specifically

  9. Remodeling of leaf cellular glycerolipid composition under drought and re-hydration conditions in grasses from the Lolium-Festuca complex

    Directory of Open Access Journals (Sweden)

    Dawid Perlikowski

    2016-07-01

    Full Text Available Drought tolerant plant genotypes are able to maintain stability and integrity of cellular membranes in unfavorable conditions, and to regenerate damaged membranes after stress cessation. The profiling of cellular glycerolipids during drought stress performed on model species such as Arabidopsis thaliana does not fully cover the picture of lipidome in monocots, including grasses. Herein, two closely related introgression genotypes of Lolium multiflorum (Italian ryegrass × Festuca arundinacea (tall fescue were used as a model for other grass species to describe lipid rearrangements during drought and re-hydration. The genotypes differed in their level of photosynthetic capacity during drought, and in their capacity for membrane regeneration after stress cessation. A total of 120 lipids, comprising the classes of monogalactosyldiacyloglycerol, digalactosyldiacyloglycerol, sulfoquinovosyldiacylglycerol, phosphatidylglycerol, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, diacylglicerol and triacylglicerol, were analyzed. The results clearly showed that water deficit had a significant impact on lipid metabolism in studied forage grasses. It was revealed that structural and metabolic lipid species changed their abundance during drought and re-watering periods and some crucial genotype-dependent differences were also observed. The introgression genotype characterized by an ability to regenerate membranes after re-hydration demonstrated a higher accumulation level of most chloroplast and numerous extra-chloroplast membrane lipid species at the beginning of drought. Furthermore, this genotype also revealed a significant reduction in the accumulation of most chloroplast lipids after re-hydration, compared with the other introgression genotype without the capacity for membrane regeneration. The potential influence of observed lipidomic alterations on a cellular membrane stability and photosynthetic capacity, are

  10. Effects of Hydrated Potato Starch on the Quality of Low-fat Ttoekgalbi (Korean Traditional Patty Packaged in Modified Atmosphere Conditions during Storage

    Directory of Open Access Journals (Sweden)

    S. M. Kang Muhlisin

    2012-05-01

    Full Text Available This study was carried out to investigate the effects of hydrated potato starch on the quality of low-fat ttoekgalbi (Korean traditional patty packaged in modified atmosphere conditions during storage. The ttoekgalbi was prepared from 53.2% lean beef, 13.9% lean pork, 9.3% pork fat, and 23.6% other ingredients. Two low-fat ttoekgalbi treatments were prepared by substituting pork fat with hydrated potato starch; either by 50% fat replacement (50% FR or 100% fat replacement (100% FR. Both 50% and 100% FR increased the moisture, crude protein, and decreased fat content, cooking loss, and hardness. For MAP studies, 200 g of ttoekgalbi were placed on the tray and filled with gas composed of 70% O2: 30% CO2 (70% O2-MAP and 30% CO2: 70% N2 (70% N2-MAP, and were stored at 5°C for 12 d. During the storage time, both 50% and 100% FR showed higher protein deterioration, while no differences were found in CIE a*, CIE L*, lipid oxidation, and bacterial counts in comparison to control. The ttoekgalbi with 70% O2-MAP was more red, lighter in color, and showed higher TBARS values compared with 70% N2-MAP. The meat with 70% N2-MAP showed lower aerobic bacterial counts in control than those with 70% O2-MAP. The lower anaerobic bacterial counts were observed only in 50% FR and 100% FR packed with 70% N2-MAP in comparison with 70% O2-MAP. In conclusion, the fat replacement with hydrated potato starch showed no negative effects on the quality of low fat ttoekgalbi during storage and 70% N2-MAP was better than 70% O2-MAP for low-fat ttoekgalbi packaging.

  11. Hydro-bio-geomechanical properties of hydrate-bearing sediments from Nankai Trough

    Science.gov (United States)

    Santamarina, J.C.; Dai, Shifeng; Terzariol, M.; Jang, Jeonghwan; Waite, William F.; Winters, William J.; Nagao, J.; Yoneda, J.; Konno, Y.; Fujii, T.; Suzuki, K.

    2015-01-01

    Natural hydrate-bearing sediments from the Nankai Trough, offshore Japan, were studied using the Pressure Core Characterization Tools (PCCTs) to obtain geomechanical, hydrological, electrical, and biological properties under in situ pressure, temperature, and restored effective stress conditions. Measurement results, combined with index-property data and analytical physics-based models, provide unique insight into hydrate-bearing sediments in situ. Tested cores contain some silty-sands, but are predominantly sandy- and clayey-silts. Hydrate saturations Sh range from 0.15 to 0.74, with significant concentrations in the silty-sands. Wave velocity and flexible-wall permeameter measurements on never-depressurized pressure-core sediments suggest hydrates in the coarser-grained zones, the silty-sands where Sh exceeds 0.4, contribute to soil-skeletal stability and are load-bearing. In the sandy- and clayey-silts, where Sh < 0.4, the state of effective stress and stress history are significant factors determining sediment stiffness. Controlled depressurization tests show that hydrate dissociation occurs too quickly to maintain thermodynamic equilibrium, and pressure–temperature conditions track the hydrate stability boundary in pure-water, rather than that in seawater, in spite of both the in situ pore water and the water used to maintain specimen pore pressure prior to dissociation being saline. Hydrate dissociation accompanied with fines migration caused up to 2.4% vertical strain contraction. The first-ever direct shear measurements on never-depressurized pressure-core specimens show hydrate-bearing sediments have higher sediment strength and peak friction angle than post-dissociation sediments, but the residual friction angle remains the same in both cases. Permeability measurements made before and after hydrate dissociation demonstrate that water permeability increases after dissociation, but the gain is limited by the transition from hydrate saturation

  12. Flow assurance intervention, hydrates remediation

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-01

    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)

  13. Sulfates on Mars: A systematic Raman spectroscopic study of hydration states of magnesium sulfates

    Science.gov (United States)

    Wang, A.; Freeman, J.J.; Jolliff, B.L.; Chou, I.-Ming

    2006-01-01

    The martian orbital and landed surface missions, OMEGA on Mar Express and the two Mars Explorations Rovers, respectively, have yielded evidence pointing to the presence of magnesium sulfates on the martian surface. In situ identification of the hydration states of magnesium sulfates, as well as the hydration states of other Ca- and Fe- sulfates, will be crucial in future landed missions on Mars in order to advance our knowledge of the hydrologic history of Mars as well as the potential for hosting life on Mars. Raman spectroscopy is a technique well-suited for landed missions on the martian surface. In this paper, we report a systematic study of the Raman spectra of the hydrates of magnesium sulfate. Characteristic and distinct Raman spectral patterns were observed for each of the 11 distinct hydrates of magnesium sulfates, crystalline and non-crystalline. The unique Raman spectral features along with the general tendency of the shift of the position of the sulfate ??1 band towards higher wavenumbers with a decrease in the degree of hydration allow in situ identification of these hydrated magnesium sulfates from the raw Raman spectra of mixtures. Using these Raman spectral features, we have started the study of the stability field of hydrated magnesium sulfates and the pathways of their transformations at various temperature and relative humidity conditions. In particular we report on the Raman spectrum of an amorphous hydrate of magnesium sulfate (MgSO4??2H2O) that may have specific relevance for the martian surface. ?? 2006 Elsevier Inc. All rights reserved.

  14. 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)

    2007-03-15

    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)

  15. Modes of occurrence and accumulation mechanism of methane hydrate -result of meti exploratory test wells ''Tokai-Oki To Kumano-Nada''

    Energy Technology Data Exchange (ETDEWEB)

    Fujii, Tetsuya; Namikawa, Takatoshi; Nakamizu, Masaru; Tsuji, Yoshihiro; Okui, Toshiharu; Kawasaki, Masayuki; Ochiai, Koji

    2005-07-01

    In the Nankai Trough, offshore central Japan, seismic data indicates widespread existence of BSR, which is interpreted as an indicator of bottom boundary of methane hydrate bearing zone. Methane hydrate is regarded as future possible natural gas resource. However, the volume, distribution and occurrence of hydrate have been poorly understood. In order to obtain data for the understanding of methane hydrate occurrence and volume estimation, METI exploratory test wells ''Tokai-oki to Kumano-nada'' were drilled from January to May in 2004. First, LWD (Logging While Drilling) was carried out at 16 sites that were selected based on 2D and 3D seismic interpretation. Secondly, coring was carried out at 4 sites where high concentration of methane hydrate was expected based on resistivity log curve. In addition, continuous formation temperature measurement was carried out in order to investigate in-situ temperature condition in hydrate bearing sediments. Coring was carried out using both ODP type core sampler and PTCS (Pressure Temperature Core Sampler). PTCS coring were mainly focused on the hydrate bearing zone. Hydrate was confirmed in the pore space of turbidite sandstone layer in two of these sites, while it was confirmed as massive or layered condition in mud in one of the sites. Coring results suggest that most of hydrate were concentrated in sand layers in the alternation of sand and mud. The evidence may indicates permeable sandstone is ideal for hydrate accumulation. Hydrate dissociation and gas measurement test on board was also carried out and natural hydrate saturation data, which may calibrate logging results, was obtained. (Author)

  16. Numerical simulation of heat and mass transport during hydration of Portland cement mortar in semi-adiabatic and steam curing conditions

    OpenAIRE

    Hernandez-Bautista, E.; Bentz, D. P.; Sandoval-Torres, S.; de Cano-Barrita, P. F. J.

    2016-01-01

    A model that describes hydration and heat-mass transport in Portland cement mortar during steam curing was developed. The hydration reactions are described by a maturity function that uses the equivalent age concept, coupled to a heat and mass balance. The thermal conductivity and specific heat of mortar with water-to-cement mass ratio of 0.30 was measured during hydration, using the Transient Plane Source method. The parameters for the maturity equation and the activation energy were obtaine...

  17. Dissolution Coupled Biodegradation of Pce by Inducing In-Situ Biosurfactant Production Under Anaerobic Conditions

    Science.gov (United States)

    Dominic, J.; Nambi, I. M.

    2013-12-01

    Biosurfactants have proven to enhance the bioavailability and thereby elevate the rate of degradation of Light Non Aqueous Phase Liquids (LNAPLs) such as crude oil and petroleum derivatives. In spite of their superior characteristics, use of these biomolecules for remediation of Dense Non Aqueous Phase Liquids (DNAPLs) such as chlorinated solvents is still not clearly understood. In this present study, we have investigated the fate of tetrachloroethylene (PCE) by inducing in-situ biosurfactants production, a sustainable option which hypothesizes increase in bioavailability of LNAPLs. In order to understand the effect of biosurfactants on dissolution and biodegradation under the inducement of in-situ biosurfactant production, batch experiments were conducted in pure liquid media. The individual influence of each process such as biosurfactant production, dissolution of PCE and biodegradation of PCE were studied separately for getting insights on the synergistic effect of each process on the fate of PCE. Finally the dissolution coupled biodegradation of non aqueous phase PCE was studied in conditions where biosurfactant production was induced by nitrate limitation. The effect of biosurfactants was differentiated by repeating the same experiments were the biosurfactant production was retarded. The overall effect of in-situ biosurfactant production process was evaluated by use of a mathematical model. The process of microbial growth, biosurfactant production, dissolution and biodegradation of PCE were translated as ordinary differential equations. The modelling exercise was mainly performed to get insight on the combined effects of various processes that determine the concentration of PCE in its aqueous and non-aqueous phases. Model simulated profiles of PCE with the kinetic coefficients evaluated earlier from individual experiments were compared with parameters fitted for observations in experiments with dissolution coupled biodegradation process using optimization

  18. Imaging microbial metal metabolism in situ under conditions of the deep-sea hydrothermal vents

    Science.gov (United States)

    Oger, P. M.; Daniel, I.; Simionovici, A.; Picard, A.

    2006-12-01

    High-pressure biotopes are the most widely spread biotopes on Earth. They represent one possible location for the origin of life. They also share striking similarities with extraterrestrial biotopes such as those postulated for Europe or Mars. In absence of light, dissimilatory reduction of metals (DMR) is fueling the ecosystem. Monitoring the metabolism of the deep-sea hydrothermal vent microbial fauna under P, T and chemical conditions relevant to their isolation environment can be difficult because of the confinement and because most spectroscopic probes do not sense metallic ions in solution. We demonstrated the possibility to use Xray spectroscopy to monitor the speciation of metallic species in solution. Experiments were performed at The ESRF using Selenium (Se) detoxification by Agrobacterium tumefaciens as an analog of DMR. The reduction of Se from selenite to the metal was monitored by a combiantion of two Xray spectroscopic techniques (XANES and μXRF). Cells were incubated in the low pressure DAC in growth medium supplemented with 5mM Selenite and incubated under pressures up to 60 Mpa at 30°C for 24h. The evolution of the speciation can be easily monitored and the concentration of each Se species determined from the Xray spectra by linear combinations of standard spectra. Selenite is transformed by the bacterium into a mixture of metal Se and methylated Se after 24 hours. Se detoxification is observed in situ up to at least 25 MPa. The technique, developped for Se can be adapted to monitor other elements more relevant to DMR such as As, Fe or S, which should allow to monitor in situ under controlled pressure and temperature the metabolism of vent organisms. It is also amenable to the monitoring of toxic metals. Xray spectroscopy and the lpDAC are compatible with other spectroscopic techniques, such as Raman, UV or IR spectroscopies, allowing to probe other metabolic activities. Hence, enlarging the range of metabolic information that can be obtained in

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

    Directory of Open Access Journals (Sweden)

    Jianzhong Zhao

    2015-01-01

    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.

  20. Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments

    Science.gov (United States)

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

    2014-12-01

    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

  1. Gas Hydrate Investigations Using Pressure Core Analysis: Current Practice

    Science.gov (United States)

    Schultheiss, P.; Holland, M.; Roberts, J.; Druce, M.

    2006-12-01

    Recently there have been a number of major gas hydrate expeditions, both academic and commercially oriented, that have benefited from advances in the practice of pressure coring and pressure core analysis, especially using the HYACINTH pressure coring systems. We report on the now mature process of pressure core acquisition, pressure core handling and pressure core analysis and the results from the analysis of pressure cores, which have revealed important in situ properties along with some remarkable views of gas hydrate morphologies. Pressure coring success rates have improved as the tools have been modified and adapted for use on different drilling platforms. To ensure that pressure cores remain within the hydrate stability zone, tool deployment, recovery and on-deck handling procedures now mitigate against unwanted temperature rises. Core analysis has been integrated into the core transfer protocol and automated nondestructive measurements, including P-wave velocity, gamma density, and X-ray imaging, are routinely made on cores. Pressure cores can be subjected to controlled depressurization experiments while nondestructive measurements are being made, or cores can be stored at in situ conditions for further analysis and subsampling.

  2. Hydro-mechanical properties of pressure core sediments recovered from the Krishna-Godavari Basin during India's National Gas Hydrate Program Expedition NGHP-02

    Science.gov (United States)

    Yoneda, J.; Oshima, M.; Kida, M.; Kato, A.; Konno, Y.; Jin, Y.; Waite, W. F.; Jang, J.; Kumar, P.; Tenma, N.

    2017-12-01

    Pressure coring and analysis technology allows for gas hydrate to be recovered from the deep seabed, transferred to the laboratory and characterized while continuously maintaining gas hydrate stability. For this study, dozens of hydrate-bearing pressure core sediment subsections recovered from the Krishna-Godavari Basin during India's National Gas Hydrate Program Expedition NGHP-02 were tested with Pressure Core Non-destructive Analysis Tools (PNATs) through a collaboration between Japan and India. PNATs, originally developed by AIST as a part of the Japanese National hydrate research program (MH21, funded by METI) conducted permeability, compression and consolidation tests under various effective stress conditions, including the in situ stress state estimated from downhole bulk density measurements. At the in situ effective stress, gas hydrate-bearing sediments had an effective permeability range of 0.01-10mD even at pore-space hydrate saturations above 60%. Permeability increased by 10 to 100 times after hydrate dissociation at the same effective stress, but these post-dissociation gains were erased when effective stress was increased from in situ values ( 1 MPa) to 10MPa in a simulation of the depressurization method for methane extraction from hydrate. Vertical-to-horizontal permeability anisotropy was also investigated. First-ever multi-stage loading tests and strain-rate alternation compression tests were successfully conducted for evaluating sediment strengthening dependence on the rate and magnitude of effective confining stress changes. In addition, oedometer tests were performed up to 40MPa of consolidation stress to simulate the depressurization method in ultra-deep sea environments. Consolidation curves measured with and without gas hydrate were investigated over a wide range of effective confining stresses. Compression curves for gas hydrate-bearing sediments were convex downward due to high hydrate saturations. Consolidation tests show that

  3. Evaluation of gas migration characteristics of compacted bentonite considering in-situ conditions of disposal facility

    International Nuclear Information System (INIS)

    Tanaka, Yukihisa; Hironaga, Michihiko

    2012-01-01

    In the current concept of repository for radioactive waste disposal, compacted bentonite will be used as an engineered barrier mainly for inhibiting migration of radioactive nuclides. Hydrogen gas can be generated inside the engineered barrier by anaerobic corrosion of metals used for containers, etc. If the gas generation rate exceeds the diffusion rate of gas molecules inside of the engineered barrier, gas will accumulate in the void space inside of the engineered barrier until its pressure becomes large enough for it to enter the bentonite as a discrete gaseous phase. It is expected to be not easy for gas to entering into the bentonite as a discrete gaseous phase because the pore of compacted bentonite is so minute. Therefore it is necessary to investigate the effect of gas pressure generation and gas migration on the engineered barrier, peripheral facilities and ground. CRIEPI already proposed an analytical method for simulating gas migration through the compacted bentonite using the model of two phase flow through deformable porous media. Though validity of the analytical code of CRIEPI was examined by comparing existing gas migration test results with the calculated results, further validation is needed because in situ conditions, such as stress conditions and boundary condition, are different from conventional laboratory gas migration tent. In this study, gas migration tests whose initial axial stress is larger than initial radial stress and gas migration tests whose gas inlet is small. Simulation of the test results is also conducted. Comparing the test results with the calculated results, it is revealed that the analytical code of CRIEPI can simulate gas migration behavior through compacted bentonite with accuracy. (author)

  4. Migration of 99Tc in unsaturated Chinese loess under artificial rainfall condition: an in situ test

    International Nuclear Information System (INIS)

    Liu, C.L.; Wang, X.Y.; Wang, H.F.; Li, R.J.; Tang, L.T.

    2001-01-01

    The migration of 99 Tc in unsaturated Chinese loess under artificial rainfall condition was investigated in situ. Water suckers were buried at different depths under the bottom of an experimental pit of 2 m x 2 m x 1 m (deep). Quartz containing 3 H and 99 Tc was introduced into the experimental pit to an area of 40 cm x 40 cm and the pit was backfilled to a thickness of 30 cm. An artificial rainfall of 5 mm/h was applied to the experimental pit 4 h a day for 3 months. Moisture water samples were sucked with the help of a vacuum pumping system and the activity of 3 H and 99 Tc in the samples was determined. Breakthrough curves of 3 H and 99 Tc indicated that 99 Tc was slightly retarded. The calculated average apparent distribution coefficient of 99 Tc in the medium was (1.98 ± 0.42) x 10 -2 ml/g. (orig.)

  5. In situ electrochemical impedance spectroscopy of Zr-1%Nb under VVER primary circuit conditions

    International Nuclear Information System (INIS)

    Nagy, Gabor; Kerner, Zsolt; Pajkossy, Tamas

    2002-01-01

    Oxide layers were grown on tubular samples of Zr-1%Nb under conditions simulating those in VVER-type pressurised water reactors, viz. in near-neutral borate solutions in an autoclave at 290 deg. C. These samples were investigated using electrochemical impedance spectroscopy which was found to be suitable to follow in situ the corrosion process. A -CPE ox parallel R ox - element was used to characterise the oxide layer on Zr-1%Nb. Both the CPE ox coefficient, σ ox , and the parallel resistance, R ox , were found to be thickness dependent. The layer thickness, however, can only be calculated after a calibration procedure. The temperature dependence of the CPE ox element was also found to be anomalous while the temperature dependence of R ox indicates that the oxide layer has semiconductor properties. The relaxation time - defined as (R ox σ ox ) 1/α - was found to be quasi-independent of oxidation time and temperature; thus it is characteristic to the oxide layer on Zr-1%Nb

  6. Macroinvertebrates and fishes in the part of the Danube flowing through the Iron Gate national park and possibilities of their protection under in situ and ex situ conditions

    Directory of Open Access Journals (Sweden)

    Simić Vladica M.

    2004-01-01

    Full Text Available Comparison of the results of later investigations of the Danube in the part flowing through in the Iron Gate (Đerdap National Park with those of research conducted earlier (20 to 40 years ago shows that changes have occurred in regard to the presence and especially the abundance of certain hydrobionts on this sector of the river, a finding that applies to all groups examined. The paper discusses the potential and results of conservation measures realized through both legal regulations and medium-term plans for the advancement of fishing in this region. In addition to in situ study during the period from 1999 to 2003, a large number of species (especially of macroinvertebrates and fish were also investigated under artificial conditions (in the Kragujevac Aquarium in order to gain a better understanding of their ecological characteristics, especially their sensitivity to various environmental stress factors. The presented results indicate that weight of specimens and success of culturing under ex situ conditions are correlated with their sensitivity under natural conditions.

  7. Characterisation of lead-calcium alloys ageing in anisothermal conditions by calorimetric, resistance and hardness in-situ measurements

    Energy Technology Data Exchange (ETDEWEB)

    Rossi, F.; Lambertin, M. [Arts et Metiers ParisTech, LaBoMaP, Cluny (France); Delfaut-Durut, L. [CEA, Centre de Valduc, (SEMP, LECM), Is-sur-Tille (France); Maitre, A. [SPCTS, UFR Sciences et techniques, Limoges (France); Vilasi, M. [LCSM, Univ. Nancy I, Vandoeuvre les Nancy (France)

    2010-02-15

    Transformations undergone by lead-calcium alloys are numerous and have different kinetics from a few minutes to a few years. Anisothermal calorimetric measurements were performed to be able to identify these transformations quickly. It was then possible to identify five transformations. Complementary measurements have enabled us to define transformations with an in-situ electrical resistance measurement to follow the evolution of the calcium in solid solution and with an in-situ hardness measurement to characterise the mechanical properties. The aim of these results is to simulate the ageing and overageing of the alloy in isothermal conditions. (orig.)

  8. Theoretical study on the interactions between chlordecone hydrate and acidic surface groups of activated carbon under basic pH conditions.

    Science.gov (United States)

    Melchor-Rodríguez, Kenia; Gamboa-Carballo, Juan José; Ferino-Pérez, Anthuan; Passé-Coutrin, Nady; Gaspard, Sarra; Jáuregui-Haza, Ulises Javier

    2018-05-01

    A theoretical study of the influence of acidic surface groups (SG) of activated carbon (AC) on chlordecone hydrate (CLDh) adsorption is presented, in order to help understanding the adsorption process under basic pH conditions. A seven rings aromatic system (coronene) with a functional group in the edge was used as a simplified model of AC to evaluate the influence of SG in the course of adsorption from aqueous solution at basic pH conditions. Two SG were modeled in their deprotonated form: carboxyl and hydroxyl (COO - and O - ), interacting with CLDh. In order to model the solvation process, all systems under study were calculated with up to three water molecules. Multiple Minima Hypersurface (MMH) methodology was employed to study the interactions of CLDh with SG on AC using PM7 semiempirical Hamiltonian, to explore the potential energy surfaces of the systems and evaluate their thermodynamic association energies. The re-optimization of representative structures obtained from MMH was done using M06-2X Density Functional Theory. The Quantum Theory of Atoms in Molecules (QTAIM) was used to characterize the interaction types. As result, the association of CLDh with acidic SG at basic pH conditions preferentially occurs between the two alcohol groups of CLDh with COO - and O - groups and by dispersive interactions of chlorine atoms of CLDh with the graphitic surface. On the other hand, the presence of covalent interactions between the negatively charged oxygen of SG and one hydrogen atom of CLDh alcohol groups (O - ⋯HO interactions) without water molecules, was confirmed by QTAIM study. It can be concluded that the interactions of CLDh with acidic SG of AC under basic pH conditions confirms the physical mechanisms of adsorption process. Copyright © 2018 Elsevier Inc. All rights reserved.

  9. Using Hydrated Salt Phase Change Materials for Residential Air Conditioning Peak Demand Reduction and Energy Conservation in Coastal and Transitional Climates in the State of California

    Science.gov (United States)

    Lee, Kyoung Ok

    The recent rapid economic and population growth in the State of California have led to a significant increase in air conditioning use, especially in areas of the State with coastal and transitional climates. This fact makes that the electric peak demand be dominated by air conditioning use of residential buildings in the summer time. This extra peak demand caused by the use of air conditioning equipment lasts only a few days out of the year. As a result, unavoidable power outages have occurred when electric supply could not keep up with such electric demand. This thesis proposed a possible solution to this problem by using building thermal mass via phase change materials to reduce peak air conditioning demand loads. This proposed solution was tested via a new wall called Phase Change Frame Wall (PCFW). The PCFW is a typical residential frame wall in which Phase Change Materials (PCMs) were integrated to add thermal mass. The thermal performance of the PCFWs was first evaluated, experimentally, in two test houses, built for this purpose, located in Lawrence, KS and then via computer simulations of residential buildings located in coastal and transitional climates in California. In this thesis, a hydrated salt PCM was used, which was added in concentrations of 10% and 20% by weight of the interior sheathing of the walls. Based on the experimental results, under Lawrence, KS weather, the PCFWs at 10% and 20% of PCM concentrations reduced the peak heat transfer rates by 27.0% and 27.3%, on average, of all four walls, respectively. Simulated results using California climate data indicated that PCFWs would reduce peak heat transfer rates by 8% and 19% at 10% PCM concentration and 12.2% and 27% at 20% PCM concentration for the coastal and transitional climates, respectively. Furthermore, the PCFWs, at 10% PCM concentration, would reduce the space cooling load and the annual energy consumption by 10.4% and 7.2%, on average in both climates, respectively.

  10. Comparing the ensemble and extended Kalman filters for in situ soil moisture assimilation with contrasting conditions

    Directory of Open Access Journals (Sweden)

    D. Fairbairn

    2015-12-01

    Full Text Available Two data assimilation (DA methods are compared for their ability to produce an accurate soil moisture analysis using the Météo-France land surface model: (i SEKF, a simplified extended Kalman filter, which uses a climatological background-error covariance, and (ii EnSRF, the ensemble square root filter, which uses an ensemble background-error covariance and approximates random rainfall errors stochastically. In situ soil moisture observations at 5 cm depth are assimilated into the surface layer and 30 cm deep observations are used to evaluate the root-zone analysis on 12 sites in south-western France (SMOSMANIA network. These sites differ in terms of climate and soil texture. The two methods perform similarly and improve on the open loop. Both methods suffer from incorrect linear assumptions which are particularly degrading to the analysis during water-stressed conditions: the EnSRF by a dry bias and the SEKF by an over-sensitivity of the model Jacobian between the surface and the root-zone layers. These problems are less severe for the sites with wetter climates. A simple bias correction technique is tested on the EnSRF. Although this reduces the bias, it modifies the soil moisture fluxes and suppresses the ensemble spread, which degrades the analysis performance. However, the EnSRF flow-dependent background-error covariance evidently captures seasonal variability in the soil moisture errors and should exploit planned improvements in the model physics. Synthetic twin experiments demonstrate that when there is only a random component in the precipitation forcing errors, the correct stochastic representation of these errors enables the EnSRF to perform better than the SEKF. It might therefore be possible for the EnSRF to perform better than the SEKF with real data, if the rainfall uncertainty was accurately captured. However, the simple rainfall error model is not advantageous in our real experiments. More realistic rainfall error models are

  11. In-situ interferometric measurements of compacted smectite under hyper-alkaline condition - 59124

    International Nuclear Information System (INIS)

    Satoh, Hisao; Kurosawa, Susumu; Ishii, Tomoko; Owada, Hitoshi

    2012-01-01

    Document available in abstract form only. Full text of publication follows: Alteration of bentonite buffer at the repository for radioactive waste is an unavoidable phenomenon. However, precise kinetic data is useful for evaluation of the endurance for long-term safety. Alkaline attack to bentonite by cement-leachates may enhance alteration of smectite into the other phase such as zeolite. Until recently, there are a number of detailed dissolution studies (e.g., Cama et al., 2000; Yokoyama et al., 2005; Rozalen et al., 2008) for suspended smectite, using high precision measurements by ICPMS and AFM analyses. In contrast, dissolution study of compacted smectite is very limited (e.g., Nakayama et al., 2003). In order to verify the previous data, the dissolution rate of compacted smectite with realistic density needs to be confirmed experimentally. We have, for the first time, applied in-situ vertical scanning interferometry (VSI) along with the auto-compaction cell for measuring dissolution rates of smectite compacted at 0.04-20.0 MPa and 70 deg. C in 0.3 M NaOH (pH 12.1). At less-compaction (0.04 MPa), Kunipia-P smectite initially showed a relatively fast dissolution of ∼2E-11 mol/m 2 /s which is comparable to the rate for suspended smectite under same pH-T condition. At high-compaction ( 2 /s, but at higher compaction (>5 MPa), smectite dissolution was enhanced again to ∼5E-13 mol/ m 2 /s

  12. Rapid in situ detection of alkaloids in plant tissue under ambient conditions using desorption electrospray ionization.

    Science.gov (United States)

    Talaty, Nari; Takáts, Zoltán; Cooks, R Graham

    2005-12-01

    Desorption electrospray ionization (DESI) mass spectrometry is applied to the in situ detection of alkaloids in the tissue of poison hemlock (Conium maculatum), jimsonweed (Datura stramonium) and deadly nightshade (Atropa belladonna). The experiment is carried out by electrospraying micro-droplets of solvent onto native or freshly-cut plant tissue surfaces. No sample preparation is required and the mass spectra are recorded under ambient conditions, in times of a few seconds. The impact of the sprayed droplets on the surface produces gaseous ions from organic compounds originally present in the plant tissue. The effects of operating parameters, including the electrospray high voltage, heated capillary temperature, the solvent infusion rate and the carrier gas pressure on analytical performance are evaluated and optimized. Different types of plant material are analyzed including seeds, stems, leaves, roots and flowers. All the previously reported alkaloids have been detected in C. maculatum, while fifteen out of nineteen known alkaloids for D. stramonium and the principal alkaloids of A. belladonna were also identified. All identifications were confirmed by tandem mass spectrometry. Results obtained show similar mass spectra, number of alkaloids, and signal intensities to those obtained when extraction and separation processes are performed prior to mass spectrometric analysis. Evidence is provided that DESI ionization occurs by both a gas-phase ionization process and by a droplet pick-up mechanism. Quantitative precision of DESI is compared with conventional electrospray ionization mass spectrometry (after sample workup) and the RSD values for the same set of 25 dicotyledonous C. maculatum seeds (one half of each seed analyzed by ESI and the other by DESI) are 9.8% and 5.2%, respectively.

  13. Development of an In-Situ Decommissioning Sensor Network Test Bed for Structural Condition Monitoring - 12156

    Energy Technology Data Exchange (ETDEWEB)

    Zeigler, Kristine E.; Ferguson, Blythe A. [Savannah River National Laboratory, Aiken, South Carolina 29808 (United States)

    2012-07-01

    The Savannah River National Laboratory (SRNL) has established an In Situ Decommissioning (ISD) Sensor Network Test Bed, a unique, small scale, configurable environment, for the assessment of prospective sensors on actual ISD system material, at minimal cost. The Department of Energy (DOE) is presently implementing permanent entombment of contaminated, large nuclear structures via ISD. The ISD end state consists of a grout-filled concrete civil structure within the concrete frame of the original building. Validation of ISD system performance models and verification of actual system conditions can be achieved through the development a system of sensors to monitor the materials and condition of the structure. The ISD Sensor Network Test Bed has been designed and deployed to addresses the DOE-Environmental Management Technology Need to develop a remote monitoring system to determine and verify ISD system performance. Commercial off-the-shelf sensors have been installed on concrete blocks taken from walls of the P Reactor Building at the Savannah River Site. Deployment of this low-cost structural monitoring system provides hands-on experience with sensor networks. The initial sensor system consists of groutable thermistors for temperature and moisture monitoring, strain gauges for crack growth monitoring, tilt-meters for settlement monitoring, and a communication system for data collection. Baseline data and lessons learned from system design and installation and initial field testing will be utilized for future ISD sensor network development and deployment. The Sensor Network Test Bed at SRNL uses COTS sensors on concrete blocks from the outer wall of the P Reactor Building to measure conditions expected to occur in ISD structures. Knowledge and lessons learned gained from installation, testing, and monitoring of the equipment will be applied to sensor installation in a meso-scale test bed at FIU and in future ISD structures. The initial data collected from the sensors

  14. Novel understanding of calcium silicate hydrate from dilute hydration

    KAUST Repository

    Zhang, Lina

    2017-05-13

    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.

  15. Dehydration behaviour of hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Dette, S.S.; Stelzer, T.; Jones, M.J.; Ulrich, J. [Martin-Luther-Universitaet Halle-Wittenberg, Zentrum fuer Ingenieurwissenschaften, Verfahrenstechnik/TVT, 06099 Halle (Germany)

    2010-07-15

    Immersing a crystalline solvate in a suitable anti-solvent can induce phase transformation to solvent-free solid phase. In certain cases the solvent-mediated phase transition results in the generation of hollow, tubular structures. Both the tube dimensions of sodium-2-keto-L-gulonate anhydrate (skga) and the dehydration kinetics of sodium-2-keto-L-gulonate monohydrate (skgm) can be modified by the antisolvent employed. An explanation for the variable dehydration behaviour of skgm in the antisolvents is presented here. Furthermore, other crystalline hydrates were dehydrated in dry methanol. Providing an operational window can be found, any hydrate material could possibly find use in the production of tubes (micro- or nanotubes for different applications). The experimental conditions selected (dry methanol as antisolvent, dehydration temperature at 25 C) for the dehydration did not lead to the anhydrate tube growth for all hydrates investigated. Based upon the results presented here a first hypothesis is presented to explain this effect. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  16. In situ synchrotron X-ray powder diffraction study of the early hydration of α-tricalcium phosphate/tricalcium silicate composite bone cement

    Energy Technology Data Exchange (ETDEWEB)

    Morejon-Alonso, Loreley; Correa, Jose Raul, E-mail: lmorejon@fq.uh.cu [Departamento de Quimica General, Facultad de Quimica, Universidad de La Habana, UH (Cuba); Motisuke, Mariana [Universidade Federal de Sao Paulo (UNIFESP), Sao Jose dos Campos, SP (Brazil); Carrodeguas, Raul Garcia [Universidade Federal de Campina Grande (UFCG), Campina Grande, PB (Brazil). Laboratorio de Avaliacao e Desenvolvimento de Biomateriais do Nordeste; Santos, Luis Alberto dos [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Escola de Engenharia. Departamento de Materiais

    2015-01-15

    Bioactivity, osteogenicity and mechanical properties of α-tricalcium phosphate (α-TCP) based phosphates cements can be improved by adding tricalcium silicate (C{sub 3}S); however, the addition of C{sub 3}S delays the precipitation and growth of calcium deficient hydroxyapatite (CDHA). Thus, the aim of this work was the study of in situ setting reaction of α-TCP/C{sub 3}S composite bone cement under high energy X-ray generated by a synchrotron source within the first 72h. The results showed that the addition of C{sub 3}S induces the precipitation of nanosized CDHA at early times depending on the added content. Calculated crystallite sizes showed that the higher the content of C{sub 3}S, the smaller the crystal size at the beginning of the precipitation. These results are different from those obtained by conventional XRD method, suggesting that the proposed technique is a powerful tool in determining the composition and extent of reaction of CPCs surfaces in real time. (author)

  17. Laser Based In Situ Techniques: Novel Methods for Generating Extreme Conditions in TEM Samples

    Energy Technology Data Exchange (ETDEWEB)

    Taheri, M; Lagrange, T; Reed, B; Armstrong, M; Campbell, G; DeHope, W; Kim, J; King, W; Masiel, D; Browning, N

    2008-02-25

    The Dynamic Transmission Electron Microscope (DTEM) is introduced as a novel tool for in situ processing of materials. Examples of various types of dynamic studies outline the advantages and differences of laser-based heating in the DTEM in comparison to conventional (resistive) heating in situ TEM methods. We demonstrate various unique capabilities of the drive laser, namely, in situ processing of nanoscale materials, rapid and high temperature phase transformations, and controlled thermal activation of materials. These experiments would otherwise be impossible without the use of the DTEM drive laser. Thus, the potential of the DTEM to as a new technique to process and characterize the growth of a myriad of micro and nanostructures is demonstrated.

  18. Reconsideration on Hydration of Sodium Ion: From Micro-Hydration to Bulk Hydration

    Science.gov (United States)

    Yongquan, Zhou; Chunhui, Fang; Yan, Fang; Fayan, Zhu; Haiwen, Ge; Hongyan, Liu

    2017-12-01

    Micro hydration structures of the sodium ion, [Na(H2O) n ]+, n = 1-12, were probed by density functional theory (DFT) at B3LYP/aug-cc-pVDZ level in both gaseous and aqueous phase. The predicted equilibrium sodium-oxygen distance of 0.240 nm at the present level of theory. The four-, five- and six-coordinated cluster can transform from each other at the ambient condition. The analysis of the successive water binding energy and natural charge population (NBO) on Na+ clearly shows that the influence of Na+ on the surrounding water molecules goes beyond the first hydration shell with the hydration number of 6. The Car-Parrinello molecular dynamic simulation shows that only the first hydration sphere can be found, and the hydration number of Na+ is 5.2 and the hydration distance ( r Na-O) is 0.235 nm. All our simulations mentioned in the present paper show an excellent agreement with the diffraction result from X-ray scattering study.

  19. In situ ligand synthesis with the UO22+ cation under hydrothermal conditions

    International Nuclear Information System (INIS)

    Frisch, Mark; Cahill, Christopher L.

    2007-01-01

    A novel uranium (VI) coordination polymer, (UO 2 ) 2 (C 2 O 4 )(C 5 H 6 NO 3 ) 2 (1), has been prepared under the hydrothermal reaction of uranium nitrate hexahydrate and L-pyroglutamic acid. Compound 1 (monoclinic, C2/c, a=22.541(6) A, b=5.7428(15) A, c=15.815(4) A, β=119.112(4) o , Z=4, R 1 =0.0237, wR 2 =0.0367) consists of uranium pentagonal bipyramids linked via L-pyroglutamate and oxalate anions to form an overall two-dimensional (2D) structure. With the absence of oxalic acid within the starting materials, the oxalate anions are hypothesized to form in situ whereby decarboxylation of L-pyroglutamic acid occurs followed by coupling of CO 2 to form the oxalate linkages as observed in the crystal structure. Addition of copper (II) to this system appears to promote oxalate formation in that synthetic moolooite (Cu(C 2 O 4 ).nH 2 O; 0≤n≤1) and a known uranyl oxalate [(UO 2 ) 2 (C 2 O 4 )(OH) 2 (H 2 O) 2 .H 2 O], co-crystallize in significant quantity. Compound 1 exhibits the characteristic uranyl emission spectrum upon either direct uranyl excitation or ligand excitation, the latter of which shows an increase in relative intensity. This subsequent increase in the intensity indicates an energy transfer from the ligand to the uranyl cations thus illustrating an example of the antenna effect in the solid state. - Graphical abstract: A novel homometallic coordination polymer (UO 2 ) 2 (C 2 O 4 )(C 5 H 6 NO 3 ) 2 , in the uranium-L-pyroglutamic acid system has been synthesized under hydrothermal conditions. The title compound consists of uranium pentagonal bipyramids bridged through both L-pyroglutamate and oxalate linkages to produce a 3D crystal structure. The oxalate anions are theorized to result from decarboxylation of L-pyroglutamic acid followed by subsequent coupling of CO 2

  20. Hydration of Watson-Crick base pairs and dehydration of Hoogsteen base pairs inducing structural polymorphism under molecular crowding conditions.

    Science.gov (United States)

    Miyoshi, Daisuke; Nakamura, Kaori; Tateishi-Karimata, Hisae; Ohmichi, Tatsuo; Sugimoto, Naoki

    2009-03-18

    It has been revealed recently that molecular crowding, which is one of the largest differences between in vivo and in vitro conditions, is a critical factor determining the structure, stability, and function of nucleic acids. However, the effects of molecular crowding on Watson-Crick and Hoogsteen base pairs remain unclear. In order to investigate directly and quantitatively the molecular crowding effects on base pair types in nucleic acids, we designed intramolecular parallel- and antiparallel-stranded DNA duplexes consisting of Hoogsteen and Watson-Crick base pairs, respectively, as well as an intramolecular parallel-stranded triplex containing both types of base pairs. Thermodynamic analyses demonstrated that the values of free energy change at 25 degrees C for Hoogsteen base-pair formations decreased from +1.45 +/- 0.15 to +1.09 +/- 0.13 kcal mol(-1), and from -1.89 +/- 0.13 to -2.71 +/- 0.11 kcal mol(-1) in the intramolecular duplex and triplex, respectively, when the concentration of PEG 200 (polyethylene glycol with average molecular weight 200) increased from 0 to 20 wt %. However, corresponding values for Watson-Crick formation in the duplex and triplex increased from -10.2 +/- 0.2 to -8.7 +/- 0.1 kcal mol(-1), and from -10.8 +/- 0.2 to -9.2 +/- 0.2 kcal mol(-1), respectively. Furthermore, it was revealed that the opposing effects of molecular crowding on the Hoogsteen and Watson-Crick base pairs were due to different behaviors of water molecules binding to the DNA strands.

  1. In situ Raman Spectroscopy of Oxide Films on Zirconium Alloy in Simulated PWR Primary Water Condition

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Tae Ho; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Ji Hyun [UNIST, Ulsan (Korea, Republic of)

    2016-05-15

    The two layered oxide structure is formed in pre-transition oxide for the zirconium alloy in high temperature water environment. It is known that the corrosion rate is related to the volume fraction of zirconium oxide and the pores in the oxides; therefore, the aim of this paper is to investigate the oxidation behavior in the pretransition zirconium oxide in high-temperature water chemistry. In this work, Raman spectroscopy was used for in situ investigations for characterizing the phase of zirconium oxide. In situ Raman spectroscopy is a well-suited technique for investigating in detail the characteristics of oxide films in a high-temperature corrosion environment. In previous studies, an in situ Raman system was developed for investigating the oxides on nickel-based alloys and low alloy steels in high-temperature water environment. Also, the early stage oxidation behavior of zirconium alloy with different dissolved hydrogen concentration environments in high temperature water was treated in the authors' previous study. In this study, a specific zirconium alloy was oxidized and investigated with in situ Raman spectroscopy for 100 d oxidation, which is close to the first transition time of the zirconium alloy oxidation. The ex situ investigation methods such as transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) were used to further characterize the zirconium oxide structure. As oxidation time increased, the Raman peaks of tetragonal zirconium oxide were merged or became weaker. However, the monoclinic zirconium oxide peaks became distinct. The tetragonal zirconium oxide was just found near the O/M interface and this could explain the Raman spectra difference between the 30 d result and others.

  2. Indian National Gas Hydrate Program Expedition 01 report

    Science.gov (United States)

    Collett, Timothy S.; Riedel, M.; Boswell, R.; Presley, J.; Kumar, P.; Sathe, A.; Sethi, A.; Lall, M.V.; ,

    2015-01-01

    Gas hydrate is a naturally occurring “ice-like” combination of natural gas and water that has the potential to serve as an immense resource of natural gas from the world’s oceans and polar regions. However, gas-hydrate recovery is both a scientific and a technical challenge and much remains to be learned about the geologic, engineering, and economic factors controlling the ultimate energy resource potential of gas hydrate. The amount of natural gas contained in the world’s gas-hydrate accumulations is enormous, but these estimates are speculative and range over three orders of magnitude from about 2,800 to 8,000,000 trillion cubic meters of gas. By comparison, conventional natural gas accumulations (reserves and undiscovered, technically recoverable resources) for the world are estimated at approximately 440 trillion cubic meters. Gas recovery from gas hydrate is hindered because the gas is in a solid form and because gas hydrate commonly occurs in remote Arctic and deep marine environments. Proposed methods of gas recovery from gas hydrate generally deal with disassociating or “melting” in situ gas hydrate by heating the reservoir beyond the temperature of gas-hydrate formation, or decreasing the reservoir pressure below hydrate equilibrium. The pace of energy-related gas hydrate assessment projects has accelerated over the past several years.

  3. Thermal conductivity of hydrate-bearing sediments

    Science.gov (United States)

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

    2009-01-01

    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.

  4. The Exchange Reaction Between Methane Hydrate and Carbon Dioxide: An Oceanic Feasibility Test

    Science.gov (United States)

    Dunk, R. M.; Brewer, P. G.; Peltzer, E. T.; Walz, P. M.; Hester, K. C.; Sloan, E. D.

    2006-12-01

    The conversion of CH4 hydrate to CO2 hydrate offers, in principle, a way of sequestering CO2, with the additional recovery of CH4 gas as an energy source. We report results from the first in-situ oceanic experiment on this reaction, carried out in August 2006 at the massive thermogenic hydrate mounds in 850 m water depth, Barkley Canyon, offshore from Vancouver Island (48° 18.642' N, 126° 3.903' W), using MBARI's ROV Tiburon deployed from the R/V Western Flyer. Two small cores (10 cm length, 4 cm diameter) of white hydrate were collected from exposed outcrops using an ROV operated tool and hydraulically ejected into a glass walled, closed top, reaction chamber. Approximately 2 L of liquid CO2 were dispensed into the chamber, and the chamber transferred to an aluminium base plate to seal the system. Under ambient conditions (P = 870 dbar, T = 4.0 °C, S = 34.2), the densities of natural gas hydrate and liquid CO2 are closely matched and less than that of seawater, where the hydrate cores floated at the top of the chamber fully immersed within the buoyant liquid CO2. Over the following ~48 hours, the system was inspected periodically with the ROV HDTV camera prior to examination with the sea-going laser Raman spectrometer, DORISS II. For this, the chamber was transferred to a Precision Underwater Positioner (PUP) that enabled focusing of the laser beam with sub- mm precision. Our choice of where to focus the laser was based upon the need to explore all phases the cored natural gas hydrate, liquid CO2, any created CO2 hydrate, and any liberated CH4 gas. The natural gas hydrate was composed primarily of CH4, with minor amounts of C2H6 and C3H8, indicating the presence of Structure II hydrate. To date, laboratory experiments have focused on the reaction between pure Structure I CH4 hydrate and CO2 vapour, where the difference in free energy between the CH4 and CO2 hydrate states provides a thermodynamic argument in favour of conversion. However for a Structure II

  5. A comparative study of different methods for the generation of tetra-n-butyl ammonium bromide clathrate hydrate slurry in a cold storage air-conditioning system

    International Nuclear Information System (INIS)

    Shi, X.J.; Zhang, P.

    2013-01-01

    Highlights: ► Four kinds of TBAB CHS generation methods are experimentally investigated. ► Accession of CHS into supercooled solution can be helpful to the generation. ► Higher flow rate results in higher energy efficiency of CHS generation. - Abstract: A cold storage air-conditioning system using tetra-n-butyl ammonium bromide (TBAB) clathrate hydrate slurry (CHS) as cold storage medium was built to investigate the high-efficiency method of TBAB CHS generation. In the present study, four kinds of different TBAB CHS generation methods were experimentally investigated and compared, and these methods included continuously cooling, turning off refrigerator while crystals appearing, supercooling release and accession of TBAB CHS into supercooled TBAB aqueous solution. The results showed that continuously cooling would lead to severe adhesion of crystal to the heat exchanger wall, and supercooling release took place with a big stochastic characteristic, hence the first and third method were concluded not reliable. Both the second and fourth methods could maintain the temperature of heat exchanger wall at a relatively higher level, therefore the crystal adhesion to the heat exchanger wall would be reduced significantly, which led to higher coefficient of performance (COP). In addition, accession of TBAB CHS into TBAB supercooled solution could shorten the time of supercooling release, resulting in about 21.8–35.4% shorter generation time than other methods. Moreover, the influence of flow rate on the CHS generation process was investigated, and the results showed that higher flow rate generally resulted in higher system COP

  6. Methane hydrate dissociation using inverted five-spot water flooding method in cubic hydrate simulator

    International Nuclear Information System (INIS)

    Li, Gang; Li, Xiao-Sen; Li, Bo; Wang, Yi

    2014-01-01

    The combination forms of the hydrate dissociation methods in different well systems are divided into 6 main patterns. Dissociation processes of methane hydrate in porous media using the inverted five-spot water flooding method (Pattern 4) are investigated by the experimental observation and numerical simulation. In situ methane hydrate is synthesized in the Cubic Hydrate Simulator (CHS), a 5.832-L cubic reactor. A center vertical well is used as the hot water injection well, while the four vertical wells at the corner are the gas and water production wells. The gas production begins simultaneously with the hot water injection, while after approximately 20 min of compression, the water begins to be produced. One of the common characteristics of the inverted five-spot water flooding method is that both the gas and water production rates decrease with the reduction of the hydrate dissociation rate. The evaluation of the energy efficiency ratio might indicate the inverted five-spot water flooding as a promising gas producing method from the hydrate reservoir. - Highlights: • A three-dimensional 5.8-L cubic pressure vessel is developed. • Gas production of hydrate using inverted five-spot flooding method is studied. • Water/gas production rate and energy efficiency ratio are evaluated. • Temperature distributions of numerical simulation and experiment agree well. • Hydrate dissociation process is a moving boundary problem in this study

  7. ADAPTATION OF THE OBTAINED in vitro Gentiana lutea L. PLANTS TO ex vitro AND in situ CONDITIONS

    Directory of Open Access Journals (Sweden)

    О. Yu.

    2015-12-01

    Full Text Available The objective of the research was to develop the technology of introduction of the obtained by microclonal propagation Gentiana lutea L. plants into conditions in situ. Methods of cultivation of plant objects in vitro were used. There were chosen optimal conditions for rooting G. lutea shoots obtained through microclonal propagation in vitro: МS/2 medium with twice decreased concentration of NH4NO3 without vitamins and sucrose supplemented with 3 g/l of mannite and 0.05 mg/l kinetin, and agar (4 mg/l in combination with perlite (16 g/l used as a maintaining substrate; or the nutrient medium (MS/2 without vitamins and smaller concentration of N4NO3 with gradual decrease of carbohydrates from 10 g/l to 2 g/l, and further rooting experimental shoots in tap water. Rooted plants were adapted to conditions ex vitro through planting them into flowerpots with soil and gradual changing hothouse regime for exposed one. The share of adapted to in situ conditions plants (21% after a year of planting proves the suggested method to be efficient and promising. There was suggested this technology is the most efficient ones for revival of disturbed G. lutea populations that includes repatriation of rooted and adapted to ex vitro conditions plants obtained through microclonal propagation in vitro.

  8. Artificial Hydration and Nutrition

    Science.gov (United States)

    ... Crisis Situations Pets and Animals myhealthfinder Food and Nutrition Healthy Food Choices Weight Loss and Diet Plans ... Your Health Resources Healthcare Management Artificial Hydration and Nutrition Artificial Hydration and Nutrition Share Print Patients who ...

  9. Development of hydrate risk quantification in oil and gas production

    Science.gov (United States)

    Chaudhari, Piyush N.

    Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in

  10. Reliability of a Cryoscopic Micro-Osmometer Using 15-µL Plasma Samples to Measure Hydration Status in Varied Environmental Conditions

    Science.gov (United States)

    Scanlan, Aaron T.; Richter-Stretton, Gina L.; Madueno, Maria C.; Borges, Nattai R.; Fenning, Andrew S.

    2017-01-01

    Measurement of plasma osmolality (P[subscript osm]) remains popular for assessing hydration status in exercise science. However, a controlled reliability assessment of micro-osmometry using small sample volumes to measure Posm remains to be performed. This study aimed to examine the reliability of a cryoscopic micro-osmometer requiring 15-µL…

  11. Influence of the redox state on the neptunium sorption under alkaline conditions. Batch sorption studies on titanium dioxide and calcium silicate hydrates

    International Nuclear Information System (INIS)

    Tits, Jan; Laube, Andreas; Wieland, Erich; Gaona, Xavier

    2014-01-01

    Wet chemistry experiments were carried out to investigate the effect of the redox state and aqueous speciation on the uptake of neptunium by titanium dioxide (TiO 2 ) and by calcium silicate hydrates (C-S-H) under alkaline conditions. TiO 2 was chosen as a reference sorbent to determine the surface complexation behaviour of neptunium under alkaline conditions. C-S-H phases are important constituents of cement and concrete. They may contribute significantly to radionuclide retention due to their high recrystallization rates making incorporation the dominating sorption mechanism for many radionuclides (e.g. the actinides) on these materials. The sorption of neptunium on both solids was found to depend strongly on the degree of hydrolysis. On TiO 2 R d values for Np(IV), Np(V) and Np(VI) are identical at pH = 10 and decrease with progressing hydrolysis in case of Np(V) and Np(VI). On C-S-H phases, R d values for the three redox states are also identical at pH = 10. While the R d values for Np(VI) sorption on C-S-H phases decrease with progressing hydrolysis, the R d values for Np(IV) and Np(V) sorption are not affected by the pH. In addition to the effect of hydrolysis, the presence of Ca is found to promote Np(V) and Np(VI) sorption on TiO 2 whereas on C-S-H phases, the present wet chemistry data do not give unambiguous evidence. Thus, the aqueous speciation appears to have a similar influence on the sorption of the actinides on both types of solids despite the different sorption mechanism. The similar R d values for Np(IV,V,VI) sorption at pH = 10 can be explained qualitatively by invoking inter-ligand electrostatic repulsion between OH groups in the coordination sphere of Np(V) and Np(VI). This mechanism was proposed earlier in the literature for the prediction of actinide complexation constants with inorganic ligands. A limiting coordination number for each Np redox state, resulting from the inter-ligand electrostatic repulsion, allows the weaker sorption of the

  12. In situ particle acceleration and physical conditions in radio tail galaxies

    International Nuclear Information System (INIS)

    Pacholczyk, A.G.; Scott, J.S.

    1976-01-01

    A model for the objects known as radio tail galaxies is presented. Independent plasmons emerging from an active radio galaxy into an intracluster medium become turbulent due to Rayleigh-Taylor and Kelvin-Helmholtz instabilities. The turbulence produces both in situ betatron and second order Fermi acceleration. Predictions of the dependence of spectral index and flux on distance along the tail match observations well. Fitting provides values of physical parameters in the tail. The relevance of this method of particle acceleration for the problem of the origin of X-ray emission in clusters of galaxies is discussed

  13. Morphology studies on gas hydrates interacting with silica gel

    Energy Technology Data Exchange (ETDEWEB)

    Beltran, J.; Servio, P. [McGill Univ., Montreal, PQ (Canada). Dept. of Chemical Engineering

    2008-07-01

    Clathrate hydrates or gas hydrates are non-stoichiometric, crystalline compounds that form when small molecules come in contact with water at certain temperatures and pressures. Natural gas hydrates are found in the ocean bottom and in permafrost regions. It is thought that the amount of energy stored in natural hydrates is at least twice that of all other fossil fuels combined. In addition, trapping carbon dioxide as a hydrate in the bottom of the ocean has been suggested as an alternative means of reducing atmospheric carbon dioxide levels. Naturally occurring clathrates are found in close interaction with fine grained particles of very small mean pore diameters. Even though an increasing amount of hydrate equilibrium data for small diameter porous media has become available, the morphological behavior of hydrates subject to such conditions is yet to be explored. This paper presented a study that visually examined hydrate formation and decomposition of gas hydrates while interacting with fine grains of silica gel. The study showed still frames from high-resolution video recordings for hydrate formation and decomposition. The paper discussed the experiment including the apparatus as well as the results of hydrate formation and hydrate dissociation. This study enabled for the first time to observe clathrate morphology while hydrates interacted closely with fine grain particles with small mean pore diameters. 9 refs., 8 figs.

  14. Comparing ignitability for in situ burning of oil spills for an asphaltenic, a waxy and a light crude oil as a function of weathering conditions under arctic conditions

    DEFF Research Database (Denmark)

    Fritt-Rasmussen, Janne; Brandvik, Per Johan; Villumsen, Arne

    2012-01-01

    (asphalthenic), Kobbe (light oil) and Norne (waxy), for ignitability as a function of ice conditions and weathering degree. The crude oils (9 L) were weathered in a laboratory basin (4.8 m3) under simulated arctic conditions (0, 50 and 90% ice cover). The laboratory burning tests show that the ignitability...... is dependent on oil composition, ice conditions and weathering degree. In open water, oil spills rapidly become “not ignitable” due to the weathering e.g. high water content and low content of residual volatile components. The slower weathering of oil spills in ice (50 and 90% ice cover) results in longer time......-windows for the oil to be ignitable. The composition of the oils is important for the window of opportunity. The asphalthenic Grane crude oil had a limited timewindow for in situ burning (9 h or less), while the light Kobbe crude oil and the waxy Norne crude oil had the longest time-windows for in situ burning (from...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-07-01

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

  16. Methods to determine hydration states of minerals and cement hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com [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)

    2014-11-15

    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.

  17. Methods to determine hydration states of minerals and cement hydrates

    International Nuclear Information System (INIS)

    Baquerizo, Luis G.; Matschei, Thomas; Scrivener, Karen L.; Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars

    2014-01-01

    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 2 SO 4 –H 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

  18. Gravimetric and volumetric approaches adapted for hydrogen sorption measurements with in situ conditioning on small sorbent samples

    International Nuclear Information System (INIS)

    Poirier, E.; Chahine, R.; Tessier, A.; Bose, T.K.

    2005-01-01

    We present high sensitivity (0 to 1 bar, 295 K) gravimetric and volumetric hydrogen sorption measurement systems adapted for in situ sample conditioning at high temperature and high vacuum. These systems are designed especially for experiments on sorbents available in small masses (mg) and requiring thorough degassing prior to sorption measurements. Uncertainty analysis from instrumental specifications and hydrogen absorption measurements on palladium are presented. The gravimetric and volumetric systems yield cross-checkable results within about 0.05 wt % on samples weighing from (3 to 25) mg. Hydrogen storage capacities of single-walled carbon nanotubes measured at 1 bar and 295 K with both systems are presented

  19. Simulation and Characterization of Methane Hydrate Formation

    Science.gov (United States)

    Dhakal, S.; Gupta, I.

    2017-12-01

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

  20. Formation rate of natural gas hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Mork, Marit

    2002-07-01

    The rate of methane hydrate and natural gas hydrate formation was measured in a 9.5 litre stirred tank reactor of standard design. The experiments were performed to better understand the performance and scale-up of a reactor for continuous production of natural gas hydrates. The hydrate formation rate was measured at steady-state conditions at pressures between 70 and 90 bar and temperatures between 7 and 15 deg C. Between 44 and 56 % of the gas continuously supplied to the reactor was converted to hydrate. The experimental results show that the rate of hydrate formation is strongly influenced by gas injection rate and pressure. The effect of stirring rate is less significant and subcooling has no observable effect on the formation rate. Hydrate crystal concentration and gas composition do not influence the hydrate formation rate. Observations of produced hydrate crystals indicate that the crystals are elongated, about 5 micron in diameter and 10 micron long. Analysis of the results shows that the rate of hydrate formation is dominated by gas-liquid mass transfer. A mass transfer model, the bubble-to-crystal model, was developed for the hydrate formation rate in a continuous stirred tank reactor, given in terms of concentration driving force and an overall mass transfer coefficient. The driving force is the difference between the gas concentration at the gas-liquid interface and at the hydrate crystal surface. These concentrations correspond to the solubility of gas in water at experimental temperature and pressure and the solubility of gas at hydrate equilibrium temperature and experimental pressure, respectively. The overall mass transfer coefficient is expressed in terms of superficial gas velocity and impeller power consumption, parameters commonly used in study of stirred tank reactors. Experiments and modeling show that the stirred tank reactor has a considerable potential for increased production capacity. However, at higher hydrate production rates the

  1. In situ Removal of Hydrogen Sulfide During Biogas Fermentation at Microaerobic Condition.

    Science.gov (United States)

    Wu, Mengmeng; Zhang, Yima; Ye, Yuanyuan; Lin, Chunmian

    2016-11-01

    In this paper, rice straw was used as a raw material to produce biogas by anaerobic batch fermentation at 35 °C (mesophilic) or 55 °C (thermophilic). The hydrogen sulfide in biogas can be converted to S 0 or sulfate and removed in-situ under micro-oxygen environment. Trace oxygen was conducted to the anaerobic fermentation tank in amount of 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, or 10.0 times stoichiometric equivalence, respectively, and the control experiment without oxygen addition was carried out. The results showed that the initial H 2 S concentrations of biogas are about 3235 ± 185 mg/m 3 (mesophilic) or 3394 ± 126 mg/m 3 (thermophilic), respectively. The desulfurization efficiency is 72.3 % (mesophilic) or 65.6 % (thermophilic), respectively, with oxygen addition by stoichiometric relation. When the oxygen feeded in amount of 2∼4 times, theoretical quantity demanded the removal efficiency of hydrogen sulfide could be over 92 %, and the oxygen residue in biogas could be maintained less than 0.5 %, which fit the requirement of biogas used as vehicle fuel or combined to the grid. Though further more oxygen addition could promote the removal efficiency of hydrogen sulfide (about 93.6 %), the oxygen residue in biogas would be higher than the application limit concentration (0.5 %). Whether mesophilic or thermophilic fermentation with the extra addition of oxygen, there were no obvious changes in the gas production and methane concentration. In conclusion, in-situ desulfurization can be achieved in the anaerobic methane fermentation system under micro-oxygen environment. In addition, air could be used as a substitute oxygen resource on the situation without strict demand for the methane content of biogas.

  2. Performance Analysis of Retrofitted Tribo-Corrosion Test Rig for Monitoring In Situ Oil Conditions

    Directory of Open Access Journals (Sweden)

    Arpith Siddaiah

    2017-09-01

    Full Text Available Oils and lubricants, once extracted after use from a mechanical system, can hardly be reused, and should be refurbished or replaced in most applications. New methods of in situ oil and lubricant efficiency monitoring systems have been introduced for a wide variety of mechanical systems, such as automobiles, aerospace aircrafts, ships, offshore wind turbines, and deep sea oil drilling rigs. These methods utilize electronic sensors to monitor the “byproduct effects” in a mechanical system that are not indicative of the actual remaining lifecycle and reliability of the oils. A reliable oil monitoring system should be able to monitor the wear rate and the corrosion rate of the tribo-pairs due to the inclusion of contaminants. The current study addresses this technological gap, and presents a novel design of a tribo-corrosion test rig for oils used in a dynamic system. A pin-on-disk tribometer test rig retrofitted with a three electrode-potentiostat corrosion monitoring system was used to analyze the corrosion and wear rate of a steel tribo-pair in industrial grade transmission oil. The effectiveness of the retrofitted test rig was analyzed by introducing various concentrations of contaminants in an oil medium that usually leads to a corrosive working environment. The results indicate that the retrofitted test rig can effectively monitor the in situ tribological performance of the oil in a controlled dynamic corrosive environment. It is a useful method to understand the wear–corrosion synergies for further experimental work, and to develop accurate predictive lifecycle assessment and prognostic models. The application of this system is expected to have economic benefits and help reduce the ecological oil waste footprint.

  3. Performance Analysis of Retrofitted Tribo-Corrosion Test Rig for Monitoring In Situ Oil Conditions.

    Science.gov (United States)

    Siddaiah, Arpith; Khan, Zulfiqar Ahmad; Ramachandran, Rahul; Menezes, Pradeep L

    2017-09-28

    Oils and lubricants, once extracted after use from a mechanical system, can hardly be reused, and should be refurbished or replaced in most applications. New methods of in situ oil and lubricant efficiency monitoring systems have been introduced for a wide variety of mechanical systems, such as automobiles, aerospace aircrafts, ships, offshore wind turbines, and deep sea oil drilling rigs. These methods utilize electronic sensors to monitor the "byproduct effects" in a mechanical system that are not indicative of the actual remaining lifecycle and reliability of the oils. A reliable oil monitoring system should be able to monitor the wear rate and the corrosion rate of the tribo-pairs due to the inclusion of contaminants. The current study addresses this technological gap, and presents a novel design of a tribo-corrosion test rig for oils used in a dynamic system. A pin-on-disk tribometer test rig retrofitted with a three electrode-potentiostat corrosion monitoring system was used to analyze the corrosion and wear rate of a steel tribo-pair in industrial grade transmission oil. The effectiveness of the retrofitted test rig was analyzed by introducing various concentrations of contaminants in an oil medium that usually leads to a corrosive working environment. The results indicate that the retrofitted test rig can effectively monitor the in situ tribological performance of the oil in a controlled dynamic corrosive environment. It is a useful method to understand the wear-corrosion synergies for further experimental work, and to develop accurate predictive lifecycle assessment and prognostic models. The application of this system is expected to have economic benefits and help reduce the ecological oil waste footprint.

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

    Science.gov (United States)

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

    2017-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-12-15

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

  6. Controls on Gas Hydrate Formation and Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Miriam Kastner; Ian MacDonald

    2006-03-03

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

  7. In situ corrosion studies on selected high level waste packaging materials under simulated disposal conditions in rock salt

    International Nuclear Information System (INIS)

    Smailos, E.; Schwarzkopf, W.; Koester, R.

    1988-01-01

    In order to qualify corrosion resistant materials for high level waste (HLW) packagings acting as a long-term barrier in a rock salt repository, the corrosion behavior of preselected materials is being investigated in laboratory-scale and in-situ experiments. This work reports about in-situ corrosion experiments on unalloyed steels, Ti 99.8-Pd, Hastelloy C4, and iron-base alloys, as nodular cast iron, Ni-Resist D4 and Si-cast iron, under simulated disposal conditions. The results of the investigations can be summarized as follows: (1) all materials investigated exhibited high resistance to corrosion under the conditions prevailing in the Brine Migration Test; (2) all materials and above all the materials with passivating oxide layers such as Ti 99.8-Pd and Hastelloy C4 which may corrode selectively already in the presence of minor amounts of brine had been resistant with respect to any type of local corrosion attack; the gamma-radiation of 3 · 10 2 Gy/h did not exert an influence on the corrosion behavior of the materials

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  9. In Situ Infrared Spectroscopy of Oligoaniline Intermediates Created under Alkaline Conditions.

    Science.gov (United States)

    Šeděnková, Ivana; Stejskal, Jaroslav; Trchová, Miroslava

    2014-12-26

    The progress of the oxidation of aniline with ammonium peroxydisulfate in an alkaline aqueous medium has been monitored in situ by attenuated total reflection (ATR) Fourier transform infrared spectroscopy. The growth of the microspheres and of the film at the ATR crystal surface, as well as the changes proceeding in the surrounding aqueous medium, are reflected in the spectra. The evolution of the spectra and the changes in the molecular structure occurring during aniline oxidation in alkaline medium are discussed with the help of differential spectra. Several processes connected with the various stages of aniline oxidation were distinguished. The progress of hydrolysis of the aniline in water and further an oxidation of aminophenol to benzoquinone imines in the presence of peroxydisulfate in alkaline medium have been detected in the spectra in real time. The precipitated solid oxidation product was analyzed by mass spectrometry. It is composed of oligomers, mainly trimers to octamers, of various molecular structures incorporating in addition to aniline constitutional units also p-benzoquinone or p-benzoquinoneimine moieties.

  10. Experiences from in-situ monitoring of pavement under weather conditions change

    Directory of Open Access Journals (Sweden)

    Likar Barbara

    2016-01-01

    Full Text Available Very strong winters with temperatures under 0°C and hot summers with temperatures more than 30°C are observed in the South East part of Slovenia. Those big differences in temperature during the year and especially temperatures below freezing point have strong influence on asphalt layer and sub base of road pavement. The freeze/thaw cycles lead to formation of ice lenses in base course causing cracks in asphalt layers and degrade the pavement usually in a few years. For this reason one section of the national road in the South East part of Slovenia was rebuilt with cold in-situ pavement retreatment. A test field with inbuilt sensors for measuring water content, temperature and deformation in various depths and locations was constructed during the remediation works to study the mechanism of freeze-thaw degradation of pavements. The main goal of the test field is to determine water content in sub base, freezing depth, temperature distribution and deformations, which lead to cracks in asphalt layer after the remediation work in the road construction.

  11. Synchrotron in-situ deformation experiments of perovskite + (Mg,Fe)O aggregates under shallow lower mantle conditions (Invited)

    Science.gov (United States)

    Girard, J.; Amulele, G.; Farla, R. J.; Liu, Z.; Mohiuddin, A.; Karato, S.

    2013-12-01

    Experimental studies on rheological properties of mantle's minerals are crucial to understand the dynamics of Earth's interior, but direct experimental studies under the relevant lower mantle conditions are challenging. Most of the earlier studies were performed at lower mantle pressures but low temperatures using DAC (diamond anvil cell) (e.g., Merkel et al., 2003)), and in DAC experiments strain-rate and stress are unknown. Some previous studies were carried out under high pressures and high temperatures (e.g, Cordier et al., 2004) , but quantitative results on rheological behaviour of said minerals were not obtained. Here we present the results of the first in-situ deformation experiments of perovskite + (Mg,Fe)O (Pv + fp) aggregates using RDA (rotational Drickamer apparatus). The RDA has a better support for the anvils at high pressure than the more commonly used D-DIA apparatus and hence we can reach higher pressures and temperatures than the D-DIA. We have recently made new modifications to the cell assembly to reach the lower mantle conditions with less interference in X-ray diffraction patterns by the surrounding materials. The starting material was ringwoodite synthesized using a multi-anvil. In-situ deformation experiments were then carried at pressure up to 28 GPa (calculated from thermal EOS of Pt) and estimated temperatures up to 2200 K using RDA. Under these conditions, ringwoodite transformed to Pv + fp. We subsequently deformed the sample between strain rates of 10-4 to 10-5 s-1. Stress and strain were measured in-situ using X-ray synchrotron beam. The recovered sample analyses show evidence of perovskite+(Mg,Fe)O microstructure (Fig. 1). The radial X-ray diffraction data are being analysed to determine the stress levels of two minerals. Also microstructures of deformed specimens are studied to understand the deformation mechanisms and strain partitioning. The results will contribute towards our understanding of the rheological properties of the

  12. Gas hydrate in nature

    Science.gov (United States)

    Ruppel, Carolyn D.

    2018-01-17

    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.

  13. In situ ligand synthesis with the UO22+ cation under hydrothermal conditions

    Science.gov (United States)

    Frisch, Mark; Cahill, Christopher L.

    2007-09-01

    A novel uranium (VI) coordination polymer, (UO 2) 2(C 2O 4)(C 5H 6NO 3) 2 ( 1), has been prepared under the hydrothermal reaction of uranium nitrate hexahydrate and L-pyroglutamic acid. Compound 1 (monoclinic, C2/ c, a=22.541(6) Å, b=5.7428(15) Å, c=15.815(4) Å, β=119.112(4)°, Z=4, R1=0.0237, w R2=0.0367) consists of uranium pentagonal bipyramids linked via L-pyroglutamate and oxalate anions to form an overall two-dimensional (2D) structure. With the absence of oxalic acid within the starting materials, the oxalate anions are hypothesized to form in situ whereby decarboxylation of L-pyroglutamic acid occurs followed by coupling of CO 2 to form the oxalate linkages as observed in the crystal structure. Addition of copper (II) to this system appears to promote oxalate formation in that synthetic moolooite (Cu(C 2O 4)· nH 2O; 0⩽ n⩽1) and a known uranyl oxalate [(UO 2) 2(C 2O 4)(OH) 2(H 2O) 2·H 2O], co-crystallize in significant quantity. Compound 1 exhibits the characteristic uranyl emission spectrum upon either direct uranyl excitation or ligand excitation, the latter of which shows an increase in relative intensity. This subsequent increase in the intensity indicates an energy transfer from the ligand to the uranyl cations thus illustrating an example of the antenna effect in the solid state.

  14. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    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.

  15. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    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.

  16. Efecto del almacenamiento al ambiente en semillas de Leucaena leucocephala cv. Cunningham sometidas a hidratación parcial Effect of storage under ambient conditions on seeds from Leucaena leucocephala cv. Cunningham subject to partial hydration

    Directory of Open Access Journals (Sweden)

    Yolanda González

    2012-12-01

    Full Text Available El objetivo del trabajo fue estudiar el efecto del almacenamiento al ambiente en la germinación de las semillas de Leucaena leucocephala cv. Cunningham sometidas a hidratación parcial. Los tratamientos fueron: control, sin escarificación (T0; escarificación térmica (ET con H2O a 80°C, durante dos minutos (T1; ET más hidratación parcial, en bandeja con agua corriente por 28 horas (T2; ET más hidratación parcial, en saco de yute humedecido con agua corriente por 28 horas (T3; ET más hidratación parcial, en bandeja con agua corriente y TMTD al 0,1% (plaguicida por 28 horas (T4; ET más hidratación parcial, en saco de yute humedecido con agua corriente y TMTD al 0,1% (plaguicida por 28 horas (T5. Las semillas hidratadas se deshidrataron durante 72 horas al aire y a la sombra, antes de almacenarlas. Se midió la germinación y la viabilidad a 0, 1, 2, 3, 4, 6, 18, 30 y 42 meses. Se utilizó un diseño totalmente aleatorizado y cuatro réplicas por tratamiento. Hubo diferencias significativas (PThe objective of the work was to study the effect of storage under ambient conditions on the germination of seeds from Leucaena leucocephala cv. Cunningham subject to partial hydration. The treatments were: control, no scarification (T0; thermal scarification (TS with H2O at 80ºC, for two minutes (T1; TS plus partial hydration, on tray with tap water for 28 hours (T2; TS plus partial hydration, in jute sac moist with tap water for 28 hours (T3; TS plus partial hydration in tray with tap water and TMTD at 0,1% (pesticide for 28 hours (T4; TS plus partial hydration, in jute sac moist with tap water and TMTD at 0,1% (pesticide for 28 hours (T5. The hydrated seeds were dehydrated during 72 hours exposed to air and under shade, before being stored. Germination and viability were measured after 0, 1, 2, 3, 4, 6, 18, 30 and 42 months. A completely randomized design and four replications per treatment were used. There were significant differences (P<0

  17. NMR Studies of Protein Hydration and Protein-Ligand Interactions

    Science.gov (United States)

    Chong, Yuan

    Water on the surface of a protein is called hydration water. Hydration water is known to play a crucial role in a variety of biological processes including protein folding, enzymatic activation, and drug binding. Although the significance of hydration water has been recognized, the underlying mechanism remains far from being understood. This dissertation employs a unique in-situ nuclear magnetic resonance (NMR) technique to study the mechanism of protein hydration and the role of hydration in alcohol-protein interactions. Water isotherms in proteins are measured at different temperatures via the in-situ NMR technique. Water is found to interact differently with hydrophilic and hydrophobic groups on the protein. Water adsorption on hydrophilic groups is hardly affected by the temperature, while water adsorption on hydrophobic groups strongly depends on the temperature around 10 C, below which the adsorption is substantially reduced. This effect is induced by the dramatic decrease in the protein flexibility below 10 C. Furthermore, nanosecond to microsecond protein dynamics and the free energy, enthalpy, and entropy of protein hydration are studied as a function of hydration level and temperature. A crossover at 10 C in protein dynamics and thermodynamics is revealed. The effect of water at hydrophilic groups on protein dynamics and thermodynamics shows little temperature dependence, whereas water at hydrophobic groups has stronger effect above 10 C. In addition, I investigate the role of water in alcohol binding to the protein using the in-situ NMR detection. The isotherms of alcohols are first measured on dry proteins, then on proteins with a series of controlled hydration levels. The free energy, enthalpy, and entropy of alcohol binding are also determined. Two distinct types of alcohol binding are identified. On the one hand, alcohols can directly bind to a few specific sites on the protein. This type of binding is independent of temperature and can be

  18. Hydration states of AFm cement phases

    Energy Technology Data Exchange (ETDEWEB)

    Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com [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; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)

    2015-07-15

    The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFm phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.

  19. Electrical in situ and post-irradiation properties of ceramics relevant to fusion irradiation conditions

    International Nuclear Information System (INIS)

    Shikama, Tatsuo; Zinkle, S.J.

    2002-01-01

    Electrical properties of ceramic candidate materials for the next-generation nuclear fusion devices under relevant irradiation conditions are reviewed. A main focal point is placed on the degradation behavior of the electrical insulating ability during and after irradiation. Several important radiation induced effects play important roles: radiation induced conductivity, thermally stimulated electrical conductivity, radiation induced electrical charge separation, and radiation induced electromotive force. These phenomena will interact with each other under fusion relevant irradiation conditions. The design of electrical components for the next-generation fusion devices should take into account these complicated interactions among the radiation induced phenomena

  20. In situ mobility of uranium in the presence of nitrate following sulfate-reducing conditions.

    Science.gov (United States)

    Paradis, Charles J; Jagadamma, Sindhu; Watson, David B; McKay, Larry D; Hazen, Terry C; Park, Melora; Istok, Jonathan D

    2016-04-01

    Reoxidation and mobilization of previously reduced and immobilized uranium by dissolved-phase oxidants poses a significant challenge for remediating uranium-contaminated groundwater. Preferential oxidation of reduced sulfur-bearing species, as opposed to reduced uranium-bearing species, has been demonstrated to limit the mobility of uranium at the laboratory scale yet field-scale investigations are lacking. In this study, the mobility of uranium in the presence of nitrate oxidant was investigated in a shallow groundwater system after establishing conditions conducive to uranium reduction and the formation of reduced sulfur-bearing species. A series of three injections of groundwater (200 L) containing U(VI) (5 μM) and amended with ethanol (40 mM) and sulfate (20 mM) were conducted in ten test wells in order to stimulate microbial-mediated reduction of uranium and the formation of reduced sulfur-bearing species. Simultaneous push-pull tests were then conducted in triplicate well clusters to investigate the mobility of U(VI) under three conditions: 1) high nitrate (120 mM), 2) high nitrate (120 mM) with ethanol (30 mM), and 3) low nitrate (2 mM) with ethanol (30 mM). Dilution-adjusted breakthrough curves of ethanol, nitrate, nitrite, sulfate, and U(VI) suggested that nitrate reduction was predominantly coupled to the oxidation of reduced-sulfur bearing species, as opposed to the reoxidation of U(IV), under all three conditions for the duration of the 36-day tests. The amount of sulfate, but not U(VI), recovered during the push-pull tests was substantially more than injected, relative to bromide tracer, under all three conditions and further suggested that reduced sulfur-bearing species were preferentially oxidized under nitrate-reducing conditions. However, some reoxidation of U(IV) was observed under nitrate-reducing conditions and in the absence of detectable nitrate and/or nitrite. This suggested that reduced sulfur-bearing species may not be fully effective at

  1. Combining Multicomponent Seismic Attributes, New Rock Physics Models, and In Situ Data to Estimate Gas-Hydrate Concentrations in Deep-Water, Near-Seafloor Strata of the Gulf of Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Bureau of Economic Geology

    2009-04-30

    The Bureau of Economic Geology was contracted to develop technologies that demonstrate the value of multicomponent seismic technology for evaluating deep-water hydrates across the Green Canyon area of the Gulf of Mexico. This report describes the methodologies that were developed to create compressional (P-P) and converted-shear (P-SV) images of near-seafloor geology from four-component ocean-bottom-cable (4C OBC) seismic data and the procedures used to integrate P-P and P-SV seismic attributes with borehole calibration data to estimate hydrate concentration across two study areas spanning 16 and 25 lease blocks (or 144 and 225 square miles), respectively. Approximately 200 km of two-dimensional 4C OBC profiles were processed and analyzed over the course of the 3-year project. The strategies we developed to image near-seafloor geology with 4C OBC data are unique, and the paper describing our methodology was peer-recognized with a Best Paper Award by the Society of Exploration Geophysicists in the first year of the project (2006). Among the valuable research findings demonstrated in this report, the demonstrated ability to image deep-water near-seafloor geology with sub-meter resolution using a standard-frequency (10-200 Hz) air gun array on the sea surface and 4C sensors on the seafloor has been the accomplishment that has received the most accolades from professional peers. Our study found that hydrate is pervasive across the two study areas that were analyzed but exists at low concentrations. Although our joint inversion technique showed that in some limited areas, and in some geologic units across those small areas, hydrates occupied up to 40-percent of the sediment pore space, we found that when hydrate was present, hydrate concentration tended to occupy only 10-percent to 20-percent of the pore volume. We also found that hydrate concentration tended to be greater near the base of the hydrate stability zone than it was within the central part of the stability

  2. Natural gas hydrates. Experimental techniques and their applications

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Yuguang; Liu, Changling (eds.) [Qingdao Institute of Marine Geology (China). Gas Hydrate Laboratory

    2013-07-01

    Focuses on gas hydrate experiment in laboratory. Intends to provide practical significant parameters for gas hydrate exploration and exploitation in the oceanic and permafrost environments. Consists of different themes that present up-to-date information on hydrate experiments. ''Natural Gas Hydrates: Experimental Techniques and Their Applications'' attempts to broadly integrate the most recent knowledge in the fields of hydrate experimental techniques in the laboratory. The book examines various experimental techniques in order to provide useful parameters for gas hydrate exploration and exploitation. It provides experimental techniques for gas hydrates, including the detection techniques, the thermo-physical properties, permeability and mechanical properties, geochemical abnormalities, stability and dissociation kinetics, exploitation conditions, as well as modern measurement technologies etc.

  3. Preservation of methane hydrate at 1 atm

    Science.gov (United States)

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

    2001-01-01

    A "pressure-release" method that enables reproducible bulk preservation of pure, porous, methane hydrate at conditions 50 to 75 K above its equilibrium T (193 K) at 1 atm is refined. The amount of hydrate preserved by this method appears to be greatly in excess of that reported in the previous citations, and is likely the result of a mechanism different from ice shielding.

  4. Basics of development of gas hydrate deposits

    Energy Technology Data Exchange (ETDEWEB)

    Makogon, Yuri F.; Holditch, Stephen A.; Makogon, Taras Y.

    2005-07-01

    Natural gas hydrate deposits could possibly be an important energy resource during this century. However, many problems associated with producing these deposits must first be solved. The industry must develop new technologies to produce the gas, to forecast possible tectonic cataclysms in regions of gas hydrate accumulations, and to prevent damage to the environment. These global issues must be addressed by every company or country who wants to produce gas hydrate deposits. Cooperative research between industry and universities can lead to technology breakthroughs in coming years. This paper reviews the Messoyakha field and the Blake Ridge and Nankai areas to explain a methodology for estimating how much gas might be producible from gas hydrate deposits (GHDs) under various conditions. The Messoyakha field is located on land, while the Blake Ridge and Nankai areas are offshore. Messoyakha is the first and the only GHD where gas production from hydrates has reached commercial flow rates. The Blake Ridge GHD has been studied for 20 years and 11 wells have been drilled to collect gas-hydrate samples. The potential resources of gas (gas in place) from Blake Ridge is estimated at 37.7Oe10{sup 12} m{sup 3} (1.330 Tcf) in hydrate form and 19.3Oe10{sup 12}m{sup 3} (681 Bcf) [5] in free gas. To estimate how much of the potential resource can be produced we need a thorough understanding of both the geologic and the thermodynamic characteristics of the formations. (Author)

  5. Gas Hydrates Research Programs: An International Review

    Energy Technology Data Exchange (ETDEWEB)

    Jorge Gabitto; Maria Barrufet

    2009-12-09

    Gas hydrates sediments have the potential of providing a huge amount of natural gas for human use. Hydrate sediments have been found in many different regions where the required temperature and pressure conditions have been satisfied. Resource exploitation is related to the safe dissociation of the gas hydrate sediments. Basic depressurization techniques and thermal stimulation processes have been tried in pilot efforts to exploit the resource. There is a growing interest in gas hydrates all over the world due to the inevitable decline of oil and gas reserves. Many different countries are interested in this valuable resource. Unsurprisingly, developed countries with limited energy resources have taken the lead in worldwide gas hydrates research and exploration. The goal of this research project is to collect information in order to record and evaluate the relative strengths and goals of the different gas hydrates programs throughout the world. A thorough literature search about gas hydrates research activities has been conducted. The main participants in the research effort have been identified and summaries of their past and present activities reported. An evaluation section discussing present and future research activities has also been included.

  6. Extraction of compositional and hydration information of sulfates from laser-induced plasma spectra recorded under Mars atmospheric conditions — Implications for ChemCam investigations on Curiosity rover

    International Nuclear Information System (INIS)

    Sobron, Pablo; Wang, Alian; Sobron, Francisco

    2012-01-01

    Given the volume of spectral data required for providing accurate compositional information and thereby insight in mineralogy and petrology from laser-induced breakdown spectroscopy (LIBS) measurements, fast data processing tools are a must. This is particularly true during the tactical operations of rover-based planetary exploration missions such as the Mars Science Laboratory rover, Curiosity, which will carry a remote LIBS spectrometer in its science payload. We have developed: an automated fast pre-processing sequence of algorithms for converting a series of LIBS spectra (typically 125) recorded from a single target into a reliable SNR-enhanced spectrum; a dedicated routine to quantify its spectral features; and a set of calibration curves using standard hydrous and multi-cation sulfates. These calibration curves allow deriving the elemental compositions and the degrees of hydration of various hydrous sulfates, one of the two major types of secondary minerals found on Mars. Our quantitative tools are built upon calibration-curve modeling, through the correlation of the elemental concentrations and the peak areas of the atomic emission lines observed in the LIBS spectra of standard samples. At present, we can derive the elemental concentrations of K, Na, Ca, Mg, Fe, Al, S, O, and H in sulfates, as well as the hydration degrees of Ca- and Mg-sulfates, from LIBS spectra obtained in both Earth atmosphere and Mars atmospheric conditions in a Planetary Environment and Analysis Chamber (PEACh). In addition, structural information can be potentially obtained for various Fe-sulfates. - Highlights: ► Routines for LIBS spectral data fast automated processing. ► Identification of elements and determination of the elemental composition. ► Calibration curves for sulfate samples in Earth and Mars atmospheric conditions. ► Fe curves probably related to the crystalline structure of Fe-sulfates. ► Extraction of degree of hydration in hydrous Mg-, Ca-, and Fe-sulfates.

  7. In Situ Irradiation and Measurement of Triple Junction Solar Cells at Low Intensity, Low Temperature (LILT) Conditions

    Science.gov (United States)

    Harris, R.D.; Imaizumi, M.; Walters, R.J.; Lorentzen, J.R.; Messenger, S.R.; Tischler, J.G.; Ohshima, T.; Sato, S.; Sharps, P.R.; Fatemi, N.S.

    2008-01-01

    The performance of triple junction InGaP/(In)GaAs/Ge space solar cells was studied following high energy electron irradiation at low temperature. Cell characterization was carried out in situ at the irradiation temperature while using low intensity illumination, and, as such, these conditions reflect those found for deep space, solar powered missions that are far from the sun. Cell characterization consisted of I-V measurements and quantum efficiency measurements. The low temperature irradiations caused substantial degradation that differs in some ways from that seen after room temperature irradiations. The short circuit current degrades more at low temperature while the open circuit voltage degrades more at room temperature. A room temperature anneal after the low temperature irradiation produced a substantial recovery in the degradation. Following irradiation at both temperatures and an extended room temperature anneal, quantum efficiency measurement suggests that the bulk of the remaining damage is in the (In)GaAs sub-cell

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

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-03-01

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

  9. Carbon dioxide gas hydrates accumulation in freezing and frozen sediments

    Energy Technology Data Exchange (ETDEWEB)

    Chuvilin, E.; Guryeva, O. [Moscow State Univ., Moscow (Russian Federation). Dept. of Geology

    2008-07-01

    Carbon dioxide (CO{sub 2}) hydrates and methane hydrates can be formed, and exist under natural conditions. The permafrost area has been considered as an environment for the potential disposal of CO{sub 2}. The favorable factors for preserving CO{sub 2} in liquid and gas hydrate states in frozen sediments and under permafrost horizons are great thickness of frozen sediments; low permeability in comparison with thawed sediments; and favourable conditions for hydrates formation. Therefore, research on the formation and existence conditions of CO{sub 2} gas hydrates in permafrost and under permafrost sediments are of great importance for estimation of CO{sub 2} disposal conditions in permafrost, and for working out specific sequestration schemes. This paper presented the results of an experimental study on the process of carbon dioxide (CO{sub 2}) gas hydrates formation in the porous media of sediments under positive and negative temperatures. Sediment samples of various compositions including those selected in the permafrost area were used. The research was conducted in a special pressure chamber, which allowed to monitor pressure and temperature. The study used the monitoring results in order to make quantitative estimation of the kinetics of CO{sub 2} hydrates accumulation in the model sediments. Results were presented in terms of kinetics of CO{sub 2} hydrates accumulation in the porous media at positive and negative temperatures; kinetics of CO{sub 2} hydrates accumulation in various porous media; gas hydrate-former influence on kinetics of hydrates accumulation in frozen sediments; and influence of freezing on CO{sub 2} hydrates accumulation in porous media. It was concluded that hydrate accumulation took an active place in porous media not only under positive, but also under high negative temperatures, when the water was mainly in the form of ice in porous media. 27 refs., 3 tabs., 5 figs.

  10. Methane hydrate stability and anthropogenic climate change

    Directory of Open Access Journals (Sweden)

    D. Archer

    2007-07-01

    Full Text Available Methane frozen into hydrate makes up a large reservoir of potentially volatile carbon below the sea floor and associated with permafrost soils. This reservoir intuitively seems precarious, because hydrate ice floats in water, and melts at Earth surface conditions. The hydrate reservoir is so large that if 10% of the methane were released to the atmosphere within a few years, it would have an impact on the Earth's radiation budget equivalent to a factor of 10 increase in atmospheric CO2.

    Hydrates are releasing methane to the atmosphere today in response to anthropogenic warming, for example along the Arctic coastline of Siberia. However most of the hydrates are located at depths in soils and ocean sediments where anthropogenic warming and any possible methane release will take place over time scales of millennia. Individual catastrophic releases like landslides and pockmark explosions are too small to reach a sizable fraction of the hydrates. The carbon isotopic excursion at the end of the Paleocene has been interpreted as the release of thousands of Gton C, possibly from hydrates, but the time scale of the release appears to have been thousands of years, chronic rather than catastrophic.

    The potential climate impact in the coming century from hydrate methane release is speculative but could be comparable to climate feedbacks from the terrestrial biosphere and from peat, significant but not catastrophic. On geologic timescales, it is conceivable that hydrates could release as much carbon to the atmosphere/ocean system as we do by fossil fuel combustion.

  11. In Situ Visualization of the Phase Behavior of Oil Samples Under Refinery Process Conditions.

    Science.gov (United States)

    Laborde-Boutet, Cedric; McCaffrey, William C

    2017-02-21

    To help address production issues in refineries caused by the fouling of process units and lines, we have developed a setup as well as a method to visualize the behavior of petroleum samples under process conditions. The experimental setup relies on a custom-built micro-reactor fitted with a sapphire window at the bottom, which is placed over the objective of an inverted microscope equipped with a cross-polarizer module. Using reflection microscopy enables the visualization of opaque samples, such as petroleum vacuum residues, or asphaltenes. The combination of the sapphire window from the micro-reactor with the cross-polarizer module of the microscope on the light path allows high-contrast imaging of isotropic and anisotropic media. While observations are carried out, the micro-reactor can be heated to the temperature range of cracking reactions (up to 450 °C), can be subjected to H2 pressure relevant to hydroconversion reactions (up to 16 MPa), and can stir the sample by magnetic coupling. Observations are typically carried out by taking snapshots of the sample under cross-polarized light at regular time intervals. Image analyses may not only provide information on the temperature, pressure, and reactive conditions yielding phase separation, but may also give an estimate of the evolution of the chemical (absorption/reflection spectra) and physical (refractive index) properties of the sample before the onset of phase separation.

  12. Extreme Sea Conditions in Shallow Water: Estimation based on in-situ measurements

    Science.gov (United States)

    Le Crom, Izan; Saulnier, Jean-Baptiste

    2013-04-01

    The design of marine renewable energy devices and components is based, among others, on the assessment of the environmental extreme conditions (winds, currents, waves, and water level) that must be combined together in order to evaluate the maximal loads on a floating/fixed structure, and on the anchoring system over a determined return period. Measuring devices are generally deployed at sea over relatively short durations (a few months to a few years), typically when describing water free surface elevation, and extrapolation methods based on hindcast data (and therefore on wave simulation models) have to be used. How to combine, in a realistic way, the action of the different loads (winds and waves for instance) and which correlation of return periods should be used are highly topical issues. However, the assessment of the extreme condition itself remains a not-fully-solved, crucial, and sensitive task. Above all in shallow water, extreme wave height, Hmax, is the most significant contribution in the dimensioning process of EMR devices. As a case study, existing methodologies for deep water have been applied to SEMREV, the French marine energy test site. The interest of this study, especially at this location, goes beyond the simple application to SEMREV's WEC and floating wind turbines deployment as it could also be extended to the Banc de Guérande offshore wind farm that are planned close by. More generally to pipes and communication cables as it is a redundant problematic. The paper will first present the existing measurements (wave and wind on site), the prediction chain that has been developed via wave models, the extrapolation methods applied to hindcast data, and will try to formulate recommendations for improving this assessment in shallow water.

  13. Hydrate Control for Gas Storage Operations

    Energy Technology Data Exchange (ETDEWEB)

    Jeffrey Savidge

    2008-10-31

    The overall objective of this project was to identify low cost hydrate control options to help mitigate and solve hydrate problems that occur in moderate and high pressure natural gas storage field operations. The study includes data on a number of flow configurations, fluids and control options that are common in natural gas storage field flow lines. The final phase of this work brings together data and experience from the hydrate flow test facility and multiple field and operator sources. It includes a compilation of basic information on operating conditions as well as candidate field separation options. Lastly the work is integrated with the work with the initial work to provide a comprehensive view of gas storage field hydrate control for field operations and storage field personnel.

  14. Colloid characterization and in situ release in shallow groundwater under different hydrogeology conditions.

    Science.gov (United States)

    Zhou, Jingjing; Liu, Dan; Zhang, Wenjing; Chen, Xuequn; Huan, Ying; Yu, Xipeng

    2017-06-01

    Changes to groundwater hydrodynamics and chemistry can lead to colloid release that can have a major impact on the groundwater environment. To analyze the effects of colloid release caused by artificial groundwater recharge, field and laboratory tests on colloid characterization and colloid release were conducted. The field tests were carried out at an artificial recharge test site in Shandong Province. In the field investigation, one recharge water sample and five groundwater samples were collected and filtered through three levels of ultrafiltration membranes, with pore sizes of 0.45 μm, 100 kDa, and 50 kDa. The field results indicated that the colloid mass concentrations in groundwater retained between membranes with pore sizes of 100 kDa-0.45 μm and 50 kDa-100 kDa were 19 and 62 mg/L, respectively. In recharge water, the colloid mass concentrations retained by 100-kDa-0.45-μm and 50-kDa-100-kDa membranes were 3 and 99 mg/L, respectively. Colloids detected on the ultrafiltration membranes were mainly inorganic between 100 kDa and 0.45 μm, and mainly organic between 50 and 100 kDa. Based on the field colloid investigation results, the organic colloid was chosen in the laboratory experiments to reveal its release behavior under different conditions. Porous media diameter, flux, ionic strength (IS), and ion valence were changed to determine their influences on organic colloid concentration outflow from undisturbed porous media. The experiment's results indicate that decreasing the diameter, and increasing the flux, ionic strength, and the number of divalent cations, can promote organic colloid release. The organic colloid release rate in the early stage was high and is thus likely to affect the quality of groundwater. The results provide a useful scientific basis for minimizing changes to hydrodynamic and hydrochemical conditions during artificial recharge, thus safeguarding groundwater quality.

  15. Modeling and in situ measurements of biometeorological conditions in microenvironments within the Athens University Campus, Greece

    Science.gov (United States)

    Nastos, Panagiotis T.; Polychroni, Iliana D.

    2016-10-01

    The objective of this research is to assess and analyze the biometeorological perception in complex microenvironments in the Athens University Campus (AUC) using urban micromodels, such as RayMan. The human thermal sensation in such a place was considered of great significance due to the great gathering of student body and staff of the University. The quantification of the biometeorological conditions was succeeded by the estimation of the physiologically equivalent temperature (PET), which is a biometeorological index based on the human energy balance. We carried out, on one hand, field measurements of air temperature, relative humidity, wind speed, and global solar irradiance for different sites (building atrium, open area, and green atrium) of the examined microurban environment in order to calculate PET during January-July 2013. Additionally, on the other hand, PET modeling was performed using different sky-view factors and was compared to a reference site (meteorological station of Laboratory of Climatology and Atmospheric Environment, University of Athens). The global radiation was transferred to the examined sites with the RayMan model, which considers the sky-view factors for the adaptation of the radiation fluxes to simple and complex environments. The results of this study reveal the crucial importance of the existence of trees and green cover in a complex environment, as a factor that could be the solution to the efforts of stake holders in order to mitigate strong heat stress and improve people's living quality in urban areas.

  16. Modeling dissociation behaviour of methane hydrate in porous soil media

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  17. Hydration rate of obsidian.

    Science.gov (United States)

    Friedman, I; Long, W

    1976-01-30

    The hydration rates of 12 obsidian samples of different chemical compositions were measured at temperatures from 95 degrees to 245 degrees C. An expression relating hydration rate to temperature was derived for each sample. The SiO(2) content and refractive index are related to the hydration rate, as are the CaO, MgO, and original water contents. With this information it is possible to calculate the hydration rate of a sample from its silica content, refractive index, or chemical index and a knowledge of the effective temperature at which the hydration occurred. The effective hydration temperature can be either measured or approximated from weather records. Rates have been calculated by both methods, and the results show that weather records can give a good approximation to the true EHT, particularly in tropical and subtropical climates. If one determines the EHT by any of the methods suggested, and also measures or knows the rate of hydration of the particular obsidian used, it should be possible to carry out absolute dating to +/- 10 percent of the true age over periods as short as several years and as long as millions of years.

  18. Replacement of CH4 in the hydrate by use of liquid CO2

    International Nuclear Information System (INIS)

    Ota, Masaki; Morohashi, Kenji; Abe, Yuki; Watanabe, Masaru; Smith, Richard Lee Jr.; Inomata, Hiroshi

    2005-01-01

    The dynamics of CH 4 replacement in the CH 4 hydrate with saturated liquid CO 2 at 273.2 K was measured with a high pressure optical cell. The results showed that CH 4 in the hydrate gradually moved to the liquid CO 2 phase while CO 2 in the liquid phase penetrated into the hydrate from the quantitative analysis. The decomposing process of the CH 4 hydrate during the replacement was analyzed with in situ Raman spectroscopy, which allowed us to distinguish the cage structure of the CH 4 hydrate and discuss the microscopic view of the replacement in the hydrate. It was found that the decomposition of the medium cage (M-cage) in the CH 4 hydrate proceeded faster than that of the small cage (S-cage). The observed rate difference could be related to the stability of the S-cage in the CH 4 hydrate or the re-formation tendency of CH 4 and water molecules in the S-cage after decomposing the hydrate structure, whereas the guest molecule exchange of CH 4 with CO 2 could occur in the M-cage. Based on the experimental data, we developed a kinetic model for calculation of the CH 4 remaining in the hydrate considering the decomposition rate difference between the M-cage and S-cage in the CH 4 hydrate. The results indicate that the driving force could be the fugacity difference between the fluid phase and the hydrate phase for the replacement process

  19. Gas hydrate resource quantification in Uruguay

    International Nuclear Information System (INIS)

    Tomasini, J.; De Santa Ana, H.; Veroslavsky, G.

    2012-01-01

    The gas hydrates are crystalline solids formed by natural gas (mostly methane) and water, which are stable in thermobaric conditions given under high pressures and low temperatures. These conditions are given in permafrost zones and continental margin basins offshore in the nature

  20. In situ investigation of wet chemical processes for chalcopyrite solar cells by L-edge XAS under ambient conditions

    Energy Technology Data Exchange (ETDEWEB)

    Greil, Stefanie M. [Helmholtz-Zentrum Berlin fuer Materialien und Energie, Albert-Einstein-Strasse 15, 12489 Berlin (Germany); Lauermann, Iver, E-mail: Iver.lauermann@helmholtz-berlin.d [Helmholtz-Zentrum Berlin fuer Materialien und Energie, Albert-Einstein-Strasse 15, 12489 Berlin (Germany); Ennaoui, Ahmed; Kropp, Timo; Lange, Kathrin M.; Weber, Matthieu [Helmholtz-Zentrum Berlin fuer Materialien und Energie, Albert-Einstein-Strasse 15, 12489 Berlin (Germany); Aziz, Emad F., E-mail: Emad.Aziz@helmholtz-berlin.d [Helmholtz-Zentrum Berlin fuer Materialien und Energie, Albert-Einstein-Strasse 15, 12489 Berlin (Germany)

    2010-02-15

    Two instrumental setups for in situ soft X-ray absorption spectroscopy in liquid systems are demonstrated in this work. One for investigating chemical reactions in solutions and a new one for the solid component of a liquid / (as in both / absorber) solid interface. We used these setups for investigating two production processes for chalcopyrite solar cells under ambient conditions, probing the L-edge of Zn and Cu. The first one is a flow cell with a silicon nitride membrane to study the chemical bath deposition process for Cd-free buffer layers. Examining the electronic structure of involved Zn complexes allows to determine the exact reaction mechanism taking place during this process. The second setup is a rotating disk for investigating the bath/absorber interface upon the etching process of superficial binary copper compounds of the absorber as a function of time. The time resolution of the chemical reaction demonstrated in this study ranges from the second to minute time scale.

  1. In situ investigation of wet chemical processes for chalcopyrite solar cells by L-edge XAS under ambient conditions

    International Nuclear Information System (INIS)

    Greil, Stefanie M.; Lauermann, Iver; Ennaoui, Ahmed; Kropp, Timo; Lange, Kathrin M.; Weber, Matthieu; Aziz, Emad F.

    2010-01-01

    Two instrumental setups for in situ soft X-ray absorption spectroscopy in liquid systems are demonstrated in this work. One for investigating chemical reactions in solutions and a new one for the solid component of a liquid / (as in both / absorber) solid interface. We used these setups for investigating two production processes for chalcopyrite solar cells under ambient conditions, probing the L-edge of Zn and Cu. The first one is a flow cell with a silicon nitride membrane to study the chemical bath deposition process for Cd-free buffer layers. Examining the electronic structure of involved Zn complexes allows to determine the exact reaction mechanism taking place during this process. The second setup is a rotating disk for investigating the bath/absorber interface upon the etching process of superficial binary copper compounds of the absorber as a function of time. The time resolution of the chemical reaction demonstrated in this study ranges from the second to minute time scale.

  2. In situ investigation of wet chemical processes for chalcopyrite solar cells by L-edge XAS under ambient conditions

    Science.gov (United States)

    Greil, Stefanie M.; Lauermann, Iver; Ennaoui, Ahmed; Kropp, Timo; Lange, Kathrin M.; Weber, Matthieu; Aziz, Emad F.

    2010-02-01

    Two instrumental setups for in situ soft X-ray absorption spectroscopy in liquid systems are demonstrated in this work. One for investigating chemical reactions in solutions and a new one for the solid component of a liquid / (as in both / absorber) solid interface. We used these setups for investigating two production processes for chalcopyrite solar cells under ambient conditions, probing the L-edge of Zn and Cu. The first one is a flow cell with a silicon nitride membrane to study the chemical bath deposition process for Cd-free buffer layers. Examining the electronic structure of involved Zn complexes allows to determine the exact reaction mechanism taking place during this process. The second setup is a rotating disk for investigating the bath/absorber interface upon the etching process of superficial binary copper compounds of the absorber as a function of time. The time resolution of the chemical reaction demonstrated in this study ranges from the second to minute time scale.

  3. Electrochemical and in situ TM-AFM studies of the polymerization conditions on poly(o-methoxyaniline) film morphology

    International Nuclear Information System (INIS)

    Szklarczyk, Marek; Wierzbinski, Emil; Bienkowski, Krzysztof; Strawski, Marcin

    2005-01-01

    The in situ atomic force microscopy and the electrochemical studies on electropolymerization of the o-methoxyaniline in the 0.0-0.8 V versus NHE range of the electrode potential are described. It is proved that in the 0.0-0.3 V versus NHE a redox process takes place, resulting in the formation of poly(o-methoxyaniline) in its reduced form, leucoemeraldine. The different morphologies are exhibited by poly(o-methoxyaniline) under different polymerization conditions. The microscopic results show that with the increase of the monomer concentration in the bulk of electrolyte solution the globular morphology, related to the coil like molecular structure, is replaced by the fibrilar one, related to the opened-up, more conductive extended coil structure. It is shown that oxidation of a leucoemeraldine state of polymer to its emeraldine state results in the change of the morphology from the chain like structure to the massive fibrilar like structure. The reduction of oxidized polymer results in its irreversible fragmentation

  4. Effect of different storage conditions on the physical properties of bleached enamel: An in vitro vs. in situ study.

    Science.gov (United States)

    Zeczkowski, Marília; Tenuta, Livia Maria Andaló; Ambrosano, Gláucia Maria Bovi; Aguiar, Flávio Henrique Baggio; Lima, Débora Alves Nunes Leite

    2015-09-01

    Evaluate the effect of different storage conditions on bleached enamel using Knoop microhardness (KHN) and colour variation. Forty-eight tooth blocks were divided into four groups (n=12), based on storage media (SM): purified water (PW), artificial saliva (AS), natural saliva (NS), in situ (IS). Three whitening sessions were carried out using 35% hydrogen peroxide, with a week interval. Colour and KHN measurements were taken before the samples were placed in the SM (t1), after 24h in the SM (t2), and after 24h at the end of the bleaching treatment (t3). Two extra samples from each group were analysed using a scanning electron microscope (SEM). KHN results were analysed by PROC-MIXED and Tukey-Kramer test (α=0.05), and colour changes were evaluated using ΔL, Δa, Δb, ΔE between the different times Δ1(t1-t2), Δ2(t2-t3) using the Kruskal-Wallis test and Dunn's test (α=0.05). Significant statistical difference was noted in KHN at t3, with the lowest values found for PW. As for colour analysis in ΔE2 and Δb2, IS showed values that were statistically lower when compared to AS. Likewise, there were differences between PW and AS in relation to IS when evaluating ΔL2. In addition, NS showed similar values to IS. The storage conditions had different effects on the physical properties of bleached enamel. NS was the only SM that showed similar behaviour to IS. NS proved an effective SM in the protection and recovery of damage caused by bleaching and is a viable SM for in vitro studies. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Numerical analysis of wellbore instability in gas hydrate formation during deep-water drilling

    Science.gov (United States)

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

    2018-02-01

    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

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

    Directory of Open Access Journals (Sweden)

    Yong Pan

    2015-05-01

    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.

  7. The economics of exploiting gas hydrates

    International Nuclear Information System (INIS)

    Döpke, Lena-Katharina; Requate, Till

    2014-01-01

    We investigate the optimal exploitation of methane hydrates, a recent discovery of methane resources under the sea floor, mainly located along the continental margins. Combustion of methane (releasing CO2) and leakage through blow-outs (releasing CH4) contribute to the accumulation of greenhouse gases. A second externality arises since removing solid gas hydrates from the sea bottom destabilizes continental margins and thus increases the risk of marine earthquakes. We show that in such a model three regimes can occur: i) resource exploitation will be stopped in finite time, and some of the resource will stay in situ, ii) the resource will be used up completely in finite time, and iii) the resource will be exhausted in infinite time. We also show how to internalize the externalities by policy instruments. - Highlights: • We set up a model of optimal has hydrate exploitation • We incorporate to types of damages: contribution to global warming and geo-hazards • We characterize optimal exploitation paths and study decentralization with an exploitation tax. • Three regimes can occur: • i) exploitation in finite time and some of the stock remaining in situ, • ii) exploitation in finite time and the resource will be exhausted, • iii) exploitation and exhaustion in infinite time

  8. Unexpected Hydration of a Triple Bond During DNA Synthesis

    DEFF Research Database (Denmark)

    Fatthalla, Maha I.; Pedersen, Erik B.

    2016-01-01

    acidic conditions, polarizes the triple bond in the intercalator and this makes hydration of the triple bond possible during the DNA synthesis and an oligonucleotide with 1-(indol-3-yl)-2-(pyren-1-yl)ethanone as the intercalator is formed. Insertion of the unhydrated and hydrated linker systems gave...

  9. Hydration in soccer: a review

    Directory of Open Access Journals (Sweden)

    Monteiro Cristiano Ralo

    2003-01-01

    Full Text Available 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. The rates that carbohydrate and water are absorbed by the organism are limited by the rates of gastric emptying and intestinal absorption. The composition of drinks offered to the players should be influenced by the relative importance of the need of supplying carbohydrates or water; it should be remembered that the depletion of carbohydrate can result in fatigue and decrease of performance, but it is not usually a life-threatening condition. The addition of carbohydrate in these drinks increases the concentrations of blood glucose, increases the use of external fuel through the increase of the glucose oxidation in the muscles and it spares muscle glycogen. So, the ingestion of carbohydrate before and during the exercise can delay the emergence of fatigue and increase the players' performance. Several tactics can be used to avoid dehydration, like hyperhydration before exercise and player's acclimatization. The ideal situation to restore the player's fluid losses is between the sessions of exercises. Since soccer is a sport with quite peculiar characteristics related to hydration, the players should be concerned and educated about the importance of fluid ingestion before, during and after the exercise.

  10. Thermal expansion properties of calcium aluminate hydrates

    International Nuclear Information System (INIS)

    Song, Tae Woong

    1986-01-01

    In order to eliminate the effect of impurities and aggregates on the thermomechanical properties of the various calcium aluminate hydrates, and to prepare clinkers in which all calcium aluminates are mixed homogeneously, chemically pure CaO and Al 2 O 3 were weighed, blended and heated in various conditions. After quantitative X-ray diffractometry(QXRD), the synthesized clinker was hydrated and cured under the conditions of 30 deg C, W/C=0.5, relative humidity> 90% respectively during 24 hours. And then differential thermal analysis(DTA), thermogravimetry(TG), micro calorimetry, thermomechanical analysis(TMA) and scanning electron microanalysis(SEM) were applied to examine the thermal properties of samples containing, calcium aluminate hydrates in various quantity. (Author)

  11. Overview of the science activities for the 2002 Mallik gas hydrate production research well program, Mackenzie Delta, N.W.T., Canada

    Science.gov (United States)

    Dallimore, S. R.; Collett, T. S.; Uchida, T.; Weber, M.

    2003-04-01

    the measurement of in situ formation conditions. A wide- ranging science and engineering research program included the collection of gas-hydrate-bearing core samples and downhole geophysical logging. Laboratory and modeling studies undertaken during the field program, and subsequently as part of a post-field research program, will document the sedimentology, physical/petrophysical properties, geochemistry, geophysics, reservoir characteristics and production behavior of the Mallik gas hydrate accumulation. The research team, including some 100 participant scientists from over 20 institutes in 7 countries, expects to publish the scientific results in 2004.

  12. Impact of Compound Hydrate Dynamics on Phase Boundary Changes

    Science.gov (United States)

    Osegovic, J. P.; Max, M. D.

    2006-12-01

    Compound hydrate reactions are affected by the local concentration of hydrate forming materials (HFM). The relationship between HFM composition and the phase boundary is as significant as temperature and pressure. Selective uptake and sequestration of preferred hydrate formers (PF) has wide ranging implications for the state and potential use of natural hydrate formation, including impact on climate. Rising mineralizing fluids of hydrate formers (such as those that occur on Earth and are postulated to exist elsewhere in the solar system) will sequester PF before methane, resulting in a positive relationship between depth and BTU content as ethane and propane are removed before methane. In industrial settings the role of preferred formers can separate gases. When depressurizing gas hydrate to release the stored gas, the hydrate initial composition will set the decomposition phase boundary because the supporting solution takes on the composition of the hydrate phase. In other settings where hydrate is formed, transported, and then dissociated, similar effects can control the process. The behavior of compound hydrate systems can primarily fit into three categories: 1) In classically closed systems, all the material that can form hydrate is isolated, such as in a sealed laboratory vessel. In such systems, formation and decomposition are reversible processes with observed hysteresis related to mass or heat transfer limitations, or the order and magnitude in which individual hydrate forming gases are taken up from the mixture and subsequently released. 2) Kinetically closed systems are exposed to a solution mass flow across a hydrate mass. These systems can have multiple P-T phase boundaries based on the local conditions at each face of the hydrate mass. A portion of hydrate that is exposed to fresh mineralizing solution will contain more preferred hydrate formers than another portion that is exposed to a partially depleted solution. Examples of kinetically closed

  13. In situ N{sub 2}O emissions are not mitigated by hippuric and benzoic acids under denitrifying conditions

    Energy Technology Data Exchange (ETDEWEB)

    Krol, D.J., E-mail: dominika.krol@teagasc.ie; Forrestal, P.J.; Lanigan, G.J.; Richards, K.G.

    2015-04-01

    Ruminant urine patches deposited onto pasture are a significant source of greenhouse gas nitrous oxide (N{sub 2}O) from livestock agriculture. Increasing food demand is predicted to lead to a rise in ruminant numbers globally, which, in turn will result in elevated levels of urine-derived N{sub 2}O. Therefore mitigation strategies are urgently needed. Urine contains hippuric acid and together with one of its breakdown products, benzoic acid, has previously been linked to mitigating N{sub 2}O emissions from urine patches in laboratory studies. However, the sole field study to date found no effect of hippuric and benzoic acid concentration on N{sub 2}O emissions. Therefore the aim of this study was to investigate the in situ effect of these urine constituents on N{sub 2}O emissions under conditions conducive to denitrification losses. Unadulterated bovine urine (0 mM of hippuric acid, U) was applied, as well as urine amended with either benzoic acid (96 mM, U + BA) or varying rates of hippuric acid (8 and 82 mM, U + HA1, U + HA2). Soil inorganic nitrogen (N) and N{sub 2}O fluxes were monitored over a 66 day period. Urine application resulted in elevated N{sub 2}O flux for 44 days. The largest N{sub 2}O fluxes accounting for between 13% (U) and 26% (U + HA1) of total loss were observed on the day of urine application. Between 0.9 and 1.3% of urine-N was lost as N{sub 2}O. Cumulative N{sub 2}O loss from the control was 0.3 kg N{sub 2}O–N ha{sup −1} compared with 11, 9, 12, and 10 kg N{sub 2}O–N ha{sup −1} for the U, U + HA1, U + HA2, and U + BA treatments, respectively. Incremental increases in urine HA or increase in BA concentrations had no effect on N{sub 2}O emissions. Although simulation of dietary manipulation to reduce N{sub 2}O emissions through altering individual urine constituents appears to have no effect, there may be other manipulations such as reducing N content or inclusion of synthetic inhibitory products that warrant further investigation

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

    International Nuclear Information System (INIS)

    Sun Changyu; Chen Guangjin; Zhang Lingwei

    2010-01-01

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

  15. Geochemical effects of CO2 sequestration in sandstones under simulated in situ conditions of deep saline aquifers

    International Nuclear Information System (INIS)

    Wigand, M.; Carey, J.W.; Schuett, H.; Spangenberg, E.; Erzinger, J.

    2008-01-01

    The geochemical effects of brine and supercritical CO 2 (SCCO 2 ) on reservoir rocks from deep (1500-2000 m) saline aquifers were examined via experimental simulation at in situ conditions. Dry sandstone samples were mounted in a triaxial cell and autoclave system, evacuated, and saturated with 1 M NaCl solution. The brine-rock system was allowed to react at 30 MPa confining pressure, 15 MPa pore fluid pressure, and 60 deg. C while SCCO 2 was injected at a pressure gradient of 1-2 MPa. The experiment was conducted for a period of 1496 h, during which fluids were periodically sampled and analyzed. The pH measured in partially degassed fluid samples at 25 deg. C decreased from a starting value of 7.0-4.3 (9 days) and finally 5.1 after saturation with SCCO 2 . Fluid analyses indicate that most of the major (e.g. Ca, Mg, Fe, Mn) and trace elements (e.g. Sr, Ba, Pb) of the sandstone increase in concentration during the reaction with brine and SCCO 2 . These results are supported by scanning electron microscopy which indicates dissolution of dolomite cement, K-feldspar, and albite. In addition to dissolution reactions the formation of montmorillonite was observed. By adjusting surface area and reaction rates of dissolution and precipitation, geochemical modeling of the experiments could reproduce long-term trends in solution chemistry and indicated limited rates of dissolution as the system remained strongly undersaturated with most minerals, including carbonates. The geochemical models could not account for decreases in concentration of some elements, changes in solution composition resulting from changes in imposed pressure gradient, and the observed Ca/Mg and Si/Al ratios in solution

  16. 3D characterization of coal strains induced by compression, carbon dioxide sorption, and desorption at in-situ stress conditions

    International Nuclear Information System (INIS)

    Pone, J. Denis N.; Halleck, Phillip M.; Mathews, Jonathan P.

    2010-01-01

    Sequestration of carbon dioxide in unmineable coal seams is an option to combat climate change and an opportunity to enhance coalbed methane production. Prediction of sequestration potential in coal requires characterization of porosity, permeability, sorption capacity and the magnitude of swelling due to carbon dioxide uptake or shrinkage due to methane and water loss. Unfortunately, the majority of data characterizing coal-gas systems have been obtained from powdered, unconfined coal samples. Little is known about confined coal behavior during carbon dioxide uptake and methane desorption. The present work focuses on the characterization of lithotype specific deformation, and strain behavior during CO 2 uptake at simulated in-situ stress conditions. It includes the evaluation of three-dimensional strain induced by the confining stress, the sorption, and the desorption of carbon dioxide. X-ray computed tomography allowed three-dimensional characterization of the bituminous coal deformation samples under hydrostatic stress. The application of 6.9 MPa of confining stress contributes an average of - 0.34% volumetric strain. Normal strains due to confining stress were - 0.08%, - 0.15% and - 0.11% along the x, y and z axes respectively. Gas injection pressure was 3.1 MPa and the excess sorption was 0.85 mmol/g. Confined coal exposed to CO 2 for 26 days displays an average volumetric expansion of 0.4%. Normal strains due to CO 2 sorption were 0.11%, 0.22% and 0.11% along x, y and z axes. Drainage of the CO 2 induced an average of - 0.33% volumetric shrinkage. Normal strains due to CO 2 desorption were - 0.23%, - 0.08% and - 0.02% along x, y and z axes. Alternating positive and negative strain values observed along the sample length during compression, sorption and desorption respectively emphasized that both localized compression/compaction and expansion of coal will occur during CO 2 sequestration. (author)

  17. Use of in-vitro experimental results to model in-situ experiments: bio-denitrification under geological disposal conditions.

    Science.gov (United States)

    Masuda, Kaoru; Murakami, Hiroshi; Kurimoto, Yoshitaka; Kato, Osamu; Kato, Ko; Honda, Akira

    2013-01-01

    Some of the low level radioactive wastes from reprocessing of spent nuclear fuels contain nitrates. Nitrates can be present in the form of soluble salts and can be reduced by various reactions. Among them, reduction by metal compounds and microorganisms seems to be important in the underground repository. Reduction by microorganism is more important in near field area than inside the repository because high pH and extremely high salt concentration would prevent microorganism activities. In the near field, pH is more moderate (pH is around 8) and salt concentration is lower. However, the electron donor may be limited there and it might be the control factor for microorganism's denitrification activities. In this study, in-vitro experiments of the nitrate reduction reaction were conducted using model organic materials purported to exist in underground conditions relevant to geological disposal. Two kinds of organic materials were selected. A super plasticizer was selected as being representative of the geological disposal system and humic acid was selected as being representative of pre-existing organic materials in the bedrock. Nitrates were reduced almost to N2 gas in the existence of super plasticizer. In the case of humic acids, although nitrates were reduced, the rate was much lower and, in this case, dead organism was used as an electron donor instead of humic acids. A reaction model was developed based on the in-vitro experiments and verified by running simulations against data obtained from in-situ experiments using actual groundwaters and microorganisms. The simulation showed a good correlation with the experimental data and contributes to the understanding of microbially mediated denitrification in geological disposal systems.

  18. Behaviour of gas production from type 3 hydrate reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Pooladi-Darvish, M. [Calgary Univ., AB (Canada). Dept. of Chemical and Petroleum Engineering]|[Fekete Associates Inc., Calgary, AB (Canada); Zatsepina, O. [Calgary Univ., AB (Canada). Dept. of Chemical and Petroleum Engineering; Hong, H. [Fekete Associates Inc., Calgary, AB (Canada)

    2008-07-01

    The possible role of gas hydrates as a potential energy resource was discussed with particular reference to methods for estimating the rate of gas production from hydrate reservoirs under different operating conditions. This paper presented several numerical simulations studies of gas production from type 3 hydrate reservoirs in 1-D and 2-D geometries. Type 3 reservoirs include gas production from hydrate-reservoirs that lie totally within the hydrate stability zone and are sandwiched by impermeable layers on top and bottom. The purpose of this study was to better understand hydrate decomposition by depressurization. The study questioned whether 1-D modeling of type 3 hydrate reservoirs is a reasonable approximation. It also determined whether gas rate increases or decreases with time. The important reservoir characteristics for determining the rate of gas production were identified. Last, the study determined how competition between fluid and heat flow affects hydrate decomposition. This paper also described the relation and interaction between the heat and fluid flow mechanisms in depressurization of type 3 hydrate reservoirs. All results of 1-D and 2-D numerical simulation and analyses were generated using the STARS simulator. It was shown that the rate of gas production depends on the initial pressure/temperature conditions and permeability of the hydrate bearing formation. A high peak rate may be achieved under favourable conditions, but this peak rate is obtained after an initial period where the rate of gas production increases with time. The heat transfer in the direction perpendicular to the direction of fluid flow is significant, requiring 2D modeling. The hydraulic diffusivity is low because of the low permeability of hydrate-bearing formations. This could result in competition between heat and fluid flow, thereby influencing the behaviour of decomposition. 6 refs., 3 tabs., 12 figs.

  19. Gas composition and isotopic geochemistry of cuttings, core, and gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well

    Science.gov (United States)

    Lorenson, T.D.

    1999-01-01

    Molecular and isotopic composition of gases from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well demonstrate that the in situ gases can be divided into three zones composed of mixtures of microbial and thermogenic gases. Sediments penetrated by the well are thermally immature; thus the sediments are probably not a source of thermogenic gas. Thermogenic gas likely migrated from depths below 5000 m. Higher concentrations of gas within and beneath the gas hydrate zone suggest that gas hydrate is a partial barrier to gas migration. Gas hydrate accumulations occur wholly within zone 3, below the base of permafrost. The gas in gas hydrate resembles, in part, the thermogenic gas in surrounding sediments and gas desorbed from lignite. Gas hydrate composition implies that the primary gas hydrate form is Structure I. However, Structure II stabilizing gases are more concentrated and isotopically partitioned in gas hydrate relative to the sediment hosting the gas hydrate, implying that Structure II gas hydrate may be present in small quantities.

  20. A preliminary analysis and assessment of hydrogeological conditions for in-situ leach mining of sandstone-type uranium deposit in northern Ordos basin

    International Nuclear Information System (INIS)

    Chen Fazheng; Zhao Jinfeng; Chang Baocheng; Gao Junyi

    2006-01-01

    A systematic analysis and assessment on hydrogeologic condition, the lithology and hydrogeologic structure of ore-hosting aquitfers, hydrodynamic condition, hydrochemical characteristics at a sandstone-type uranium deposit in northern Ordos basin is made in this paper. It has been concluded, that hydrogeologic condition in the study area is favorable, meeting the requirements for in-situ leach mining of the deposit. Aimed at the low artesian pressure head and low water output and based on the results of pumping-injection tests which led to the significant increase of water output, a technical scheme of pressured water injection has been proposed to artificially raise the artesian pressure head and increase the output of groundwater to satisfy the requirements of in-situ leach mining. (authors)

  1. Prospects of gas hydrate presence in the Chukchi sea

    Directory of Open Access Journals (Sweden)

    Т. В. Матвеева

    2017-08-01

    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.

  2. HYDRATE CORE DRILLING TESTS

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-11-01

    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

  3. A role for subducted super-hydrated kaolinite in Earth’s deep water cycle

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Huijeong; Seoung, Donghoon; Lee, Yongjae; Liu, Zhenxian; Liermann, Hanns-Peter; Cynn, Hyunchae; Vogt, Thomas; Kao, Chi-Chang; Mao, Ho-Kwang

    2017-11-20

    Water is the most abundant volatile component in the Earth. It continuously enters the mantle through subduction zones, where it reduces the melting temperature of rocks to generate magmas. The dehydration process in subduction zones, which determines whether water is released from the slab or transported into the deeper mantle, is an essential component of the deep water cycle. Here we use in situ and time-resolved high-pressure/high-temperature synchrotron X-ray diffraction and infrared spectra to characterize the structural and chemical changes of the clay mineral kaolinite. At conditions corresponding to a depth of about 75 km in a cold subducting slab (2.7 GPa and 200 °C), and in the presence of water, we observe the pressure-induced insertion of water into kaolinite. This super-hydrated phase has a unit cell volume that is about 31% larger, a density that is about 8.4% lower than the original kaolinite and, with 29 wt% H2O, the highest water content of any known aluminosilicate mineral in the Earth. As pressure and temperature approach 19 GPa and about 800 °C, we observe the sequential breakdown of super-hydrated kaolinite. The formation and subsequent breakdown of super-hydrated kaolinite in cold slabs subducted below 200 km leads to the release of water that may affect seismicity and help fuel arc volcanism at the surface.

  4. A role for subducted super-hydrated kaolinite in Earth's deep water cycle

    Science.gov (United States)

    Hwang, Huijeong; Seoung, Donghoon; Lee, Yongjae; Liu, Zhenxian; Liermann, Hanns-Peter; Cynn, Hyunchae; Vogt, Thomas; Kao, Chi-Chang; Mao, Ho-Kwang

    2017-12-01

    Water is the most abundant volatile component in the Earth. It continuously enters the mantle through subduction zones, where it reduces the melting temperature of rocks to generate magmas. The dehydration process in subduction zones, which determines whether water is released from the slab or transported into the deeper mantle, is an essential component of the deep water cycle. Here we use in situ and time-resolved high-pressure/high-temperature synchrotron X-ray diffraction and infrared spectra to characterize the structural and chemical changes of the clay mineral kaolinite. At conditions corresponding to a depth of about 75 km in a cold subducting slab (2.7 GPa and 200 °C), and in the presence of water, we observe the pressure-induced insertion of water into kaolinite. This super-hydrated phase has a unit cell volume that is about 31% larger, a density that is about 8.4% lower than the original kaolinite and, with 29 wt% H2O, the highest water content of any known aluminosilicate mineral in the Earth. As pressure and temperature approach 19 GPa and about 800 °C, we observe the sequential breakdown of super-hydrated kaolinite. The formation and subsequent breakdown of super-hydrated kaolinite in cold slabs subducted below 200 km leads to the release of water that may affect seismicity and help fuel arc volcanism at the surface.

  5. Methane hydrates in quaternary climate change

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  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

    2008-03-31

    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. Soil behavior under earthquake loading conditions. In situ impulse test for determination of shear modulus for seismic response analyses. Progress report

    International Nuclear Information System (INIS)

    1974-06-01

    Progress is reported in the determination of the best methods of evaluation and prediction of soil behavior of potential nuclear power plant sites under seismic loading conditions. Results are reported of combined experimental and analytical studies undertaken to continue development of an in situ impulse test for determination of the soil shear modulus. Emphasis of the field work was directed toward making the field measurements at frequent depth intervals and at shear strains in the strong motion earthquake range. Emphasis of the analytical work was aimed toward supporting the field effort through processing and evaluation of the experimental test results combined with additional calculations required to gain insight into data interpretation and the in situ test setup itself. Continuing studies to evaluate free field soil behavior under earthquake loading conditions are discussed. (U.S.)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-12-01

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

  9. 3D characterization of coal strains induced by compression, carbon dioxide sorption, and desorption at in-situ stress conditions

    Energy Technology Data Exchange (ETDEWEB)

    Pone, J. Denis N.; Halleck, Phillip M.; Mathews, Jonathan P. [Department of Energy and Mineral Engineering and The EMS Energy Institute, The Pennsylvania State University, University Park, PA 16802 (United States)

    2010-06-01

    Sequestration of carbon dioxide in unmineable coal seams is an option to combat climate change and an opportunity to enhance coalbed methane production. Prediction of sequestration potential in coal requires characterization of porosity, permeability, sorption capacity and the magnitude of swelling due to carbon dioxide uptake or shrinkage due to methane and water loss. Unfortunately, the majority of data characterizing coal-gas systems have been obtained from powdered, unconfined coal samples. Little is known about confined coal behavior during carbon dioxide uptake and methane desorption. The present work focuses on the characterization of lithotype specific deformation, and strain behavior during CO{sub 2} uptake at simulated in-situ stress conditions. It includes the evaluation of three-dimensional strain induced by the confining stress, the sorption, and the desorption of carbon dioxide. X-ray computed tomography allowed three-dimensional characterization of the bituminous coal deformation samples under hydrostatic stress. The application of 6.9 MPa of confining stress contributes an average of - 0.34% volumetric strain. Normal strains due to confining stress were - 0.08%, - 0.15% and - 0.11% along the x, y and z axes respectively. Gas injection pressure was 3.1 MPa and the excess sorption was 0.85 mmol/g. Confined coal exposed to CO{sub 2} for 26 days displays an average volumetric expansion of 0.4%. Normal strains due to CO{sub 2} sorption were 0.11%, 0.22% and 0.11% along x, y and z axes. Drainage of the CO{sub 2} induced an average of - 0.33% volumetric shrinkage. Normal strains due to CO{sub 2} desorption were - 0.23%, - 0.08% and - 0.02% along x, y and z axes. Alternating positive and negative strain values observed along the sample length during compression, sorption and desorption respectively emphasized that both localized compression/compaction and expansion of coal will occur during CO{sub 2} sequestration. (author)

  10. In situ enhancement of the blue photoluminescence of colloidal Ga2O3 nanocrystals by promotion of defect formation in reducing conditions.

    Science.gov (United States)

    Wang, Ting; Radovanovic, Pavle V

    2011-07-07

    We demonstrate redox control of defect-based photoluminescence efficiency of colloidal γ-Ga(2)O(3) nanocrystals. Reducing environment leads to an increase in photoluminescence intensity by enhancing the concentration of oxygen vacancies, while the blue emission is suppressed in oxidative conditions. These results enable optimization of nanocrystal properties by in situ defect manipulation. This journal is © The Royal Society of Chemistry 2011

  11. Effect of changes in seafloor temperature and sea-level on gas hydrate stability

    Energy Technology Data Exchange (ETDEWEB)

    Garg, S.K.; Pritchett, W. [Science Applications International Corp., San Diego, CA (United States)

    2008-07-01

    Natural gas hydrates occur in oceanic sediments and in permafrost regions around the world. As a greenhouse gas, large amounts of methane released from the global hydrate reservoir would have a significant impact on Earth's climate. The role of methane released by hydrate dissociation in climate change is uncertain. However, changes in global climate such as glaciation and warming can destabilize the hydrates. During the last glacial maximum, the sea level dropped about 100 meters. It has been suggested that the sea-level fall was associated with gas hydrate instability and seafloor slumping. This paper investigated the effect of changes in seafloor temperature and sea level on gas hydrate stability and on gas venting at the seafloor. A one-dimensional numerical computer model (simulator) was developed to describe methane hydrate formation, decomposition, reformation, and distribution with depth below the seafloor in the marine environment. The simulator was utilized to model hydrate distributions at two sites, notably Blake Ridge, located offshore South Carolina and Hydrate Ridge, located off the coast of Oregon. The numerical models for the two sites were conditioned by matching the sulfate, chlorinity, and hydrate distribution measurements. The effect of changes in seafloor temperature and sea-level on gas hydrate stability were then investigated. It was concluded that for Blake Ridge, changes in hydrate concentration were small. Both the changes in seafloor temperature and sea-level led to a substantial increase in gas venting at the seafloor for Hydrate Ridge. 17 refs., 8 figs.

  12. The evaluation of in-situ leaching hydrological-geologic condition in a sandstone-type uranium deposits of a low-grade and thick ledge

    International Nuclear Information System (INIS)

    Jiang Yan

    2014-01-01

    The ore aquifer of a sandstone-type uranium deposits is thick, the grade, and uranium amount per square meter is low. To demonstrate the economic rationality of the in-situ leaching deposit, the Pumping test on the spot, recovery of water levels test, Pumping test and Injection test, Injection test in a Drilling hole, the pumping and injection balance test are carried out. And the hydro geological parameters of mineral aquifer are acquired. The parameters includes coefficient of transmissibility, Coefficient of permeability, Specific discharge of a well and Water injection. Radius of influence etc. The relation between discharge of drilling and Drawdown is researched. The capability of pumping and injection by a drilling hole is determined. The Hydraulic between the aquifer with mineral and the upper and lower aquifer is researched. The reasonable Mining drawdown is testified, the hydrogeological conditions of in-Situ leaching of the mining deposit is found out, this provides necessary parameters and basis for this kind of Situ-leach uranium mining wells, the designing of Spacing of wells, and the economic evaluation of In-situ leaching technology. (author)

  13. Hydro-geomechanical behaviour of gas-hydrate bearing soils during gas production through depressurization and CO2 injection

    Science.gov (United States)

    Deusner, C.; Gupta, S.; Kossel, E.; Bigalke, N.; Haeckel, M.

    2015-12-01

    Results from recent field trials suggest that natural gas could be produced from marine gas hydrate reservoirs at compatible yields and rates. It appears, from a current perspective, that gas production would essentially be based on depressurization and, when facing suitable conditions, be assisted by local thermal stimulation or gas hydrate conversion after injection of CO2-rich fluids. Both field trials, onshore in the Alaska permafrost and in the Nankai Trough offshore Japan, were accompanied by different technical issues, the most striking problems resulting from un-predicted geomechanical behaviour, sediment destabilization and catastrophic sand production. So far, there is a lack of experimental data which could help to understand relevant mechanisms and triggers for potential soil failure in gas hydrate production, to guide model development for simulation of soil behaviour in large-scale production, and to identify processes which drive or, further, mitigate sand production. We use high-pressure flow-through systems in combination with different online and in situ monitoring tools (e.g. Raman microscopy, MRI) to simulate relevant gas hydrate production scenarios. Key components for soil mechanical studies are triaxial systems with ERT (Electric resistivity tomography) and high-resolution local strain analysis. Sand production control and management is studied in a novel hollow-cylinder-type triaxial setup with a miniaturized borehole which allows fluid and particle transport at different fluid injection and flow conditions. Further, the development of a large-scale high-pressure flow-through triaxial test system equipped with μ-CT is ongoing. We will present results from high-pressure flow-through experiments on gas production through depressurization and injection of CO2-rich fluids. Experimental data are used to develop and parametrize numerical models which can simulate coupled process dynamics during gas-hydrate formation and gas production.

  14. Properties of samples containing natural gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well, determined using Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI)

    Science.gov (United States)

    Winters, W.J.

    1999-01-01

    As part of an ongoing laboratory study, preliminary acoustic, strength, and hydraulic conductivity results are presented from a suite of tests conducted on four natural-gas-hydrate-containing samples from the Mackenzie Delta JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well. The gas hydrate samples were preserved in pressure vessels during transport from the Northwest Territories to Woods Hole, Massachusetts, where multistep tests were performed using GHASTLI (Gas Hydrate And Sediment Test Laboratory Instrument), which recreates pressure and temperature conditions that are stable for gas hydrate. Properties and changes in sediment behaviour were measured before, during, and after controlled gas hydrate dissociation. Significant amounts of gas hydrate occupied the sample pores and substantially increased acoustic velocity and shear strength.

  15. Gas hydrate identified in sand-rich inferred sedimentary section using downhole logging and seismic data in Shenhu area, South China Sea

    Science.gov (United States)

    Wang, Xiujuan; Lee, Myung W.; Collett, Timothy S.; Yang, Shengxiong; Guo, Yiqun; Wu, Shiguo

    2014-01-01

    Downhole wireline log (DWL) data was acquired from eight drill sites during China's first gas hydrate drilling expedition (GMGS-1) in 2007. Initial analyses of the acquired well log data suggested that there were no significant gas hydrate occurrences at Site SH4. However, the re-examination of the DWL data from Site SH4 indicated that there are two intervals of high resistivity, which could be indicative of gas hydrate. One interval of high resistivity at depth of 171–175 m below seafloor (mbsf) is associated with a high compressional- wave (P-wave) velocities and low gamma ray log values, which suggests the presence of gas hydrate in a potentially sand-rich (low clay content) sedimentary section. The second high resistivity interval at depth of 175–180 mbsf is associated with low P-wave velocities and low gamma values, which suggests the presence of free gas in a potentially sand-rich (low clay content) sedimentary section. Because the occurrence of free gas is much shallower than the expected from the regional depth of the bottom simulating reflector (BSR), the free gas could be from the dissociation of gas hydrate during drilling or there may be a local anomaly in the depth to the base of the gas hydrate stability zone. In order to determine whether the low P-wave velocity with high resistivity is caused by in-situ free gas or dissociated free gas from the gas hydrate, the surface seismic data were also used in this analysis. The log analysis incorporating the surface seismic data through the construction of synthetic seismograms using various models indicated the presence of free gas directly in contact with an overlying gas hydrate-bearing section. The occurrence of the anomalous base of gas hydrate stability at Site SH4 could be caused by a local heat flow conditions. This paper documents the first observation of gas hydrate in what is believed to be a sand-rich sediment in Shenhu area of the South China Sea.

  16. Dry Sliding Wear Behavior of A356 Alloy/Mg2Sip Functionally Graded in-situ Composites: Effect of Processing Conditions

    Directory of Open Access Journals (Sweden)

    S.C. Ram

    2016-09-01

    Full Text Available In present study, the effect of dry sliding wear conditions of A356 alloy/Mg2Sip functionally graded in-situ composites developed by centrifugal casting method has been studied. A pure commercial A356 alloy (Al–7.5Si–0.3Mg was selected to be the matrix of the composites and primary Mg2Sip reinforcing particles were formed by in-situ chemical reaction with an average grain size of 40-47.8 µm. The Al–(Mg2Sip functionally graded metal matrix composites (FGMMC’s were synthesized by centrifugal casting technique with radial geometry, using two different mould rotating speeds ( 1200 and 1600 rpm. The X-ray diffraction (XRD characterization technique was carried out to confirm the in-situ formed Mg2Si particles in composites. Optical microscopy examination was carried out to reveals the grain refinement of Al-rich grains due to in-situ formed Mg2Si particles. Scanning electron microscope (SEM and Energy dispersive X-ray spectroscopy (EDS techniques were carried out to reveal the distribution of phases, morphological characteristics and confirmation of primary Mg2Si particles in the matrix. The sliding wear behavior was studied using a Pin-on-Disc set-up machine with sliding wear parameters: effect of loads (N, effect of sliding distances (m and effect of Mg on wear at room temperature with a high-carbon chromium steel disc (HRC-64 as counter surfaces. A good correlation was evidenced between the dry sliding behaviour of functionally graded in-situ composites and the distribution of Mg2Si reinforcing particles. Beside the above processing conditions, the dominant wear mechanisms of functionally graded in-situ composites have been correlated with the microstructures. The hardness and wear resistance properties of these composites increase with increasing volume percent of reinforced primary Si/Mg2Si particles toward inner zone of cast cylindrical shapes. The objective of this works was to study the tribological characteristics under dry sliding

  17. Magnetic Resonance Microscopy for Assessment of Morphological Changes in Hydrating Hydroxypropylmethylcellulose Matrix Tablets In Situ–Is it Possible to Detect Phenomena Related to Drug Dissolution Within the Hydrated Matrices?

    OpenAIRE

    Kulinowski, Piotr; Młynarczyk, Anna; Jasiński, Krzysztof; Talik, Przemysław; Gruwel, Marco L. H.; Tomanek, Bogusław; Węglarz, Władysław P.; Dorożyński, Przemysław

    2014-01-01

    ABSTRACT Purpose So far, the hydrated part of the HPMC matrix has commonly been denoted as a “gel” or “pseudogel” layer. No MRI-based results have been published regarding observation of internal phenomena related to drug dissolution inside swelling polymeric matrices during hydration. The purpose of the study was to detect such phenomena. Methods Multiparametric, spatially and temporally resolved T2 MR relaxometry, in situ, was applied to study formation of the hydration progress in HPMC mat...

  18. Molecular analysis of petroleum derived compounds that adsorb onto gas hydrate surfaces

    International Nuclear Information System (INIS)

    Borgund, Anna E.; Hoiland, Sylvi; Barth, Tanja; Fotland, Per; Askvik, Kjell M.

    2009-01-01

    Field observations have shown that some streams of water, gas and crude oil do not form gas hydrate plugs during petroleum production even when operating within thermodynamic conditions for hydrate formation. Also, when studied under controlled laboratory conditions, some oils are found to form hydrate dispersed systems whereas others form plugs. Oils with low tendency to form hydrate plugs are believed to contain natural hydrate plug inhibiting components (NICs) that adsorb onto the hydrate surface, making them less water-wet and preventing the particles from agglomerating into large hydrate clusters. The molecular structure of the NICs is currently unknown. In this work, hydrate adsorbing components were extracted from crude oils using freon hydrates as an extraction phase. The fractions were found to be enriched in polar material, and more polar material is associated with hydrates generated in biodegraded crude oils than in non-biodegraded oils. Various fractionation schemes and analytical techniques have been applied in the search for molecular characterisation. The average molecular weights were found to be approximately 500 g/mole. GC-MS chromatograms show a large UCM (Unresolved Complex Mixture). Thus, GC-MS has a limited potential for identification of compounds. A commercial biosurfactant was used as a model compound in the search for similar structures in the extracts. The results from analysis of the hydrate adsorbing components suggest that the type and structure are more important for hydrate morphology than the amount of material adsorbed.

  19. 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)

    2014-11-18

    hydrate systems are pivotal in the fundamental understanding of crystalline clathrate hydrates and the discovery of new clathrate hydrate properties and novel materials for a broad spectrum of energy applications, including: energy storage (hydrogen, natural gas); carbon dioxide sequestration; controlling hydrate formation in oil/gas transportation in subsea pipelines. The Project has also enabled the training of undergraduate, graduate and postdoctoral students in computational methods, molecular spectroscopy and diffraction, and measurement methods at extreme conditions of high pressure and low temperature.

  20. Gas Hydrate-Sediment Morphologies Revealed by Pressure Core Analysis

    Science.gov (United States)

    Holland, M.; Schultheiss, P.; Roberts, J.; Druce, M.

    2006-12-01

    Analysis of HYACINTH pressure cores collected on IODP Expedition 311 and NGHP Expedition 1 showed gas hydrate layers, lenses, and veins contained in fine-grained sediments as well as gas hydrate contained in coarse-grained layers. Pressure cores were recovered from sediments on the Cascadia Margin off the North American West Coast and in the Krishna-Godavari Basin in the Western Bay of Bengal in water depths of 800- 1400 meters. Recovered cores were transferred to laboratory chambers without loss of pressure and nondestructive measurements were made at in situ pressures and controlled temperatures. Gamma density, P-wave velocity, and X-ray images showed evidence of grain-displacing and pore-filling gas hydrate in the cores. Data highlights include X-ray images of fine-grained sediment cores showing wispy subvertical veins of gas hydrate and P-wave velocity excursions corresponding to grain-displacing layers and pore-filling layers of gas hydrate. Most cores were subjected to controlled depressurization experiments, where expelled gas was collected, analyzed for composition, and used to calculate gas hydrate saturation within the core. Selected cores were stored under pressure for postcruise analysis and subsampling.

  1. XRMON-GF: A novel facility for solidification of metallic alloys with in situ and time-resolved X-ray radiographic characterization in microgravity conditions

    Science.gov (United States)

    Nguyen-Thi, H.; Reinhart, G.; Salloum Abou Jaoude, G.; Mathiesen, R. H.; Zimmermann, G.; Houltz, Y.; Voss, D.; Verga, A.; Browne, D. J.; Murphy, A. G.

    2013-07-01

    As most of the phenomena involved during the growth of metallic alloys from the melt are dynamic, in situ and time-resolved X-ray imaging should be retained as the method of choice for investigating the solidification front evolution. On Earth, the gravity force is the major source of various disturbing effects (natural convection, buoyancy/sedimentation, and hydrostatic pressure) which can significantly modify or mask certain physical mechanisms. Therefore solidification under microgravity is an efficient way to eliminate such perturbations to provide unique benchmark data for the validation of models and numerical simulations. Up to now, in situ observation during microgravity solidification experiments were limited to the investigations on transparent organic alloys, using optical methods. On the other hand, in situ observation on metallic alloys generally required synchrotron facilities. This paper reports on a novel facility we have designed and developed to investigate directional solidification on metallic alloys in microgravity conditions with in situ X-ray radiography observation. The facility consists of a Bridgman furnace and an X-ray radiography device specifically devoted to the study of Al-based alloys. An unprecedented experiment was recently performed on board a sounding rocket, with a 6 min period of microgravity. Radiographs were successfully recorded during the entire experiment including the melting and solidification phases of the sample, with a Field-of-View of about 5 mm×5 mm, a spatial resolution of about 4 µm and a frequency of 2 frames per second. Some preliminary results are presented on the solidification of the Al-20 wt% Cu sample, which validate the apparatus and confirm the potential of in situ X-ray characterization for the investigation of dynamical phenomena in materials processing, and particularly for the studying of metallic alloys solidification.

  2. Chemical alteration of cement hydrates by dissolution

    International Nuclear Information System (INIS)

    Sugiyama, Daisuke; Fujita, Tomonari; Nakanishi, Kiyoshi

    2000-01-01

    Cementitious material is a potential waste packaging and backfilling material for the radioactive waste disposal, and is expected to provide both physical and chemical containment. In particular, the sorption of radionuclides onto cementitious material and the ability to provide a high pH condition are very important parameters when considering the release of radionuclides from radioactive wastes. For the long term, in the geological disposal environment, cement hydrates will be altered by, for example, dissolution, chemical reaction with ions in the groundwater, and hydrothermal reaction. Once the composition or crystallinity of the constituent minerals of a cement hydrate is changed by these processes, the pH of the repository buffered by cementitious material and its sorption ability might be affected. However, the mechanism of cement alteration is not yet fully understood. In this study, leaching experiments of some candidate cements for radioactive waste disposal were carried out. Hydrated Ordinary Portland Cement (OPC), Blast Furnace Slag blended cement (OPC/BFS) and Highly containing Flyash and Silicafume Cement (HFSC) samples were contacted with distilled water at liquid:solid ratios of 10:1, 100:1 and 1000:1 at room temperature for 200 days. In the case of OPC, Ca(OH) 2 dissolved at high liquid:solid ratios. The specific surface area of all cement samples increased by leaching process. This might be caused by further hydration and change of composition of constituent minerals. A model is presented which predicts the leaching of cement hydrates and the mineral composition in the hydrated cement solid phase, including the incongruent dissolution of CSH gel phases and congruent dissolution of Ca(OH) 2 , Ettringite and Hydrotalcite. Experimental results of dissolution of Ca-O-H and Ca-Si-O-H phases were well predicted by this model. (author)

  3. Skin Hydration Assessment through Modern Non-Invasive Bioengineering Technologies.

    Science.gov (United States)

    Constantin, Maria-Magdalena; Poenaru, Elena; Poenaru, Calin; Constantin, Traian

    2014-03-01

    Non-invasive bioengineering technologies continuously discovered and developed in recent decades provide a significant input to research development and remarkably contribute to the improvement of medical education and care to our patients. Assessing skin hydration by using the capacitance method for a group of patients with allergic contact dermatitis versus healthy subjects, before and after applying a moisturiser (assessing the immediate and long-term effectiveness of hydration). For both groups, but especially for the patients with dry skin, there was a clear improvement of hydration, statistically significant after applying the moisturiser. In the case of the patients with allergic contact dermatitis, hydration was at a maximum immediately after the first application, and then maintained an increased level after 7 and 28 days, respectively. In the healthy subjects, the increase in hydration was lower, but progressive. The moisturiser determined an increase in hydration for all age groups, but those who showed the most obvious effect were the young adults (18-29 years old) with an increase of 19.9%.The maintenance effect of hydration lasted for 28 days, while the improvement was important for allergic skin (17.1%) and significant for healthy skin (10.9%). The assessment of epidermal hydration performed by using the corneometer showed very good hydration of the stratum corneum for both groups studied, with immediate and long-term effect. This study also showed that the degree of skin hydration was inversely proportional with age. The corneometer is easy to use, efficient and widely utilised in international studies for measurements in healthy or pathological conditions, for quantitative assessment of the effectiveness of various preparations intended for application to the skin surface, under well-controlled and standardised conditions.

  4. In situ and laboratory studies on the fate of specific organic compounds in an anaerobic landfill leachate plume, 1. Experimental conditions and fate of phenolic compounds

    Science.gov (United States)

    Nielsen, Per H.; Albrechtsen, Hans-Jørgen; Heron, Gorm; Christensen, Thomas H.

    1995-11-01

    The transformation of specific organic compounds was investigated by in situ and laboratory experiments in an anaerobic landfill leachate pollution plume at four different distances from the landfill. This paper presents the experimental conditions in the in situ microcosm and laboratory batch microcosm experiments performed and the results on the fate of 7 phenolic compounds. Part 2 of this series of papers, also published in this issue, presents the results on the fate of 8 aromatic compounds and 4 chlorinated aliphatic compounds. The redox conditions in the plume were characterized as methanogenic, Fe(III)-reducing and NO 3--reducing by the redox sensitive species present in groundwater and sediment and by bioassays. With a few exceptions the aquifer redox conditions were maintained throughout the experiments as monitored by redox sensitive species present in groundwater during the experiments, by redox sensitive species present in the sediment after the experiments and by bioassays performed after the experiments. Transformation of nitrophenol was very fast close to the landfill in strongly reducing conditions, while transformation was slower in the more oxidized part of the plume. Lag phases for the nitrophenols were short (maximum 10 days). Phenol was only transformed in the more distant part of the plume in experiments where NO 3-, Fe(III) and Mn(IV) reduction was dominant. Lag phases for phenol were either absent or lasted up to 2 months. Dichlorophenols were only transformed in experiments representing strongly reducing, presumably methanogenic, redox conditions close to the landfill after lag phases of up to 3 months. Transformation of o-cresol was not observed in any of the experiments throughout the plume. Generally, there was good accordance between the results obtained by in situ and laboratory experiments, both concerning redox conditions and the fate of the phenolic compounds. However, for phenol and 2,4-dichlorophenol, transformation was observed

  5. Towards CO2 sequestration and applications of CO2 hydrates: the effects of tetrahydrofuran on the phase equilibria of CO2 hydrates

    International Nuclear Information System (INIS)

    Khalik, M.S.; Peters, C.J.

    2006-01-01

    The increasing quantity of carbon dioxide (CO 2 ) in the atmosphere has caused widespread global concerns. Capturing CO 2 from its sources and stored it in the form of gas hydrates and application of CO 2 hydrates are among the proposed methods to overcome this problem. In order to make hydrate-based process more attractive, the use of cyclic ethers as promoters is suggested to reduce the required hydrate formation pressure and enhancing the corresponding kinetic rate. In the present work, tetrahydrofuran (THF) is chosen as a hydrate promoter, participating in forming hydrates and produces mixed hydrate together with CO 2 . The pressure and temperature ranges of hydrate stability region are carefully determined through phase equilibrium measurement of the ternary CO 2 , tetrahydrofuran (THF) and water systems. From the experimental results, it is confirmed that the presence of THF in CO 2 + water systems will extend the hydrate formation region to higher temperature at a constant pressure. The extension of the hydrate stability region is depended on the overall concentration of the ternary system. Moreover, four-phase equilibrium of H-Lw-Lv-V is observed in the system, which may be due to a liquid phase split. In the region where the four-phase equilibrium exists, the ternary system loses its concentration dependency of the hydrate equilibrium conditions. (Author)

  6. Proposal of experimental device for the continuous accumulation of primary energy in natural gas hydrates

    Directory of Open Access Journals (Sweden)

    Siažik Ján

    2017-01-01

    Full Text Available Hydrates of the natural gas in the lithosphere are a very important potential source of energy that will be probably used in the coming decades. It seems as promising accumulation of the standard gas to form hydrates synthetically, stored, and disengage him when is peak demand. Storage of natural gas or biomethane in hydrates is advantageous not only in terms of storage capacity, but also from the aspect of safety storage hydrates. The gas stored in such form may occurs at relatively high temperatures and low pressures in comparison to other Technologies of gas- storage. In one cubic meter of hydrate can be stored up to 150 m3 of natural gas, depending on the conditions of thermobaric hydrate generation. This article discusses the design of the facility for the continuous generation of hydrates of natural gas measurement methodology and optimal conditions for their generation.

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

    Directory of Open Access Journals (Sweden)

    Kumar Saw V.

    2015-11-01

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

  8. Overview: Nucleation of clathrate hydrates.

    Science.gov (United States)

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

    2016-12-07

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

  9. Overview: Nucleation of clathrate hydrates

    Science.gov (United States)

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

    2016-12-01

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

  10. Methane hydrate induced permeability modification for multiphase flow in unsaturated porous media

    Science.gov (United States)

    Seol, Yongkoo; Kneafsey, Timothy J.

    2011-08-01

    An experimental study was performed using X-ray computed tomography (CT) scanning to capture three-dimensional (3-D) methane hydrate distributions and potential discrete flow pathways in a sand pack sample. A numerical study was also performed to develop and analyze empirical relations that describe the impacts of hydrate accumulation habits within pore space (e.g., pore filling or grain cementing) on multiphase fluid migration. In the experimental study, water was injected into a hydrate-bearing sand sample that was monitored using an X-ray CT scanner. The CT images were converted into numerical grid elements, providing intrinsic sample data including porosity and phase saturations. The impacts of hydrate accumulation were examined by adapting empirical relations into the flow simulations as additional relations governing the evolution of absolute permeability of hydrate bearing sediment with hydrate deposition. The impacts of pore space hydrate accumulation habits on fluid migration were examined by comparing numerical predictions with experimentally measured water saturation distributions and breakthrough curves. A model case with 3-D heterogeneous initial conditions (hydrate saturation, porosity, and water saturation) and pore body-preferred hydrate accumulations best captured water migration behavior through the hydrate-bearing sample observed in the experiment. In the best matching model, absolute permeability in the hydrate bearing sample does not decrease significantly with increasing hydrate saturation until hydrate saturation reaches about 40%, after which it drops rapidly, and complete blockage of flow through the sample can occur as hydrate accumulations approach 70%. The result highlights the importance of permeability modification due to hydrate accumulation habits when predicting multiphase flow through high-saturation, reservoir quality hydrate-bearing sediments.

  11. Experimental hydrate formation and gas production scenarios based on CO{sub 2} sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Stevens, J.C.; Howard, J.J. [ConocoPhillips, Bartlesville, OK (United States). Reservoir Laboratories; Baldwin, B.A. [Green Country Petrophysics LLC, Dewey, OK (United States); Ersland, G.; Husebo, J.; Graue, A. [Bergen Univ., Bergen (Norway). Dept. of Physics and Technology

    2008-07-01

    Gas hydrate production strategies have focused on depressurization or thermal stimulation of the reservoir, which in turn leads to hydrate dissociation. In order to evaluate potential production scenarios, the recovery efficiency of the natural gas from hydrate must be known along with the corresponding amounts of produced water. This study focused on the exchange of carbon dioxide (CO{sub 2}) with the natural gas hydrate and the subsequent release of free methane (CH{sub 4}). Laboratory experiments that investigated the rates and mechanisms of hydrate formation in coarse-grained porous media have shown the significance of initial water saturation and salinity on forming methane hydrates. Many of the experiments were performed in a sample holder fitted with an MRI instrument for monitoring hydrate formation. Hydrate-saturated samples were subjected to different procedures to release methane. The rates and efficiency of the exchange process were reproducible over a series of initial conditions. The exchange process was rapid and efficient in that no free water was observed in the core with MRI measurements. Injection of CO{sub 2} into the whole-core hydrate-saturated pore system resulted in methane production at the outlet end. Permeability measurements on these hydrate saturated cores during hydrate formation decreased to low values, but enough for gas transport. The lower permeability values remained constant during the methane-carbon dioxide exchange process in the hydrate structure. 12 refs., 9 figs.

  12. Winter frost resistance of Pinus cembra measured in situ at the alpine timberline as affected by temperature conditions.

    Science.gov (United States)

    Buchner, Othmar; Neuner, Gilbert

    2011-11-01

    Winter frost resistance (WFR), midwinter frost hardening and frost dehardening potential of Pinus cembra L. were determined in situ by means of a novel low-temperature freezing system at the alpine timberline ecotone (1950 m a.s.l., Mt Patscherkofel, Innsbruck, Austria). In situ liquid nitrogen (LN₂)-quenching experiments should check whether maximum WFR of P. cembra belonging to the frost hardiest conifer group, being classified in US Department of Agriculture climatic zone 1, suffices to survive dipping into LN₂ (-196 °C). Viability was assessed in a field re-growth test. Maximum in situ WFR (LT₅₀) of leaves was frost hardening treatment (12 days at -20 °C followed by 3 days at -50 °C) to induce maximum WFR. Temperature treatments applied in the field significantly affected the actual WFR. In January a frost hardening treatment (21 days at -20 °C) led to a significant increase of WFR (buds: -62 °C to frost dehardening (buds: -32.6 °C to -10.2 °C; leaves: -32.7 to -16.4 °C) followed by significantly earlier bud swelling and burst in late winter. Strikingly, both temperature treatments, either increased air temperature (+10.1 °C) or increased soil temperature (+6.5 °C), were similarly effective. This high readiness to frost harden and deharden in winter in the field must be considered to be of great significance for future winter survival of P. cembra. Determination of WFR in field re-growth tests appears to be a valuable tool for critically judging estimates of WFR obtained on detached twigs in an ecological context.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

  14. Manufacture of Methane Hydrate using Carbon Nano Tubes

    International Nuclear Information System (INIS)

    Park, Sung Seek

    2010-02-01

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

  15. Hydration dynamics near a model protein surface

    International Nuclear Information System (INIS)

    Russo, Daniela; Hura, Greg; Head-Gordon, Teresa

    2003-01-01

    The evolution of water dynamics from dilute to very high concentration solutions of a prototypical hydrophobic amino acid with its polar backbone, N-acetyl-leucine-methylamide (NALMA), is studied by quasi-elastic neutron scattering and molecular dynamics simulation for both the completely deuterated and completely hydrogenated leucine monomer. We observe several unexpected features in the dynamics of these biological solutions under ambient conditions. The NALMA dynamics shows evidence of de Gennes narrowing, an indication of coherent long timescale structural relaxation dynamics. The translational water dynamics are analyzed in a first approximation with a jump diffusion model. At the highest solute concentrations, the hydration water dynamics is significantly suppressed and characterized by a long residential time and a slow diffusion coefficient. The analysis of the more dilute concentration solutions takes into account the results of the 2.0M solution as a model of the first hydration shell. Subtracting the first hydration layer based on the 2.0M spectra, the translational diffusion dynamics is still suppressed, although the rotational relaxation time and residential time are converged to bulk-water values. Molecular dynamics analysis shows spatially heterogeneous dynamics at high concentration that becomes homogeneous at more dilute concentrations. We discuss the hydration dynamics results of this model protein system in the context of glassy systems, protein function, and protein-protein interfaces

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

    Science.gov (United States)

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

    2010-01-01

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

  17. Gas hydrate cool storage system

    Science.gov (United States)

    Ternes, M.P.; Kedl, R.J.

    1984-09-12

    The invention presented relates to the development of a process utilizing a gas hydrate as a cool storage medium for alleviating electric load demands during peak usage periods. Several objectives of the invention are mentioned concerning the formation of the gas hydrate as storage material in a thermal energy storage system within a heat pump cycle system. The gas hydrate was formed using a refrigerant in water and an example with R-12 refrigerant is included. (BCS)

  18. THERMODYNAMIC MODEL OF GAS HYDRATES

    OpenAIRE

    Недоступ, В. И.; Недоступ, О. В.

    2015-01-01

    The interest to gas hydrates grows last years. Therefore working out of reliable settlement-theoretical methods of definition of their properties is necessary. The thermodynamic model of gas hydrates in which the central place occupies a behaviour of guest molecule in cell is described. The equations of interaction of molecule hydrate formative gas with cell are received, and also an enthalpy and energy of output of molecule from a cell are determined. The equation for calculation of thermody...

  19. Amount of gas hydrate estimated from compressional- and shear-wave velocities at the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well

    Science.gov (United States)

    Lee, M.W.

    1999-01-01

    The amount of in situ gas hydrate concentrated in the sediment pore space at the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well was estimated by using compressional-wave (P-wave) and shear-wave (S-wave) downhole log measurements. A weighted equation developed for relating the amount of gas hydrate concentrated in the pore space of unconsolidated sediments to the increase of seismic velocities was applied to the acoustic logs with porosities derived from the formation density log. A weight of 1.56 (W=1.56) and the exponent of 1 (n=1) provided consistent estimates of gas hydrate concentration from the S-wave and the P-wave logs. Gas hydrate concentration is as much as 80% in the pore spaces, and the average gas hydrate concentration within the gas-hydrate-bearing section from 897 m to 1110 m (excluding zones where there is no gas hydrate) was calculated at 39.0% when using P-wave data and 37.8% when using S-wave data.

  20. A constitutive mechanical model for gas hydrate bearing sediments incorporating inelastic mechanisms

    KAUST Repository

    Sánchez, Marcelo

    2016-11-30

    Gas hydrate bearing sediments (HBS) are natural soils formed in permafrost and sub-marine settings where the temperature and pressure conditions are such that gas hydrates are stable. If these conditions shift from the hydrate stability zone, hydrates dissociate and move from the solid to the gas phase. Hydrate dissociation is accompanied by significant changes in sediment structure and strongly affects its mechanical behavior (e.g., sediment stiffenss, strength and dilatancy). The mechanical behavior of HBS is very complex and its modeling poses great challenges. This paper presents a new geomechanical model for hydrate bearing sediments. The model incorporates the concept of partition stress, plus a number of inelastic mechanisms proposed to capture the complex behavior of this type of soil. This constitutive model is especially well suited to simulate the behavior of HBS upon dissociation. The model was applied and validated against experimental data from triaxial and oedometric tests conducted on manufactured and natural specimens involving different hydrate saturation, hydrate morphology, and confinement conditions. Particular attention was paid to model the HBS behavior during hydrate dissociation under loading. The model performance was highly satisfactory in all the cases studied. It managed to properly capture the main features of HBS mechanical behavior and it also assisted to interpret the behavior of this type of sediment under different loading and hydrate conditions.

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

    Science.gov (United States)

    Murshed, M Mangir; Kuhs, Werner F

    2009-04-16

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

  2. Phase behavior of methane hydrate in silica sand

    International Nuclear Information System (INIS)

    Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang; Liu, Yu-Feng

    2014-01-01

    Highlights: • Hydrate p-T trace in coarse-grained sediment is consistent with that in bulk water. • Fine-grained sediment affects hydrate equilibrium for the depressed water activity. • Hydrate equilibrium in sediment is related to the pore size distribution. • The application of hydrate equilibrium in sediment depends on the actual condition. -- Abstract: Two kinds of silica sand powder with different particle size were used to investigate the phase behavior of methane hydrate bearing sediment. In coarse-grained silica sand, the measured temperature and pressure range was (281.1 to 284.2) K and (5.9 to 7.8) MPa, respectively. In fine-grained silica sand, the measured temperature and pressure range was (281.5 to 289.5) K and (7.3 to 16.0) MPa, respectively. The results show that the effect of coarse-grained silica sand on methane hydrate phase equilibrium can be ignored; however, the effect of fine-grained silica sand on methane hydrate phase equilibrium is significant, which is attributed to the depression of water activity caused by the hydrophilicity and negatively charged characteristic of silica particle as well as the pore capillary pressure. Besides, the analysis of experimental results using the Gibbs–Thomson equation shows that methane hydrate phase equilibrium is related to the pore size distribution of silica sand. Consequently, for the correct application of phase equilibrium data of hydrate bearing sediment, the geological condition and engineering requirement should be taken into consideration in gas production, resource evaluation, etc

  3. In-situ observation of intergranular stress corrosion cracking in AA2024-T3 under constant load conditions

    International Nuclear Information System (INIS)

    Liu Xiaodong; Frankel, G.S.; Zoofan, B.; Rokhlin, S.I.

    2007-01-01

    A specially designed setup was used to apply a constant load to a thin sheet sample of AA2024-T3 and, using microfocal X-ray radiography, to observe in situ the resulting intergranular stress corrosion cracking (IGSCC) from the exposed edge of the sample. The growth of and competition between multiple IGSCC sites was monitored. In many experiments twin cracks initiated close to each other. Furthermore, the deepest crack at the beginning of every experiment was found to slow or stop growing, and was then surpassed by another crack that eventually penetrated through the sample. These observations cannot be explained by the theory of fracture mechanics in inert environments. The possible mechanisms underlying the competition between cracks are discussed

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

    Directory of Open Access Journals (Sweden)

    Yanli Guo

    2016-09-01

    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.

  5. Novel understanding of calcium silicate hydrate from dilute hydration

    KAUST Repository

    Zhang, Lina; Yamauchi, Kazuo; Li, Zongjin; Zhang, Xixiang; Ma, Hongyan; Ge, Shenguang

    2017-01-01

    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

  6. Zirconium molybdate hydrate precipitates in spent nuclear fuel reprocessing

    International Nuclear Information System (INIS)

    Magnaldo, A.; Noire, M.H.; Esbelin, E.; Dancausse, J.P.; Picart, S.

    2004-01-01

    This paper presents through 2 posters a general overview studies realised by CEA teams on deposits observed in the La Hague plant dissolution facilities. Their main constituents are metallic debris bound together with zirconium molybdate hydrate. A comprehensive study of zirconium molybdate hydrate formation included nucleation and growth kinetics was developed. Fouling mechanisms were consequently explained as influenced by the operation conditions. Pu insertion was also overviewed. Its behaviour is important when curative and preventive chemical treatments are considered. (authors)

  7. CLATHRATE HYDRATES FORMATION IN SHORT-PERIOD COMETS

    International Nuclear Information System (INIS)

    Marboeuf, Ulysse; Mousis, Olivier; Petit, Jean-Marc; Schmitt, Bernard

    2010-01-01

    The initial composition of current models of cometary nuclei is only based on two forms of ice: crystalline ice for long-period comets and amorphous ice for short-period comets. A third form of ice, i.e., clathrate hydrate, could exist within the short-period cometary nuclei, but the area of formation of this crystalline structure in these objects has never been studied. Here, we show that the thermodynamic conditions in the interior of short-period comets allow the existence of clathrate hydrates in Halley-type comets. We show that their existence is viable in the Jupiter family comets only when the equilibrium pressure of CO clathrate hydrate is at least 1 order of magnitude lower than the usually assumed theoretical value. We calculate that the amount of volatiles that could be trapped in the clathrate hydrate layer may be orders of magnitude greater than the daily amount of gas released at the surface of the nucleus at perihelion. The formation and the destruction of the clathrate hydrate cages could then explain the diversity of composition of volatiles observed in comets, as well as some pre-perihelion outbursts. We finally show that the potential clathrate hydrate layer in comet 67P/Churyumov-Gerasimenko would, unfortunately, be deep inside the nucleus, out of reach of the Rosetta lander. However, such a clathrate hydrate layer would show up by the gas composition of the coma.

  8. Ab initio modelling of methane hydrate thermophysical properties.

    Science.gov (United States)

    Jendi, Z M; Servio, P; Rey, A D

    2016-04-21

    The key thermophysical properties of methane hydrate were determined using ab initio modelling. Using density functional theory, the second-order elastic constants, heat capacity, compressibility, and thermal expansion coefficient were calculated. A wide and relevant range of pressure-temperature conditions were considered, and the structures were assessed for stability using the mean square displacement and radial distribution functions. Methane hydrate was found to be elastically isotropic with a linear dependence of the bulk modulus on pressure. Equally significant, multi-body interactions were found to be important in hydrates, and water-water interactions appear to strongly influence compressibility like in ice Ih. While the heat capacity of hydrate was found to be higher than that of ice, the thermal expansion coefficient was significantly lower, most likely due to the lower rigidity of hydrates. The mean square displacement gave important insight into stability, heat capacity, and elastic moduli, and the radial distribution functions further confirmed stability. The presented results provide a much needed atomistic thermoelastic characterization of methane hydrates and are essential input for the large-scale applications of hydrate detection and production.

  9. Examination of Hydrate Formation Methods: Trying to Create Representative Samples

    Energy Technology Data Exchange (ETDEWEB)

    Kneafsey, T.J.; Rees, E.V.L.; Nakagawa, S.; Kwon, T.-H.

    2011-04-01

    Forming representative gas hydrate-bearing laboratory samples is important so that the properties of these materials may be measured, while controlling the composition and other variables. Natural samples are rare, and have often experienced pressure and temperature changes that may affect the property to be measured [Waite et al., 2008]. Forming methane hydrate samples in the laboratory has been done a number of ways, each having advantages and disadvantages. The ice-to-hydrate method [Stern et al., 1996], contacts melting ice with methane at the appropriate pressure to form hydrate. The hydrate can then be crushed and mixed with mineral grains under controlled conditions, and then compacted to create laboratory samples of methane hydrate in a mineral medium. The hydrate in these samples will be part of the load-bearing frame of the medium. In the excess gas method [Handa and Stupin, 1992], water is distributed throughout a mineral medium (e.g. packed moist sand, drained sand, moistened silica gel, other porous media) and the mixture is brought to hydrate-stable conditions (chilled and pressurized with gas), allowing hydrate to form. This method typically produces grain-cementing hydrate from pendular water in sand [Waite et al., 2004]. In the dissolved gas method [Tohidi et al., 2002], water with sufficient dissolved guest molecules is brought to hydrate-stable conditions where hydrate forms. In the laboratory, this is can be done by pre-dissolving the gas of interest in water and then introducing it to the sample under the appropriate conditions. With this method, it is easier to form hydrate from more soluble gases such as carbon dioxide. It is thought that this method more closely simulates the way most natural gas hydrate has formed. Laboratory implementation, however, is difficult, and sample formation is prohibitively time consuming [Minagawa et al., 2005; Spangenberg and Kulenkampff, 2005]. In another version of this technique, a specified quantity of gas

  10. Design studies on the engineered barrier system and on the in-situ experiments under the conditions of geological environment in Horonobe

    International Nuclear Information System (INIS)

    Kurihara, Yuji; Yui, Mikazu; Tanai, Kenji

    2004-04-01

    Following studies have been done in this papers in order to apply the technologies based on H12 report to the actual geological conditions of Horonobe underground research laboratory. 1) Reconsidering the process of repository design, the design process charts of a repository were presented. In the H12 report, the design process of the engineering barrier system was followed by the facility design process. In this paper, the both processes were placed in parallel position. 2) The relation between geological conditions and the performance of engineering barrier systems and the specifications of engineering barrier systems was arranged and the geological information needed for design of engineering barrier were selected. 3) The appropriate form of geological information as input-data for design were showed and the procedure for setting input-data was presented. 4) Based on the state of geological investigations at Horonobe, mechanical input-data were arranged for the design of the in-situ experiments on engineered barrier system at HORONOBE. 5) The stability of the hall for the in-situ experiments was studied by numerical analysis and the results indicated that there are difference in stability between the depth of 500 m and 570 m. (author)

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

    International Nuclear Information System (INIS)

    Tajima, Hideo; Yamasaki, Akihiro; Kiyono, Fumio

    2004-01-01

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

  12. Flue gas injection into gas hydrate reservoirs for methane recovery and carbon dioxide sequestration

    International Nuclear Information System (INIS)

    Yang, Jinhai; Okwananke, Anthony; Tohidi, Bahman; Chuvilin, Evgeny; Maerle, Kirill; Istomin, Vladimir; Bukhanov, Boris; Cheremisin, Alexey

    2017-01-01

    Highlights: • Flue gas was injected for both methane recovery and carbon dioxide sequestration. • Kinetics of methane recovery and carbon dioxide sequestration was investigated. • Methane-rich gas mixtures can be produced inside methane hydrate stability zones. • Up to 70 mol% of carbon dioxide in the flue gas was sequestered as hydrates. - Abstract: Flue gas injection into methane hydrate-bearing sediments was experimentally investigated to explore the potential both for methane recovery from gas hydrate reservoirs and for direct capture and sequestration of carbon dioxide from flue gas as carbon dioxide hydrate. A simulated flue gas from coal-fired power plants composed of 14.6 mol% carbon dioxide and 85.4 mol% nitrogen was injected into a silica sand pack containing different saturations of methane hydrate. The experiments were conducted at typical gas hydrate reservoir conditions from 273.3 to 284.2 K and from 4.2 to 13.8 MPa. Results of the experiments show that injection of the flue gas leads to significant dissociation of the methane hydrate by shifting the methane hydrate stability zone, resulting in around 50 mol% methane in the vapour phase at the experimental conditions. Further depressurisation of the system to pressures well above the methane hydrate dissociation pressure generated methane-rich gas mixtures with up to 80 mol% methane. Meanwhile, carbon dioxide hydrate and carbon dioxide-mixed hydrates were formed while the methane hydrate was dissociating. Up to 70% of the carbon dioxide in the flue gas was converted into hydrates and retained in the silica sand pack.

  13. Hydrate-CASM for modeling Methane Hydrate-Bearing Sediments

    Science.gov (United States)

    De La Fuente Ruiz, M.; Vaunat, J.; Marin Moreno, H.

    2017-12-01

    A clear understanding of the geomechanical behavior of methane hydrate-bearing sediments (MHBS) is crucial to assess the stability of the seafloor and submarine infrastructures to human and natural loading changes. Here we present the Hydrate-CASM, a new elastoplastic constitutive model to predict the geomechanical behavior of MHBS. Our model employs the critical state model CASM (Clay and Sand Model) because of its flexibility in describing the shape of the yield surface and its proven ability to predict the mechanical behavior of sands, the most commercially viable hydrate reservoirs. The model considers MHBS as a deformable elastoplastic continuum, and hydrate-related changes in the stress-strain behavior are predicted by a densification mechanism. The densification attributes the mechanical contribution of hydrate to; a reduction of the available void ratio; a decrease of the swelling line slope; and an increase of the volumetric yield stress. It is described by experimentally derived physical parameters except from the swelling slope coefficient that requires empirical calibration. The Hydrate-CASM is validated against published triaxial laboratory tests performed at different confinement stresses, hydrate saturations, and hydrate morphologies. During the validation, we focused on capturing the mechanical behavior of the host sediment and consider perturbations of the sediment's mechanical properties that could result from the sample preparation. Our model successfully captures the experimentally observed influence of hydrate saturation in the magnitude and trend of the stiffness, shear strength, and dilatancy of MHBS. Hence, we propose that hydrate-related densification changes might be a major factor controlling the geomechanical response of MHBS.

  14. Simulating the effect of hydrate dissociation on wellhead stability during oil and gas development in deepwater

    Science.gov (United States)

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

    2018-02-01

    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.

  15. In situ measurement of magnesium carbonate formation from CO2 using static high-pressure and -temperature 13C NMR.

    Science.gov (United States)

    Surface, J Andrew; Skemer, Philip; Hayes, Sophia E; Conradi, Mark S

    2013-01-02

    We explore a new in situ NMR spectroscopy method that possesses the ability to monitor the chemical evolution of supercritical CO(2) in relevant conditions for geological CO(2) sequestration. As a model, we use the fast reaction of the mineral brucite, Mg(OH)(2), with supercritical CO(2) (88 bar) in aqueous conditions at 80 °C. The in situ conversion of CO(2) into metastable and stable carbonates is observed throughout the reaction. After more than 58 h of reaction, the sample was depressurized and analyzed using in situ Raman spectroscopy, where the laser was focused on the undisturbed products through the glass reaction tube. Postreaction, ex situ analysis was performed on the extracted and dried products using Raman spectroscopy, powder X-ray diffraction, and magic-angle spinning (1)H-decoupled (13)C NMR. These separate methods of analysis confirmed a spatial dependence of products, possibly caused by a gradient of reactant availability, pH, and/or a reaction mechanism that involves first forming hydroxy-hydrated (basic, hydrated) carbonates that convert to the end-product, anhydrous magnesite. This carbonation reaction illustrates the importance of static (unmixed) reaction systems at sequestration-like conditions.

  16. Measuring ignitability for in situ burning of oil spills weathered under Arctic conditions: From laboratory studies to large-scale field experiments

    DEFF Research Database (Denmark)

    Fritt-Rasmussen, Janne; Brandvik, Per Johan

    2011-01-01

    This paper compares the ignitability of Troll B crude oil weathered under simulated Arctic conditions (0%, 50% and 90% ice cover). The experiments were performed in different scales at SINTEF’s laboratories in Trondheim, field research station on Svalbard and in broken ice (70–90% ice cover......) in the Barents Sea. Samples from the weathering experiments were tested for ignitability using the same laboratory burning cell. The measured ignitability from the experiments in these different scales showed a good agreement for samples with similar weathering. The ice conditions clearly affected the weathering...... process, and 70% ice or more reduces the weathering and allows a longer time window for in situ burning. The results from the Barents Sea revealed that weathering and ignitability can vary within an oil slick. This field use of the burning cell demonstrated that it can be used as an operational tool...

  17. Ductile flow of methane hydrate

    Science.gov (United States)

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

    2003-01-01

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

  18. Thermodynamic stability and guest distribution of CH4/N2/CO2 mixed hydrates for methane hydrate production using N2/CO2 injection

    International Nuclear Information System (INIS)

    Lim, Dongwook; Ro, Hyeyoon; Seo, Yongwon; Seo, Young-ju; Lee, Joo Yong; Kim, Se-Joon; Lee, Jaehyoung; Lee, Huen

    2017-01-01

    Highlights: • We examine the thermodynamic stability and guest distribution of CH 4 /N 2 /CO 2 mixed hydrates. • Phase equilibria of the CH 4 /N 2 /CO 2 mixed hydrates were measured to determine the thermodynamic stability. • The N 2 /CO 2 ratio of the hydrate phase is almost constant despite the enrichment of CO 2 in the hydrate phase. • 13 C NMR results indicate the preferential occupation of N 2 and CO 2 in the small and large cages of sI hydrates, respectively. - Abstract: In this study, thermodynamic stability and cage occupation behavior in the CH 4 – CO 2 replacement, which occurs in natural gas hydrate reservoirs by injecting flue gas, were investigated with a primary focus on phase equilibria and composition analysis. The phase equilibria of CH 4 /N 2 /CO 2 mixed hydrates with various compositions were measured to determine the thermodynamic stability of gas hydrate deposits replaced by N 2 /CO 2 gas mixtures. The fractional experimental pressure differences (Δp/p) with respect to the CSMGem predictions were found to range from −0.11 to −0.02. The composition analysis for various feed gas mixtures with a fixed N 2 /CO 2 ratio (4.0) shows that CO 2 is enriched in the hydrate phase, and the N 2 /CO 2 ratio in the hydrate phase is independent of the feed CH 4 fractions. Moreover, 13 C NMR measurements indicate that N 2 molecules preferentially occupy the small 5 12 cages of sI hydrates while the CO 2 molecules preferentially occupy the large 5 12 6 2 cages, resulting in an almost constant area ratio of CH 4 molecules in the large to small cages of the CH 4 /N 2 /CO 2 mixed hydrates. The overall experimental results provide a better understanding of stability conditions and guest distributions in natural gas hydrate deposits during CH 4 – flue gas replacement.

  19. Petrophysical Characterization and Reservoir Simulator for Methane Gas Production from Gulf of Mexico Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Kishore Mohanty; Bill Cook; Mustafa Hakimuddin; Ramanan Pitchumani; Damiola Ogunlana; Jon Burger; John Shillinglaw

    2006-06-30

    Gas hydrates are crystalline, ice-like compounds of gas and water molecules that are formed under certain thermodynamic conditions. Hydrate deposits occur naturally within ocean sediments just below the sea floor at temperatures and pressures existing below about 500 meters water depth. Gas hydrate is also stable in conjunction with the permafrost in the Arctic. Most marine gas hydrate is formed of microbially generated gas. It binds huge amounts of methane into the sediments. Estimates of the amounts of methane sequestered in gas hydrates worldwide are speculative and range from about 100,000 to 270,000,000 trillion cubic feet (modified from Kvenvolden, 1993). Gas hydrate is one of the fossil fuel resources that is yet untapped, but may play a major role in meeting the energy challenge of this century. In this project novel techniques were developed to form and dissociate methane hydrates in porous media, to measure acoustic properties and CT properties during hydrate dissociation in the presence of a porous medium. Hydrate depressurization experiments in cores were simulated with the use of TOUGHFx/HYDRATE simulator. Input/output software was developed to simulate variable pressure boundary condition and improve the ease of use of the simulator. A series of simulations needed to be run to mimic the variable pressure condition at the production well. The experiments can be matched qualitatively by the hydrate simulator. The temperature of the core falls during hydrate dissociation; the temperature drop is higher if the fluid withdrawal rate is higher. The pressure and temperature gradients are small within the core. The sodium iodide concentration affects the dissociation pressure and rate. This procedure and data will be useful in designing future hydrate studies.

  20. Balancing Accuracy and Computational Efficiency for Ternary Gas Hydrate Systems

    Science.gov (United States)

    White, M. D.

    2011-12-01

    Geologic accumulations of natural gas hydrates hold vast organic carbon reserves, which have the potential of meeting global energy needs for decades. Estimates of vast amounts of global natural gas hydrate deposits make them an attractive unconventional energy resource. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. Producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. The guest-molecule exchange technology releases CH4 by replacing it with a more thermodynamically stable molecule (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, liquid CO2, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulation of the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and

  1. Maximum Recoverable Gas from Hydrate Bearing Sediments by Depressurization

    KAUST Repository

    Terzariol, Marco

    2017-11-13

    The estimation of gas production rates from hydrate bearing sediments requires complex numerical simulations. This manuscript presents a set of simple and robust analytical solutions to estimate the maximum depressurization-driven recoverable gas. These limiting-equilibrium solutions are established when the dissociation front reaches steady state conditions and ceases to expand further. Analytical solutions show the relevance of (1) relative permeabilities between the hydrate free sediment, the hydrate bearing sediment, and the aquitard layers, and (2) the extent of depressurization in terms of the fluid pressures at the well, at the phase boundary, and in the far field. Close form solutions for the size of the produced zone allow for expeditious financial analyses; results highlight the need for innovative production strategies in order to make hydrate accumulations an economically-viable energy resource. Horizontal directional drilling and multi-wellpoint seafloor dewatering installations may lead to advantageous production strategies in shallow seafloor reservoirs.

  2. A study on dehydration of rare earth chloride hydrate

    International Nuclear Information System (INIS)

    Cho, Yong Zun; Eun, Hee Chul; Son, Sung Mo; Lee, Tae Kyo; Hwang, Taek Sung

    2012-01-01

    The dehydration schemes of rare earth (La, Ce, Nd, Pr, Sm. Eu, Gd, Y) chloride hydrates was investigated by using a dehydration apparatus. To prevent the formation of the rare earth oxychlorides, the operation temperature was changed step by step (80→150→230 degree C) based on the TGA (thermo-gravimetric analysis) results of the rare earth chloride hydrates. A vacuum pump and preheated Ar gas were used to effectively remove the evaporated moisture and maintain an inert condition in the dehydration apparatus. The dehydration temperature of the rare earth chloride hydrate was increased when the atomic number of the rare earth nuclide was increased. The content of the moisture in the rare earth chloride hydrate was decreased below 10% in the dehydration apparatus.

  3. High salinity tolerance of the Red Sea coral Fungia granulosa under desalination concentrate discharge conditions: an in situ photophysiology experiment

    KAUST Repository

    Van Der Merwe, Riaan

    2014-11-10

    Seawater reverse osmosis desalination concentrate may have chronic and/or acute impacts on the marine ecosystems in the near-field area of the discharge. Environmental impact of the desalination plant discharge is supposedly site- and volumetric- specific, and also depends on the salinity tolerance of the organisms inhabiting the water column in and around a discharge environment. Scientific studies that aim to understand possible impacts of elevated salinity levels are important to assess detrimental effects to organisms, especially for species with no mechanism of osmoregulation, e.g., presumably corals. Previous studies on corals indicate sensitivity toward hypo- and hyper-saline environments with small changes in salinity already affecting coral physiology. In order to evaluate sensitivity of Red Sea corals to increased salinity levels, we conducted a long-term (29 days) in situ salinity tolerance transect study at an offshore seawater reverse osmosis (SWRO) discharge on the coral Fungia granulosa. While we measured a pronounced increase in salinity and temperature at the direct outlet of the discharge structure, effects were indistinguishable from the surrounding environment at a distance of 5 m. Interestingly, corals were not affected by varying salinity levels as indicated by measurements of the photosynthetic efficiency. Similarly, cultured coral symbionts of the genus Symbiodinium displayed remarkable tolerance levels in regard to hypo- and hypersaline treatments. Our data suggest that increased salinity and temperature levels from discharge outlets wear off quickly in the surrounding environment. Furthermore, F. granulosa seem to tolerate levels of salinity that are distinctively higher than reported for other corals previously. It remains to be determined whether Red Sea corals in general display increased salinity tolerance, and whether this is related to prevailing levels of high(er) salinity in the Red Sea in comparison to other oceans.

  4. Gas hydrates: entrance to a methane age or climate threat?

    International Nuclear Information System (INIS)

    Krey, Volker; Nakicenovic, Nebojsa; Grubler, Arnulf; O'Neill, Brian; Riahi, Keywan; Canadell, Josep G; Abe, Yuichi; Andruleit, Harald; Archer, David; Hamilton, Neil T M; Johnson, Arthur; Kostov, Veselin; Lamarque, Jean-Francois; Langhorne, Nicholas; Nisbet, Euan G; Riedel, Michael; Wang Weihua; Yakushev, Vladimir

    2009-01-01

    Methane hydrates, ice-like compounds in which methane is held in crystalline cages formed by water molecules, are widespread in areas of permafrost such as the Arctic and in sediments on the continental margins. They are a potentially vast fossil fuel energy source but, at the same time, could be destabilized by changing pressure-temperature conditions due to climate change, potentially leading to strong positive carbon-climate feedbacks. To enhance our understanding of both the vulnerability of and the opportunity provided by methane hydrates, it is necessary (i) to conduct basic research that improves the highly uncertain estimates of hydrate occurrences and their response to changing environmental conditions, and (ii) to integrate the agendas of energy security and climate change which can provide an opportunity for methane hydrates-in particular if combined with carbon capture and storage-to be used as a 'bridge fuel' between carbon-intensive fossil energies and zero-emission energies. Taken one step further, exploitation of dissociating methane hydrates could even mitigate against escape of methane to the atmosphere. Despite these opportunities, so far, methane hydrates have been largely absent from energy and climate discussions, including global hydrocarbon assessments and the Fourth Assessment Report of the Intergovernmental Panel on Climate Change.

  5. Calcium Aluminate Cement Hydration Model

    Directory of Open Access Journals (Sweden)

    Matusinović, T.

    2011-01-01

    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

  6. In situ developmental responses of tropical sea urchin larvae to ocean acidification conditions at naturally elevated pCO2 vent sites.

    Science.gov (United States)

    Lamare, Miles D; Liddy, Michelle; Uthicke, Sven

    2016-11-30

    Laboratory experiments suggest that calcifying developmental stages of marine invertebrates may be the most ocean acidification (OA)-sensitive life-history stage and represent a life-history bottleneck. To better extrapolate laboratory findings to future OA conditions, developmental responses in sea urchin embryos/larvae were compared under ecologically relevant in situ exposures on vent-elevated pCO 2 and ambient pCO 2 coral reefs in Papua New Guinea. Echinometra embryos/larvae were reared in meshed chambers moored in arrays on either venting reefs or adjacent non-vent reefs. After 24 and 48 h, larval development and morphology were quantified. Compared with controls (mean pH (T) = 7.89-7.92), larvae developing in elevated pCO 2 vent conditions (pH (T) = 7.50-7.72) displayed a significant reduction in size and increased abnormality, with a significant correlation of seawater pH with both larval size and larval asymmetry across all experiments. Reciprocal transplants (embryos from vent adults transplanted to control conditions, and vice versa) were also undertaken to identify if adult acclimatization can translate resilience to offspring (i.e. transgenerational processes). Embryos originating from vent adults were, however, no more tolerant to reduced pH. Sea temperature and chlorophyll-a concentrations (i.e. larval nutrition) did not contribute to difference in larval size, but abnormality was correlated with chlorophyll levels. This study is the first to examine the response of marine larvae to OA scenarios in the natural environment where, importantly, we found that stunted and abnormal development observed in situ are consistent with laboratory observations reported in sea urchins, in both the direction and magnitude of the response. © 2016 The Author(s).

  7. EQUILGAS: Program to estimate temperatures and in situ two-phase conditions in geothermal reservoirs using three combined FT-HSH gas equilibria models

    Science.gov (United States)

    Barragán, Rosa María; Núñez, José; Arellano, Víctor Manuel; Nieva, David

    2016-03-01

    Exploration and exploitation of geothermal resources require the estimation of important physical characteristics of reservoirs including temperatures, pressures and in situ two-phase conditions, in order to evaluate possible uses and/or investigate changes due to exploitation. As at relatively high temperatures (>150 °C) reservoir fluids usually attain chemical equilibrium in contact with hot rocks, different models based on the chemistry of fluids have been developed that allow deep conditions to be estimated. Currently either in water-dominated or steam-dominated reservoirs the chemistry of steam has been useful for working out reservoir conditions. In this context, three methods based on the Fischer-Tropsch (FT) and combined H2S-H2 (HSH) mineral-gas reactions have been developed for estimating temperatures and the quality of the in situ two-phase mixture prevailing in the reservoir. For these methods the mineral buffers considered to be controlling H2S-H2 composition of fluids are as follows. The pyrite-magnetite buffer (FT-HSH1); the pyrite-hematite buffer (FT-HSH2) and the pyrite-pyrrhotite buffer (FT-HSH3). Currently from such models the estimations of both, temperature and steam fraction in the two-phase fluid are obtained graphically by using a blank diagram with a background theoretical solution as reference. Thus large errors are involved since the isotherms are highly nonlinear functions while reservoir steam fractions are taken from a logarithmic scale. In order to facilitate the use of the three FT-HSH methods and minimize visual interpolation errors, the EQUILGAS program that numerically solves the equations of the FT-HSH methods was developed. In this work the FT-HSH methods and the EQUILGAS program are described. Illustrative examples for Mexican fields are also given in order to help the users in deciding which method could be more suitable for every specific data set.

  8. Estimation of potential distribution of gas hydrate in the northern South China Sea

    Science.gov (United States)

    Wang, Chunjuan; Du, Dewen; Zhu, Zhiwei; Liu, Yonggang; Yan, Shijuan; Yang, Gang

    2010-05-01

    Gas hydrate research has significant importance for securing world energy resources, and has the potential to produce considerable economic benefits. Previous studies have shown that the South China Sea is an area that harbors gas hydrates. However, there is a lack of systematic investigations and understanding on the distribution of gas hydrate throughout the region. In this paper, we applied mineral resource quantitative assessment techniques to forecast and estimate the potential distribution of gas hydrate resources in the northern South China Sea. However, current hydrate samples from the South China Sea are too few to produce models of occurrences. Thus, according to similarity and contrast principles of mineral outputs, we can use a similar hydrate-mining environment with sufficient gas hydrate data as a testing ground for modeling northern South China Sea gas hydrate conditions. We selected the Gulf of Mexico, which has extensively studied gas hydrates, to develop predictive models of gas hydrate distributions, and to test errors in the model. Then, we compared the existing northern South China Sea hydrate-mining data with the Gulf of Mexico characteristics, and collated the relevant data into the model. Subsequently, we applied the model to the northern South China Sea to obtain the potential gas hydrate distribution of the area, and to identify significant exploration targets. Finally, we evaluated the reliability of the predicted results. The south seabed area of Taiwan Bank is recommended as a priority exploration target. The Zhujiang Mouth, Southeast Hainan, and Southwest Taiwan Basins, including the South Bijia Basin, also are recommended as exploration target areas. In addition, the method in this paper can provide a useful predictive approach for gas hydrate resource assessment, which gives a scientific basis for construction and implementation of long-term planning for gas hydrate exploration and general exploitation of the seabed of China.

  9. Shifting Focus: From Hydration for Performance to Hydration for Health.

    Science.gov (United States)

    Perrier, Erica T

    2017-01-01

    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

  10. Limitation of biocompatibility of hydrated nanocrystalline hydroxyapatite

    Science.gov (United States)

    Minaychev, V. V.; Teleshev, A. T.; Gorshenev, V. N.; Yakovleva, M. A.; Fomichev, V. A.; Pankratov, A. S.; Menshikh, K. A.; Fadeev, R. S.; Fadeeva, I. S.; Senotov, A. S.; Kobyakova, M. I.; Yurasova, Yu B.; Akatov, V. S.

    2018-04-01

    Nanostructured hydroxyapatite (HA) in the form of hydrated paste is considered to be a promising material for a minor-invasive surgical curing of bone tissue injure. However questions about adhesion of cells on this material and its biocompatibility still remain. In this study biocompatibility of paste-formed nanosized HA (nano-HA) by in vitro methods is investigated. Nano-HA (particles sized about 20 nm) was synthesized under conditions of mechano-acoustic activation of an aqueous reaction mixture of ammonium hydrophosphate and calcium nitrate. It was ascertained that nanocrystalline paste was not cytotoxic although limitation of adhesion, spreading and growth of the cells on its surface was revealed. The results obtained point on the need of modification of hydrated nano-HA in the aims of increasing its biocompatibility and osteoplastic potential.

  11. Dissociation behavior of pellet shaped mixed gas hydrate samples that contain propane as a guest

    International Nuclear Information System (INIS)

    Kawamura, Taro; Sakamoto, Yasuhide; Ohtake, Michika; Yamamoto, Yoshitaka; Komai, Takeshi; Haneda, Hironori; Yoon, Ji-Ho; Ohga, Kotaro

    2006-01-01

    The dissociation kinetics of mixed gas hydrates that contain propane as a guest molecule have been investigated. The mixed gas hydrates used in this work were artificially prepared using the binary gas mixture of methane-propane and the ternary gas mixture of methane-ethane-propane. The crystal structures and the guest compositions of the mixed hydrates were clearly identified by using Raman spectroscopy and gas chromatography. The dissociation rates of the gas hydrates observed under several isothermal and isobaric conditions were discussed with an analytical model. The isobaric conditions were achieved by pressurizing with mixed gases using buffer cylinders, which had similar compositions to those of the initial gases used for synthesizing each hydrate sample. Interestingly, the calculated result agreed well with the experimentally observed results only when the composition of the vapor phase was assumed to be identical with that of the hydrate phase instead of the bulk (equilibrium) gas composition

  12. Effects of Attenuation of Gas Hydrate-bearing Sediments on Seismic Data: Example from Mallik, Northwest Territories, Canada

    Science.gov (United States)

    Bellefleur, G.; Riedel, M.; Brent, T.

    2007-05-01

    Wave attenuation is an important physical property of hydrate-bearing sediments that is rarely taken into account in site characterization with seismic data. We present a field example showing improved images of hydrate- bearing sediments on seismic data after compensation of attenuation effects. Compressional quality factors (Q) are estimated from zero-offset Vertical Seismic Profiling data acquired at Mallik, Northwest Territories, Canada. During the last 10 years, two internationally-partnered research drilling programs have intersected three major intervals of sub-permafrost gas hydrates at Mallik, and have successfully extracted core samples containing significant amount of gas hydrates. Individual gas hydrate intervals are up to 40m in thickness and are characterized by high in situ gas hydrate saturation, sometimes exceeding 80% of pore volume of unconsolidated clastic sediments having average porosities ranging from 25% to 40%. The Q-factors obtained from the VSP data demonstrate significant wave attenuation for permafrost and hydrate- bearing sediments. These results are in agreement with previous attenuation estimates from sonic logs and crosshole data at different frequency intervals. The Q-factors obtained from VSP data were used to compensate attenuation effects on surface 3D seismic data acquired over the Mallik gas hydrate research wells. Intervals of gas hydrate on surface seismic data are characterized by strong reflectivity and effects from attenuation are not perceptible from a simple visual inspection of the data. However, the application of an inverse Q-filter increases the resolution of the data and improves correlation with log data, particularly for the shallowest gas hydrate interval. Compensation of the attenuation effects of the permafrost likely explains most of the improvements for the shallow gas hydrate zone. Our results show that characterization of the Mallik gas hydrates with seismic data not corrected for attenuation would tend to

  13. The temperature hydration kinetics

    Directory of Open Access Journals (Sweden)

    Mircea Oroian

    2017-07-01

    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.

  14. 3D pore-type digital rock modeling of natural gas hydrate for permafrost and numerical simulation of electrical properties

    Science.gov (United States)

    Dong, Huaimin; Sun, Jianmeng; Lin, Zhenzhou; Fang, Hui; Li, Yafen; Cui, Likai; Yan, Weichao

    2018-02-01

    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.

  15. Effects of cyclopentane on CO2 hydrate formation and dissociation as a co-guest molecule for desalination

    International Nuclear Information System (INIS)

    Zheng, Jia-nan; Yang, Ming-jun; Liu, Yu; Wang, Da-yong; Song, Yong-chen

    2017-01-01

    Highlights: • CP decreases CO 2 hydrate phase equilibrium pressure by forming CO 2 -CP hydrates. • The increase of CP can’t decrease hydrates phase equilibrium pressure unlimitedly. • Higher CP concentration lowers CO 2 hydrate gas uptake. • The optimal CP molar ratio is 0.01 based on hydrate phase equilibrium and gas uptake. - Abstract: Cyclopentane (CP) is considered to be a potential co-guest molecule in carbon dioxide (CO 2 ) hydrate-based desalination. The experimental thermodynamic data of CO 2 -CP hydrates were measured for a salt solution, where CP was chosen as a hydrate promoter. Seven experimental cases (62 cycles) were studied with different molar ratios of CP/water (0, 0.0025, 0.005, 0.0075, 0.01, 0.02, and 0.03). Hydrate phase equilibrium data were generated using an isochoric method, and the hydrate saturations were calculated based on gas uptake. The results indicated that the increase in CP concentration significantly decreased the CO 2 hydrate equilibrium pressure to a certain limit; the hydrate saturation also decreased during this process. Also, it was determined that CP encouraged the formation of s-II double CO 2 -CP hydrates, which are different from s-I simple CO 2 hydrate. The CO 2 -CP guest provides a strengthened stability and moderate hydrate phase equilibrium conditions for hydrate-based desalination. The recommended optimal molar ratio of CP is 0.01 when the increase in equilibrium was more than 10 K, and the decrease in hydrate saturation was less than 2%.

  16. Permafrost-associated gas hydrate: is it really approximately 1% of the global system?

    Science.gov (United States)

    Ruppel, Carolyn

    2015-01-01

    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

  17. High-pressure structures of methane hydrate

    International Nuclear Information System (INIS)

    Hirai, H; Uchihara, Y; Fujihisa, H; Sakashita, M; Katoh, E; Aoki, K; Yamamoto, Y; Nagashima, K; Yagi, T

    2002-01-01

    Three high-pressure structures of methane hydrate, a hexagonal structure (str. A) and two orthorhombic structures (str. B and str. C), were found by in situ x-ray diffractometry and Raman spectroscopy. The well-known structure I (str. I) decomposed into str. A and fluid at 0.8 GPa. Str. A transformed into str. B at 1.6 GPa, and str. B further transformed into str. C at 2.1 GPa which survived above 7.8 GPa. The fluid solidified as ice VI at 1.4 GPa, and the ice VI transformed to ice VII at 2.1 GPa. The bulk moduli, K 0 , for str. I, str. A, and str. C were calculated to be 7.4, 9.8, and 25.0 GPa, respectively

  18. HistoFlex-a microfluidic device providing uniform flow conditions enabling highly sensitive, reproducible and quantitative in situ hybridizations

    DEFF Research Database (Denmark)

    Søe, Martin Jensen; Okkels, Fridolin; Sabourin, David

    2011-01-01

    A microfluidic device (the HistoFlex) designed to perform and monitor molecular biological assays under dynamic flow conditions on microscope slide-substrates, with special emphasis on analyzing histological tissue sections, is presented. Microscope slides were reversibly sealed onto a cast polyd...

  19. Alcohol cosurfactants in hydrate antiagglomeration.

    Science.gov (United States)

    York, J Dalton; Firoozabadi, Abbas

    2008-08-28

    Because of availability, as well as economical and environmental considerations, natural gas is projected to be the premium fuel of the 21st century. Natural gas production involves risk of the shut down of onshore and offshore operations because of blockage from hydrates formed from coproduced water and hydrate-forming species in natural gas. Industry practice has been usage of thermodynamic inhibitors such as alcohols often in significant amounts, which have undesirable environmental and safety impacts. Thermodynamic inhibitors affect bulk-phase properties and inhibit hydrate formation. An alternative is changing surface properties through usage of polymers and surfactants, effective at 0.5 to 3 weight % of coproduced water. One group of low dosage hydrate inhibitors (LDHI) are kinetic inhibitors, which affect nucleation rate and growth. A second group of LDHI are antiagglomerants, which prevent agglomeration of small hydrate crystallites. Despite great potential, work on hydrate antiagglomeration is very limited. This work centers on the effect of small amounts of alcohol cosurfactant in mixtures of two vastly different antiagglomerants. We use a model oil, water, and tetrahydrofuran as a hydrate-forming species. Results show that alcohol cosurfactants may help with antiagglomeration when traditional antiagglomerants alone are ineffective. Specifically, as low as 0.5 wt. % methanol cosurfactant used in this study is shown to be effective in antiagglomeration. Without the cosurfactant there will be agglomeration independent of the AA concentration. To our knowledge, this is the first report of alcohol cosurfactants in hydrate antiagglomerants. It is also shown that a rhamnolipid biosurfactant is effective down to only 0.5 wt. % in such mixtures, yet a quaternary ammonium chloride salt, i. e., quat, results in hydrate slurries down to 0.01 wt. %. However, biochemical surfactants are less toxic and biodegradable, and thus their use may prove beneficial even if at

  20. Measurement of ambient aerosol hydration state at Great Smoky Mountains National Park in the southeastern United States

    Directory of Open Access Journals (Sweden)

    N. F. Taylor

    2011-12-01

    Full Text Available We present results from two field deployments of a unique tandem differential mobility analyzer (TDMA configuration with two primary capabilities: identifying alternative stable or meta-stable ambient aerosol hydration states associated with hysteresis in aerosol hydration behavior and determining the actual Ambient hydration State (AS-TDMA. This data set is the first to fully classify the ambient hydration state of aerosols despite recognition that hydration state significantly impacts the roles of aerosols in climate, visibility and heterogeneous chemistry. The AS-TDMA was installed at a site in eastern Tennessee on the border of Great Smoky Mountains National Park for projects during the summer of 2006 and winter of 2007–2008. During the summer, 12% of the aerosols sampled in continuous AS-TDMA measurements were found to posses two possible hydration states under ambient conditions. In every case, the more hydrated of the possible states was occupied. The remaining 88% did not posses multiple possible states. In continuous measurements during the winter, 49% of the aerosols sampled possessed two possible ambient hydration states; the remainder possessed only one. Of those aerosols with multiple possible ambient hydration states, 65% occupied the more hydrated state; 35% occupied the less hydrated state. This seasonal contrast is supported by differences in the fine particulate (PM2.5 composition and ambient RH as measured during the two study periods. In addition to seasonal summaries, this work includes case studies depicting the variation of hydration state with changing atmospheric conditions.

  1. Visualising reacting single atoms under controlled conditions: Advances in atomic resolution in situ Environmental (Scanning) Transmission Electron Microscopy (E(S)TEM)

    Science.gov (United States)

    Boyes, Edward D.; Gai, Pratibha L.

    2014-02-01

    Advances in atomic resolution Environmental (Scanning) Transmission Electron Microscopy (E(S)TEM) for probing gas-solid catalyst reactions in situ at the atomic level under controlled reaction conditions of gas environment and temperature are described. The recent development of the ESTEM extends the capability of the ETEM by providing the direct visualisation of single atoms and the atomic structure of selected solid state heterogeneous catalysts in their working states in real-time. Atomic resolution E(S)TEM provides a deeper understanding of the dynamic atomic processes at the surface of solids and their mechanisms of operation. The benefits of atomic resolution-E(S)TEM to science and technology include new knowledge leading to improved technological processes with substantial economic benefits, improved healthcare, reductions in energy needs and the management of environmental waste generation. xml:lang="fr"

  2. Corrosion behaviour of selected high-level waste packaging materials under gamma irradiation and in-situ disposal conditions in rock salt

    International Nuclear Information System (INIS)

    Smailos, E.; Schwarzkopf, W.; Koester, R.

    1988-07-01

    Corrosion studies performed until now on a number of materials have shown that unalloyed steels, Hastelloy C4 and Ti 99.8-Pd are the most promising materials for a long-term resistant packaging to be used in high-level waste (HLW) canister disposal in rock salt formations. To characterize their corrosion behaviour in more detail, additional studies have been performed. The influence has been examined which is exerted by the gamma dose rate (1 Gy/h to 100 Gy/h) on the corrosion of three preselected steels and Hastelloy C4 at 90 0 C in a salt brine (Q-brine) rich in MgCl 2 , i.e., conditions relevant to accident scenarios in a repository. In addition, in-situ corrosion experiments have been carried out in the Asse salt mine at elevated temperatures (120 0 C to 210 0 C) in the absence and in the presence of a gamma radiation field of 3 x 10 2 Gy/h, within the framework of the German/US Brine Migration Test. Under the test conditions the gamma radiation did not exert a significant influence on the corrosion of the steels investigated, whereas Hastelloy C4, exposed to dose rates of 10 Gy/h and 100 Gy/h, underwent pitting and crevice corrosion (20 μm/a at the maximum).The low amounts of migrated salt brine (140 ml after 900 days) in the in-situ- experiment did not produce noticeable corrosion of the materials. (orig./RB) [de

  3. Experimental determination of methane hydrate formation in the presence of ammonia

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  4. In situ Ge(Li)-spectrometric measurements of gamma radiation from radon daughters under different weather conditions

    International Nuclear Information System (INIS)

    Finck, R.R.; Persson, B.R.R.

    1980-01-01

    The photon fluence from radionuclides in the ground and air was measured continuously with a Ge(Li) spectrometer during several weeks. The most prominent change in photon fluence rate near the ground was obtained during periods of heavy rainfall. Deposition of the short-lived radon daughters 214 Pb and 214 Bi on the ground surface can cause a temporary increase in the external absorbed dose rate of approximately 2μrads/h. The photon fluence from airborne radon daughters can be correlated to the degree of atmospheric stability. During stable conditions the photon fluence increases and the activity ratio 214 Bi/ 214 Pb decreases

  5. Evolution of deformation structures under varying loading conditions followed in situ by high angular resolution 3DXRD

    DEFF Research Database (Denmark)

    Pantleon, Wolfgang; Wejdemann, Christian; Jakobsen, B.

    2009-01-01

    copper to different loading conditions are presented: during uninterrupted tensile deformation, formation of subgrains can be observed concurrently with broadening of the Bragg reflection shortly after onset of plastic deformation. With continued tensile deformation, the subgrain structure develops...... intermittently. When the traction is terminated, stress relaxation occurs and number, size and orientation of subgrains are found to be constant. The subgrain structure freezes and only a minor clean-up of the dislocation structure is observed. When changing the tensile direction after pre-deformation in tension...

  6. Ex situ protection of the European mudminnow (Umbra krameri Walbaum, 1792: Spawning substrate preference for larvae rearing under controlled conditions

    Directory of Open Access Journals (Sweden)

    Kucska Balázs

    2016-01-01

    Full Text Available Captive breeding programs of endangered fish species, such as the European mudminnow Umbra krameri, are essential for population restoration. To improve captive spawning and larvae rearing under controlled conditions, two experiments were carried out. In the first, the spawning substrate preference was tested in triplicate, where five different types of artificial surface were provided for mudminnow pairs:(isand, (iiartificial plants, (iiigravel, (ivsand + artificial plants and(vgravel + artificial plants. All fish preferred the gravel + artificial plant combination, which indicates that this type of surface could be the most appropriate for spawning in captivity. In the second trial, three feeding protocols were tested in triplicate under controlled conditions. In the first treatment fish were fed exclusively with Artemia nauplii; in the second treatment fish were fed with Artemiafor the first ten days then Artemia was gradually replaced with dry feed; for the third group the transition period started after 5 days of Artemia feeding. Although the survival rate of larvae could be maintained at a high level in some of the feeding protocols, a strong decrease in the growth rate was obvious in all diets containing dry food, which means that live food is essential for the first three weeks of mudminnow larvae rearing.

  7. CO2 injection into submarine, CH4-hydrate bearing sediments: Parameter studies towards the development of a hydrate conversion technology

    Science.gov (United States)

    Deusner, Christian; Bigalke, Nikolaus; Kossel, Elke; Haeckel, Matthias

    2013-04-01

    In the recent past, international research efforts towards exploitation of submarine and permafrost hydrate reservoirs have increased substantially. Until now, findings indicate that a combination of different technical means such as depressurization, thermal stimulation and chemical activation is the most promising approach for producing gas from natural hydrates. Moreover, emission neutral exploitation of CH4-hydrates could potentially be achieved in a combined process with CO2 injection and storage as CO2-hydrate. In the German gas hydrate initiative SUGAR, a combination of experimental and numerical studies is used to elucidate the process mechanisms and technical parameters on different scales. Experiments were carried out in the novel high-pressure flow-through system NESSI (Natural Environment Simulator for sub-Seafloor Interactions). Recent findings suggest that the injection of heated, supercritical CO2 is beneficial for both CH4 production and CO2 retention. Among the parameters tested so far are the CO2 injection regime (alternating vs. continuous injection) and the reservoir pressure / temperature conditions. Currently, the influence of CO2 injection temperature is investigated. It was shown that CH4 production is optimal at intermediate reservoir temperatures (8 ° C) compared to lower (2 ° C) and higher temperatures (10 ° C). The reservoir pressure, however, was of minor importance for the production efficiency. At 8 ° C, where CH4- and CO2-hydrates are thermodynamically stable, CO2-hydrate formation appears to be slow. Eventual clogging of fluid conduits due to CO2-rich hydrate formation force open new conduits, thereby tapping different regions inside the CH4-hydrate sample volume for CH4gas. In contrast, at 2 ° C immediate formation of CO2-hydrate results in rapid and irreversible obstruction of the entire pore space. At 10 ° C pure CO2-hydrates can no longer be formed. Consequently the injected CO2 flows through quickly and interaction with

  8. Obsidian hydration dates glacial loading?

    Science.gov (United States)

    Friedman, I; Pierce, K L; Obradovich, J D; Long, W D

    1973-05-18

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming. The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow.

  9. Hydration water and microstructure in calcium silicate and aluminate hydrates

    International Nuclear Information System (INIS)

    Fratini, Emiliano; Ridi, Francesca; Chen, Sow-Hsin; Baglioni, Piero

    2006-01-01

    Understanding the state of the hydration water and the microstructure development in a cement paste is likely to be the key for the improvement of its ultimate strength and durability. In order to distinguish and characterize the reacted and unreacted water, the single-particle dynamics of water molecules in hydrated calcium silicates (C 3 S, C 2 S) and aluminates (C 3 A, C 4 AF) were studied by quasi-elastic neutron scattering, QENS. The time evolution of the immobile fraction represents the hydration kinetics and the mobile fraction follows a non-Debye relaxation. Less sophisticated, but more accessible and cheaper techniques, like differential scanning calorimetry, DSC, and near-infrared spectroscopy, NIR, were validated through QENS results and they allow one to easily and quantitatively follow the cement hydration kinetics and can be widely applied on a laboratory scale to understand the effect of additives (i.e., superplasticizers, cellulosic derivatives, etc) on the thermodynamics of the hydration process. DSC provides information on the free water index and on the activation energy involved in the hydration process while the NIR band at 7000 cm -1 monitors, at a molecular level, the increase of the surface-interacting water. We report as an example the effect of two classes of additives widely used in the cement industry: superplasticizers, SPs, and cellulose derivatives. SPs interact at the solid surface, leading to a consistent increment of the activation energy for the processes of nucleation and growth of the hydrated phases. In contrast, the cellulosic additives do not affect the nucleation and growth activation energy, but cause a significant increment in the water availability: in other words the hydration process is more efficient without any modification of the solid/liquid interaction, as also evidenced by the 1 H-NMR. Additional information is obtained by scanning electron microscopy (SEM), ultra small angle neutron scattering (USANS) and wide

  10. Cryogenic-SEM investigation of CO{sub 2} hydrate morphologies

    Energy Technology Data Exchange (ETDEWEB)

    Camps, A.P.; Milodowski, A.; Rochelle, C.; Williams, J.F.; Jackson, P. D. [British Geological Survey, Keyworth, Nottinghamshire (United Kingdom); Camps, A.P; Lovell, M.; Williams, J.F. [Leicester Univ., Leicester (United Kingdom). Dept. of Geology

    2008-07-01

    Gas hydrates occur naturally around the world in the shallow-marine geosphere, and are seen as a drilling hazard in the petroleum industry due to their role in the carbon cycle, and their possible contribution in past and present climate change. Hydrates are ice-like structures composed of cages of water molecules containing one or more guest molecules, such as methane and carbon dioxide (CO{sub 2}). CO{sub 2} hydrates also occur naturally on earth and are being investigated for their potential to store large volumes of CO{sub 2} to reduce atmospheric emissions of greenhouse gases as a climate change mitigation strategy. However, the mineralogy and formation processes of hydrates are relatively poorly understood. Different imaging techniques have been utilized to study gas hydrates, such as nuclear magnetic resonance, magnetic resonance imaging, and x-ray computed tomography. Scanning Electron Microscopy (SEM) at cryogenic temperatures is another technique to study hydrates, and has been used successfully for investigation of methane and CO{sub 2} hydrates. This paper presented a study that investigated CO{sub 2} hydrates formed in laboratories, using a cryogenic-SEM. The paper presented the study methods and observations, including euhedral crystalline carbon dioxide hydrate; acicular carbon dioxide hydrate; granoblastic carbon dioxide hydrate; and gas rich carbon dioxide hydrate. It was concluded that the investigation produced various different hydrate morphologies resulting from different formation conditions. Morphologies ranged from well-defined euhedral crystals to acicular needles, and more complex, intricate forms. 22 refs., 6 figs., 1 appendix.

  11. Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface

    Science.gov (United States)

    Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

    2018-04-01

    We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface—controlled by a crossover in how methane is supplied from the gas and liquid phases—which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.

  12. Influence of surfactants on gas-hydrate formation' kinetics in water-oil emulsion

    Science.gov (United States)

    Zemenkov, Yu D.; Shirshova, A. V.; Arinstein, E. A.; Shuvaev, A. N.

    2018-05-01

    The kinetics of gas hydrate formation of propane in a water-oil emulsion is experimentally studied when three types of surfactants (SAA (surface acting agent)) - anionic type emulsifiers - are added to the aqueous phase. It is shown that all three types of surfactants decelerate the growth of the gas-hydrate in the emulsion and can be considered as anti-agglutinating and kinetic low-dose inhibitors. The most effective inhibitor of hydrate formation in water-oil emulsion of SV-102 surfactant was revealed. For comparison, experimental studies of gas-hydrate formation under the same conditions for bulk water have been carried out. It is shown that in bulk water, all the surfactants investigated act as promoters (accelerators) of hydrate formation. A qualitative explanation of the action mechanisms of emulsifiers in the process of gas-hydrate formation in water-oil emulsion is given.

  13. Hydration dependent dynamics in RNA

    International Nuclear Information System (INIS)

    Olsen, Greg L.; Bardaro, Michael F.; Echodu, Dorothy C.; Drobny, Gary P.; Varani, Gabriele

    2009-01-01

    The essential role played by local and collective motions in RNA function has led to a growing interest in the characterization of RNA dynamics. Recent investigations have revealed that even relatively simple RNAs experience complex motions over multiple time scales covering the entire ms-ps motional range. In this work, we use deuterium solid-state NMR to systematically investigate motions in HIV-1 TAR RNA as a function of hydration. We probe dynamics at three uridine residues in different structural environments ranging from helical to completely unrestrained. We observe distinct and substantial changes in 2 H solid-state relaxation times and lineshapes at each site as hydration levels increase. By comparing solid-state and solution state 13 C relaxation measurements, we establish that ns-μs motions that may be indicative of collective dynamics suddenly arise in the RNA as hydration reaches a critical point coincident with the onset of bulk hydration. Beyond that point, we observe smaller changes in relaxation rates and lineshapes in these highly hydrated solid samples, compared to the dramatic activation of motion occurring at moderate hydration

  14. High-resolution well-log derived dielectric properties of gas-hydrate-bearing sediments, Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

    Science.gov (United States)

    Sun, Y.; Goldberg, D.; Collett, T.; Hunter, R.

    2011-01-01

    A dielectric logging tool, electromagnetic propagation tool (EPT), was deployed in 2007 in the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well (Mount Elbert Well), North Slope, Alaska. The measured dielectric properties in the Mount Elbert well, combined with density log measurements, result in a vertical high-resolution (cm-scale) estimate of gas hydrate saturation. Two hydrate-bearing sand reservoirs about 20 m thick were identified using the EPT log and exhibited gas-hydrate saturation estimates ranging from 45% to 85%. In hydrate-bearing zones where variation of hole size and oil-based mud invasion are minimal, EPT-based gas hydrate saturation estimates on average agree well with lower vertical resolution estimates from the nuclear magnetic resonance logs; however, saturation and porosity estimates based on EPT logs are not reliable in intervals with substantial variations in borehole diameter and oil-based invasion.EPT log interpretation reveals many thin-bedded layers at various depths, both above and below the thick continuous hydrate occurrences, which range from 30-cm to about 1-m thick. Such thin layers are not indicated in other well logs, or from the visual observation of core, with the exception of the image log recorded by the oil-base microimager. We also observe that EPT dielectric measurements can be used to accurately detect fine-scale changes in lithology and pore fluid properties of hydrate-bearing sediments where variation of hole size is minimal. EPT measurements may thus provide high-resolution in-situ hydrate saturation estimates for comparison and calibration with laboratory analysis. ?? 2010 Elsevier Ltd.

  15. The effect of metals on condition and pathologies of European eel (Anguilla anguilla): in situ and laboratory experiments.

    Science.gov (United States)

    Esteve, Consuelo; Alcaide, Elena; Ureña, Rocio

    2012-03-01

    Forty-nine wild eels (Anguilla anguilla) caught in the Albufera Lake (Spain), measuring 24.0-75.0 cm in length and 25.0-637.7 g in weight, were examined for metals (Cd, Co, Cr, Cu, Fe, Hg, Mn, Pb, Se and Zn), condition (CI and HSI indices), as well as for diseases (Anguillicola infestation; bacterial infections). Total metal load significantly increased in eel liver tissue parallel to total length and body weight (log), while silvering females (W(B) > 200 g; L ≥ 500 mm) exhibited the highest amounts of Co, Cu, Hg, Se and Zn. Diverse effects may be expected in these big eels due to long-term metal exposure. In fact, IMBI (individual mean (multi-metal) bioaccumulation index) and copper load (Ln) in particular, were significantly related with a decrease in the HSI, reflecting lower eel fitness. In addition, most silvering females (75%) showed a CI below 0.2, and this size group presented the highest prevalence of chronic diseases, at significant levels, that are non-lethal in the short term, but degenerative in the long term. Amounts of hepatic iron were not correlated with eel size; however, a significant, strong negative correlation between this metal (Ln) and HSI and CI was found for wild eels suffering from diseases of any aetiology. This also included small eels (W(B) <67 g; L < 350 mm), as this size group presented a significant prevalence of acute diseases caused by single virulent bacterial pathogens (i.e. Edwardsiella tarda and Vibrio vulnificus biotype 2). To assess the effect of metals on susceptibility to disease, yellow eels were maintained and exposed to iron, copper, and pathogens, in captivity under laboratory conditions. Co-exposure of eels to iron (9 μg of Fe/g of fish) and bacterial pathogens by intraperitoneal injection (IP), yielded a hundred-fold reduction in the LD50 of all bacteria assayed (i.e. E. tarda, V. vulnificus, and motile Aeromonas), and also the time taken to cause eel death. Short-term aqueous exposure of eels to 0.4, 0.7, 1.7 and

  16. Fast x-ray fluorescence microtomography of hydrated biological samples.

    Directory of Open Access Journals (Sweden)

    Enzo Lombi

    Full Text Available Metals and metalloids play a key role in plant and other biological systems as some of them are essential to living organisms and all can be toxic at high concentrations. It is therefore important to understand how they are accumulated, complexed and transported within plants. In situ imaging of metal distribution at physiological relevant concentrations in highly hydrated biological systems is technically challenging. In the case of roots, this is mainly due to the possibility of artifacts arising during sample preparation such as cross sectioning. Synchrotron x-ray fluorescence microtomography has been used to obtain virtual cross sections of elemental distributions. However, traditionally this technique requires long data acquisition times. This has prohibited its application to highly hydrated biological samples which suffer both radiation damage and dehydration during extended analysis. However, recent advances in fast detectors coupled with powerful data acquisition approaches and suitable sample preparation methods can circumvent this problem. We demonstrate the heightened potential of this technique by imaging the distribution of nickel and zinc in hydrated plant roots. Although 3D tomography was still impeded by radiation damage, we successfully collected 2D tomograms of hydrated plant roots exposed to environmentally relevant metal concentrations for short periods of time. To our knowledge, this is the first published example of the possibilities offered by a new generation of fast fluorescence detectors to investigate metal and metalloid distribution in radiation-sensitive, biological samples.

  17. Mechanism of gypsum hydration

    Directory of Open Access Journals (Sweden)

    Pacheco, G.

    1991-06-01

    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.

  18. Adherence of platelets to in situ albumin-binding surfaces under flow conditions: role of surface-adsorbed albumin

    International Nuclear Information System (INIS)

    Guha Thakurta, Sanjukta; Miller, Robert; Subramanian, Anuradha

    2012-01-01

    Surfaces that preferentially bind human serum albumin (HSA) were generated by grafting albumin-binding linear peptide (LP1) onto silicon surfaces. The research aim was to evaluate the adsorption pattern of proteins and the adhesion of platelets from platelet-poor plasma and platelet-rich plasma, respectively, by albumin-binding surfaces under physiological shear rate (96 and 319 s −1 ) conditions. Bound proteins were quantified using enzyme-linked immunosorbent assays (ELISAs) and two-dimensional gel electrophoresis. A ratio of ∼1000:100:1 of adsorbed HSA, human immunoglobulin (HIgG) and human fibrinogen (HFib) was noted, respectively, on LP1-functionalized surfaces, and a ratio of ∼5:2:1 of the same was noted on control surfaces, as confirmed by ELISAs. The surface-adsorbed von Willebrand factor was undetectable by sensitive ELISAs. The amount of adhered platelets correlated with the ratio of adsorbed HSA/HFib. Platelet morphology was more rounded on LP1-functionalized surfaces when compared to control surfaces. The platelet adhesion response on albumin-binding surfaces can be explained by the reduction in the co-adsorption of other plasma proteins in a surface environment where there is an excess of albumin molecules, coupled with restrictions in the conformational transitions of other surface-adsorbed proteins into hemostatically active forms. (paper)

  19. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com [Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045 (United States)

    2016-06-15

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  20. Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

    International Nuclear Information System (INIS)

    Nguyen, Luan; Tao, Franklin

    2016-01-01

    Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

  1. Hydrate Evolution in Response to Ongoing Environmental Shifts

    Energy Technology Data Exchange (ETDEWEB)

    Rempel, Alan [Univ. of Oregon, Eugene, OR (United States)

    2015-12-31

    Natural gas hydrates have the potential to become a vital domestic clean-burning energy source. However, past changes in environmental conditions have caused hydrates to become unstable and trigger both massive submarine landslides and the development of crater-like pockmarks, thereby releasing methane into the overlying seawater and atmosphere, where it acts as a powerful greenhouse gas. This project was designed to fill critical gaps in our understanding of domestic hydrate resources and improve forecasts for their response to environmental shifts. Project work can be separated into three interrelated components, each involving the development of predictive mathematical models. The first project component concerns the role of sediment properties on the development and dissociation of concentrated hydrate anomalies. To this end, we developed numerical models to predict equilibrium solubility of methane in twophase equilibrium with hydrate as a function of measureable porous medium characteristics. The second project component concerned the evolution of hydrate distribution in heterogeneous reservoirs. To this end, we developed numerical models to predict the growth and decay of anomalies in representative physical environments. The third project component concerned the stability of hydrate-bearing slopes under changing environmental conditions. To this end, we developed numerical treatments of pore pressure evolution and consolidation, then used "infinite-slope" analysis to approximate the landslide potential in representative physical environments, and developed a "rate-and-state" frictional formulation to assess the stability of finite slip patches that are hypothesized to develop in response to the dissociation of hydrate anomalies. The increased predictive capabilities that result from this work provide a framework for interpreting field observations of hydrate anomalies in terms of the history of environmental forcing that led to their development. Moreover

  2. Mode-I Fracture Toughness Testing and Coupled Cohesive Zone Modeling at In Situ P, T, and Chemical (H2O-CO2-NaCl) Conditions

    Science.gov (United States)

    Dewers, T. A.; Choens, R. C., II; Regueiro, R. A.; Eichhubl, P.; Bryan, C. R.; Rinehart, A. J.; Su, J. C.; Heath, J. E.

    2017-12-01

    Propagation of mode I cracks is fundamental to subsurface engineering endeavors, but the majority of fracture toughness measurements are performed at ambient conditions. A novel testing apparatus was used to quantify the relationship between supercritical carbon dioxide (scCO2), water vapor, and fracture toughness in analogs for reservoir rock and caprock lithologies at temperature and pressure conditions relevant to geologic carbon storage. Samples of Boise Sandstone and Marcellus Shale were subject to fracture propagation via a novel short rod fracture toughness tester composed of titanium and Hastelloy® and designed to fit inside a pressure vessel. The tester is controlled by a hydraulically-driven ram and instrumented with a LVDT to monitor displacement. We measure fracture toughness under conditions of dry supercritical CO2 (scCO2), scCO2-saturated brine, and scCO2 with varying water content ( 25%, 90%, and 100% humidity) at 13.8 MPa and 70oC. Water film development as a function of humidity is determined in situ during the experiments with a quartz crystal microbalance. Two orientations of the Marcellus are included in the testing matrix. Dry CO2 has a negligible to slightly strengthening effect compared to a control, however hydrous scCO2 can decrease the fracture toughness, and the effect increases with increasing humidity, which likely is due to capillary condensation of reactive water films at nascent crack tips and associated subcritical weakening. A 2D poromechanical finite element model with cohesive surface elements (CSEs) and a chemo-plasticity phenomenology is being used to describe the chemical weakening/softening effects observed in the testing. The reductions in fracture toughness seen in this study could be important in considerations of borehole stability, in situ stress measurements, changes in fracture gradient, and reservoir caprock integrity during CO2 injection and storage. Sandia National Laboratories is a multimission laboratory managed

  3. Preliminary Experimental Examination Of Controls On Methane Expulsion During Melting Of Natural Gas Hydrate Systems

    Science.gov (United States)

    Kneafsey, T. J.; Flemings, P. B.; Bryant, S. L.; You, K.; Polito, P. J.

    2013-12-01

    Global climate change will cause warming of the oceans and land. This will affect the occurrence, behavior, and location of subseafloor and subterranean methane hydrate deposits. We suggest that in many natural systems local salinity, elevated by hydrate formation or freshened by hydrate dissociation, may control gas transport through the hydrate stability zone. We are performing experiments and modeling the experiments to explore this behavior for different warming scenarios. Initially, we are exploring hydrate association/dissociation in saline systems with constant water mass. We compare experiments run with saline (3.5 wt. %) water vs. distilled water in a sand mixture at an initial water saturation of ~0.5. We increase the pore fluid (methane) pressure to 1050 psig. We then stepwise cool the sample into the hydrate stability field (~3 degrees C), allowing methane gas to enter as hydrate forms. We measure resistivity and the mass of methane consumed. We are currently running these experiments and we predict our results from equilibrium thermodynamics. In the fresh water case, the modeled final hydrate saturation is 63% and all water is consumed. In the saline case, the modeled final hydrate saturation is 47%, the salinity is 12.4 wt. %, and final water saturation is 13%. The fresh water system is water-limited: all the water is converted to hydrate. In the saline system, pore water salinity is elevated and salt is excluded from the hydrate structure during hydrate formation until the salinity drives the system to three phase equilibrium (liquid, gas, hydrate) and no further hydrate forms. In our laboratory we can impose temperature gradients within the column, and we will use this to investigate equilibrium conditions in large samples subjected to temperature gradients and changing temperature. In these tests, we will quantify the hydrate saturation and salinity over our meter-long sample using spatially distributed temperature sensors, spatially distributed

  4. Understanding hydration of Zn(2+) in hydrothermal fluids with ab initio molecular dynamics

    NARCIS (Netherlands)

    Liu, X.; Lu, X.; Wang, R.; Meijer, E.J.

    2011-01-01

    With ab initio molecular dynamics simulations, the free-energy profiles of hydrated Zn2+ are calculated for both gaseous and aqueous systems from ambient to supercritical conditions, and from the derived free-energy information, the speciation of hydrated Zn2+ has been revealed. It is shown that the

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-01

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

  6. A high yield process for hydrate formation

    Energy Technology Data Exchange (ETDEWEB)

    Giavarini, C.; Maccioni, F. [Univ. of Roma La Sapienza, Roma (Italy). Dept. of Chemical Engineering

    2008-07-01

    Due to the large quantities of natural gas stored in deep ocean hydrates, hydrate reservoirs are a substantial energy resource. Hydrates concentrate methane by as much as a factor of 164. As such, several natural gas transportation and storage systems using gas hydrates have been studied, and many of them are nearing practical use. In these systems, the hydrate is produced as a slurry by a spray process at approximately 7 megapascal (MPa), and then shaped into pellets. The use of a spray process, instead of a conventional stirred vessel is necessary in order to reach high hydrate concentrations in the hydrate-ice system. This paper presented a new procedure to produce a bulk of concentrated methane hydrate in a static traditional reactor at moderate pressure, controlling pressure and temperature in the interval between ice melting and the hydrate equilibrium curve. This paper discussed the experimental procedure which included formation of methane hydrate at approximately 5 MPa and 2 degrees Celsius in a reaction calorimeter at a volume of two liters. Results were also discussed. It was concluded that the procedure seemed suitable for the development of a gas hydrate storage and transport technology. It was found that the spray procedure took more time, but could be sped up and made continuous by using two vessels, one for hydrate formation and the other for hydrate concentration. The advantage was the production of a concentrated hydrate, using a simpler equipment and working at lower pressures respect to the spray process. 9 refs., 5 figs.

  7. A sample cell to study hydrate formation with x-ray scattering

    International Nuclear Information System (INIS)

    Conrad, Heiko; Lehmkuehler, Felix; Sternemann, Christian; Feroughi, Omid; Tolan, Metin; Simonelli, Laura; Huotari, Simo

    2009-01-01

    We present a new sample cell for measuring nonresonant inelastic x-ray scattering spectra of a tetrahydrofuran (THF)-water liquid mixture and THF hydrate. The hydrate is formed inside the cell after nucleation seeds have been offered by a special magnetic stirring mechanism. Hydrate formation was verified by wide angle x-ray scattering and nonresonant x-ray Raman scattering spectra at the oxygen K-edge. A broad range of scattering angles can be studied with this cell which is necessary for momentum transfer dependent inelastic x-ray scattering. This cell is ideal to examine other liquid hydrate formers or other liquid samples, which have to be mixed in situ during the measurements.

  8. 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

    2008-03-01

    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.

  9. The impact of permafrost-associated microorganisms on hydrate formation kinetics

    Science.gov (United States)

    Luzi-Helbing, Manja; Liebner, Susanne; Spangenberg, Erik; Wagner, Dirk; Schicks, Judith M.

    2016-04-01

    The relationship between gas hydrates, microorganisms and the surrounding sediment is extremely complex: On the one hand, microorganisms producing methane provide the prerequisite for gas hydrate formation. As it is known most of the gas incorporated into natural gas hydrates originates from biogenic sources. On the other hand, as a result of microbial activity gas hydrates are surrounded by a great variety of organic compounds which are not incorporated into the hydrate structure but may influence the formation or degradation process. For gas hydrate samples from marine environments such as the Gulf of Mexico a direct association between microbes and gas hydrates was shown by Lanoil et al. 2001. It is further assumed that microorganisms living within the gas hydrate stability zone produce biosurfactants which were found to enhance the hydrate formation process significantly and act as nucleation centres (Roger et al. 2007). Another source of organic compounds is sediment organic matter (SOM) originating from plant material or animal remains which may also enhance hydrate growth. So far, the studies regarding this relationship were focused on a marine environment. The scope of this work is to extend the investigations to microbes originating from permafrost areas. To understand the influence of microbial activity in a permafrost environment on the methane hydrate formation process and the stability conditions of the resulting hydrate phase we will perform laboratory studies. Thereby, we mimic gas hydrate formation in the presence and absence of methanogenic archaea (e.g. Methanosarcina soligelidi) and other psychrophilic bacteria isolated from permafrost environments of the Arctic and Antarctic to investigate their impact on hydrate induction time and formation rates. Our results may contribute to understand and predict the occurrences and behaviour of potential gas hydrates within or adjacent to the permafrost. Lanoil BD, Sassen R, La Duc MT, Sweet ST, Nealson KH

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  11. Vertical hydraulic conductivity of a clayey-silt aquitard: accelerated fluid flow in a centrifuge permeameter compared with in situ conditions

    Science.gov (United States)

    Timms, W. A.; Crane, R.; Anderson, D. J.; Bouzalakos, S.; Whelan, M.; McGeeney, D.; Rahman, P. F.; Guinea, A.; Acworth, R. I.

    2014-03-01

    Evaluating the possibility of leakage through low permeability geological strata is critically important for sustainable water supplies, extraction of fuels from strata such as coal beds, and confinement of waste within the earth. Characterizing low or negligible flow rates and transport of solutes can require impractically long periods of field or laboratory testing, but is necessary for evaluations over regional areas and over multi-decadal timescales. The current work reports a custom designed centrifuge permeameter (CP) system, which can provide relatively rapid and reliable hydraulic conductivity (K) measurement compared to column permeameter tests at standard gravity (1g). Linear fluid velocity through a low K porous sample is linearly related to g-level during a CP flight unless consolidation or geochemical reactions occur. The CP module is designed to fit within a standard 2 m diameter, geotechnical centrifuge with a capacity for sample dimensions of 30 to 100 mm diameter and 30 to 200 mm in length. At maximum RPM the resultant centrifugal force is equivalent to 550g at base of sample or a total stress of ~2 MPa. K is calculated by measuring influent and effluent volumes. A custom designed mounting system allows minimal disturbance of drill core samples and a centrifugal force that represents realistic in situ stress conditions is applied. Formation fluids were used as influent to limit any shrink-swell phenomena which may alter the resultant K value. Vertical hydraulic conductivity (Kv) results from CP testing of core from the sites in the same clayey silt formation varied (10-7 to 10-9 m s-1, n = 14) but higher than 1g column permeameter tests of adjacent core using deionized water (10-9 to 10-11 m s-1, n = 7). Results at one site were similar to in situ Kv values (3 × 10-9 m s-1) from pore pressure responses within a 30 m clayey sequence in a homogenous area of the formation. Kv sensitivity to sample heterogeneity was observed, and anomalous flow via

  12. Imaging hydrated microbial extracellular polymers: Comparative analysis by electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Dohnalkova, A.C.; Marshall, M. J.; Arey, B. W.; Williams, K. H.; Buck, E. C.; Fredrickson, J. K.

    2011-01-01

    Microbe-mineral and -metal interactions represent a major intersection between the biosphere and geosphere but require high-resolution imaging and analytical tools for investigating microscale associations. Electron microscopy has been used extensively for geomicrobial investigations and although used bona fide, the traditional methods of sample preparation do not preserve the native morphology of microbiological components, especially extracellular polymers. Herein, we present a direct comparative analysis of microbial interactions using conventional electron microscopy approaches of imaging at room temperature and a suite of cryogenic electron microscopy methods providing imaging in the close-to-natural hydrated state. In situ, we observed an irreversible transformation of the hydrated bacterial extracellular polymers during the traditional dehydration-based sample preparation that resulted in their collapse into filamentous structures. Dehydration-induced polymer collapse can lead to inaccurate spatial relationships and hence could subsequently affect conclusions regarding nature of interactions between microbial extracellular polymers and their environment.

  13. Clinker mineral hydration at reduced relative humidities

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede; Hansen, Per Freiesleben; Lachowski, Eric E.

    1999-01-01

    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......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...

  14. Storage capacity of hydrogen in gas hydrates

    International Nuclear Information System (INIS)

    Tsuda, Takaaki; Ogata, Kyohei; Hashimoto, Shunsuke; Sugahara, Takeshi; Sato, Hiroshi; Ohgaki, Kazunari

    2010-01-01

    The storage capacity of H 2 in the THF, THT, and furan hydrates was studied by p-V-T measurements. We confirmed that the storage and release processes of H 2 in all hydrates could be performed reversibly by pressure swing without destroying of hydrate cages. H 2 absorption in both THT and furan hydrates is much faster than THF hydrate in spite of same unit-cell structure. On the other hand, the storage amounts of H 2 are coincident in the all additive hydrates and would reach at about 1.0 mass% asymptotically.

  15. Study on gas hydrate as a new energy resource in the 21th century

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Byeong-Jae; Kwak Young-Hoon; Kim, Won-Sik [Korea Institute of Geology Mining and Materials, Taejon (KR)] (and others)

    1999-12-01

    Natural gas hydrate, a special type of clathrate hydrates, is a metastable solid compound which mainly consists of methane and water, and generally called as gas hydrate. It is stable in the specific low-temperature/high-pressure conditions. Gas hydrates play an important role as major reservoir of methane on the earth. On the other hand, the formation and dissociation of gas hydrates could cause the plugging in pipeline, gas kick during production, atmospheric pollution and geohazard. To understand the formation and dissociation of the gas hydrate, the experimental equilibrium conditions of methane hydrate were measured in pure water, 3 wt.% NaCl and MgCl{sub 2} solutions. The equilibrium conditions of propane hydrates were also measured in pure water. The relationship between methane hydrate formation time and overpressure was also analyzed through the laboratory work. The geophysical surveys using air-gun system and multibeam echo sounder were implemented to develop exploration techniques and to evaluate the gas hydrate potential in the East Sea, Korea. General indicators of submarine gas hydrates on seismic data is commonly inferred from the BSR developed parallel to the see floor, amplitude blanking at the upper part of the BSR, and phase reversal and decrease of the interval velocity at BSR. The field data were processed using Geobit 2.9.5 developed by KIGAM to detect the gas hydrate indicators. The accurate velocity analysis was performed by XVA (X-window based Velocity Analysis). Processing results show that the strong reflector occurred parallel to the sea floor were shown at about 1800 ms two way travel time. The interval velocity decrease at this strong reflector and at the reflection phase reversal corresponding to the reflection at the sea floor. Gas hydrate stability field in the study area was determined using the data of measured hydrate equilibrium condition, hydrothermal gradient and geothermal gradient. The depth of BSR detected in the seismic

  16. Formation and dissociation of CO{sub 2} and CO{sub 2}-THF hydrates compared to CH{sub 4} and CH{sub 4}-THF hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Giavarini, C.; Maccioni, F.; Broggi, A. [Roma Univ. La Sapienza, Roma (Italy). Dept. of Chemical Engineering; Politi, M. [ENEL-RICERCHE, Brindisi (Italy)

    2008-07-01

    Carbon sequestration involves the removal of greenhouse gases from industrial or utility plant streams and their long term storage so that they cannot interact with the climate system. Different methods for selective carbon dioxide (CO{sub 2}) removal are in commercial use and are based on, gas absorption, membrane process, and cryogenic fractionation. In addition, disposal of captured CO{sub 2} in the ocean and in geological reservoirs has been proposed by researchers. Another challenge is to take advantage of the properties of CO{sub 2} hydrates for carbon sequestration since it could have a number of uses such as chemical production. As such, it is important to understand the hydrate decomposition kinetics during storage, transportation, and disposal. This paper presented a project that involved the separation of carbon dioxide from the flue gases of powers plants, in the form of hydrate. The project also involved the storage, use, and disposal of the hydrate. The purpose of the study was to evaluate the decomposition kinetics of CO{sub 2} hydrate containing different quantities of ice, at low pressures and temperatures between -3 and 0 degrees Celsius. In addition, in order to evaluate the tetrahydrofuran (THF) stabilization effect, the study examined the influence of THF on the formation and decomposition kinetics of mixed THF-methane (CH{sub 4}) and THF-CO{sub 2} hydrates. Preservation tests were conducted to determine the best pressure and temperature conditions for the mixed-hydrates conservation, with reference to the simple hydrates. The paper described the apparatus for the formation and dissociation tests which consisted of a jacketed stainless steel reactor, equipped with stirrer. The paper also described the hydrate formation procedure as well as hydrate characterization. Last, the paper discussed the hydrate dissociation tests that were conducted immediately after hydrate formation in the reactor. It was concluded that the hydrophilic and hydrophobic

  17. Dynamical Conditions of Ice Supersaturation and Ice Nucleation in Convective Systems: A Comparative Analysis Between in Situ Aircraft Observations and WRF Simulations

    Science.gov (United States)

    D’Alessandro, John J.; Diao, Minghui; Wu, Chenglai; Liu, Xiaohong; Chen, Ming; Morrison, Hugh; Eidhammer, Trude; Jensen, Jorgen B.; Bansemer, Aaron; Zondlo, Mark A.; hide

    2017-01-01

    Occurrence frequency and dynamical conditions of ice supersaturation (ISS, where relative humidity with respect to ice (RHi) greater than 100%) are examined in the upper troposphere around convective activity. Comparisons are conducted between in situ airborne observations and the Weather Research and Forecasting model simulations using four double-moment microphysical schemes at temperatures less than or or equal to -40degdegC. All four schemes capture both clear-sky and in-cloud ISS conditions. However, the clear-sky (in-cloud) ISS conditions are completely (significantly) limited to the RHi thresholds of the Cooper parameterization. In all of the simulations, ISS occurrence frequencies are higher by approximately 3-4 orders of magnitude at higher updraft speeds (greater than 1 m s(exp -1) than those at the lower updraft speeds when ice water content (IWC) greater than 0.01 gm(exp -3), while observations show smaller differences up to approximately 1-2 orders of magnitude. The simulated ISS also occurs less frequently at weaker updrafts and downdrafts than observed. These results indicate that the simulations have a greater dependence on stronger updrafts to maintain/generate ISS at higher IWC. At lower IWC (less than or equal or 0.01 gm(exp -3), simulations unexpectedly show lower ISS frequencies at stronger updrafts. Overall, the Thompson aerosol-aware scheme has the closest magnitudes and frequencies of ISS greater than 20% to the observations, and the modified Morrison has the closest correlations between ISS frequencies and vertical velocity at higher IWC and number density. The Cooper parameterization often generates excessive ice crystals and therefore suppresses the frequency and magnitude of ISS, indicating that it should be initiated at higher ISS (e.g.,lees than or equal to 25%).

  18. Automated microdialysis-based system for in situ microsampling and investigation of lead bioavailability in terrestrial environments under physiologically based extraction conditions.

    Science.gov (United States)

    Rosende, María; Magalhães, Luis M; Segundo, Marcela A; Miró, Manuel

    2013-10-15

    In situ automatic microdialysis sampling under batch-flow conditions is herein proposed for the first time for expedient assessment of the kinetics of lead bioaccessibility/bioavailability in contaminated and agricultural soils exploiting the harmonized physiologically based extraction test (UBM). Capitalized upon a concentric microdialysis probe immersed in synthetic gut fluids, the miniaturized flow system is harnessed for continuous monitoring of lead transfer across the permselective microdialysis membrane to mimic the diffusive transport of metal species through the epithelium of the stomach and of the small intestine. Besides, the addition of the UBM gastrointestinal fluid surrogates at a specified time frame is fully mechanized. Distinct microdialysis probe configurations and membranes types were investigated in detail to ensure passive sampling under steady-state dialytic conditions for lead. Using a 3-cm-long polysulfone membrane with averaged molecular weight cutoff of 30 kDa in a concentric probe and a perfusate flow rate of 2.0 μL min(-1), microdialysis relative recoveries in the gastric phase were close to 100%, thereby omitting the need for probe calibration. The automatic leaching method was validated in terms of bias in the analysis of four soils with different physicochemical properties and containing a wide range of lead content (16 ± 3 to 1216 ± 42 mg kg(-1)) using mass balance assessment as a quality control tool. No significant differences between the mass balance and the total lead concentration in the suite of analyzed soils were encountered (α = 0.05). Our finding that the extraction of soil-borne lead for merely one hour in the GI phase suffices for assessment of the bioavailable fraction as a result of the fast immobilization of lead species at near-neutral conditions would assist in providing risk assessment data from the UBM test on a short notice.

  19. Natural Gas Hydrates in the Offshore Beaufort-Mackenzie Basin-Study of a Feasible Energy Source II

    International Nuclear Information System (INIS)

    Majorowicz, J. A.; Hannigan, P. K.

    2000-01-01

    In the offshore part of Beaufort-Mackenzie Basin depth of methane hydrate stability reaches more than 1.5 km. However, there are areas in the western part of the basin where there are no conditions of methane hydrate stability. Construction of the first contour maps displaying thickness of hydrate stability zones as well as hydrate stability zone thicknesses below permafrost in the offshore area, shows that these zones can reach 1200 m and 900 m, respectively. Depth to the base of ice-bearing relict permafrost under the sea (depth of the -1 o C isotherm-ice-bearing permafrost base) and regional variations of geothermal gradient are the main controlling factors. Hydrostatic pressures in the upper 1500 m are the rule. History of methane hydrate stability zone is related mainly to the history of permafrost and it reached maximum depth in early Holocene. More recently, the permafrost and hydrate zone is diminishing because of sea transgression. Reevaluation of the location of possible gas hydrate occurrences is done from the analysis of well logs and other indicators in conjunction with knowledge of the hydrate stability zone. In the offshore Beaufort-Mackenzie Basin, methane hydrate occurs in 21 wells. Nine of these locations coincides with underlying conventional hydrocarbon occurrences. Previous analyses place some of the hydrate occurrences at greater depths than proposed for the methane hydrate-stability zone described in this study. Interpretation of geological cross sections and maps of geological sequences reveals that hydrates are occurring in the Iperk-Kugmallit sequence. Hydrate-gas contact zones, however, are possible in numerous situations. As there are no significant geological seals in the deeper part of the offshore basin (all hydrates are within Iperk), it is suggested that overlying permafrost and hydrate stability zone acted as the only trap for upward migrating gas during the last tens of thousand of years (i.e., Sangamonian to Holocene)

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

    International Nuclear Information System (INIS)

    Eslamimanesh, Ali

    2012-01-01

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

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

    Science.gov (United States)

    Zhang, Zhengcai; Guo, Guang-Jun

    2017-07-26

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

  2. Thermal properties of methane hydrate by experiment and modeling and impacts upon technology

    Energy Technology Data Exchange (ETDEWEB)

    Warzinski, R.P.; Gamwo, I.K.; Rosenbaum, E.J. [United States Dept. of Energy, Pittsburgh, PA (United States). National Energy Technology Laboratory; Myshakin, E.M. [NETL Support Contractor, South Park, PA (United States); Jiang, H.; Jordan, K.D. [Pittsburgh Univ., Pittsburgh, PA (United States). Dept. of Chemistry; English, N.J. [Dublin University College, Dublin (Ireland). Conway Inst. of Biomolecular and Biomedical Research, Centre for Synthesis and Chemical Biology; Shaw, D.W. [Geneva College, Beaver Falls, PA (United States). Dept. of Engineering

    2008-07-01

    The current hydrate research at the National Energy Technology Laboratory (NETL) involves both experimental and theoretical work on developing models and methods for predicting the behaviour of gas hydrates in their natural environment under production of climate change scenarios. The modeling efforts include both fundamental and reservoir scale simulations and economic modeling. The thermal properties of methane hydrate are important for hydrate production, seafloor stability and climate change scenarios. A new experimental technique and advanced molecular dynamics simulation (MDS) have determined the thermal properties of pure methane hydrate under conditions similar to naturally occurring hydrate-bearing sediments. The thermal conductivity and thermal diffusivity values of low-porosity methane hydrate formed in the laboratory were measured using an innovative single-sided, Transient Plane Source (TPS) technique. The results were in good agreement with results from an equilibrium MDS method using in-plane polarization of the water molecules. MDS was also performed using a non-equilibrium model with a fully polarizable force field for water. The Tough+Hydrate reservoir simulator was also used to evaluate the impact of thermal conductivity on gas production from a hydrate-bearing reservoir. 42 refs., 1 tab., 5 figs.

  3. The large scale in-situ PRACLAY heater and seal tests in URL HADES, Mol, Belgium

    Energy Technology Data Exchange (ETDEWEB)

    Xiangling Li; Guangjing Chen; Verstricht, Jan; Van Marcke, Philippe; Troullinos, Ioannis [ESV EURIDICE, Mol (Belgium)

    2013-07-01

    In Belgium, the URL HADES was constructed in the Boom Clay formation at the Mol site to investigate the feasibility of geological disposal in a clay formation. Since 1995, the URL R and D programme has focused on large scale demonstration tests like the PRACLAY Heater and Seal tests. The main objective of the Heater Test is to demonstrate that the thermal load generated by the heat-emitting waste will not jeopardise the safety functions of the host rock. The primary objective of the Seal Test is to provide suitable hydraulic boundary conditions for the Heater Test. The Seal Test also provides an opportunity to investigate the in-situ behaviour of a bentonite-based EBS. The PRACLAY gallery was constructed in 2007 and the hydraulic seal was installed in 2010. The bentonite is hydrated both naturally and artificially. The swelling, total pressure and pore pressure of the bentonite are continuously measured and analysed by numerical simulations to get a better understanding of this hydration processes. The timing of switching on the heater depends on the progress of the bentonite hydration, as a sufficient seal swelling is needed to fulfill its role. A set of conditions to be met for the heater switch-on and its schedule will be given. (authors)

  4. Relation between gas hydrate and physical properties at the Mallik 2L-38 research well in the Mackenzie delta

    Science.gov (United States)

    Winters, W.J.; Dallimore, S.R.; Collett, T.S.; Jenner, K.A.; Katsube, J.T.; Cranston, R.E.; Wright, J.F.; Nixon, F.M.; Uchida, T.

    2000-01-01

    As part of an interdisciplinary field program, a 1150-m deep well was drilled in the Canadian Arctic to determine, among other goals, the location, characteristics, and properties of gas hydrate. Numerous physical properties of the host sediment were measured in the laboratory and are presented in relation to the lithology and quantity of in situ gas hydrate. Profiles of measured and derived properties presented from that investigation include: sediment wet bulk density, water content, porosity, grain density, salinity, gas hydrate content (percent occupancy of non-sediment grain void space), grain size, porosity, and post-recovery core temperature. The greatest concentration of gas hydrate is located within sand and gravel deposits between 897 and 922 m. Silty sediment between 926 and 952 m contained substantially less, or no, gas hydrate perhaps because of smaller pore size.

  5. Temporal dynamics of in-situ fiber-adherent bacterial community under ruminal acidotic conditions determined by 16S rRNA gene profiling.

    Directory of Open Access Journals (Sweden)

    Renee M Petri

    Full Text Available Subacute rumen acidotic (SARA conditions are a consequence of high grain feeding. Recent work has shown that the pattern of grain feeding can significantly impact the rumen epimural microbiota. In a continuation of these works, the objective of this study was to determine the role of grain feeding patterns on the colonization and associated changes in predicted functional properties of the fiber-adherent microbial community over a 48 h period. Eight rumen-cannulated Holstein cows were randomly assigned to interrupted or continuous 60%-grain challenge model (n = 4 per model to induce SARA conditions. Cows in the continuous model were challenged for 4 weeks, whereas cows of interrupted model had a 1-wk break in between challenges. To determine dynamics of rumen fiber-adherent microbial community we incubated the same hay from the diet samples for 24 and 48 h in situ during the baseline (no grain fed, week 1 and 4 of the continuous grain feeding model as well as during the week 1 following the break in the interrupted model. Microbial DNA was extracted and 16SrRNA amplicon (V3-V5 region sequencing was done with the Illumina MiSeq platform. A significant decrease (P 0.1% relative abundance in the rumen, 18 of which were significantly impacted by the feeding challenge model. Correlation analysis of the significant OTUs to rumen pH as an indicator of SARA showed genus Succiniclasticum had a positive correlation to SARA conditions regardless of treatment. Predictive analysis of functional microbial properties suggested that the glyoxylate/dicarboxylate pathway was increased in response to SARA conditions, decreased between 24h to 48h of incubation, negatively correlated with propanoate metabolism and positively correlated to members of the Veillonellaceae family including Succiniclasticum spp. This may indicate an adaptive response in bacterial metabolism under SARA conditions. This research clearly indicates that changes to the colonizing fiber

  6. Investigation of the internal electric field distribution under in situ x-ray irradiation and under low temperature conditions by the means of the Pockels effect

    International Nuclear Information System (INIS)

    Prekas, G; Sellin, P J; Veeramani, P; Davies, A W; Lohstroh, A; Oezsan, M E; Veale, M C

    2010-01-01

    The internal electric field distribution in cadmium zinc telluride (CdZnTe) x-ray and γ-ray detectors strongly affects their performance in terms of charge transport and charge collection properties. In CdZnTe detectors the electric field distribution is sensitively dependent on not only the nature of the metal contacts but also on the working conditions of the devices such as the temperature and the rate of external irradiation. Here we present direct measurements of the electric field profiles in CdZnTe detectors obtained using the Pockels electo-optic effect whilst under in situ x-ray irradiation. These data are also compared with alpha particle induced current pulses obtained by the transient current technique, and we discuss the influence of both low temperature and x-ray irradiation on the electric field evolution. Results from these studies reveal strong distortion of the electric field consistent with the build-up of space charge at temperatures below 250 K, even in the absence of external irradiation. Also, in the presence of x-ray irradiation levels a significant distortion in the electric field is observed even at room temperature which matches well the predicted theoretical model.

  7. Limestone calcination under calcium-looping conditions for CO2 capture and thermochemical energy storage in the presence of H2O: an in situ XRD analysis.

    Science.gov (United States)

    Valverde, Jose Manuel; Medina, Santiago

    2017-03-15

    This work reports an in situ XRD analysis of whether the calcination/carbonation behavior of natural limestone (CaCO 3 ) is affected by the addition of H 2 O to the calciner at a very low concentration under relevant Calcium-Looping (CaL) conditions for CO 2 capture in coal fired power plants (CFPP) and Thermochemical Energy Storage (TCES) in Concentrated Solar Power plants (CSP). Previous studies have demonstrated that the presence of steam in the calciner at a high concentration yields a significant increase in the reaction rate. However, a further undesired consequence is the serious deterioration of the CaO mechanical strength, which would lead to particle attrition and mass loss in any CaL process based on the use of circulating fluidized beds. The results presented in this manuscript on the time evolution of the wt% and crystallite size of the phases involved in the calcination/carbonation reactions indicate that the calcination rate is still notably increased by the presence of H 2 O at very low concentrations whereas the reactivity toward carbonation and crystal structure of the formed CaO are not essentially affected, which suggests that the CaO mechanical strength is not impaired. Thus, the benefit of using steam for calcination in the CaL process could be still retained while at the same time particle attrition would not be promoted.

  8. In-situ investigation of stress conditions during expansion of bare metal stents and PLLA-coated stents using the XRD sin(2)ψ-technique.

    Science.gov (United States)

    Kowalski, Wolfgang; Dammer, Markus; Bakczewitz, Frank; Schmitz, Klaus-Peter; Grabow, Niels; Kessler, Olaf

    2015-09-01

    Drug eluting stents (DES) consist of platform, coating and drug. The platform often is a balloon-expandable bare metal stent made of the CoCr alloy L-605 or stainless steel 316 L. The function of the coating, typically a permanent polymer, is to hold and release the drug, which should improve therapeutic outcome. Before implantation, DES are compressed (crimped) to allow implantation in the human body. During implantation, DES are expanded by balloon inflation. Crimping, as well as expansion, causes high stresses and high strains locally in the DES struts, as well as in the polymer coating. These stresses and strains are important design criteria of DES. Usually, they are calculated numerically by finite element analysis (FEA), but experimental results for validation are hardly available. In this work, the X-ray diffraction (XRD) sin(2)ψ-technique is applied to in-situ determination of stress conditions of bare metal L-605 stents, and Poly-(L-lactide) (PLLA) coated stents. This provides a realistic characterization of the near-surface stress state and a validation option of the numerical FEA. XRD-results from terminal stent struts of the bare metal stent show an increasing compressive load stress in tangential direction with increasing stent expansion. These findings correlate with numerical FEA results. The PLLA-coating also bears increasing compressive load stress during expansion. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Evaluation of the effect of Bi, Sb, Sr and cooling condition on eutectic phases in an Al–Si–Cu alloy (ADC12) by in situ thermal analysis

    Energy Technology Data Exchange (ETDEWEB)

    Farahany, S., E-mail: saeedfarahany@gmail.com [Department of Materials Engineering, Faculty of Mechanical Engineering, Universiti Teknologi Malaysia (UTM), 81310 Johor Bahru (Malaysia); Ourdjini, A.; Idrsi, M.H. [Department of Materials Engineering, Faculty of Mechanical Engineering, Universiti Teknologi Malaysia (UTM), 81310 Johor Bahru (Malaysia); Shabestari, S.G. [Center of Excellence for High Strength Alloys Technology (CEHSAT), School of Metallurgy and Materials Engineering, Iran University of Science and Technology (IUST), 16846-13114 Tehran (Iran, Islamic Republic of)

    2013-05-10

    Highlights: • Combined effect of Bi, Sb and Sr additions, and cooling condition was evaluated. • Two different scenarios of recalecense in response to cooling rate were observed. • Fraction solid increased in the order of Sr > Bi > Sb, corresponds to Si morphologies. • Only Bi decreased the nucleation temperature of Al{sub 2}Cu eutectic phase. - Abstract: Al–Si and Al–Cu eutectic phases strongly affect the properties of Al–Si–Cu cast alloys. The characteristic parameters of these two eutectic phases with addition of bismuth, antimony and strontium under different cooling rates (0.6–2 °C/s) were investigated in ADC12 alloy using in situ thermal analysis. Results show that additives affect the Al–Si phase more than the Al–Cu (Al{sub 2}Cu) phase. Addition elements showed two different scenarios in response to cooling rate in terms of recalescence of the Al–Si eutectic phase. Both Bi and Sb caused an increase in recalescence with increased cooling rate but Sr addition reduced the recalescence. Additions of Sb and Sr increased the nucleation temperature of Al{sub 2}Cu, but addition of Bi produced an opposite effect. There seems to be relationship between the solidification temperature range and fraction solid of Al–Si and Al{sub 2}Cu eutectic phases. As the cooling rate increases the fraction solid of Al–Si decreased and that of Al{sub 2}Cu increased.

  10. Evaluation of the effect of Bi, Sb, Sr and cooling condition on eutectic phases in an Al–Si–Cu alloy (ADC12) by in situ thermal analysis

    International Nuclear Information System (INIS)

    Farahany, S.; Ourdjini, A.; Idrsi, M.H.; Shabestari, S.G.

    2013-01-01

    Highlights: • Combined effect of Bi, Sb and Sr additions, and cooling condition was evaluated. • Two different scenarios of recalecense in response to cooling rate were observed. • Fraction solid increased in the order of Sr > Bi > Sb, corresponds to Si morphologies. • Only Bi decreased the nucleation temperature of Al 2 Cu eutectic phase. - Abstract: Al–Si and Al–Cu eutectic phases strongly affect the properties of Al–Si–Cu cast alloys. The characteristic parameters of these two eutectic phases with addition of bismuth, antimony and strontium under different cooling rates (0.6–2 °C/s) were investigated in ADC12 alloy using in situ thermal analysis. Results show that additives affect the Al–Si phase more than the Al–Cu (Al 2 Cu) phase. Addition elements showed two different scenarios in response to cooling rate in terms of recalescence of the Al–Si eutectic phase. Both Bi and Sb caused an increase in recalescence with increased cooling rate but Sr addition reduced the recalescence. Additions of Sb and Sr increased the nucleation temperature of Al 2 Cu, but addition of Bi produced an opposite effect. There seems to be relationship between the solidification temperature range and fraction solid of Al–Si and Al 2 Cu eutectic phases. As the cooling rate increases the fraction solid of Al–Si decreased and that of Al 2 Cu increased

  11. Study of the mechanism of a kinetic inhibitor on the crystallization of methane hydrate; Etude du mecanisme d'action d'un inhibiteur cinetique sur la cristallisation de l'hydrate de methane

    Energy Technology Data Exchange (ETDEWEB)

    Pic, J.St.

    2000-01-14

    In the offshore exploitation of liquid fuels, problems of line plugging often occur, especially due to gas hydrates crystallization. At the present time, operators resort to antifreeze additives, which efficiency is defeated either by harder operating conditions or by a more severe environmental legislation. So research recently shifted towards a new class of 'low dosage inhibitors'. In order to understand the influence of such additives, we designed a high pressure reactor, fitted with a liquid injection device and an in situ turbidimetric sensor. Access to both the particle size distribution of the suspension during the first stages of crystallization, and the total gas consumption, allows us to characterize the kinetics of methane hydration formation. First, we developed an original experimental procedure, which generates an initial 'breeding' of the solution, and thus improves the mastering of nucleation. The induction time then becomes one of the relevant parameters to investigate the performance of inhibitors. Afterwards, we performed a first series of experiments which allowed us to determine the influence of the operating conditions (pressure and stirring) on the evolution of the particle size distribution, in the absence of additives. Then, we pointed out the inhibiting effect of a model kinetic inhibitor, polyvinylpyrrolidone. When dissolved in the solution before crystallization occurs, it increases the induction delay, decreases the gas consumption rate and also slows down the birth of new particles for several hours. On the contrary, when injected in the medium during crystallization, this polymer no more affects the reaction kinetics. At last, we raise the bases for a modelling, taking into account the elementary crystallization processes of nucleation, growth and particles agglomeration. A parametric study has been confronted to the experimental data. It enables us to suggest hypotheses regarding the effect of gas hydrates kinetic

  12. In-situ corrosion studies on selected high-level waste packaging materials under simulated disposal conditions in rock salt formations

    International Nuclear Information System (INIS)

    Schwarzkopf, W.; Smailos, E.; Koester, R.

    1988-01-01

    This work reports about in situ corrosion experiments on unalloyed steels, Ti 99,8-Pd, Hastelloy C4, and iron-base alloys, as modular cast iron, Ni-Resist D4 and Si-cast iron, under simulated disposal conditions. The experiments were carried out in the frame of the German/US Brine Migration Test in heated tubed boreholes in the Asse salt mine at T = 150 0 C to 210 0 C, both in the absence and in the presence of a γ-radiation field of 3x10 2 Gy/h (Co-60 source). In addition, the material used to protect the tubing from corrosion (Inconel 600) as well as the backfill material for the annular gap (Al 2 O 3 spheres) were investigated for possible corrosion attack. All materials investigate exhibited high resistance to corrosion under the conditions prevailing in the Brine Migration Test. All material specimens corroded at much lower rates than determined in the previous laboratory-scale tests. All materials and above all the materials with passivating oxide layers such as Ti 99.8-Pd and Hastelloy C4 which may corrode selectively already in the presence of minor amounts of brine had been resistant with respect to any type of local corrosion attack. The γ-radiation of 3x10 2 Gy/h did not exert an influence on the corrosion behaviour of the materials. No corrosion attacks were observed on the Al 2 O 3 spheres. In the case of Inconel 600 traces of sulphur were detected probably resulting from the reaction of Ni with H 2 S to NiS. Measurable general and local corrosion, however, have not been observed. (orig./IHOE) [de

  13. Integrating Natural Gas Hydrates in the Global Carbon Cycle

    Energy Technology Data Exchange (ETDEWEB)

    David Archer; Bruce Buffett

    2011-12-31

    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.

  14. [Prospects for Application of Gases and Gas Hydrates to Cryopreservation].

    Science.gov (United States)

    Shishova, N V; Fesenko, E E

    2015-01-01

    In the present review, we tried to evaluate the known properties of gas hydrates and gases participating in the formation of gas hydrates from the point of view of the mechanisms of cryoinjury and cryoprotection, to consider the papers on freezing biological materials in the presence of inert gases, and to analyze the perspectives for the development of this direction. For the purpose, we searched for the information on the physical properties of gases and gas hydrates, compared processes occured during the formation of gas hydrates and water ice, analyzed the influence of the formation and growth of gas hydrates on the structure of biological objects. We prepared a short review on the biological effects of xenon, krypton, argon, carbon dioxide, hydrogen sulfide, and carbon monoxide especially on hypothermal conditions and probable application of these properties in cryopreservation technologies. The description of the existing experiments on cryopreservation of biological objects with the use of gases was analyzed. On the basis of the information we found, the most perspective directions of work in the field of cryopreservation of biological objects with the use of gases were outlined. An attempt was made to forecast the potential problems in this field.

  15. Impacts of Hydrate Distribution on the Hydro-Thermo-Mechanical Properties of Hydrate-Bearing Sediments

    Science.gov (United States)

    Dai, S.; Seol, Y.

    2015-12-01

    In general, hydrate makes the sediments hydraulically less conductive, thermally more conductive, and mechanically stronger; yet the dependency of these physical properties on hydrate saturation varies with hydrate distribution and morphology. Hydrate distribution in sediments may cause the bulk physical properties of their host sediments varying several orders of magnitude even with the same amount of hydrate. In natural sediments, hydrate morphology is inherently governed by the burial depth and the grain size of the host sediments. Compare with patchy hydrate, uniformly distributed hydrate is more destructive to fluid flow, yet leads to higher gas and water permeability during hydrate dissociation due to the easiness of forming percolation paths. Water and hydrate have similar thermal conductivity values; the bulk thermal conductivity of hydrate-bearing sediments depends critically on gas-phase saturation. 60% of gas saturation may result in evident thermal conductivity drop and hinder further gas production. Sediments with patchy hydrate yield lower stiffness than that with cementing hydrate but higher stiffness than that with pore filling and loading bearing hydrate. Besides hydrate distribution, the stress state and loading history also play an important role in the mechanical behavior of hydrate-bearing sediments.

  16. Seismic modeling of multidimensional heterogeneity scales of Mallik gas hydrate reservoirs, Northwest Territories of Canada

    Science.gov (United States)

    Huang, Jun-Wei; Bellefleur, Gilles; Milkereit, Bernd

    2009-07-01

    In hydrate-bearing sediments, the velocity and attenuation of compressional and shear waves depend primarily on the spatial distribution of hydrates in the pore space of the subsurface lithologies. Recent characterizations of gas hydrate accumulations based on seismic velocity and attenuation generally assume homogeneous sedimentary layers and neglect effects from large- and small-scale heterogeneities of hydrate-bearing sediments. We present an algorithm, based on stochastic medium theory, to construct heterogeneous multivariable models that mimic heterogeneities of hydrate-bearing sediments at the level of detail provided by borehole logging data. Using this algorithm, we model some key petrophysical properties of gas hydrates within heterogeneous sediments near the Mallik well site, Northwest Territories, Canada. The modeled density, and P and S wave velocities used in combination with a modified Biot-Gassmann theory provide a first-order estimate of the in situ volume of gas hydrate near the Mallik 5L-38 borehole. Our results suggest a range of 528 to 768 × 106 m3/km2 of natural gas trapped within hydrates, nearly an order of magnitude lower than earlier estimates which did not include effects of small-scale heterogeneities. Further, the petrophysical models are combined with a 3-D finite difference modeling algorithm to study seismic attenuation due to scattering and leaky mode propagation. Simulations of a near-offset vertical seismic profile and cross-borehole numerical surveys demonstrate that attenuation of seismic energy may not be directly related to the intrinsic attenuation of hydrate-bearing sediments but, instead, may be largely attributed to scattering from small-scale heterogeneities and highly attenuate leaky mode propagation of seismic waves through larger-scale heterogeneities in sediments.

  17. Design, development, and demonstration of a fully LabVIEW controlled in situ electrochemical Fourier transform infrared setup combined with a wall-jet electrode to investigate the electrochemical interface of nanoparticulate electrocatalysts under reaction conditions.

    Science.gov (United States)

    Nesselberger, Markus; Ashton, Sean J; Wiberg, Gustav K H; Arenz, Matthias

    2013-07-01

    We present a detailed description of the construction of an in situ electrochemical ATR-FTIR setup combined with a wall-jet electrode to investigate the electrocatalytic properties of nanoparticulate catalysts in situ under controlled mass transport conditions. The presented setup allows the electrochemical interface to be probed in combination with the simultaneous determination of reaction rates. At the same time, the high level of automation allows it to be used as a standard tool in electrocatalysis research. The performance of the setup was demonstrated by probing the oxygen reduction reaction on a platinum black catalyst in sulfuric electrolyte.

  18. Prokaryotic degradation of high molecular weight dissolved organic matter in the deep-sea waters of NW Mediterranean Sea under in situ temperature and pressure conditions during contrasted hydrological conditions

    Science.gov (United States)

    Tamburini, C.; Boutrif, M.; Garel, M.; Sempéré, R.; Repeta, D.; Charriere, B.; Nerini, D.; Panagiotopoulos, C.

    2016-02-01

    The contribution of the semi-labile dissolved organic carbon (DOC) to the global prokaryotic production has been assessed in very few previous studies. Some experiments show rapid utilization of semi-reactive DOC by prokaryotes, while other experiments show almost no utilization at all. However, all these studies did not take into account the role of hydrostatic pressure for the degradation of organic matter. In this study, we investigate (1) the degradation of "natural" high molecular weight DOM HMW-DOM (obtained after ultrafiltration) and (2) the uptake of labeled extracellular polymeric substances (3H-EPS) incubated with deep-sea water samples (2000 m-depth, NW Mediterranean Sea) under in situ pressure conditions (HP) and under atmospheric compression after decompression of the deep samples (ATM) during stratified and mixed water conditions (deep sea convection). Our results indicated that during HP incubations DOC exhibited the highest degradation rates (kHP DOC = 0.82 d-1) compared to the ATM conditions were no or few degradation was observed (kATM DOC= 0.007 d-1). An opposite trend was observed for the HP incubations from mixed deep water masses. HP incubation measurements displayed the lowest DOC degradation (kHP DOC=0.031 d-1) compared to the ATM conditions (kATM DOC=0.62 d-1). These results imply the presence of allochthonous prokaryotic cells in deep-sea samples after a winter water mass convection. Same trends were found using 3H-EPS uptake rates which were higher at HP than at ATM conditions during stratified period conditions whereas the opposite patterns were observed during deep-sea convection event. Moreover, we found than Euryarchaea were the main contributors to 3H-EPS assimilation at 2000m-depth, representing 58% of the total cells actively assimilating 3H-EPS. This study demonstrates that remineralization rates of semi-labile DOC in deep NW Med. Sea are controlled by the prokaryotic communities, which are influenced by the hydrological

  19. Equivalent formation strength as a proxy tool for exploring the existence and distribution of gas hydrates

    Science.gov (United States)

    Hamada, Y.; Yamada, Y.; Sanada, Y.; Nakamura, Y.; Kido, Y. N.; Moe, K.

    2017-12-01

    Gas hydrates bearing layer can be normally identified by a basement simulating reflector (BSR) or well logging because of their high acoustic- and electric impedance compared to the surrounding formation. These characteristics of the gas hydrate can also represent contrast of in-situ formation strength. We here attempt to describe gas hydrate bearing layers based on the equivalent strength (EST). The Indian National Gas Hydrate Program (NGHP) Expedition 02 was executed 2015 off the eastern margin of the Indian Peninsula to investigate distribution and occurrence of gas hydrates. From 25 drill sites, downhole logging data, cored samples, and drilling performance data were collected. Recorded drilling performance data was converted to the EST, which is a developed mechanical strength calculated only by drilling parameters (top drive torque, rotation per minute , rate of penetration , and drill bit diameter). At a representative site, site 23, the EST shows constant trend of 5 to 10 MPa, with some positive peaks at 0 - 270 mbsf interval, and sudden increase up to 50 MPa above BSR depth (270 - 290 mbsf). Below the BSR, the EST stays at 5-10 MPa down to the bottom of the hole (378 mbsf). Comparison of the EST with logging data and core sample description suggests that the depth profiles of the EST reflect formation lithology and gas hydrate content: the EST increase in the sand-rich layer and the gas hydrate bearing zone. Especially in the gas hydrate zone, the EST curve indicates approximately the same trend with that of P-wave velocity and resistivity measured by downhole logging. Cross plot of the increment of the EST and resistivity revealed the relation between them is roughly logarithmic, indicating the increase and decrease of the EST strongly depend on the saturation factor of gas hydrate. These results suggest that the EST, proxy of in-situ formation strength, can be an indicator of existence and amount of the gas-hydrate layer. Although the EST was calculated

  20. 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)

    2012-08-01

    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.

  1. Effect of gas hydrates melting on seafloor slope stability

    Science.gov (United States)

    Sultan, N.; Cochonat, P.; Foucher, J. P.; Mienert, J.; Haflidason, H.; Sejrup, H. P.

    2003-04-01

    Henriet, J.-P.; Mienert, J. (Ed.): Gas hydrates: relevance to world margin stability and climate change. Geological Society Special Publication, 137. The Geological Society: London, UK, p. 267-274. Handa,Y.P., 1989. Effect of Hydrostatic Pressure and Salinity on the Stability of Gas Hydrates. J.Phys.Chem., Vol.94, p.2652-2657. Henry, P., Thomas, M.; Clennell, M.B., 1999. Formation of Natural Gas Hydrates in Marine Sediments 2. Thermodynamic Calculations of Stability Conditions in Porous Sediments,” J. Geophys. Res., 104, p. 23005. Sloan, E.D. Jr., 1998. Clathrate hydrates of natural gases. Marcel Dekker Inc., 2nd edition, New York, pp. 705. Soave G, 1972. Equilibrium

  2. Phased-Resolved Strain Measuremetns in Hydrated Ordinary Portland Cement Using Synchrotron x-Rays (Prop. 2003-033)

    International Nuclear Information System (INIS)

    Biernacki, Joseph J.; Watkins, Thomas R.; Parnham, C.J.; Hubbard, Camden R.; Bai, J.

    2006-01-01

    X-ray diffraction methods developed for the determination of residual stress states in crystalline materials have been applied to study residual strains and strains because of mechanical loading of ordinary portland cement paste. Synchrotron X-rays were used to make in situ measurements of interplanar spacings in the calcium hydroxide (CH) phase of hydrated neat portland cement under uniaxial compression. The results indicate that strains on the order of 1/100 000 can be resolved providing an essentially new technique by which to measure the phase-resolved meso-scale mechanical behavior of cement under different loading conditions. Evaluation of these strain data in view of published elastic parameters for CH suggests that the CH carries a large fraction of the applied stress and that plastic interactions with the matrix are notable.

  3. Characterization of methane-hydrate formation inferred from insitu Vp-density relationship for hydrate-bearing sediment cores obtained off the eastern coast of India

    Science.gov (United States)

    Kinoshita, M.; Hamada, Y.; Hirose, T.; Yamada, Y.

    2017-12-01

    In 2015, the Indian National Gas Hydrate Program (NGHP) Drilling Expedition 02 was carried out off the eastern margin of the Indian Peninsula in order to investigate distribution and occurrence of gas hydrates. From 25 drill sites, downhole logging data, cored samples, and drilling performance data were collected. One of the target areas (area B) is located on the axial and flank of an anticline, where the BSR is identified 100 m beneath the summit of anticline. 3 sites were drilled in the crest. The lower potential hydrate zone II was suggested by downhole logging (LWD) at 270-290 m below seafloor across the top of anticline. Core samples from this interval is characterized by a higher natural gamma radiation, gamma-ray-based higher bulk density and lower porosity, and higher electrical resistivity. All these features are in good agreement with LWD results. During this expedition, numerous special core sampling operations (PCAT) were carried out, keeping its insitu pressure in a pressure-tight vessel. They enabled acquiring insitu P-wave velocity and gamma-ray attenuation density measurements. In-situ X-CT images exhibit very clear hydrate distribution as lower density patches. Hydrate-bearing sediments exhibit a Vp-density trend that is clearly different from the ordinary formation. Vp values are significantly higher than 2 km/s whereas the density remains constant at 2-2.2 g/cm3 in hydrate zones. At some hydrate-bearing sediments, we noticed that Vp is negatively correlated to the density in the deeper portion (235-285 mbsf). On the other hand, in the shallower portion they are positively correlated. From lithostratigraphy the shallower portion consists of sand, whereas deeper portion are silty-clay dominant. We infer that the sand-dominant, shallower hydrate is a pore-filling type, and Vp is correlated positively to density. On the other hand, the clay-dominant, deeper hydrate is filled in vertical veins, and Vp is negatively correlated to density. Negative

  4. Is Br2 hydration hydrophobic?

    Science.gov (United States)

    Alcaraz-Torres, A; Gamboa-Suárez, A; Bernal-Uruchurtu, M I

    2017-02-28

    The spectroscopic properties of bromine in aqueous systems suggest it can behave as either hydrophilic or hydrophobic solute. In small water clusters, the halogen bond and the hydrogen-halogen interaction are responsible for its specific way of binding. In water hydrates, it is efficiently hosted by two different cages forming the crystal structure and it has been frequently assumed that there is little or no interaction between the guest and the host. Bromine in liquid solution poses a challenging question due to its non-negligible solubility and the large blue shift measured in its absorption spectra. Using a refined semi-empirical force field, PM3-PIF, we performed a Born-Oppenheimer molecular dynamics study of bromine in liquid water. Here we present a detailed study in which we retrieved the most representative hydration structures in terms of the most frequent positions around bromine and the most common water orientations. Albeit being an approximate description of the total hydration phenomenon, it captures the contribution of the leading molecular interactions in form of the recurrent structures. Our findings confirm that the spectroscopic signature is mainly caused by the closest neighbors. The dynamics of the whole first hydration shell strongly suggests that the external molecules in that structure effectively isolate the bulk from the presence of bromine. The solvation structure fluctuates from a hydrophilic to a hydrophobic-like environment along the studied trajectory.

  5. Hydration modeling of calcium sulphates

    NARCIS (Netherlands)

    de Korte, A.C.J.; Brouwers, H.J.H.; Al-Mattarneh, Hashem; Mustapha, Kamal N.; Nuruddin, Muhd Fadhil

    2008-01-01

    The CEMHYD3D model has been extended at the University of Twente in the last ten years [1,2]. 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

  6. Numerical simulation studies of gas production scenarios from hydrate accumulations at the Mallik Site, McKenzie Delta, Canada

    International Nuclear Information System (INIS)

    Moridis, George J.; Collett, Timothy S.; Dallimore, Scott R.; Satoh, Tohru; Hancock, Stephen; Weatherill, Brian

    2002-01-01

    The Mallik site represents an onshore permafrost-associated gas hydrate accumulation in the Mackenzie Delta, Northwest Territories, Canada. An 1150 m deep gas hydrate research well was drilled at the site in 1998. The objective of this study is the analysis of various gas production scenarios from several gas-hydrate-bearing zones at the Mallik site. The TOUGH2 general-purpose simulator with the EOSHYDR2 module were used for the analysis. EOSHYDR2 is designed to model the non-isothermal CH(sub 4) (methane) release, phase behavior and flow under conditions typical of methane-hydrate deposits by solving the coupled equations of mass and heat balance, and can describe any combination of gas hydrate dissociation mechanisms. Numerical simulations indicated that significant gas hydrate production at the Mallik site was possible by drawing down the pressure on a thin free-gas zone at the base of the hydrate stability field. Gas hydrate zones with underlying aquifers yielded significant gas production entirely from dissociated gas hydrate, but large amounts of produced water. Lithologically isolated gas-hydrate-bearing reservoirs with no underlying free gas or water zones, and gas-hydrate saturations of at least 50% were also studied. In these cases, it was assumed that thermal stimulation by circulating hot water in the well was the method used to induce dissociation. Sensitivity studies indicated that the methane release from the hydrate accumulations increases with gas-hydrate saturation, the initial formation temperature, the temperature of the circulating water in the well, and the formation thermal conductivity. Methane production appears to be less sensitive to the rock and hydrate specific heat and permeability of the formation

  7. Determining the mechanism and parameters of hydrate formation and loss in glucose.

    Science.gov (United States)

    Scholl, Sarah K; Schmidt, Shelly J

    2014-11-01

    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®

  8. Hydration and Fluid Replacement Knowledge, Attitudes, Barriers, and Behaviors of NCAA Division 1 American Football Players.

    Science.gov (United States)

    Judge, Lawrence W; Kumley, Roberta F; Bellar, David M; Pike, Kim L; Pierson, Eric E; Weidner, Thomas; Pearson, David; Friesen, Carol A

    2016-11-01

    Judge, LW, Kumley, RF, Bellar, DM, Pike, KL, Pierson, EE, Weidner, T, Pearson, D, and Friesen, CA. Hydration and fluid replacement knowledge, attitudes, barriers, and behaviors of NCAA Division 1 American football players. J Strength Cond Res 30(11): 2972-2978, 2016-Hydration is an important part of athletic performance, and understanding athletes' hydration knowledge, attitudes, barriers, and behaviors is critical for sport practitioners. The aim of this study was to assess National Collegiate Athletic Association (NCAA) Division 1 (D1) American football players, with regard to hydration and fluid intake before, during, and after exercise, and to apply this assessment to their overall hydration practice. The sample consisted of 100 student-athletes from 2 different NCAA D1 universities, who participated in voluntary summer football conditioning. Participants completed a survey to identify the fluid and hydration knowledge, attitudes and behaviors, demographic data, primary football position, previous nutrition education, and barriers to adequate fluid consumption. The average Hydration Knowledge Score (HKS) for the participants in the present study was 11.8 ± 1.9 (69.4% correct), with scores ranging from 42 to 100% correct. Four key misunderstandings regarding hydration, specifically related to intervals of hydration habits among the study subjects, were revealed. Only 24% of the players reported drinking enough fluids before, during, immediately after, and 2 hours after practice. Generalized linear model analysis predicted the outcome variable HKS (χ = 28.001, p = 0.045), with nutrition education (Wald χ = 8.250, p = 0.041) and position on the football team (χ = 9.361, p = 0.025) being significant predictors. "Backs" (e.g., quarterbacks, running backs, and defensive backs) demonstrated significantly higher hydration knowledge than "Linemen" (p = 0.014). Findings indicated that if changes are not made to increase hydration awareness levels among football teams

  9. Preliminary report on the economics of gas production from natural gas hydrates

    International Nuclear Information System (INIS)

    Walsh, M.; Wilson, S.; Patil, S.; Moridis, G.; Boswell, R.; Koh, C.; Sloan, D.

    2008-01-01

    Gas hydrates are solid crystalline compounds in which gas molecules reside inside cages that are formed by hydrogen-bonded water molecules in a crystal lattice. At particularly low temperatures and high pressures, a guest molecule will combine with water to form gas hydrates. Gas hydrates are found in two different settings in which the temperature and pressure conditions are suitable for their existence, notably in Arctic permafrost regions and below the seafloor. Because of the size of this possible future resource, if any of the gas in hydrates can be proven to be economically recoverable, then production from gas hydrates could become an important portion of the world's energy portfolio as demand for natural gas increases along with the technology to compress and distribute natural gas to distant markets. This paper presented a compilation of economic research that was conducted on the resource potential of gas hydrates. The paper reported a preliminary estimate of the price of natural gas that may lead to economically-viable production from North American Arctic region hydrates. The paper also discussed the implications of a recent study on the production of class 3 marine hydrate deposits from the Gulf of Mexico. The state of the art technologies and methods in hydrate reservoir modeling and hydrate reservoir production and petrophysical testing were also discussed. It was concluded that the somewhat optimistic results presented in this report should be interpreted with caution, however, the economically-viable gas production from hydrates was not an unreasonable scenario. 23 refs., 2 tabs., 10 figs

  10. In-situ studies on volatile jet exhaust particle emissions - impacts of fuel sulfur content and environmental conditions on nuclei-mode aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, F.; Baumann, R.; Petzold, A.; Busen, R.; Schulte, P.; Fiebig, M. [DLR Deutsches Zentrum fuer Luft- und Raumfahrt e.V., Wessling (Germany). Inst. fuer Physik der Atmosphaere; Brock, C.A. [Denver Univ., CO (United States). Dept. of Engineering

    2000-02-01

    In-situ measurements of ultrafine aerosol particle emissions were performed at cruise altitudes behind the DLR ATTAS research jet (RR M45H M501 engines) and a B737-300 aircraft (CFM56-3B1 engines). Measurements were made 0.15-20 seconds after emission as the source aircraft burned fuel with sulfur contents (FSC) of 2.6, 56 or 118 mg kg{sup -1}. Particle size distributions of from 3 to 60 nm diameter were determined using CN-counters with varying lower size detection limits. Volatile particle concentrations in the aircraft plumes strongly increased as diameter decreased toward the sizes of large molecular clusters, illustrating that apparent particle emissions are extremely sensitive to the smallest particle size detectable by the instrument used. Environmental conditions and plume age alone could influence the number of detected ultrafine (volatile) aerosols within an order of magnitude, as well. The observed volatile particle emissions decreased nonlinearly as FSC decreased to 60 mg kg{sup -1}, reaching minimum values of about 2 x 10{sup 17} kg{sup -1} and 2 x 10{sup 16} kg{sup -1} for particles >3 nm and >5 nm, respectively. Volatile particle emissions did not change significantly as FSCs were further reduced below 60 mg kg{sup -1}. Volatile particle emissions did not differ significantly between the two studied engine types. In contrast, soot particle emissions from the modern CFM56-3B1 engines were 4-5 times less (4 x 10{sup 14} kg{sup -1}) than from the older RR M45H M501 engines (1.8 x 10{sup 15} kg{sup -1}). Contrail processing has been identified as an efficient sink/quenching parameter for ultrafine particles and reduces the remaining interstitial aerosol by factors 2-10 depending on particle size.

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

    DEFF Research Database (Denmark)

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

    2012-01-01

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

  12. Experimental Study on Methane Hydrate Formation and Transport from Emulsions in a “Gas Lift” Riser in a Flowloop

    OpenAIRE

    Pham , Trung-Kien; Cameirao , Ana ,; Herri , Jean-Michel; Glenat , Philippe

    2017-01-01

    Session : Flow Assurance: Transportability Strategies - GasHyDyn : Logiciel de simulation de la composition et de la stabilité des hydrates de gaz; International audience; Production of crude oil with natural gas and water at low temperature and high pressure favours conditions for gas hydrate formation which can cause many troubles, up to blockage of pipelines. This work deals with hydrate kinetics of crystallization and agglomeration together with slurry transport and deposition under flowi...

  13. Hydration Structure of the Quaternary Ammonium Cations

    KAUST Repository

    Babiaczyk, Wojtek Iwo

    2010-11-25

    Two indicators of the hydropathicity of small solutes are introduced and tested by molecular dynamics simulations. These indicators are defined as probabilities of the orientation of water molecules\\' dipoles and hydrogen bond vectors, conditional on a generalized distance from the solute suitable for arbitrarily shaped molecules. Using conditional probabilities, it is possible to distinguish features of the distributions in close proximity of the solute. These regions contain the most significant information on the hydration structure but cannot be adequately represented by using, as is usually done, joint distance-angle probability densities. Our calculations show that using our indicators a relative hydropathicity scale for the interesting test set of the quaternary ammonium cations can be roughly determined. © 2010 American Chemical Society.

  14. 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)

    2008-07-01

    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.

  15. Seismic reflections associated with submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Andreassen, K

    1996-12-31

    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.

  16. Seismic reflections associated with submarine gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Andreassen, K.

    1995-12-31

    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.

  17. Influence of fluorosurfactants on hydrate formation rates

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  18. 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)

    2003-10-01

    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.

  19. Submarine landslides triggered by destabilization of high-saturation hydrate anomalies

    Science.gov (United States)

    Handwerger, Alexander L.; Rempel, Alan W.; Skarbek, Rob M.

    2017-07-01

    Submarine landslides occur along continental margins at depths that often intersect the gas hydrate stability zone, prompting suggestions that slope stability may be affected by perturbations that arise from changes in hydrate stability. Here we develop a numerical model to identify the conditions under which the destabilization of hydrates results in slope failure. Specifically, we focus on high-saturation hydrate anomalies at fine-grained to coarse-grained stratigraphic boundaries that can transmit bridging stresses that decrease the effective stress at sediment contacts and disrupt normal sediment consolidation. We evaluate slope stability before and after hydrate destabilization. Hydrate anomalies act to significantly increase the overall slope stability due to large increases in effective cohesion. However, when hydrate anomalies destabilize there is a loss of cohesion and increase in effective stress that causes the sediment grains to rapidly consolidate and generate pore pressures that can either trigger immediate slope failure or weaken the surrounding sediment until the pore pressure diffuses away. In cases where failure does not occur, the sediment can remain weakened for months. In cases where failure does occur, we quantify landslide dynamics using a rate and state frictional model and find that landslides can display either slow or dynamic (i.e., catastrophic) motion depending on the rate-dependent properties, size of the stress perturbation, and the size of the slip patch relative to a critical nucleation length scale. Our results illustrate the fundamental mechanisms through which the destabilization of gas hydrates can pose a significant geohazard.

  20. Structural changes and intermolecular interactions of filled ice Ic structure for hydrogen hydrate under high pressure

    International Nuclear Information System (INIS)

    Machida, S; Hirai, H; Kawamura, T; Yamamoto, Y; Yagi, T

    2010-01-01

    High-pressure experiments of hydrogen hydrate were performed using a diamond anvil cell under conditions of 0.1-44.2 GPa and at room temperature. Also, high pressure Raman studies of solid hydrogen were performed in the pressure range of 0.1-43.7 GPa. X-ray diffractometry (XRD) for hydrogen hydrate revealed that a known high-pressure structure, filled ice Ic structure, of hydrogen hydrate transformed to a new high-pressure structure at approximately 35-40 GPa. A comparison of the Raman spectroscopy of a vibron for hydrogen molecules between hydrogen hydrate and solid hydrogen revealed that the extraction of hydrogen molecules from hydrogen hydrate occurred above 20 GPa. Also, the Raman spectra of a roton revealed that the rotation of hydrogen molecules in hydrogen hydrate was suppressed at around 20 GPa and that the rotation recovered under higher pressure. These results indicated that remarkable intermolecular interactions in hydrogen hydrate between neighboring hydrogen molecules and between guest hydrogen molecules and host water molecules might occur. These intermolecular interactions could produce the stability of hydrogen hydrate.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  2. Gas hydrates in gas storage caverns; Gashydrate bei der Gaskavernenspeicherung

    Energy Technology Data Exchange (ETDEWEB)

    Groenefeld, P. [Kavernen Bau- und Betriebs-GmbH, Hannover (Germany)

    1997-12-31

    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.

  3. Methane sources in gas hydrate-bearing cold seeps: Evidence from radiocarbon and stable isotopes

    Science.gov (United States)

    Pohlman, J.W.; Bauer, J.E.; Canuel, E.A.; Grabowski, K.S.; Knies, D.L.; Mitchell, C.S.; Whiticar, Michael J.; Coffin, R.B.

    2009-01-01

    Fossil methane from the large and dynamic marine gas hydrate reservoir has the potential to influence oceanic and atmospheric carbon pools. However, natural radiocarbon (14C) measurements of gas hydrate methane have been extremely limited, and their use as a source and process indicator has not yet been systematically established. In this study, gas hydrate-bound and dissolved methane recovered from six geologically and geographically distinct high-gas-flux cold seeps was found to be 98 to 100% fossil based on its 14C content. Given this prevalence of fossil methane and the small contribution of gas hydrate (??? 1%) to the present-day atmospheric methane flux, non-fossil contributions of gas hydrate methane to the atmosphere are not likely to be quantitatively significant. This conclusion is consistent with contemporary atmospheric methane budget calculations. In combination with ??13C- and ??D-methane measurements, we also determine the extent to which the low, but detectable, amounts of 14C (~ 1-2% modern carbon, pMC) in methane from two cold seeps might reflect in situ production from near-seafloor sediment organic carbon (SOC). A 14C mass balance approach using fossil methane and 14C-enriched SOC suggests that as much as 8 to 29% of hydrate-associated methane carbon may originate from SOC contained within the upper 6??m of sediment. These findings validate the assumption of a predominantly fossil carbon source for marine gas hydrate, but also indicate that structural gas hydrate from at least certain cold seeps contains a component of methane produced during decomposition of non-fossil organic matter in near-surface sediment.

  4. Effect of a new moisturizing lotion on immediate and cumulative skin hydration: Two randomized, intra-individual, vehicle- and comparator-controlled studies.

    Science.gov (United States)

    Nogueira, Alessandra; Sidou, Farzaneh; Brocard, Sylvie

    2011-08-01

    Moisturizers increase skin hydration and can serve as adjunctive care in dermatologic conditions such as xerosis, psoriasis vulgaris, atopic dermatitis and ichthyosis, in which dry skin is implicated. A non-irritating hydrating lotion (CDA lotion) was recently developed. We assessed the effect of CDA lotion on skin hydration in two randomized, evaluator-blind and intra-individual comparison studies. After a single application, CDA lotion induced significantly greater hydration than the non-treated control for at least 24 hours (p skin hydration up to 3 days after treatment cessation (p skin dryness score up to 7 days after treatment cessation (p hydration effects of CDA lotion were also compared to those of several currently available moisturizing products. In summary, application of CDA lotion increases skin hydration and alleviates the condition of skin dryness.

  5. Hydrated disease of bone

    International Nuclear Information System (INIS)

    Mishwani, A.H.; Ahmed, M.; Anwar, S.D.

    2003-01-01

    A case of primary hydatid disease of the right femur is reported that presented with pathological fracture and was diagnosed at the time of exploration for biopsy. The patient was treated by removal of all cysts, irrigation with colloidal solution, bone grafting and immobilization of the fracture followed by four cycles of oral Albendazole. Eosinophilia and serological tests reverted to normal but the patient died due to acute myocardial infarction six months later. This uncommon condition should be considered in the differential diagnosis of pathological fractures, bone pain or osteolytic lesions, especially in patients of rural and farmer background.(author)

  6. Cage occupancies of natural gas hydrates encaging methane and ethane

    Energy Technology Data Exchange (ETDEWEB)

    Kida, M.; Hachikubo, A.; Sakagami, H.; Minami, H.; Krylov, A.; Yamashita, S.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan); Kida, M. [National Inst. of Advanced Industrial Science and Technology, Toyohira-ku, Sapporo (Japan); Khlystov, O. [Limnological Inst., Irkutsk (Russian Federation). Siberian Branch of the Russian Academy of Sciences; Poort, J. [Ghent Univ., Ghent (Belgium). Renard Centre of Marine Geology; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohira-ku, Sapporo (Japan)

    2008-07-01

    Natural gas hydrates are crystalline compounds that contain large amounts of natural gas in its structure and are expected to provide natural gas resources in the future. The gas species are trapped in different types of polyhedral cages which consist of hydrogen bonded water molecules. Three main types of crystallographic structures exist, notably structure 1, structure 2 and structure H (sH). The crystallographic structure of natural gas hydrates depends on the encaged gas components. The cage occupancy is the ratio of the number of cages occupied by guest molecules to the number of total cages. It is also important to estimate the amount of natural gas, since it depends on the condition of the hydrate formation such as gas composition. The cages of natural gas hydrates mainly contain methane. However, other heavier hydrocarbons such as ethane (C{sub 2}H{sub 6}), propane (C{sub 3}H{sub 8}), and isobutane (i-C{sub 4}H{sub 1}0) may be encaged together with CH{sub 4}. Little is known about cage occupancies of natural gas hydrates including CH{sub 4} and heavier hydrocarbons. This paper discussed a study that developed cage occupancy estimations of natural gas hydrates encaging heavier hydrocarbons. 13C nuclear magnetic resonance (NMR) measurements were conducted. The assignments of resonance lines were based on 13C chemical shifts obtained by artificial sample measurements. The paper presented the experimental data and discussed the results of the study. The large cages were almost fully occupied with CH{sub 4} and C{sub 2}H{sub 6} molecules, whereas the small cage occupancies of CH{sub 4} were below 0.8. The distribution of CH{sub 4} and C{sub 2}H{sub 6} in each cage were similar to that of synthetic CH{sub 4} + C{sub 2}H{sub 6} hydrate. It was concluded that these results should be useful for optimal estimation of the amount of natural gas in gas hydrates. 18 refs., 1 tab., 3 figs.

  7. Gulf of Mexico Gas Hydrate Joint Industry Project Leg II logging-while-drilling data acquisition and analysis

    Science.gov (United States)

    Collett, Timothy S.; Lee, Wyung W.; Zyrianova, Margarita V.; Mrozewski, Stefan A.; Guerin, Gilles; Cook, Ann E.; Goldberg, Dave S.

    2012-01-01

    One of the objectives of the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II (GOM JIP Leg II) was the collection of a comprehensive suite of logging-while-drilling (LWD) data within gas-hydrate-bearing sand reservoirs in order to make accurate estimates of the concentration of gas hydrates under various geologic conditions and to understand the geologic controls on the occurrence of gas hydrate at each of the sites drilled during this expedition. The LWD sensors just above the drill bit provided important information on the nature of the sediments and the occurrence of gas hydrate. There has been significant advancements in the use of downhole well-logging tools to acquire detailed information on the occurrence of gas hydrate in nature: From using electrical resistivity and acoustic logs to identify gas hydrate occurrences in wells to 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. 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. In support of the GOM JIP Leg II effort, well-log data montages have been compiled and presented in this report which includes downhole logs obtained from all seven wells drilled during this expedition with a focus on identifying and characterizing the potential gas-hydrate-bearing sedimentary section in each of the wells. Also presented and reviewed in this report are the gas-hydrate saturation and sediment porosity logs for each of the wells as calculated from available downhole well logs.

  8. Physical properties and rock physics models of sediment containing natural and laboratory-formed methane gas hydrate

    Science.gov (United States)

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

    2004-01-01

    This paper presents results of shear strength and acoustic velocity (p-wave) measurements performed on: (1) samples containing natural gas hydrate from the Mallik 2L-38 well, Mackenzie Delta, Northwest Territories; (2) reconstituted Ottawa sand samples containing methane gas hydrate formed in the laboratory; and (3) ice-bearing sands. These measurements show that hydrate increases shear strength and p-wave velocity in natural and reconstituted samples. The proportion of this increase depends on (1) the amount and distribution of hydrate present, (2) differences, in sediment properties, and (3) differences in test conditions. Stress-strain curves from the Mallik samples suggest that natural gas hydrate does not cement sediment grains. However, stress-strain curves from the Ottawa sand (containing laboratory-formed gas hydrate) do imply cementation is present. Acoustically, rock physics modeling shows that gas hydrate does not cement grains of natural Mackenzie Delta sediment. Natural gas hydrates are best modeled as part of the sediment frame. This finding is in contrast with direct observations and results of Ottawa sand containing laboratory-formed hydrate, which was found to cement grains (Waite et al. 2004). It therefore appears that the microscopic distribution of gas hydrates in sediment, and hence the effect of gas hydrate on sediment physical properties, differs between natural deposits and laboratory-formed samples. This difference may possibly be caused by the location of water molecules that are available to form hydrate. Models that use laboratory-derived properties to predict behavior of natural gas hydrate must account for these differences.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  10. Fire extinction utilizing carbon dioxide hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Hatakeyama, T.; Aida, E.; Yokomori, T.; Ohmura, R.; Ueda, T. [Keio Univ., Hiyoshi, Kohoku-ku, Yokohama (Japan)

    2008-07-01

    Clathrate hydrates formed with nonflammable gases may be suitable for use as fire extinguishing agents because dissociation of the hydrates results in the temperature decrease in the combustion field and the nonflammable gases released from the dissociated hydrates prevent the supply of the oxygen to the combustion field. This paper discussed experiments in which ordinary ice and dry ice were used to evaluate the performance of CO{sub 2} hydrate as a fire extinguishing agent. The paper described the apparatus and procedure for the preparation of CO{sub 2} hydrate crystals. A schematic of the reactor to form CO{sub 2} hydrate and a photograph of CO{sub 2} hydrate crystal formed in the study were also presented. Other illustrations, photographs, and tables that were presented included a schematic diagram of the experimental apparatus used for the flame extinction experiments; a photograph of CO{sub 2} hydrate powder; sequential video graphs of the flame extinction by the supply of CO{sub 2} hydrate crystals to the methanol pool flame and the relevant illustration; and heat of CO{sub 2} hydrate dissociation, water vaporization and sublimation of dry ice. It was concluded that the critical mass of the CO{sub 2} hydrate required to extinguish a flame was much less than that of ordinary ice, indicating the superiority of CO{sub 2} hydrate to the ice. In addition, the experiments also revealed that the size of the CO{sub 2} hydrate particles had a significant effect on the performance of flame extinction. 5 refs., 2 tabs., 7 figs.

  11. Optothermal transient emission radiometry for studying the changes in epidermal hydration induced during ripening of tomato fruit mutants

    Science.gov (United States)

    Guo, X.; Bicanic, D.; Imhof, R.; Xiao, P.; Harbinson, J.

    2004-10-01

    Optothermal transient emission radiometry (OTTER) was used to determine the mean surface hydration and the hydration profile of three mutants (beefsteak, slicing and salad) of harvested tomatoes (Lycopersicon esculentum) that were kept under ambient conditions for as long as 51 days. Maximal sensitivity of OTTER to water in the samples was achieved by using 2.94 μm and 13.1 μm as excitation and emission wavelengths, respectively. The surface hydration increases rapidly and reaches a constant level during the remaining period. The hydrolysis of pectic substances that occur in tomatoes while ripening might be a possible cause for the observed change in hydration.

  12. Volatile inventories in clathrate hydrates formed in the primordial nebula.

    Science.gov (United States)

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

    2010-01-01

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

  13. Multi-channel electrical impedance tomography for regional tissue hydration monitoring.

    Science.gov (United States)

    Chen, Xiaohui; Kao, Tzu-Jen; Ashe, Jeffrey M; Boverman, Gregory; Sabatini, James E; Davenport, David M

    2014-06-01

    Poor assessment of hydration status during hemodialysis can lead to under- or over-hydration in patients with consequences of increased morbidity and mortality. In current practice, fluid management is largely based on clinical assessments to estimate dry weight (normal hydration body weight). However, hemodialysis patients usually have co-morbidities that can make the signs of fluid status ambiguous. Therefore, achieving normal hydration status remains a major challenge for hemodialysis therapy. Electrical impedance technology has emerged as a promising method for hydration monitoring due to its non-invasive nature, low cost and ease-of-use. Conventional electrical impedance-based hydration monitoring systems employ single-channel current excitation (either 2-electrode or 4-electrode methods) to perturb and extract averaged impedance from bulk tissue and use generalized models from large populations to derive hydration estimates. In the present study, a prototype, single-frequency electrical impedance tomography (EIT) system with simultaneous multi-channel current excitation was used to enable regional hydration change detection. We demonstrated the capability to detect a difference in daily impedance change between left leg and right leg in healthy human subjects, who wore a compression sock only on one leg to reduce daily gravitational fluid accumulation. The impedance difference corresponded well with the difference of lower leg volume change between left leg and right leg measured by volumetry, which on average is ~35 ml, accounting for 0.7% of the lower leg volume. We have demonstrated the feasibility of using multi-channel EIT to extract hydration information in different tissue layers with minimal skin interference. Our simultaneous, multi-channel current excitation approach provides an effective method to separate electrode contact impedance and skin condition artifacts from hydration signals. The prototype system has the potential to be used in clinical

  14. Borehole Tool for the Comprehensive Characterization of Hydrate-bearing Sediments

    KAUST Repository

    Dai, Sheng; Santamarina, Carlos

    2018-01-01

    Reservoir characterization and simulation require reliable parameters to anticipate hydrate deposits responses and production rates. The acquisition of the required fundamental properties currently relies on wireline logging, pressure core testing, and/or laboratory ob-servations of synthesized specimens, which are challenged by testing capabilities and in-nate sampling disturbances. The project reviews hydrate-bearing sediments, properties, and inherent sampling effects, albeit lessen with the developments in pressure core technology, in order to develop robust correlations with index parameters. The resulting information is incorporated into a tool for optimal field characterization and parameter selection with un-certainty analyses. Ultimately, the project develops a borehole tool for the comprehensive characterization of hydrate-bearing sediments at in situ, with the design recognizing past developments and characterization experience and benefited from the inspiration of nature and sensor miniaturization.

  15. Borehole Tool for the Comprehensive Characterization of Hydrate-bearing Sediments

    KAUST Repository

    Dai, Sheng

    2018-02-01

    Reservoir characterization and simulation require reliable parameters to anticipate hydrate deposits responses and production rates. The acquisition of the required fundamental properties currently relies on wireline logging, pressure core testing, and/or laboratory ob-servations of synthesized specimens, which are challenged by testing capabilities and in-nate sampling disturbances. The project reviews hydrate-bearing sediments, properties, and inherent sampling effects, albeit lessen with the developments in pressure core technology, in order to develop robust correlations with index parameters. The resulting information is incorporated into a tool for optimal field characterization and parameter selection with un-certainty analyses. Ultimately, the project develops a borehole tool for the comprehensive characterization of hydrate-bearing sediments at in situ, with the design recognizing past developments and characterization experience and benefited from the inspiration of nature and sensor miniaturization.

  16. Borehole Tool for the Comprehensive Characterization of Hydrate-bearing Sediments

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Sheng [Georgia Inst. of Technology, Atlanta, GA (United States); Santamarina, J. Carlos [Georgia Inst. of Technology, Atlanta, GA (United States); King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia)

    2017-12-30

    Reservoir characterization and simulation require reliable parameters to anticipate hydrate deposits responses and production rates. The acquisition of the required fundamental properties currently relies on wireline logging, pressure core testing, and/or laboratory observations of synthesized specimens, which are challenged by testing capabilities and innate sampling disturbances. The project reviews hydrate-bearing sediments, properties, and inherent sampling effects, albeit lessen with the developments in pressure core technology, in order to develop robust correlations with index parameters. The resulting information is incorporated into a tool for optimal field characterization and parameter selection with uncertainty analyses. Ultimately, the project develops a borehole tool for the comprehensive characterization of hydrate-bearing sediments at in situ, with the design recognizing past developments and characterization experience and benefited from the inspiration of nature and sensor miniaturization.

  17. Carbohydrates as efficient catalysts for the hydration of α-amino nitriles.

    Science.gov (United States)

    Chitale, Sampada; Derasp, Joshua S; Hussain, Bashir; Tanveer, Kashif; Beauchemin, André M

    2016-11-01

    Directed hydration of α-amino nitriles was achieved under mild conditions using simple carbohydrates as catalysts exploiting temporary intramolecularity. A broadly applicable procedure using both formaldehyde and NaOH as catalysts efficiently hydrated a variety of primary and secondary susbtrates, and allowed the hydration of enantiopure substrates to proceed without racemization. This work also provides a rare comparison of the catalytic activity of carbohydrates, and shows that the simple aldehydes at the basis of chemical evolution are efficient organocatalysts mimicking the function of hydratase enzymes. Optimal catalytic efficiency was observed with destabilized aldehydes, and with difficult substrates only simple carbohydrates such as formaldehyde and glycolaldehyde proved reliable.

  18. Is Obsidian Hydration Dating Affected by Relative Humidity?

    Science.gov (United States)

    Friedman, I.; Trembour, F.W.; Smith, G.I.; Smith, F.L.

    1994-01-01

    Experiments carried out under temperatures and relative humidities that approximate ambient conditions show that the rate of hydration of obsidian is a function of the relative humidity, as well as of previously established variables of temperature and obsidian chemical composition. Measurements of the relative humidity of soil at 25 sites and at depths of between 0.01 and 2 m below ground show that in most soil environments, at depths below about 0.25 m, the relative humidity is constant at 100%. We have found that the thickness of the hydrated layer developed on obsidian outcrops exposed to the sun and to relative humidities of 30-90% is similar to that formed on other portions of the outcrop that were shielded from the sun and exposed to a relative humidity of approximately 100%. Surface samples of obsidian exposed to solar heating should hydrate more rapidly than samples buried in the ground. However, the effect of the lower mean relative humidity experiences by surface samples tends to compensate for the elevated temperature, which may explain why obsidian hydration ages of surface samples usually approximate those derived from buried samples.

  19. Experimental and modeling investigation on structure H hydrate formation kinetics

    International Nuclear Information System (INIS)

    Mazraeno, M. Seyfi; Varaminian, F.; Vafaie sefti, M.

    2013-01-01

    Highlights: • Applying affinity model for the formation kinetics of sH hydrate and two stage kinetics. • Performing the experiments of hydrate formation of sH with MCP. • A unique path for the SH hydrate formation. - Abstract: In this work, the kinetics of crystal H hydrate and two stage kinetics formation is modeled by using the chemical affinity model for the first time. The basic idea is that there is a unique path for each experiment by which the crystallization process decays the affinity. The experiments were performed at constant temperatures of 274.15, 275.15, 275.65, 276.15 and 277.15 K. The initial pressure of each experiment is up to 25 bar above equilibrium pressure of sI. Methylcyclohexane (MCH), methylcyclopentane (MCP) and tert-butyl methyl ether (TBME) are used as sH former and methane is used as a help gas. The parameters of the affinity model (A r and t k ) are determined and the results show that the parameter of (A r )/(RT) has not a constant value when temperature changes in each group of experiments. The results indicate that this model can predict experimental data very well at several conditions

  20. Predictions of hydrate plug dissociation with electrical heating

    Energy Technology Data Exchange (ETDEWEB)

    Davies, S.R.; Ivanic, J.; Sloan, E.D.

    2005-07-01

    The rate of dissociation for cylindrical hydrate plugs by the application of radial electrical heating was investigated for structure I and structure II hydrates for pressures of 7 MPa (1000 psia) and 14 MPa (2000 psia). Heating rates of 2.3 kWm{sup -3}, 4.5 kWm-3 and 6.8 kWm{sup -3} were investigated for a plug 91.4 cm (36 inches) in length and 2.54 cm (1 inch) in diameter. A heat transfer model was developed in cylindrical coordinates based on Fourier's Law with a boundary condition of constant heat flux at the pipe wall. The equation set was solved numerically using a finite difference grid and the standard explicit scheme. The model was found to replicate well the experimental observations with no fitted parameters. A computer program was formulated to allow the practicing engineer to simulate the dissociation of industrial hydrates with minimal complexity. This program was incorporated into the latest version of our CSMPlug program which has been used by a number of energy companies to predict hydrate plug dissociation rates in the field. (Author)

  1. A DFT based equilibrium study of a chemical mixture Tachyhydrite and their lower hydrates for long term heat storage

    NARCIS (Netherlands)

    Pathak, A.D.; Gaastra - Nedea, S.V.; Zondag, H.A.; Rindt, C.C.M.; Smeulders, D.M.J.

    2016-01-01

    Chloride based salt hydrates are promising materials for seasonal heat storage. However, hydrolysis, a side reaction, deteriorates, their cycle stability. To improve the kinetics and durability, we have investigated the optimum operating conditions of a chemical mixture of CaCl2 and MgCl2 hydrates.

  2. Clinker mineral hydration at reduced relative humidities

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede

    1998-01-01

    This report deals with gas phase hydration of pure cement clinker minerals at reduced relative humidities. This is an important subject in relation to modern high performance concrete which may self-desiccate during hydration. In addition the subject has relevance to storage stability where...... prehydration may occur. In the report both theoretical considerations and experimental data are presented. It is suggested that the initiation of hydration during water vapour exposure is nucleation controlled....

  3. Prestack Waveform Inversion and Well Log Examination at GC955 and WR313 in the Gulf of Mexico for Estimation of Methane Hydrate Concentrations

    Science.gov (United States)

    Fortin, W.; Goldberg, D.; Kucuk, H. M.

    2017-12-01

    Gas hydrates are naturally occurring compounds, which, at a molecular scale, are lattice structures of ice embedded with various gas molecules in the lattice voids. Volumetric estimates of associated hydrocarbons vary greatly due to the difficulty in remotely estimating hydrate concentrations in marine sediments but embedded hydrocarbon stores are thought to represent a significant portion of global deposits. Inherent hydrate instabilities obscure our understanding of and complicates processes related to resource extraction and hydrate response to disturbances in the local environment. Understanding the spatial extent and variability of hydrate deposits have important implications for potential economic production, climate change, and assessing natural hazards risks. Seismic reflection techniques are capable of determining the extent of gas hydrate deposits, often through the observation of bottom simulating reflectors (BSRs). However, BSRs are not present everywhere gas hydrates exist. Using high resolution prestack time migrated seismic data and prestack waveform inversion (PWI) we produce highly resolved velocity models and compare them to co-located well logs. Coupling our PWI results with velocity-porosity relationships and nearby well control, we map hydrate properties at GC955 and WR313. Integrating small scale heterogeneities and variations along the velocity model with in-situ measurements, we develop a workflow aimed to quantify hydrate concentrations observed in seismic data over large areas in great detail regardless of the existence of a BSR.

  4. Accelerated hydration of high silica cements

    International Nuclear Information System (INIS)

    Walker, Colin; Yui, Mikazu

    2012-01-01

    Current Japanese designs for high level radioactive waste (HLW) repositories anticipate the use of both bentonite (buffer and backfill material) and cement based materials. Using hydrated Ordinary Portland Cement (OPC) as a grouting material is undesirable because the associated high pH buffer will have an undisputed detrimental effect on the performance of the bentonite buffer and backfill and of the host rock by changing its porosity. Instead, hydrated low pH cement (LopHC) grouting materials are being developed to provide a pH inferior or equal to 11 to reduce these detrimental effects. LopHC grouting materials use mixtures of superfine OPC (SOPC) clinker and silica fume (SF), and are referred as high silica cements (HSC). The focus of the present study was to identify the development of the unhydrated and hydrated mineral assemblage and the solution chemistry during the hydration of HSC. Since hydration experiments of cementitious materials are notably slow, a ball mill was used to accelerate hydration. This was done for two reasons. Firstly, to develop a method to rapidly hydrate cement based materials without the need for higher temperatures (which can alter the mineral assemblage), and secondly, to ensure that the end point of hydration was reached in a reasonable time frame and so to realize the final mineralogy and solution chemistry of hydrated HSC

  5. Microstructure of natural hydrate host sediments

    International Nuclear Information System (INIS)

    Jones, K.W.; Kerkar, P.B.; Mahajan, D.; Lindquist, W.B.; Feng, H.

    2007-01-01

    There is worldwide interest in the study of natural gas hydrate because of its potential impact on world energy resources, control on seafloor stability, significance as a drilling hazard and probable impact on climate as a reservoir of a major greenhouse gas. Gas hydrates can (a) be free floating in the sediment matrix (b) contact, but do not cement, existing sediment grains, or (c) actually cement and stiffen the bulk sediment. Seismic surveys, often used to prospect for hydrates over a large area, can provide knowledge of the location of large hydrate concentrations because the hydrates within the sediment pores modify seismic properties. The ability to image a sample at the grain scale and to determine the porosity, permeability and seismic profile is of great interest since these parameters can help in determining the location of hydrates with certainty. We report here on an investigation of the structure of methane hydrate sediments at the grain-size scale using the synchrotron radiation-based computed microtomography (CMT) technique. Work has started on the measurements of the changes occurring as tetrahydrofuran hydrate, a surrogate for methane hydrate, is formed in the sediment

  6. X-ray Tomography and Impregnation Methods to Analyze Pore Space Hetrerogeneities at the Hydrated State

    International Nuclear Information System (INIS)

    Pret, D.; Ferrage, E.; Tertre, E.; Robinet, J.C.; Faurel, M.; Hubert, F.; Pelletier, M.; Bihannic, I.

    2013-01-01

    environmental conditions and preparations are used. In case of methods able to deal with wet atmospheres and nanometre resolution, sub-sampling millimetre or micrometre size hydrated samples without inducing shearing or fractures is also not still proven. Optimization of impregnation procedure for water saturated clay samples still plays a pivotal role for applying the most advanced imaging techniques at the nanometre scale. In addition, natural clay rocks in sedimentary basins or engineered barriers in deep repositories could not swell or shrink by changing their macroscopic volume. Such case corresponds to constrained swelling conditions that implies a distribution of pore and water highly contrasting with dry state and hydrated state in free swelling conditions. Moreover, swelling rate could potentially be limited down to the crystal scale. As probing in-situ the organization of hydrated and compacted clay materials into an odometer set-up is challenging, it is really poorly documented in literature. Note that opening an odometer setup and analyzing a sample is not a constrained swelling condition: immediate swelling and change of pore space occurs. Natural clayey rocks in sedimentary basins display additional spatial variations of mineral and porosity distributions with contrasted spatial frequencies or gradual evolutions due to sedimentation cycles, temporal evolutions of climate, variations of sources, diagenesis, etc. At the scale of a laboratory sample, geological history still imposes a heterogeneous spatial distribution of mineral and pore space down-scaling to the crystal scale. Localizing samples with a millimetre size or less against the heterogeneities encountered at larger scale is thus important before analyzing it with a nanometre resolution. The best is to follow a continuous down-scaling approach all along the characterization of the organization, keeping the sample in a similar state between each technique. Here we propose a method to fully impregnate up to

  7. Heat Transfer Analysis of Methane Hydrate Sediment Dissociation in a Closed Reactor by a Thermal Method

    Directory of Open Access Journals (Sweden)

    Mingjun Yang

    2012-05-01

    Full Text Available The heat transfer analysis of hydrate-bearing sediment involved phase changes is one of the key requirements of gas hydrate exploitation techniques. In this paper, experiments were conducted to examine the heat transfer performance during hydrate formation and dissociation by a thermal method using a 5L volume reactor. This study simulated porous media by using glass beads of uniform size. Sixteen platinum resistance thermometers were placed in different position in the reactor to monitor the temperature differences of the hydrate in porous media. The influence of production temperature on the production time was also investigated. Experimental results show that there is a delay when hydrate decomposed in the radial direction and there are three stages in the dissociation period which is influenced by the rate of hydrate dissociation and the heat flow of the reactor. A significant temperature difference along the radial direction of the reactor was obtained when the hydrate dissociates and this phenomenon could be enhanced by raising the production temperature. In addition, hydrate dissociates homogeneously and the temperature difference is much smaller than the other conditions when the production temperature is around the 10 °C. With the increase of the production temperature, the maximum of ΔToi grows until the temperature reaches 40 °C. The period of ΔToi have a close relation with the total time of hydrate dissociation. Especially, the period of ΔToi with production temperature of 10 °C is twice as much as that at other temperatures. Under these experimental conditions, the heat is mainly transferred by conduction from the dissociated zone to the dissociating zone and the production temperature has little effect on the convection of the water in the porous media.

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

    Science.gov (United States)

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

    2006-01-01

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

  9. Considering multiple occupancy of cavities in clathrate hydrate phase equilibrium calculations

    Energy Technology Data Exchange (ETDEWEB)

    Asiaee, Alireza; Raeissi, Sona [Natural Gas Engineering Department, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345 (Iran, Islamic Republic of); Shariati, Alireza, E-mail: shariati@shirazu.ac.i [Natural Gas Engineering Department, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345 (Iran, Islamic Republic of)

    2011-05-15

    Research highlights: A model is presented to predict dissociation pressures of gas hydrates at various temperatures. The present model is applicable on a wide range of equilibrium conditions. The simple calculation procedure presented here saves considerably the calculation time. - Abstract: One of the major assumptions of the original van der Waals-Platteeuw (vdWP) model is the single occupancy of hydrate cavities. In this work, the vdWP model is modified to also account for multiple occupancies of hydrate cavities by small molecules. The developed model is evaluated by calculating the hydrate equilibrium conditions with either oxygen or nitrogen as guest molecules in pure form, as well as mixtures of nitrogen and propane (molecules of these pure gases and those in (nitrogen + propane) have double occupancy in large cavities of structure II up to a certain concentration of propane). The results of this modified model show good agreement with the experimental data reported in the literature.

  10. Considering multiple occupancy of cavities in clathrate hydrate phase equilibrium calculations

    International Nuclear Information System (INIS)

    Asiaee, Alireza; Raeissi, Sona; Shariati, Alireza

    2011-01-01

    Research highlights: → A model is presented to predict dissociation pressures of gas hydrates at various temperatures. → The present model is applicable on a wide range of equilibrium conditions. → The simple calculation procedure presented here saves considerably the calculation time. - Abstract: One of the major assumptions of the original van der Waals-Platteeuw (vdWP) model is the single occupancy of hydrate cavities. In this work, the vdWP model is modified to also account for multiple occupancies of hydrate cavities by small molecules. The developed model is evaluated by calculating the hydrate equilibrium conditions with either oxygen or nitrogen as guest molecules in pure form, as well as mixtures of nitrogen and propane (molecules of these pure gases and those in (nitrogen + propane) have double occupancy in large cavities of structure II up to a certain concentration of propane). The results of this modified model show good agreement with the experimental data reported in the literature.

  11. Application of empirical hydration distribution functions around polar atoms for assessing hydration structures of proteins

    International Nuclear Information System (INIS)

    Matsuoka, Daisuke; Nakasako, Masayoshi

    2013-01-01

    Highlights: ► Empirical distribution functions of water molecules in protein hydration are made. ► The functions measure how hydrogen-bond geometry in hydration deviate from ideal. ► The functions assess experimentally identified hydration structures of protein. - Abstract: To quantitatively characterize hydrogen-bond geometry in local hydration structures of proteins, we constructed a set of empirical hydration distribution functions (EHDFs) around polar protein atoms in the main and side chains of 11 types of hydrophilic amino acids (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 113 (2009) 11274). The functions are the ensemble average of possible hydration patterns around the polar atoms, and describe the anisotropic deviations from ideal hydrogen bond geometry. In addition, we defined probability distribution function of hydration water molecules (PDFH) over the hydrophilic surface of a protein as the sum of EHDFs of solvent accessible polar protein atoms. The functions envelop most of hydration sites identified in crystal structures of proteins (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 114 (2010) 4652). Here we propose the application of EHDFs and PDFHs for assessing crystallographically identified hydration structures of proteins. First, hydration water molecules are classified with respect to the geometry in hydrogen bonds in referring EHDFs. Difference Fourier electron density map weighted by PDFH of protein is proposed to identify easily density peaks as candidates of hydration water molecules. A computer program implementing those ideas was developed and used for assessing hydration structures of proteins

  12. Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

    Science.gov (United States)

    Barlag, Rebecca; Nyasulu, Frazier

    2011-01-01

    The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

  13. Thickness and growth-condition dependence of in-situ mobility and carrier density of epitaxial thin-film Bi2Se3

    International Nuclear Information System (INIS)

    Hellerstedt, Jack; Fuhrer, Michael S.; Edmonds, Mark T.; Zheng, C. X.; Chen, J. H.; Cullen, William G.

    2014-01-01

    Bismuth selenide Bi 2 Se 3 was grown by molecular beam epitaxy, while carrier density and mobility were measured directly in situ as a function of film thickness. Carrier density shows high interface n-doping (1.5 × 10 13  cm −2 ) at the onset of film conduction and bulk dopant density of ∼5 × 10 11  cm −2 per quintuple-layer unit, roughly independent of growth temperature profile. Mobility depends more strongly on the growth temperature and is related to the crystalline quality of the samples quantified by ex-situ atomic force microscopy measurements. These results indicate that Bi 2 Se 3 as prepared by widely employed parameters is n-doped before exposure to atmosphere, the doping is largely interfacial in origin, and dopants are not the limiting disorder in present Bi 2 Se 3 films.

  14. In situ groundwater bioremediation

    Energy Technology Data Exchange (ETDEWEB)

    Hazen, Terry C.

    2009-02-01

    In situ groundwater bioremediation of hydrocarbons has been used for more than 40 years. Most strategies involve biostimulation; however, recently bioaugmentation have been used for dehalorespiration. Aquifer and contaminant profiles are critical to determining the feasibility and strategy for in situ groundwater bioremediation. Hydraulic conductivity and redox conditions, including concentrations of terminal electron acceptors are critical to determine the feasibility and strategy for potential bioremediation applications. Conceptual models followed by characterization and subsequent numerical models are critical for efficient and cost effective bioremediation. Critical research needs in this area include better modeling and integration of remediation strategies with natural attenuation.

  15. A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides

    Science.gov (United States)

    One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this...

  16. Experimental flowloop study on methane hydrate formation and agglomeration in high water cut emulsion systems

    OpenAIRE

    Pham , Trung-Kien; Cameirao , Ana ,; Herri , Jean-Michel

    2016-01-01

    Thème de cette communication: International Conference on Integrated Petroleum Engineering (IPE); International audience; hydrate risk also increases. Especially in the offshore systems, operating at low temperature and high pressure, conditions are favourable to the formation of gas hydrate, from the combination of liquid water and gas molecules, under the form of a solid phase. It is a serious issue in the flow assurance; it may cause many troubles, up to plugging.This work brings new under...

  17. Hydration and Proton Conductivity of Ionomers: The Model Case of Sulfonated Aromatic Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Knauth, Philippe, E-mail: philippe.knauth@univ-amu.fr [Madirel (UMR 7246), CNRS, Aix Marseille Université, Marseille (France); Di Vona, Maria Luisa [Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, Roma (Italy)

    2014-11-06

    The hydration of proton-conducting ionomers is described in terms of a simplified model, where only osmotic and elastic contributions to the Gibbs free energy of hydration are considered. Although only two physically meaningful parameters are used – the deformation parameter, inversely proportional to the elastic modulus of the ionomer, and the free volume parameter – simulated hydration isotherms are in good agreement with the experiment. The proton mobility u inside the electrolyte solution of the ionomer is calculated from the proton conductivity determined at various hydration numbers. Its variation with the proton concentration c reveals the percolation threshold of hydrated nanometric channels and the tortuosity of the membrane. Above the percolation threshold, a power law u ~ c{sup −3} is observed, in agreement with the “universal” law for 3-dimensional percolation. The proton conductivity σ shows at 100°C a maximum of 0.2 S/cm at a hydration number ~90. The σ = f(c) plot allows to predict, which hydration conditions are necessary for a desired area specific resistance.

  18. Hydration and proton conductivity of ionomers: the model case of Sulfonated Aromatic Polymers

    Directory of Open Access Journals (Sweden)

    Philippe eKnauth

    2014-11-01

    Full Text Available The hydration of proton-conducting ionomers is described in terms of a simplified model, where only osmotic and elastic contributions to the Gibbs free energy of hydration are considered. Although only two physically meaningful parameters are used - the deformation parameter, inversely proportional to the elastic modulus of the ionomer, and the free volume parameter – simulated hydration isotherms are in good agreement with the experiment. The proton mobility u inside the electrolyte solution of the ionomer is calculated from the proton conductivity determined at various hydration numbers. Its variation with the proton concentration c reveals the percolation threshold of hydrated nanometric channels and the tortuosity of the membrane. Above the percolation threshold, a power law u ~ c-3 is observed, in agreement with the universal law for 3-dimensional percolation. The proton conductivity  shows at 100°C a maximum of 0.2 S/cm at a hydration number ~90. The  = f(c plot allows to predict which hydration conditions are necessary for a desired area specific resistance.

  19. Controls on methane expulsion during melting of natural gas hydrate systems. Topic area 2

    Energy Technology Data Exchange (ETDEWEB)

    Flemings, Peter [Univ. of Texas, Austin, TX (United States)

    2016-01-14

    1.1. Project Goal The project goal is to predict, given characteristic climate-induced temperature change scenarios, the conditions under which gas will be expelled from existing accumulations of gas hydrate into the shallow ocean or directly to the atmosphere. When those conditions are met, the fraction of the gas accumulation that escapes and the rate of escape shall be quantified. The predictions shall be applicable in Arctic regions and in gas hydrate systems at the up dip limit of the stability zone on