Dissociation behavior of methane gas hydrate in porous media

Energy Technology Data Exchange (ETDEWEB)

Qiang, C.; Yu-gang, Y.; Chang-ling, L. [Ministry of Land and Resources, Quindao (China). Qingdao Inst. of Marine Geology; Qing-guo, M. [Qingdao Univ. College of Chemical Engineering and Environment, Shandong, Qingdao (China)

2008-07-01

Gas hydrates are ice-like compounds that form by natural gas and water and are considered to be a new energy resource. In order to make good use of this resource, it is important to know the hydrate dissociation process. This paper discussed an investigation of methane hydrate dissociation through a simulation experiment. The paper discussed the gas hydrates dissociation experiment including the apparatus and experiment equipment, including methane gas supply; reaction cell; temperature controller; pressure maintainer; and gas flow meter. The paper also presented the method and material including iso-volumetric dissociation and normal pressure dissociation. Last, results and discussion of the results were presented. A comparison of five different particle sizes did not reveal any obvious effects that were related to the porous media, mostly likely because the particle size was too large. 15 refs., 2 tabs., 4 figs.

Mechanical behavior of a composite interface: Calcium-silicate-hydrates

Energy Technology Data Exchange (ETDEWEB)

Palkovic, Steven D.; Moeini, Sina; Büyüköztürk, Oral, E-mail: obuyuk@mit.edu [Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Yip, Sidney [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

2015-07-21

The generalized stacking fault (GSF) is a conceptual procedure historically used to assess shear behavior of defect-free crystalline structures through molecular dynamics or density functional theory simulations. We apply the GSF technique to the spatially and chemically complex quasi-layered structure of calcium-silicate-hydrates (C-S-H), the fundamental nanoscale binder within cementitious materials. A failure plane is enforced to calculate the shear traction-displacement response along a composite interface containing highly confined water molecules, hydroxyl groups, and calcium ions. GSF simulations are compared with affine (homogeneous) shear simulations, which allow strain to localize naturally in response to the local atomic environment. Comparison of strength and deformation behavior for the two loading methods shows the composite interface controls bulk shear deformation. Both models indicate the maximum shear strength of C-S-H exhibits a normal-stress dependency typical of cohesive-frictional materials. These findings suggest the applicability of GSF techniques to inhomogeneous structures and bonding environments, including other layered systems such as biological materials containing organic and inorganic interfaces.

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates

International Nuclear Information System (INIS)

Krishnan, N. M. Anoop; Wang, Bu; Falzone, Gabriel; Le Pape, Yann; Neithalath, Narayanan

2016-01-01

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development, and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C–S–H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C–S–H shows a sudden increase when the CaO/SiO_2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C–S–H’s nanostructure. We identify that confinement is dictated by the topology of the C–S–H’s atomic network. Altogether, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates.

Science.gov (United States)

Krishnan, N M Anoop; Wang, Bu; Falzone, Gabriel; Le Pape, Yann; Neithalath, Narayanan; Pilon, Laurent; Bauchy, Mathieu; Sant, Gaurav

2016-12-28

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development, and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C-S-H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C-S-H shows a sudden increase when the CaO/SiO 2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C-S-H's nanostructure. We identify that confinement is dictated by the topology of the C-S-H's atomic network. Taken together, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.

Research opportunities in salt hydrates for thermal energy storage

Science.gov (United States)

Braunstein, J.

1983-11-01

The state of the art of salt hydrates as phase change materials for low temperature thermal energy storage is reviewed. Phase equilibria, nucleation behavior and melting kinetics of the commonly used hydrate are summarized. The development of efficient, reliable inexpensive systems based on phase change materials, especially salt hydrates for the storage (and retrieval) of thermal energy for residential heating is outlined. The use of phase change material thermal energy storage systems is not yet widespread. Additional basic research is needed in the areas of crystallization and melting kinetics, prediction of phase behavior in ternary systems, thermal diffusion in salt hydrate systems, and in the physical properties pertinent to nonequilibrium and equilibrium transformations in these systems.

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

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

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.

Phase equilibrium measurements and the tuning behavior of new sII clathrate hydrates

Energy Technology Data Exchange (ETDEWEB)

Shin, Woongchul; Park, Seongmin; Ro, Hyeyoon; Koh, Dong-Yeun; Seol, Jiwoong [Department of Chemical and Biomolecular Engineering (BK21 Program), KAIST, Daejeon 305-701 (Korea, Republic of); Lee, Huen, E-mail: h_lee@kaist.ac.kr [Department of Chemical and Biomolecular Engineering (BK21 Program), KAIST, Daejeon 305-701 (Korea, Republic of); Graduate School of EEWS, KAIST, Daejeon 305-701 (Korea, Republic of)

2012-01-15

Graphical abstract: Pyrrolidine and piperidine act as sII clathrate hydrate formers under methane gas. Highlights: > New sII clathrate hydrate formers were proposed: pyrrolidine and piperidine. > Formation of gas hydrate with methane as help gas was confirmed. > NMR, Raman, and XRD patterns were analyzed to identify the hydrate structures. > We measured (L + H + V) phase equilibrium with proposed hydrate formers. > Tuning phenomena increase gas storage in (pyrrolidine + CH{sub 4}) clathrate hydrates. - Abstract: We suggest two types of new amine-type sII formers: pyrrolidine and piperidine. These guest compounds fail to form clathrate hydrate structures with host water, but instead have to combine with light gaseous guest molecules (methane) for enclathration. First, two binary clathrate hydrates of (pyrrolidine + methane) and (piperidine + methane) were synthesized at various amine concentrations. {sup 13}C NMR and Raman analysis were done to identify the clathrate hydrate structure and guest distribution over sII-S and sII-L cages. XRD was also used to find the exact structure and corresponding cell parameters. At a dilute pyrrolidine concentration of less than 5.56 mol%, the tuning phenomenon is observed such that methane molecules surprisingly occupy sII-L cages. At the critical guest concentration of about 0.1 mol%, the cage occupancy ratio reaches the maximum of approximately 0.5. At very dilute guest concentration below 0.1 mol%, the methane molecules fail to occupy large cages on account of their rarefied distribution in the network. Direct-release experiments were performed to determine the actual guest compositions in the clathrate hydrate phases. Finally, we measured the clathrate hydrate phase equilibria of (pyrrolidine + methane) and (piperidine + methane).

Phase equilibrium measurements and the tuning behavior of new sII clathrate hydrates

International Nuclear Information System (INIS)

Shin, Woongchul; Park, Seongmin; Ro, Hyeyoon; Koh, Dong-Yeun; Seol, Jiwoong; Lee, Huen

2012-01-01

Graphical abstract: Pyrrolidine and piperidine act as sII clathrate hydrate formers under methane gas. Highlights: → New sII clathrate hydrate formers were proposed: pyrrolidine and piperidine. → Formation of gas hydrate with methane as help gas was confirmed. → NMR, Raman, and XRD patterns were analyzed to identify the hydrate structures. → We measured (L + H + V) phase equilibrium with proposed hydrate formers. → Tuning phenomena increase gas storage in (pyrrolidine + CH 4 ) clathrate hydrates. - Abstract: We suggest two types of new amine-type sII formers: pyrrolidine and piperidine. These guest compounds fail to form clathrate hydrate structures with host water, but instead have to combine with light gaseous guest molecules (methane) for enclathration. First, two binary clathrate hydrates of (pyrrolidine + methane) and (piperidine + methane) were synthesized at various amine concentrations. 13 C NMR and Raman analysis were done to identify the clathrate hydrate structure and guest distribution over sII-S and sII-L cages. XRD was also used to find the exact structure and corresponding cell parameters. At a dilute pyrrolidine concentration of less than 5.56 mol%, the tuning phenomenon is observed such that methane molecules surprisingly occupy sII-L cages. At the critical guest concentration of about 0.1 mol%, the cage occupancy ratio reaches the maximum of approximately 0.5. At very dilute guest concentration below 0.1 mol%, the methane molecules fail to occupy large cages on account of their rarefied distribution in the network. Direct-release experiments were performed to determine the actual guest compositions in the clathrate hydrate phases. Finally, we measured the clathrate hydrate phase equilibria of (pyrrolidine + methane) and (piperidine + methane).

Influence of smectite hydration and swelling on atrazine sorption behavior.

Science.gov (United States)

Chappell, Mark A; Laird, David A; Thompson, Michael L; Li, Hui; Teppen, Brian J; Aggarwal, Vaneet; Johnston, Cliff T; Boyd, Stephen A

2005-05-01

Smectites, clay minerals commonly found in soils and sediments, vary widely in their ability to adsorb organic chemicals. Recent research has demonstrated the importance of surface charge density and properties of exchangeable cations in controlling the affinity of smectites for organic molecules. In this study, we induced hysteresis in the crystalline swelling of smectites to test the hypothesis that the extent of crystalline swelling (or interlayer hydration status) has a large influence on the ability of smectites to adsorb atrazine from aqueous systems. Air-dried K-saturated Panther Creek (PC) smectite swelled less (d(001) = 1.38 nm) than never-dried K-PC (d(001) = 1.7 nm) when rehydrated in 20 mM KCl. Correspondingly, the air-dried-rehydrated K-PC had an order of magnitude greater affinity for atrazine relative to the never-dried K-PC. Both air-dried-rehydrated and never-dried Ca-PC expanded to approximately 2.0 nm in 10 mM CaCl2 and both samples had similar affinities for atrazine that were slightly lower than that of never-dried K-PC. The importance of interlayer hydration status in controlling sorption affinity was confirmed by molecular modeling, which revealed much greater interaction between interlayer water molecules and atrazine in a three-layer hydrate relative to a one-layer hydrate. The entropy change on moving atrazine from a fully hydrated state in the bulk solution to a partially hydrated state in the smectite interlayers is believed to be a major factor influencing sorption affinity. In an application test, choice of background solution (20 mM KCl versus 10 mM CaCl2) and air-drying treatments significantly affected atrazine sorption affinities for three-smectitic soils; however, the trends were not consistent with those observed for the reference smectite. Further, extending the initial rehydration time from 24 to 240 h (prior to adding atrazine) significantly decreased the soil's sorption affinity for atrazine. We conclude that interlayer

Hydration Phase Diagram of Clay Particles from Molecular Simulations.

Science.gov (United States)

Honorio, Tulio; Brochard, Laurent; Vandamme, Matthieu

2017-11-07

Adsorption plays a fundamental role in the behavior of clays. Because of the confinement between solid clay layers on the nanoscale, adsorbed water is structured in layers, which can occupy a specific volume. The transition between these states is intimately related to key features of clay thermo-hydro-mechanical behavior. In this article, we consider the hydration states of clays as phases and the transition between these states as phase changes. The thermodynamic formulation supporting this idea is presented. Then, the results from grand canonical Monte Carlo simulations of sodium montmorillonite are used to derive hydration phase diagrams. The stability analysis presented here explains the coexistence of different hydration states at clay particle scale and improves our understanding of the irreversibilities of clay thermo-hydro-mechanical behavior. Our results provide insights into the mechanics of the elementary constituents of clays, which is crucial for a better understanding of the macroscopic behavior of clay-rich rocks and soils.

Effects of Nanosilica on Early Age Stages of Cement Hydration

Directory of Open Access Journals (Sweden)

Forood Torabian Isfahani

2017-01-01

Full Text Available Effects of nanosilica on cement hydration have been broadly investigated in the literature and early age cement hydration, as a whole, has been mainly considered, disregarding the substages of the hydration. The hydration of cement is characterized by different substages and nanosilica effect on the hydration could be a result of diverse, even contradictory, behavior of nanosilica in individual stages of the hydration. In this study, effects of nanosilica on different substages of cement hydration are investigated. Isothermal calorimetry results show that at early ages (initial 72 hours the effects of nanosilica depend on the phenomenon by which the hydration is governed: when the hydration is chemically controlled, that is, during initial reaction, dormant period, and acceleratory period, the hydration rate is accelerated by adding nanosilica; when the hydration is governed by diffusion process, that is, during postacceleratory period, the hydration rate is decelerated by adding nanosilica. The Thermal Gravimetric Analysis on the samples at the hardened state (after 28 days of curing reveals that, after adding nanosilica, the hydration degree slightly increased compared to the plain paste.

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

Magnetic behavior of cobalt bromide hydrates including a deuterated form

Energy Technology Data Exchange (ETDEWEB)

DeFotis, G.C., E-mail: gxdefo@wm.edu; Hampton, A.S.; Van Dongen, M.J.; Komatsu, C.H.; DeSanto, C.L.; Davis, C.M.

2017-04-15

The magnetic properties of little examined CoBr{sub 2}• 2H{sub 2}O and new CoBr{sub 2}• H{sub 2}O and CoBr{sub 2}• D{sub 2}O are studied. Curie-Weiss fits, χ{sub M}=C/(T-θ), yield θ of −9.9, 9.4 and 10.0 K, respectively, over a 30–80 K linear range for each. Higher temperature data are fit assuming two moderately separated low lying Kramers doublets, with exchange accounted for in a mean-field approximation. Susceptibility maxima appear at 9.5, 15.4 and 15.5 K, with χ{sub max} of 0.163, 0.375 and 0.435 emu/mol, respectively. Antiferromagnetic ordering is estimated to occur at 9.0, 13.7 and 13.8 K, in the same order. The ratio T{sub c}/T{sub max} is 0.95, 0.89 and 0.89, respectively, suggesting little low dimensional magnetic character in singly hydrated systems. Data at lower temperatures for the dihydrate are fit with an antiferromagnetic 3D-Ising model. For singly hydrated systems the large size of χ{sub max} prevents this; weakened interchain antiferromagnetic interactions yield enhanced susceptibility maxima. Magnetization data exhibit field induced transitions near 13.5 kG for the dihydrate, and near 6.5 kG for singly hydrated systems with enhanced hysteresis. These transitions are interpreted as metamagnetic in nature. - Highlights: • CoBr{sub 2}• 2H{sub 2}O has a larger susceptibility maximum at lower temperature than CoCl{sub 2}• 2H{sub 2}O. • Enhanced antiferromagnetic susceptibility maxima occur in CoBr{sub 2}·H{sub 2}O and CoBr{sub 2}• D{sub 2}O. • Metamagnetic transitions occur at much lower fields in monohydrates than dehydrate. • Interchain antiferromagnetic exchange is weaker in monohydrates than dehydrate. • CoBr{sub 2}• H{sub 2}O exhibit spin glass behavior similar to that seen previously in CoCl{sub 2}·H{sub 2}O.

Tc and Re Behavior in Borosilicate Waste Glass Vapor Hydration Tests

International Nuclear Information System (INIS)

McKeown, David A.; Buechele, Andrew C.; Pegg, Ian L.; Lukens, Wayne W.; Shuh, David K.

2007-01-01

Technetium (Tc), found in some nuclear wastes, is of particular concern with regard to long-term storage, because of its long-lived radioactivity and high mobility in the environment. Tc and rhenium (Re), commonly used as a non-radioactive surrogate for Tc, were studied to assess their behavior in borosilicate glass under hydrothermal conditions in the Vapor Hydration Test (VHT). X-ray absorption spectroscopy (XAS) and scanning electron microscopy (SEM) measurements were made on the original Tc- and Re-containing glasses and their corresponding VHT samples, and show different behavior for Tc and Re under VHT conditions. XAS indicates that, despite starting with different Tc(IV) and Tc(VII) distributions in each glass, the VHT samples have 100% Tc(IV)O 6 environments. SEM shows complete alteration of the original glass, Tc enrichment near the sample surface, and Tc depletion in the center. Perrhenate (Re(VII)O 4 - ) is dominant in both Re-containing samples before and after the VHT, where Re is depleted near the VHT sample surface and more concentrated toward the center. (authors)

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.

Dissolution mechanisms of CO2 hydrate droplets in deep seawaters

International Nuclear Information System (INIS)

Gabitto, Jorge; Tsouris, Costas

2006-01-01

Carbon dioxide dissolution at intermediate ocean depths was studied using physical and mass transfer models. Particle density and hydrate layer thickness were determined using existing field data. Pseudo-homogeneous and heterogeneous mass transfer models were proposed to study the dissolution process. Pseudo-homogeneous models do not seem to represent the dissolution process well. Although heterogeneous models interpret the physical behavior better, unresolved issues related to hydrate dissolution still remain. For example, solid hydrate forms on one side of the hydrate film while it dissolves on the other. Dissolution is a complex process that comprises at least two sequential steps. The global process is controlled by mass transfer inside the hydrate layer or by a dissolution reaction at the hydrate-water interface

Origins of saccharide-dependent hydration at aluminate, silicate, and aluminosilicate surfaces.

Science.gov (United States)

Smith, Benjamin J; Rawal, Aditya; Funkhouser, Gary P; Roberts, Lawrence R; Gupta, Vijay; Israelachvili, Jacob N; Chmelka, Bradley F

2011-05-31

Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state (1)H, (13)C, (29)Si, and (27)Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications.

Hydrate thermal dissociation behavior and dissociation enthalpies in methane-carbon dioxide swapping process

DEFF Research Database (Denmark)

Mu, Liang; von Solms, Nicolas

2018-01-01

The swapping of methane with carbon dioxide in hydrate has been proposed as a potential strategy for geologic sequestration of carbon dioxide and production of methane from natural hydrate deposits. However, this strategy requires a better understanding of the thermodynamic characteristics of CH4...... and CO2 hydrate as well as (CH4 + CO2) or (CH4 + CO2 + N2) mixed hydrates (since (CO2 + N2) gas mixture is often used as the swapping gas), along with the thermal physics property changes during gas exchange. In this study, a high pressure micro-differential scanning calorimetry (HP μ-DSC) was performed...

3D Finite Element Modeling for Possible Creeping Behavior of Gas Hydrate-related Slipstream Submarine Slide, offshore Vancouver Island, Canada

Science.gov (United States)

LONG, S.; He, T.; Lan, K.; Spence, G.; Yelisetti, S.

2017-12-01

Natural gas hydrate-related submarine landslides have been identified on worldwide continental slope. Being a potential risk for marine environment and engineering projects, it has been a hot topic of hydrate research in recent decades. The study target is Slipstream submarine landslide, one of the slope failures on the frontal ridges of the Northern Cascadia accretionary margin, off Vancouver Island, Canada. The previous studies of P- & S-wave velocity structure based on OBS (Ocean Bottom Seismometer) data of SeaJade (Seafloor Earthquake Array - Japan Canada Cascadia Experiment) project indicated that there are two high concentration gas-hydrate layers within the ridge, one is at a depth of 100 mbsf (meter beneath the seafloor) with anomalous high P-wave velocities and the other is just above the prominent BSR (bottom-simulating reflector) at a depth of 265-275 mbsf. In this study we investigated the possible creeping behavior of gas hydrate layer to examine the critical instability of the ridge slope using the finite element method for self weight and additional stress (e.g., mega earthquake) conditions. The elastic and elasticoplasticity moduli of gas hydrate layer were obtained from laboratory measurements for different uniaxial pressure tests, which indicated that the sediments behave elastically for uniaxial pressures below 6 MPa, but elasticoplastically between 6-6.77 MPa. The modeled shear stress distribution indicated that the current sliding surface is more likely connected with the shallow high-velocity gas hydrate layer and sliding process related with gas hydrate starts from the toe of the slope and then progressively retreats to the place of current headwall, in a series of triangular blocks or wedges. Since the study area is in the earthquake belt, the large seismic acceleration will greatly affect the stress field and pore pressure distribution within the ridge, and the landslide is going to happen and supposedly at the shallow high-velocity gas

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.

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

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Donn McGuire; Steve Runyon; Richard Sigal; Bill Liddell; Thomas Williams; George Moridis

2005-02-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. Hot Ice No. 1 was planned to test the Ugnu and West Sak sequences for gas hydrates and a concomitant free gas accumulation on Anadarko's 100% working interest acreage in section 30 of Township 9N, Range 8E of the Harrison Bay quadrangle of the North Slope of Alaska. The Ugnu and West Sak intervals are favorably positioned in the hydrate-stability zone over an area extending from Anadarko's acreage westward to the vicinity of the aforementioned gas-hydrate occurrences. This suggests that a large, north-to-south trending gas-hydrate accumulation may exist in that area. The presence of gas shows in the Ugnu and West Sak reservoirs in wells situated eastward and down dip of the Hot Ice location indicate that a free-gas accumulation may be trapped by gas hydrates. The Hot Ice No. 1 well was designed to core from the surface to the base of the West Sak interval using the

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Thomas E. Williams; Keith Millheim; Bill Liddell

2005-03-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Oil-field engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in Arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored the HOT ICE No. 1 on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was designed, constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. Unfortunately, no gas hydrates were encountered in this well; however, a wealth of information was generated

Temporal behavior of hydrated electron studied up to 400 deg. C by ultrafast pulse radiolysis and Monte Carlo calculation

International Nuclear Information System (INIS)

Katsumura, Yosuke; Muroya, Yusa; Lin, Mingzhang; Yu, Yan; Mehran, Mostafavi; Sanguanmith, Sunuchakan; Meesungnoen, Jintana; Jay-Gerin, Jean-Paul

2012-09-01

Pulse radiolysis is a very powerful and unique method to observe the transient species and to determine their yields and has been widely used up to now. Since the radiation-induced reactions at elevated temperatures are accelerated, precise measurement becomes difficult by the conventional pulse radiolysis systems. Then, a higher time resolved pulse radiolysis system is highly expected. Recently, an ultrafast pulse radiolysis system has been developed in the University of Tokyo and applied to water radiolysis at elevated temperatures [1]. Temporal behavior of the hydrated electron at elevated temperatures up to 400 deg C has been detected. The time dependent behavior of hydrated electron at elevated temperatures were detected and the latest version of the Monte Carlo simulation code developed at University of Sherbrooke was applied to reproduce the experimental results. From the simulation, it was made clear that the thermalization distance becomes smaller with increasing temperature. In addition, in supercritical water, the initial yield is significantly dependent on density (pressure), which is consistent with our previous evaluation. (authors)

Modeling Nanomechanical Behavior of Calcium-Silicate-Hydrate

Science.gov (United States)

2012-08-01

coefficient is effective in making the C-S-H matrix stronger. However, increasing packing density also makes the material response more brittle ...16102-16107 Pellenq, R.J. –M and Van Damme, Henri., 2004, Why Does Concrete set?: The nature of Cohesion Forces in hardened Cement-Based...Hydrated Nanocomposites: Concrete, Bone , and Shale. J. Am. Ceram. Soc., 90(9): 2677-2692. Wu, Jianzhong. and John M. Prausnitz. 2002. Generalizations for

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

KAUST Repository

Sá nchez, Marcelo; Gai, Xuerui; Santamarina, Carlos

2016-01-01

, 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

A unified approach for description of gas hydrate formation kinetics in the presence of kinetic promoters in gas hydrate converters

International Nuclear Information System (INIS)

ZareNezhad, Bahman; Varaminian, Farshad

2013-01-01

Highlights: • A unified kinetic model for description of promoted and non-promoted gas hydrate formation processes is presented. • Effects of impeller speed, promoter concentration and different kinetic promoters are investigated. • A unique region of gas hydrate formation is identified regarding gas hydrate formation processes. • The proposed model is useful for understanding the behavior of gas hydrate formation processes and design of GTH converters. - Abstract: The kinetic promoters have found wide applications in enhancing the rate of energy conversion and storage via gas hydrate formation processes. Effects of different kinetic promoters such as anionic surfactants sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid (DBSA), and sodium dodecyl benzene sulfonate (SDBS); cationic surfactants, Cetyl trimethyl ammonium bromide (CTAB), dodecyl trimethyl ammonium bromide (DTAB) and non-ionic surfactants, alkylpolyglucoside (APG), dodecyl polysaccharide glycoside (DPG), TritonX-100 (TX100) on methane (CH 4 ), ethane (C 2 H 6 ) and propane (C 3 H 8 ) gas hydrate formation processes are investigated in this work. A macroscopic kinetic model based on the time variations of reaction chemical potential is also presented for global description of gas hydrate formation processes. Experimental gas hydrate formation data are employed to validate the proposed kinetic model. Effects of promoter’s concentrations and agitation intensities on the gas consumption profiles are also investigated. A universal correlation and a unified kinetic map have been proposed for macroscopic description of gas hydrate formation kinetics in the presence or absence of kinetic promoters. According to the presented unified kinetic map, a unique region of gas hydrate formation is identified for the first time. For negligible amounts of kinetic promoters, the presented region disappears and approaches to a unique path at high agitation intensities. The presented unified approach is

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

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

Fibrillar structure and elasticity of hydrating collagen: a quantitative multiscale approach.

Science.gov (United States)

Morin, Claire; Hellmich, Christian; Henits, Peter

2013-01-21

It is well known that hydration of collagenous tissues leads to their swelling, as well as to softening of their elastic behavior. However, it is much less clear which microstructural and micromechanical "rules" are involved in this process. Here, we develop a theoretical approach cast in analytical mathematical formulations, which is experimentally validated by a wealth of independent tests on collagenous tissues, such as X-ray diffraction, vacuum drying, mass measurements, and Brillouin light scattering. The overall emerging picture is the following: air-drying leaves water only in the gap zones between the triple-helical collagen molecules; upon re-hydration, the extrafibrillar space is established at volumes directly proportional to the hydration-induced swelling of the (micro) fibrils, until the maximum equatorial distance between the long collagen molecules is reached. Thereafter, the volume of the fibrils stays constant, and only the extrafibrillar volume continues to grow. At all these hydration stages, the elastic behavior is governed by the same, hydration-invariant mechanical interaction pattern of only two, interpenetrating mechanical phases: transversely isotropic molecular collagen and isotropic water (or empty pores in the vacuum-dried case). Copyright © 2012 Elsevier Ltd. All rights reserved.

Hydration mechanism and leaching behavior of bauxite-calcination-method red mud-coal gangue based cementitious materials

International Nuclear Information System (INIS)

Zhang, Na; Li, Hongxu; Liu, Xiaoming

2016-01-01

Highlights: • Nanocrystalline regions in size of ∼5 nm were found in the amorphous C-A-S-H gel. • A hydration model was proposed to clarify the hydration mechanism. • The developed cementitious materials are environmentally acceptable. - Abstract: A deep investigation on the hydration mechanism of bauxite-calcination-method red mud-coal gangue based cementitious materials was conducted from viewpoints of hydration products and hydration heat analysis. As a main hydration product, the microstructure of C-A-S-H gel was observed using high resolution transmission electron microscopy. It was found that the C-A-S-H gel is composed of amorphous regions and nanocrystalline regions. Most of regions in the C-A-S-H gel are amorphous with continuous distribution, and the nanocrystalline regions on scale of ∼5 nm are dispersed irregularly within the amorphous regions. The hydration heat of red mud-coal gangue based cementitious materials is much lower than that of the ordinary Portland cement. A hydration model was proposed for this kind of cementitious materials, and the hydration process mainly consists of four stages which are dissolution of materials, formation of C-A-S-H gels and ettringite, cementation of hydration products, and polycondensation of C-A-S-H gels. There are no strict boundaries among these four basic stages, and they proceed crossing each other. Moreover, the leaching toxicity tests were also performed to prove that the developed red mud-coal gangue based cementitious materials are environmentally acceptable.

Hydration mechanism and leaching behavior of bauxite-calcination-method red mud-coal gangue based cementitious materials

Energy Technology Data Exchange (ETDEWEB)

Zhang, Na; Li, Hongxu [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory of Rare and Precious Metals Green Recycling and Extraction, University of Science and Technology Beijing, Beijing 100083 (China); Liu, Xiaoming, E-mail: liuxm@ustb.edu.cn [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory of Rare and Precious Metals Green Recycling and Extraction, University of Science and Technology Beijing, Beijing 100083 (China)

2016-08-15

Highlights: • Nanocrystalline regions in size of ∼5 nm were found in the amorphous C-A-S-H gel. • A hydration model was proposed to clarify the hydration mechanism. • The developed cementitious materials are environmentally acceptable. - Abstract: A deep investigation on the hydration mechanism of bauxite-calcination-method red mud-coal gangue based cementitious materials was conducted from viewpoints of hydration products and hydration heat analysis. As a main hydration product, the microstructure of C-A-S-H gel was observed using high resolution transmission electron microscopy. It was found that the C-A-S-H gel is composed of amorphous regions and nanocrystalline regions. Most of regions in the C-A-S-H gel are amorphous with continuous distribution, and the nanocrystalline regions on scale of ∼5 nm are dispersed irregularly within the amorphous regions. The hydration heat of red mud-coal gangue based cementitious materials is much lower than that of the ordinary Portland cement. A hydration model was proposed for this kind of cementitious materials, and the hydration process mainly consists of four stages which are dissolution of materials, formation of C-A-S-H gels and ettringite, cementation of hydration products, and polycondensation of C-A-S-H gels. There are no strict boundaries among these four basic stages, and they proceed crossing each other. Moreover, the leaching toxicity tests were also performed to prove that the developed red mud-coal gangue based cementitious materials are environmentally acceptable.

Modeling dissociation behaviour of methane hydrate in porous soil media

Energy Technology Data Exchange (ETDEWEB)

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

2008-07-01

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

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Ali Kadaster; Bill Liddell; Tommy Thompson; Thomas Williams; Michael Niedermayr

2005-02-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project was a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and implemented for determining physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. Final efforts of the project are to correlate geology, geophysics, logs, and drilling and

Effects of Geomechanical Mechanism on the Gas Production Behavior: A Simulation Study of Class-3 Type Four-Way-Closure Ridge Hydrate Deposit Offshore Southwestern Taiwan

Science.gov (United States)

Wu, Cheng-Yueh; Chiu, Yung-Cheng; Huang, Yi-Jyun; Hsieh, Bieng-Zih

2017-04-01

The future energy police of Taiwan will heavily rely on the clean energy, including renewable energy and low-carbon energy, to meet the target of mitigating CO2 emission. In addition to developing the renewable energies like solar and wind resources, Taiwan will increase the natural gas consumption to obtain enough electrical power with low-carbon emission. The vast resources of gas hydrates recognized in southwestern offshore Taiwan makes a great opportunity for Taiwan to have own energy resources in the future. Therefore, Taiwan put significant efforts on the evaluation of gas hydrate reserves recently. Production behavior of natural gas dissociated from gas hydrate deposits is an important issue to the hydrate reserves evaluation. The depressurization method is a useful engineering recovery method for gas production from a class-3 type hydrate deposit. The dissociation efficiency will be affected by the pressure drawdown disturbance. However, when the pore pressure of hydrate deposits is depressurized for gas production, the rock matrix will surfer more stresses and the formation deformation might be occurred. The purpose of this study was to investigate the effects of geomechanical mechanism on the gas production from a class-3 hydrate deposit using depressurization method. The case of a class-3 type hydrate deposit of Four-Way-Closure Ridge was studied. In this study a reservoir simulator, STARS, was used. STARS is a multiphase flow, heat transfer, geo-chemical and geo-mechanical mechanisms coupling simulator which is capable to simulate the dissociation/reformation of gas hydrate and the deformation of hydrate reservoirs and overburdens. The simulating ability of STARTS simulator was validated by duplicating the hydrate comparison projects of National Energy Technology Lab. The study target, Four-Way-Closure (FWC) Ridge hydrate deposit, was discovered by the bottom simulating reflectors (BSRs). The geological parameters were collected from the geological and

Observation of interstitial molecular hydrogen in clathrate hydrates.

Science.gov (United States)

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

2014-09-26

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

The application of thermal analysis, XRD and SEM to study the hydration behavior of tricalcium silicate in the presence of a polycarboxylate superplasticizer

International Nuclear Information System (INIS)

Liu, Ming; Lei, Jiaheng; Guo, Liping; Du, Xiaodi; Li, Junsheng

2015-01-01

Highlights: • The initial hydration process of C 3 S is markedly retarded by PC. • The decomposition temperature of Ca(OH) 2 is slightly lower after PC modification. • The adsorption amount of PC on C 3 S increases progressively with the hydration time. • The size of Ca(OH) 2 crystals are changed due to the adsorption of PC. - Abstract: Hydration behavior of tricalcium silicate (C 3 S) in the presence of a polycarboxylate (PC) superplasticizer was investigated by means of isothermal calorimetry, differential thermal analysis and X-ray diffraction. In addition, the adsorption characteristics of PC and morphology change of Ca(OH) 2 crystals were also examined, respectively. The results showed that initial hydration process of C 3 S was markedly retarded by PC and the retardation effect depended on the dosage of PC. The decomposition temperature of the Ca(OH) 2 was slightly lower after PC modification. Moreover, the size of Ca(OH) 2 crystals were found to be changed due to the adsorption of PC. The results obtained in this research allowed us to gain insights into the interactions between PC and cement

Experimental investigation into methane hydrate production during three-dimensional thermal stimulation with five-spot well system

International Nuclear Information System (INIS)

Wang, Yi; Li, Xiao-Sen; Li, Gang; Zhang, Yu; Li, Bo; Chen, Zhao-Yang

2013-01-01

Highlights: • The production behaviors of methane hydrate are obtained in the 3-D simulator. • The thermal stimulation method with a five-spot well is used for hydrate production. • The water and gas production, efficiency, recovery, production rate are analyzed. • The effect of injection rate change on the production behavior is investigated. - Abstract: The cubic hydrate simulator (CHS) is used to study the methane hydrate production behaviors in porous media by the thermal stimulation with a five-spot well system. The hot water injection rates range from 10.0 to 40.0 ml/min. The thermal stimulation process is analyzed, and the conclusions are that the hydrate decomposition boundary moves from the central point to the surroundings gradually and finally covers almost the entire hydrate field in the CHS during the thermal stimulation process. The heat conduction plays a more significant role than the convection for the heat diffusion in the thermal stimulation process. The increasing injection rate of the hot water enhances the rate of hydrate decomposition, shortens the production time, and decreases the water production volumes, while it has little influence on the final gas production volumes. Furthermore, the change of the hot water injection rate (R inj ) has little influence on the final gas recovery, however, the higher R inj leads to the higher average production rate and the lower energy efficiency

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

Challenges, uncertainties and issues facing gas production from gas hydrate deposits

Energy Technology Data Exchange (ETDEWEB)

Moridis, G.J.; Collett, T.S.; Pooladi-Darvish, M.; Hancock, S.; Santamarina, C.; Boswell, R.; Kneafsey, T.; Rutqvist, J.; Kowalsky, M.; Reagan, M.T.; Sloan, E.D.; Sum, A.K.; Koh, C.

2010-11-01

The current paper complements the Moridis et al. (2009) review of the status of the effort toward commercial gas production from hydrates. We aim to describe the concept of the gas hydrate petroleum system, to discuss advances, requirement and suggested practices in gas hydrate (GH) prospecting and GH deposit characterization, and to review the associated technical, economic and environmental challenges and uncertainties, including: the accurate assessment of producible fractions of the GH resource, the development of methodologies for identifying suitable production targets, the sampling of hydrate-bearing sediments and sample analysis, the analysis and interpretation of geophysical surveys of GH reservoirs, well testing methods and interpretation of the results, geomechanical and reservoir/well stability concerns, well design, operation and installation, field operations and extending production beyond sand-dominated GH reservoirs, monitoring production and geomechanical stability, laboratory investigations, fundamental knowledge of hydrate behavior, the economics of commercial gas production from hydrates, and the associated environmental concerns.

Hydration of urea and alkylated urea derivatives

Science.gov (United States)

Kaatze, Udo

2018-01-01

Compressibility data and broadband dielectric spectra of aqueous solutions of urea and some of its alkylated derivatives have been evaluated to yield their numbers Nh of hydration water molecules per molecule of solute. Nh values in a broad range of solute concentrations are discussed and are compared to hydration numbers of other relevant molecules and organic ions. Consistent with previous results, it is found that urea differs from other solutes in its unusually small hydration number, corresponding to just one third of the estimated number of nearest neighbor molecules. This remarkable hydration behavior is explained by the large density φH of hydrogen bonding abilities offered by the urea molecule. In terms of currently discussed models of reorientational motions and allied dynamics in water and related associating liquids, the large density φH causes a relaxation time close to that of undisturbed water with most parts of water encircling the solute. Therefore only a small part of disturbed ("hydration") water is left around each urea molecule. Adding alkyl groups to the basic molecule leads to Nh values which, within the series of n-alkylurea derivatives, progressively increase with the number of methyl groups per solute. With n-butylurea, Nh from dielectric spectra, in conformity with many other organic solutes, slightly exceeds the number of nearest neighbors. Compared to such Nh values, hydration numbers from compressibility data are substantially smaller, disclosing incorrect assumptions in the formula commonly used to interpret the experimental compressibilities. Similar to other series of organic solutes, effects of isomerization have been found with alkylated urea derivatives, indicating that factors other than the predominating density φH of hydrogen bond abilities contribute also to the hydration properties.

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.

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.

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...

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

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.

Modeling of Hydrate Formation Mode in Raw Natural Gas Air Coolers

Science.gov (United States)

Scherbinin, S. V.; Prakhova, M. Yu; Krasnov, A. N.; Khoroshavina, E. A.

2018-05-01

Air cooling units (ACU) are used at all the gas fields for cooling natural gas after compressing. When using ACUs on raw (wet) gas in a low temperature condition, there is a danger of hydrate plug formation in the heat exchanging tubes of the ACU. To predict possible hydrate formation, a mathematical model of the air cooler thermal behavior used in the control system shall adequately calculate not only gas temperature at the cooler's outlet, but also a dew point value, a temperature at which condensation, as well as the gas hydrate formation point, onsets. This paper proposes a mathematical model allowing one to determine the pressure in the air cooler which makes hydrate formation for a given gas composition possible.

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.

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

nature of the guest molecule caused a different behavior during the dissociation. The CO{sub 2} hydrate was more stable than the CH{sub 4} hydrate, however, this dissociation trend was inverted when CO{sub 2} and CH{sub 4} were transformed into hydrates in the presence of THF . 28 refs., 2 tabs., 14 figs.

Challenges, uncertainties, and issues facing gas production from gas-hydrate deposits

Science.gov (United States)

Moridis, G.J.; Collett, T.S.; Pooladi-Darvish, M.; Hancock, S.; Santamarina, C.; Boswel, R.; Kneafsey, T.; Rutqvist, J.; Kowalsky, M.B.; Reagan, M.T.; Sloan, E.D.; Sum, A.K.; Koh, C.A.

2011-01-01

The current paper complements the Moridis et al. (2009) review of the status of the effort toward commercial gas production from hydrates. We aim to describe the concept of the gas-hydrate (GH) petroleum system; to discuss advances, requirements, and suggested practices in GH prospecting and GH deposit characterization; and to review the associated technical, economic, and environmental challenges and uncertainties, which include the following: accurate assessment of producible fractions of the GH resource; development of methods for identifying suitable production targets; sampling of hydrate-bearing sediments (HBS) and sample analysis; analysis and interpretation of geophysical surveys of GH reservoirs; well-testing methods; interpretation of well-testing results; geomechanical and reservoir/well stability concerns; well design, operation, and installation; field operations and extending production beyond sand-dominated GH reservoirs; monitoring production and geomechanical stability; laboratory investigations; fundamental knowledge of hydrate behavior; the economics of commercial gas production from hydrates; and associated environmental concerns. ?? 2011 Society of Petroleum Engineers.

The Dependence of Water Permeability in Quartz Sand on Gas Hydrate Saturation in the Pore Space

Science.gov (United States)

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

2018-02-01

Transport of fluids in gas hydrate bearing sediments is largely defined by the reduction of the permeability due to gas hydrate crystals in the pore space. Although the exact knowledge of the permeability behavior as a function of gas hydrate saturation is of crucial importance, state-of-the-art simulation codes for gas production scenarios use theoretically derived permeability equations that are hardly backed by experimental data. The reason for the insufficient validation of the model equations is the difficulty to create gas hydrate bearing sediments that have undergone formation mechanisms equivalent to the natural process and that have well-defined gas hydrate saturations. We formed methane hydrates in quartz sand from a methane-saturated aqueous solution and used magnetic resonance imaging to obtain time-resolved, three-dimensional maps of the gas hydrate saturation distribution. These maps were fed into 3-D finite element method simulations of the water flow. In our simulations, we tested the five most well-known permeability equations. All of the suitable permeability equations include the term (1-SH)n, where SH is the gas hydrate saturation and n is a parameter that needs to be constrained. The most basic equation describing the permeability behavior of water flow through gas hydrate bearing sand is k = k0 (1-SH)n. In our experiments, n was determined to be 11.4 (±0.3). Results from this study can be directly applied to bulk flow analysis under the assumption of homogeneous gas hydrate saturation and can be further used to derive effective permeability models for heterogeneous gas hydrate distributions at different scales.

Effects of lithium nitrate admixture on early-age cement hydration

International Nuclear Information System (INIS)

Millard, M.J.; Kurtis, K.E.

2008-01-01

Although the benefits of lithium admixtures for mitigation of alkali-silica reaction (ASR) have been well documented, the potential ancillary effects of lithium compounds on cement and concrete remain largely uncharacterized. To examine the effects of the most common lithium admixture - lithium nitrate - on early-age behavior, the admixture was introduced at dosages of 0% to 400% of the recommended dosage to six cements of varying composition and to a cement-fly ash blend. Behavior was examined by isothermal calorimetry and measurements of chemical shrinkage, autogenous shrinkage, and setting time. Results indicate that lithium nitrate accelerates the early hydration of most cements but may retard hydration after 24 h. In the lowest alkali cement tested, set times were shortened in the presence of lithium nitrate by 15-22%. Higher dosages appeared to increase autogenous shrinkage after 40 days. The replacement of cement by Class F fly ash at 20% by weight appeared to diminish the early acceleration effects, but later hydration retardation and autogenous shrinkage were still observed

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

Science.gov (United States)

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

2013-07-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-12-14

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

Failure of cement hydrates: freeze-thaw and fracture

Science.gov (United States)

Ioannidou, Katerina; Del Gado, Emanuela; Ulm, Franz-Josef; Pellenq, Roland

Mechanical and viscoelastic behavior of concrete crucially depends on cement hydrates, the ``glue'' of cement. Even more than the atomistic structure, the mesoscale amorphous texture of cement hydrates over hundreds of nanometers plays a crucial role for material properties. We use simulations that combine information of the nano-scale building units of cement hydrates and on their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles.Our mesoscale model was able to reconcile different experimental results ranging from small-angle neutron scattering, SEM, adsorption/desorption of N2, and water to nanoindentation and gain the new fundamental insights into the microscopic origin of the properties measured. Our results suggest that heterogeneities developed during the early stages of hydration persist in the structure of C-S-H, impacting the rheological and mechanical performance of the hardened cement paste. In this talk I discuss recent investigation on failure mechanism at the mesoscale of hardened cement paste such as freeze-thaw and fracture. Using correlations between local volume fractions and local stress we provide a link between structural and mechanical heterogeneities during the failure mechanisms.

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.

Rapid Prototyping Amphiphilic Polymer/Hydroxyapatite Composite Scaffolds with Hydration-Induced Self-Fixation Behavior

Science.gov (United States)

Kutikov, Artem B.; Gurijala, Anvesh

2015-01-01

Two major factors hampering the broad use of rapid prototyped biomaterials for tissue engineering applications are the requirement for custom-designed or expensive research-grade three-dimensional (3D) printers and the limited selection of suitable thermoplastic biomaterials exhibiting physical characteristics desired for facile surgical handling and biological properties encouraging tissue integration. Properly designed thermoplastic biodegradable amphiphilic polymers can exhibit hydration-dependent hydrophilicity changes and stiffening behavior, which may be exploited to facilitate the surgical delivery/self-fixation of the scaffold within a physiological tissue environment. Compared to conventional hydrophobic polyesters, they also present significant advantages in blending with hydrophilic osteoconductive minerals with improved interfacial adhesion for bone tissue engineering applications. Here, we demonstrated the excellent blending of biodegradable, amphiphilic poly(D,L-lactic acid)-poly(ethylene glycol)-poly(D,L-lactic acid) (PLA-PEG-PLA) (PELA) triblock co-polymer with hydroxyapatite (HA) and the fabrication of high-quality rapid prototyped 3D macroporous composite scaffolds using an unmodified consumer-grade 3D printer. The rapid prototyped HA-PELA composite scaffolds and the PELA control (without HA) swelled (66% and 44% volume increases, respectively) and stiffened (1.38-fold and 4-fold increases in compressive modulus, respectively) in water. To test the hypothesis that the hydration-induced physical changes can translate into self-fixation properties of the scaffolds within a confined defect, a straightforward in vitro pull-out test was designed to quantify the peak force required to dislodge these scaffolds from a simulated cylindrical defect at dry versus wet states. Consistent with our hypothesis, the peak fixation force measured for the PELA and HA-PELA scaffolds increased 6-fold and 15-fold upon hydration, respectively. Furthermore, we showed that

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.

Small-Angle Neutron Scattering Investigation of Growth Modifiers on Hydrate Crystal Surfaces

Science.gov (United States)

Sun, Thomas; Hutter, Jeffrey L.; Lin, M.; King, H. E., Jr.

1998-03-01

Hydrates are crystals consisting of small molecules enclathrated within an ice-like water cage. Suppression of their growth is important in the oil industry. The presence of small quantities of specific polymers during hydrate crystallization can induce a transition from an octahedral to planar growth habit. This symmetry breaking is surprising because of the suppression of two 111 planes relative to the other six crystallographically equivalent faces. To better understand the surface effects leading to this behavior, we have studied the surface adsorption of these growth-modifing polymers onto the hydrate crytals using SANS. The total hydrate surface area, as measured by Porod scattering, increases in the presence of the growth modifier, but, no significant increase in polymer concentration on the crystal surfaces is found. Implications for possible growth mechanisms will be discussed.

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.

[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.

Hydration Properties of Ground Granulated Blast-Furnace Slag (GGBS Under Different Hydration Environments

Directory of Open Access Journals (Sweden)

Shuhua LIU

2017-02-01

Full Text Available The hydration properties of various cementitious materials containing Ground Granulated Blast-furnace Slag (GGBS, two alkali-activated slag cements (AAS-1 and AAS-2 in which sodium silicate and sodium hydroxide act as alkaline activators respectively, supersulfated cement (SSC and slag Portland cement(PSC, are compared with ordinary Portland cement (OPC to investigate the effect of activating environment on the hydration properties in this study by determining the compressive strength of the pastes, the hydration heat of binders within 96 hours, and the hydration products at age of 28 days. The results show that C-S-H gels are the main hydrated products for all cementitious systems containing GGBS. Ca(OH2 is the hydration products of OPC and PSC paste. However, ettringite and gypsum crystals instead of Ca(OH2 are detected in SSC paste. Additionally, tobermorite, a crystalline C-S-H, and calcite are hydrated products in AAS-1. Tobermorite, cowlesite and calcite are hydrated products of AAS-2 as well. Based on strength results, AAS-1 paste exhibits the highest compressive strength followed by POC, PSC, SSC in order at all testing ages and AAS-2 give the lowest compressive strength except for the early age at 3 days, which is higher than SSC but still lower than PSC. From hydration heat analysis, alkalinity in the reaction solution is a vital factor influencing the initial hydration rate and the initial hydration rate from higher to lower is AAS-2, AAS-1, OPC, PSC and SSC. Although AAS possesses a faster reaction rate in the initial hours, cumulative hydration heat of AAS is comparably lower than that of OPC, but higher than those of PSC and SSC in turn, which indicates that the hydration heat of clinkers is much higher than that of slag.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14934

Hydration study of limestone blended cement in the presence of hazardous wastes containing Cr(VI)

International Nuclear Information System (INIS)

Trezza, M.A.; Ferraiuelo, M.F.

2003-01-01

Considering the increasing use of limestone cement manufacture, the present paper tends to characterize limestone behavior in the presence of Cr(VI). The research reported herein provides information regarding the effect of Cr(VI) from industrial wastes in the limestone cement hydration. The cementitious materials were ordinary Portland cement, as reference, and limestone blended cement. The hydration and physicomechanical properties of cementitious materials and the influence of chromium at an early age were studied with X-ray diffraction (XRD), infrared spectroscopy (FTIR), conductimetric and mechanical tests. Portland cement pastes with the addition of Cr(VI) were examined and leaching behavior with respect to water and acid solution were investigated. This study indicates that Cr(VI) modifies the rate and the components obtained during the cement hydration

QUANTUM MECHANICAL STUDY OF THE COMPETITIVE HYDRATION BETWEEN PROTONATED QUINAZOLINE AND LI+, NA+, AND CA2+ IONS

Science.gov (United States)

Hydration reactions are fundamental to many biological functions and environmental processes. The energetics of hydration of inorganic and organic chemical species influences their fate and transport behavior in the environment. In this study, gas-phase quantum mechanical calcula...

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

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

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

Effect of pulverization of the bulk powder on the hydration of creatine anhydrate tablets and their pharmaceutical properties.

Science.gov (United States)

Sakata, Yukoh; Shiraishi, Sumihiro; Otsuka, Makoto

2005-12-10

The hydration behavior and expansion properties of untreated and pulverized creatine anhydrate (CRA) tablets were studied under 60 and 75%RH at 25 degrees C by using differential scanning calorimetry (DSC), and powder X-ray diffraction (PXRD). The tablet hardness of untreated and pulverized CRA tablets was significantly decreased after hydration. There was a linear relationship between the degree of hydration and the tablet hardness of untreated CRA tablets compressed at 1000 kg/cm2. In contrast, the relationship between the degree of hydration and the tablet hardness of pulverized CRA tablets was nonlinear. These results suggest that the reduction in hardness of pulverized CRA tablets does not depend solely on the hydration level of crystal water. PXRD analysis indicated that the diffraction pattern of the pulverized CRA powder was similar to that of the untreated CRA powder. However, the diffraction intensity of the pulverized CRA powder was slightly lower than that of the untreated CRA powder at high angle. The micropore radius of both untreated and pulverized CRA tablets was significantly increased after hydration, but analysis of the relationship between micropore radius and fractional hydration of crystal water showed that untreated CRA tablets were more affected than pulverized CRA tablets. Therefore, the reduction in tablet hardness depends not only on the hydration behavior but also on the crystal orientation of the CRA powder.

Stochastic Approach to Determine CO2 Hydrate Induction Time in Clay Mineral Suspensions

Science.gov (United States)

Lee, K.; Lee, S.; Lee, W.

2008-12-01

A large number of induction time data for carbon dioxide hydrate formation were obtained from a batch reactor consisting of four independent reaction cells. Using resistance temperature detector(RTD)s and a digital microscope, we successfully monitored the whole process of hydrate formation (i.e., nucleation and crystal growth) and detected the induction time. The experiments were carried out in kaolinite and montmorillonite suspensions at temperatures between 274 and 277 K and pressures ranging from 3.0 to 4.0 MPa. Each set of data was analyzed beforehand whether to be treated by stochastic manner or not. Geochemical factors potentially influencing the hydrate induction time under different experimental conditions were investigated by stochastic analyses. We observed that clay mineral type, pressure, and temperature significantly affect the stochastic behavior of the induction times for CO2 hydrate formation in this study. The hydrate formation kinetics along with stochastic analyses can provide basic understanding for CO2 hydrate storage in deep-sea sediment and geologic formation, securing its stability under the environments.

Gas hydrate concentration and characteristics within Hydrate Ridge inferred from multicomponent seismic reflection data

Science.gov (United States)

Kumar, Dhananjay; Sen, Mrinal K.; Bangs, Nathan L.

2007-12-01

A seismic experiment composed of streamer and ocean bottom seismometer (OBS) surveys was conducted in the summer of 2002 at southern Hydrate Ridge, offshore Oregon, to map the gas hydrate distribution within the hydrate stability zone. Gas hydrate concentrations within the reservoir can be estimated with P wave velocity (Vp); however, we can further constrain gas hydrate concentrations using S wave velocity (Vs), and use Vs through its relationship to Vp (Vp/Vs) to reveal additional details such as gas hydrate form within the matrix (i.e., hydrate cements the grains, becomes part of the matrix frame or floats in pore space). Both Vp and Vs can be derived simultaneously by inverting multicomponent seismic data. In this study, we use OBS data to estimate seismic velocities where both gas hydrate and free gas are present in the shallow sediments. Once Vp and Vs are estimated, they are simultaneously matched with modeled velocities to estimate the gas hydrate concentration. We model Vp using an equation based on a modification of Wood's equation that incorporates an appropriate rock physics model and Vs using an empirical relation. The gas hydrate concentration is estimated to be up to 7% of the rock volume, or 12% of the pore space. However, Vp and Vs do not always fit the model simultaneously. Vp can vary substantially more than Vs. Thus we conclude that a model, in which higher concentrations of hydrate do not affect shear stiffness, is more appropriate. Results suggest gas hydrates form within the pore space of the sediments and become part of the rock framework in our survey area.

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.

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

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

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

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

2005-02-01

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

A 2D Micromodel Study of Fines Migration and Clogging Behavior in Porous Media: Implications of Fines on Methane Extraction from Hydrate-Bearing Sediments

Science.gov (United States)

Cao, S. C.; Jang, J.; Waite, W. F.; Jafari, M.; Jung, J.

2017-12-01

Fine-grained sediment, or "fines," exist nearly ubiquitously in natural sediment, even in the predominantly coarse-grained sediments that host gas hydrates. Fines within these sandy sediments can play a crucial role during gas hydrate production activities. During methane extraction, several processes can alter the mobility and clogging potential of fines: 1) fluid flow as the formation is depressurized to release methane from hydrate; 2) pore-fluid chemistry shifts as pore-fluid brine freshens due to pure water released from dissociating hydrate; 3) the presence of a moving gas/water interface as gas evolves from dissociating hydrate and moves through the reservoir toward the production well. To evaluate fines migration and clogging behavior changes resulting from methane gas production and pore-water freshening during hydrate dissociation, 2D micromodel experiments have been conducted on a selection of pure fines, pore-fluids, and micromodel pore-throat sizes. Additionally, tests have been run with and without an invading gas phase (CO2) to test the significance of a moving meniscus on fines mobility and clogging. The endmember fine particles chosen for this research include silica silt, mica, calcium carbonate, diatoms, kaolinite, illite, and bentonite (primarily made of montmorillonite). The pore fluids include deionized water, sodium chloride brine (2M concentration), and kerosene. The microfluidic pore models, used as porous media analogs, were fabricated with pore-throat widths of 40, 60, and 100 µm. Results from this research show that in addition to the expected dependence of clogging on the ratio of particle-to-pore-throat size, pore-fluid chemistry is also a significant factor because the interaction between a particular type of fine and pore fluid influences that fine's capacity to cluster, clump together and effectively increase its particle "size" relative to the pore-throat width. The presence of a moving gas/fluid meniscus increases the clogging

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.

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.

Optimization of linear and branched alkane interactions with water to simulate hydrophobic hydration

Science.gov (United States)

Ashbaugh, Henry S.; Liu, Lixin; Surampudi, Lalitanand N.

2011-08-01

Previous studies of simple gas hydration have demonstrated that the accuracy of molecular simulations at capturing the thermodynamic signatures of hydrophobic hydration is linked both to the fidelity of the water model at replicating the experimental liquid density at ambient pressure and an accounting of polarization interactions between the solute and water. We extend those studies to examine alkane hydration using the transferable potentials for phase equilibria united-atom model for linear and branched alkanes, developed to reproduce alkane phase behavior, and the TIP4P/2005 model for water, which provides one of the best descriptions of liquid water for the available fixed-point charge models. Alkane site/water oxygen Lennard-Jones cross interactions were optimized to reproduce the experimental alkane hydration free energies over a range of temperatures. The optimized model reproduces the hydration free energies of the fitted alkanes with a root mean square difference between simulation and experiment of 0.06 kcal/mol over a wide temperature range, compared to 0.44 kcal/mol for the parent model. The optimized model accurately reproduces the temperature dependence of hydrophobic hydration, as characterized by the hydration enthalpies, entropies, and heat capacities, as well as the pressure response, as characterized by partial molar volumes.

Overview: Nucleation of clathrate hydrates.

Science.gov (United States)

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

2016-12-07

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

Overview: Nucleation of clathrate hydrates

Science.gov (United States)

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

2016-12-01

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

Exogenous origin of hydration on asteroid (16) Psyche: the role of hydrated asteroid families

Science.gov (United States)

Avdellidou, C.; Delbo', M.; Fienga, A.

2018-04-01

Asteroid (16) Psyche, which for a long time was the largest M-type with no detection of hydration features in its spectrum, was recently discovered to have a weak 3-μm band and thus it was eventually added to the group of hydrated asteroids. Its relatively high density, in combination with the high radar albedo, led researchers to classify the asteroid as a metallic object. It is believed that it is possibly a core of a differentiated body, a remnant of `hit-and-run' collisions. The detection of hydration is, in principle, inconsistent with a pure metallic origin for this body. Here, we consider the scenario in which the hydration on its surface is exogenous and was delivered by hydrated impactors. We show that impacting asteroids that belong to families whose members have the 3-μm band can deliver hydrated material to Psyche. We developed a collisional model with which we test all dark carbonaceous asteroid families, which contain hydrated members. We find that the major source of hydrated impactors is the family of Themis, with a total implanted mass on Psyche of the order of ˜1014 kg. However, the hydrated fraction could be only a few per cent of the implanted mass, as the water content in carbonaceous chondrite meteorites, the best analogue for the Themis asteroid family, is typically a few per cent of their mass.

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

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.

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.

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.)

Characterization of un-hydrated and hydrated BioAggregate™ and MTA Angelus™.

Science.gov (United States)

Camilleri, J; Sorrentino, F; Damidot, D

2015-04-01

BioAggregate™ is a novel material introduced for use as a root-end filling material. It is tricalcium silicate-based, free of aluminium and uses tantalum oxide as radiopacifier. BioAggregate contains additives to enhance the material performance. The purpose of this research was to characterize the un-hydrated and hydrated forms of BioAggregate using a combination of techniques, verify whether the additives if present affect the properties of the set material and compare these properties to those of MTA Angelus™. Un-hydrated and hydrated BioAggregate and MTA Angelus were assessed. Un-hydrated cement was tested for chemical composition, specific surface area, mineralogy and kinetics of hydration. The set material was investigated for mineralogy, microstructure and bioactivity. Scanning electron microscopy, X-ray energy dispersive spectroscopic analysis, X-ray fluorescence spectroscopy, X-ray diffraction and isothermal calorimetry were employed. The specific surface area was investigated using a gas adsorption method with nitrogen as the probe. BioAggregate was composed of tricalcium silicate, tantalum oxide, calcium phosphate and silicon dioxide and was free of aluminium. On hydration, the tricalcium silicate produced calcium silicate hydrate and calcium hydroxide. The former was deposited around the cement grains, while the latter reacted with the silicon dioxide to form additional calcium silicate hydrate. This resulted in reduction of calcium hydroxide in the aged cement. MTA Angelus reacted in a similar fashion; however, since it contained no additives, the calcium hydroxide was still present in the aged cement. Bioactivity was demonstrated by deposition of hydroxyapatite. BioAggregate exhibited a high specific surface area. Nevertheless, the reactivity determined by isothermal calorimetry appeared to be slow compared to MTA Angelus. The tantalum oxide as opposed to bismuth oxide was inert, and tantalum was not leached in solution. BioAggregate exhibited

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.

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

Enthalpy of dissociation and hydration number of methane hydrate from the Clapeyron equation

International Nuclear Information System (INIS)

Anderson, Graydon K.

2004-01-01

The enthalpies of the reactions in which methane hydrate is dissociated to methane vapor and either (1) water, or (2) ice are determined by a new analysis using the Clapeyron equation. The difference in enthalpies of the two reactions is used to infer the hydration number at the quadruple point where hydrate, ice, liquid water, and methane vapor coexist. By appropriate corrections, the hydration number at points removed from the quadruple point is also determined. The most important feature of the new analysis is the direct use of the Clapeyron equation. The method avoids the use of certain simplifying assumptions that have compromised the accuracy of previous analyses in which the Clausius-Clapeyron equation was used. The analysis takes into account the finite volumes of all phases, the non-ideality of the vapor phase, and the solubility of methane in water. The results show that the enthalpy of dissociation and hydration number are constant within experimental error over the entire (hydrate, liquid, vapor) coexistence region. The results are more accurate than but entirely consistent with almost all previous studies

Accurate description of phase diagram of clathrate hydrates on molecular level

Energy Technology Data Exchange (ETDEWEB)

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

2008-07-01

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

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.

Hydrates on tap: scientists say natural gas hydrates may be tough nut to crack

Energy Technology Data Exchange (ETDEWEB)

Mahoney, J.

2001-12-01

Gas hydrates are methane molecules trapped in cages of water molecules, yielding a substance with a slushy, sherbet-like consistency. Drilling for hydrates is similar to conventional oil and gas drilling, however, the secret to economic production still remains hidden. Hydrates exist in abundance in such places as deep ocean floor and below ground in some polar regions. The real challenge lies in producing gas from this resource, inasmuch as there is no existing technology for production of gas specifically from methane hydrates. This paper describes an international research program, involving a five-country partnership to spud the first of three wells into the permafrost of the Mackenzie River Delta in the Northwest Territories. The project, worth about $15 million, has brought together public funding and expertise from Japan, Germany, India as well as the Canadian and US Geological Surveys and the US Dept. of Energy in an effort to gain information on the production response of gas hydrates. The operator of the project is Japan Petroleum Exploration Company of Canada, a subsidiary of Japan National Oil Corporation. Since Japan is poor in domestic hydrocarbon resources, but is surrounded by deep water that contains potential for gas hydrates, Japan has a great deal riding on the success of this project. Germany and the United States are also very much interested. Current thinking is that gas is in contact with the hydrates and that it should be possible to develop a free gas reservoir as if it were a conventional deposit. As the free gas is drawn off, the pressure is reduced on the hydrates in contact with it , the hydrates dissociate from the gas and replenish the conventional reservoir. So far this is still only a theory, but it appears to be a sensible approach to hydrate production. 1 photo.

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…

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

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.

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

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)

Thermoanalytical studies of carbamazepine: hydration/dehydration, thermal decomposition, and solid phase transitions

Directory of Open Access Journals (Sweden)

Mônia Aparecida Lemos Pinto

2014-12-01

Full Text Available Carbamazepine (CBZ, a widely used anticonvulsant drug, can crystallize and exhibits four polymorphic forms and one dihydrate. Anhydrous CBZ can spontaneously absorb water and convert to the hydrate form whose different crystallinity leads to lower biological activity. The present study was concerned to the possibility of recovering the hydrated form by heating. The thermal behavior of spontaneously hydrated carbamazepine was investigated by TG/DTG-DTA and DSC in dynamic atmospheres of air and nitrogen, which revealed that the spontaneous hydration of this pharmaceutical resulted in a Form III hydrate with 1.5 water molecules. After dehydration, this anhydrous Form III converted to Form I, which melted and decomposed in a single event, releasing isocyanic acid, as shown by evolved gas analysis using TG-FTIR. Differential scanning calorimetry analyses revealed that Form III melted and crystallized as Form I, and that subsequent cooling cycles only generated Form I by crystallization. Solid state decomposition kinetic studies showed that there was no change in the substance after the elimination of water by heating to 120 °C. Activation energies of 98 ± 2 and 93 ± 2 kJ mol-1 were found for the hydrated and dried samples, respectively, and similar profiles of activation energy as a function of conversion factor were observed for these samples.

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.

Indian continental margin gas hydrate prospects : results of the Indian National Gas Hydrate Program (NGHP) expedition 01

Energy Technology Data Exchange (ETDEWEB)

Collett, T [United States Geological Survey, Denver, CO (United States); Riedel, M. [McGill Univ., Montreal, PQ (Canada). Dept. of Earth and Planetary Sciences; Cochran, J.R. [Columbia Univ., Palisades, NY (United States). Lamont Doherty Earth Observatory; Boswell, R. [United States Dept. of Energy, Morgantown, WV (United States). National Energy Technology Lab; Kumar, P. [Pushpendra Kumar Oil and Natural Gas Corp. Ltd., Mumbai (India). Inst. of Engineering and Ocean Technology; Sathe, A.V. [Oil and Natural Gas Corp. Ltd., Uttaranchal (India). KDM Inst. of Petroleum Exploration

2008-07-01

The geologic occurrence of gas hydrate deposits along the continental margins of India were investigated in the first expedition of the Indian National Gas Hydrate Program (NGHP). The objective was to determine the regional context and characteristics of the gas hydrate deposits through scientific ocean drilling, logging, and analytical activities. A research drill ship was the platform for the drilling operation. The geological and geophysical studies revealed 2 geologically distinct areas with inferred gas hydrate occurrences, notably the passive continental margins of the Indian Peninsula and along the Andaman convergent margin. The NGHP Expedition 01 focused on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these 2 diverse settings. The study established the presence of gas hydrates in Krishna-Godavari, Mahanadi and Andaman basins. Site 10 in the Krishna-Godavari Basin was discovered to be the one of the richest gas hydrate accumulations yet documented, while site 17 in the Andaman Sea had the thickest and deepest gas hydrate stability zone yet known. The existence of a fully-developed gas hydrate system in the Mahanadi Basin was also discovered. Most of the gas hydrate occurrences discovered during this expedition appeared to contain mostly methane which was generated by microbial processes. However, there was also evidence of a thermal origin for a portion of the gas within the hydrates of the Mahanadi Basin and the Andaman offshore area. Gas hydrate in the Krishna-Godavari Basin appeared to be closely associated with large scale structural features, in which the flux of gas through local fracture systems, generated by the regional stress regime, controlled the occurrence of gas hydrate. 3 refs., 1 tab., 2 figs.

Nonlinear fluid dynamics of nanoscale hydration water layer

Science.gov (United States)

Jhe, Wonho; Kim, Bongsu; Kim, Qhwan; An, Sangmin

In nature, the hydration water layer (HWL) ubiquitously exists in ambient conditions or aqueous solutions, where water molecules are tightly bound to ions or hydrophilic surfaces. It plays an important role in various mechanisms such as biological processes, abiotic materials, colloidal interaction, and friction. The HWL, for example, can be easily formed between biomaterials since most biomaterials are covered by hydrophilic molecules such as lipid bilayers, and this HWL is expected to be significant to biological and physiological functions. Here (1) we present the general stress tensor of the hydration water layer. The hydration stress tensor provided the platform form for holistic understanding of the dynamic behaviors of the confined HWL including tapping and shear dynamics which are until now individually studied. And, (2) through fast shear velocity ( 1mm/s) experiments, the elastic turbulence caused by elastic property of the HWL is indirectly observed. Our results may contribute to a deeper study of systems where the HWL plays an important role such as biomolecules, colloidal particles, and the MEMS. This work was supported by the National Research Foundation of Korea(NRF) Grant funded by the Korea government(MSIP) (2016R1A3B1908660).

Seismic Modeling Of Reservoir Heterogeneity Scales: An Application To Gas Hydrate Reservoirs

Science.gov (United States)

Huang, J.; Bellefleur, G.; Milkereit, B.

2008-12-01

Natural gas hydrates, a type of inclusion compound or clathrate, are composed of gas molecules trapped within a cage of water molecules. The occurrence of gas hydrates in permafrost regions has been confirmed by core samples recovered from the Mallik gas hydrate research wells located within Mackenzie Delta in Northwest Territories of Canada. Strong vertical variations of compressional and shear sonic velocities and weak surface seismic expressions of gas hydrates indicate that lithological heterogeneities control the distribution of hydrates. Seismic scattering studies predict that typical scales and strong physical contrasts due to gas hydrate concentration will generate strong forward scattering, leaving only weak energy captured by surface receivers. In order to understand the distribution of hydrates and the seismic scattering effects, an algorithm was developed to construct heterogeneous petrophysical reservoir models. The algorithm was based on well logs showing power law features and Gaussian or Non-Gaussian probability density distribution, and was designed to honor the whole statistical features of well logs such as the characteristic scales and the correlation among rock parameters. Multi-dimensional and multi-variable heterogeneous models representing the same statistical properties were constructed and applied to the heterogeneity analysis of gas hydrate reservoirs. The petrophysical models provide the platform to estimate rock physics properties as well as to study the impact of seismic scattering, wave mode conversion, and their integration on wave behavior in heterogeneous reservoirs. Using the Biot-Gassmann theory, the statistical parameters obtained from Mallik 5L-38, and the correlation length estimated from acoustic impedance inversion, gas hydrate volume fraction in Mallik area was estimated to be 1.8%, approximately 2x108 m3 natural gas stored in a hydrate bearing interval within 0.25 km2 lateral extension and between 889 m and 1115 m depth

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.

Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures

International Nuclear Information System (INIS)

Tan, Ming-Liang; Te, Jerez; Cendagorta, Joseph R.; Miller, Benjamin T.; Brooks, Bernard R.; Ichiye, Toshiko

2015-01-01

The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol V E as a function of ethanol mole fraction X E is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decrease is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has “brittle” hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-07-01

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

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

Half-marathon and full-marathon runners' hydration practices and perceptions.

Science.gov (United States)

O'Neal, Eric K; Wingo, Jonathan E; Richardson, Mark T; Leeper, James D; Neggers, Yasmine H; Bishop, Phil A

2011-01-01

The behaviors and beliefs of recreational runners with regard to hydration maintenance are not well elucidated. To examine which beverages runners choose to drink and why, negative performance and health experiences related to dehydration, and methods used to assess hydration status. Cross-sectional study. Marathon registration site. Men (n = 146) and women (n = 130) (age = 38.3 ± 11.3 years) registered for the 2010 Little Rock Half-Marathon or Full Marathon. A 23-item questionnaire was administered to runners when they picked up their race timing chips. Runners were separated into tertiles (Low, Mod, High) based on z scores derived from training volume, expected performance, and running experience. We used a 100-mm visual analog scale with anchors of 0 (never) and 100 (always). Total sample responses and comparisons between tertile groups for questionnaire items are presented. The High group (58±31) reported greater consumption of sport beverages in exercise environments than the Low (42 ± 35 mm) and Mod (39 ± 32 mm) groups (P performance during runs greater than 1 hour (P performance decrement, and 45% perceived dehydration to have resulted in adverse health effects. Twenty percent of runners reported monitoring their hydration status. Urine color was the method most often reported (7%), whereas only 2% reported measuring changes in body weight. Greater attention should be paid to informing runners of valid techniques to monitor hydration status and developing an appropriate individualized hydration strategy.

Hydration number of alkali metal ions determined by insertion in a conducting polymer

DEFF Research Database (Denmark)

Skaarup, Steen

2008-01-01

of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior may depend on the details of ion hydration....... The solvation of alkali metal ions has been discussed for many years without a clear consensus. This work presents a systematic study of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS...... direct calculation of the number of M+ ions entering the film, and therefore the inserted M+ mass. The mass of the water molecules is calculated as a difference. The results yield the following primary hydration numbers: Li+: 5.5-5.6; Na+: 4.0-4.1; K+: 2.0-2.5; Rb+: 0.6-1.2; Cs+: ~0. The most important...

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.

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.

Influence of spraying on the early hydration of accelerated cement pastes

International Nuclear Information System (INIS)

Salvador, Renan P.; Cavalaro, Sergio H.P.; Cano, Miguel; Figueiredo, Antonio D.

2016-01-01

In practice, most of the studies about the interaction between cement and accelerators is performed with hand-mixed pastes. However, in many applications mixing occurs through spraying, which may affect accelerators reactivity and the microstructure of the hardened paste. The objective of this study is to analyze how the mixing process influences the early hydration of accelerated cement pastes. Isothermal calorimetry, X-ray diffraction, thermogravimetry and SEM imaging were performed on cement pastes produced by hand-mixing and by spraying, using equivalent doses of an alkali-free and an alkaline accelerator and two types of cement. Results showed a great influence of the spraying process on the reactivity of accelerators and on the morphology of the precipitated hydrates. Variations in hydration kinetics caused by the mixing method are explained and the results obtained might have a significant repercussion on how future research on the behavior of accelerated mixes will be performed.

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

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

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.

Hydration and phase separation of polyethylene glycol in copolymers of tyrosine derived carbonates.

Science.gov (United States)

Sanjeeva Murthy, N.; Wang, Wenjie; Kohn, Joachim

2009-03-01

Effect of PEG fraction and its block size on the temperature-induced phase transitions and the hydration-induced phase separation were investigated in a copolymer of desaminotyrosyl tyrosine ethyl ester (DTE) and PEG using simultaneous SAXS/WAXS/DSC. The PEG segments crystallized when the block size was at least 2000 Daltons and present at ˜ 40 wt%, and raised the Tg of the polymer by ˜ 15 ^oC. The PEG blocks in dry polymers with up to 50 wt% PEG, even when crystalline, were found to be uniformly distributed with no evidence of phase separation at 10 nm length scales. The non-iodinated PEG-rich sample with 30 mole% PEG2k showed the lower critical solution temperature (LCST) behavior with PEG blocks forming a separate phase above -21 ^oC. In the iodinated version of this polymer, the PEG2k blocks were phase separated in the solid phase. In all samples, whether PEG was crystalline or not, hydration induced PEG to separate into 15 nm hydrated domains. Phase behavior was dependent on whether poly(DTE) or the PEG was the major (matrix) phase. Changes in the mobility of the chains brought about by water-mediated hydrogen-bonding, and modulated by heat, appear to be the common underlying explanation for the range of observed phase behavior.

Detection and Production of Methane Hydrate

Energy Technology Data Exchange (ETDEWEB)

George Hirasaki; Walter Chapman; Gerald Dickens; Colin Zelt; Brandon Dugan; Kishore Mohanty; Priyank Jaiswal

2011-12-31

This project seeks to understand regional differences in gas hydrate systems from the perspective of as an energy resource, geohazard, and long-term climate influence. Specifically, the effort will: (1) collect data and conceptual models that targets causes of gas hydrate variance, (2) construct numerical models that explain and predict regional-scale gas hydrate differences in 2-dimensions with minimal 'free parameters', (3) simulate hydrocarbon production from various gas hydrate systems to establish promising resource characteristics, (4) perturb different gas hydrate systems to assess potential impacts of hot fluids on seafloor stability and well stability, and (5) develop geophysical approaches that enable remote quantification of gas hydrate heterogeneities so that they can be characterized with minimal costly drilling. Our integrated program takes advantage of the fact that we have a close working team comprised of experts in distinct disciplines. The expected outcomes of this project are improved exploration and production technology for production of natural gas from methane hydrates and improved safety through understanding of seafloor and well bore stability in the presence of hydrates. The scope of this project was to more fully characterize, understand, and appreciate fundamental differences in the amount and distribution of gas hydrate and how this would affect the production potential of a hydrate accumulation in the marine environment. The effort combines existing information from locations in the ocean that are dominated by low permeability sediments with small amounts of high permeability sediments, one permafrost location where extensive hydrates exist in reservoir quality rocks and other locations deemed by mutual agreement of DOE and Rice to be appropriate. The initial ocean locations were Blake Ridge, Hydrate Ridge, Peru Margin and GOM. The permafrost location was Mallik. Although the ultimate goal of the project was to understand

Determination of membrane hydration numbers of alkali metal ions by insertion in a conducting polymer

DEFF Research Database (Denmark)

Skaarup, Steen; Junaid Mohamed Jafeen, Mohamed; Careem, M.A.

2010-01-01

, and a secondary (or outer) solvation shell, consisting of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior...... may depend on the details of ion hydration. Although the solvation of alkali metal ions in aqueous solution has been discussed for many years, there is still no clear consensus. Part of the discrepancy is simply that different methods measure over different time scales, and therefore do...... not necessarily define the same hydration shell. This work presents a systematic study of one special variant of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS-). The technique...

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

Directory of Open Access Journals (Sweden)

Sposito Garrison

2002-09-01

Full Text Available Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

Science.gov (United States)

Sutton, Rebecca; Sposito, Garrison

2002-01-01

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

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 ...

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 (PM_2.5 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.

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

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

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

Quantitative studies of kinetics of gas hydrate formation and dissociation is of a particular concern to the petroleum industry for an evaluation of environmental hazards in deep offshore areas. Gas hydrate dissociation can generate excess pore pressure that considerably decreases the strength of the soil. In this paper, we present a theoretical study of the thermodynamic chemical equilibrium of gas hydrate in soil, which is based on models previously reported by Handa (1989), Sloan (1998) and Henry (1999). Our study takes into account the influence of temperature, pressure, pore water chemistry, and the pore size distribution of the sediment. This model fully accounts for the latent heat effects, as done by Chaouch and Briaud (1997) and Delisle et al. (1998). It uses a new formulation based on the enthalpy form of the law of conservation of energy. The model allows for the evaluation of the excess pore pressure generated during gas hydrate dissociation using the Soave’s (1972) equation of state. Fluid flow in response to the excess pore pressure is simulated using the finite element method. In the second part of the paper, we present and discuss an application of the model through a back-analysis of the case of the giant Storegga slide on the Norwegian margin. Two of the most important changes during and since the last deglaciation (hydrostatic pressure due to the change of the sea level and the increase of the sea water temperature) were considered in the calculation. Simulation results are presented and discussed. Chaouch, A., &Briaud, J.-L., 1997. Post melting behavior of gas hydrates in soft ocean sediments, OTC-8298, in 29th offshore technology conference proceedings, v. 1, Geology, earth sciences and environmental factors: Society of Petroleum Engineers, p. 217-224. Delisle, G.; Beiersdorf, H.; Neben, S.; Steinmann, D., 1998. The geothermal field of the North Sulawesi accretionary wedge and a model on BSR migration in unstable depositional environments. in

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)

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

A Hydrate Database: Vital to the Technical Community

Directory of Open Access Journals (Sweden)

D Sloan

2007-06-01

Full Text Available Natural gas hydrates may contain more energy than all the combined other fossil fuels, causing hydrates to be a potentially vital aspect of both energy and climate change. This article is an overview of the motivation, history, and future of hydrate data management using a CODATA vehicle to connect international hydrate databases. The basis is an introduction to the Gas Hydrate Markup Language (GHML to connect various hydrate databases. The accompanying four articles on laboratory hydrate data by Smith et al., on field hydrate data by L?wner et al., on hydrate modeling by Wang et al., and on construction of a Chinese gas hydrate system by Xiao et al. provide details of GHML in their respective areas.

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.

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.

Well log characterization of natural gas-hydrates

Science.gov (United States)

Collett, Timothy S.; Lee, Myung W.

2012-01-01

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

Shallow methane hydrate system controls ongoing, downslope sediment transport in a low-velocity active submarine landslide complex, Hikurangi Margin, New Zealand

Science.gov (United States)

Mountjoy, Joshu J.; Pecher, Ingo; Henrys, Stuart; Crutchley, Gareth; Barnes, Philip M.; Plaza-Faverola, Andreia

2014-11-01

Morphological and seismic data from a submarine landslide complex east of New Zealand indicate flow-like deformation within gas hydrate-bearing sediment. This "creeping" deformation occurs immediately downslope of where the base of gas hydrate stability reaches the seafloor, suggesting involvement of gas hydrates. We present evidence that, contrary to conventional views, gas hydrates can directly destabilize the seafloor. Three mechanisms could explain how the shallow gas hydrate system could control these landslides. (1) Gas hydrate dissociation could result in excess pore pressure within the upper reaches of the landslide. (2) Overpressure below low-permeability gas hydrate-bearing sediments could cause hydrofracturing in the gas hydrate zone valving excess pore pressure into the landslide body. (3) Gas hydrate-bearing sediment could exhibit time-dependent plastic deformation enabling glacial-style deformation. We favor the final hypothesis that the landslides are actually creeping seafloor glaciers. The viability of rheologically controlled deformation of a hydrate sediment mix is supported by recent laboratory observations of time-dependent deformation behavior of gas hydrate-bearing sands. The controlling hydrate is likely to be strongly dependent on formation controls and intersediment hydrate morphology. Our results constitute a paradigm shift for evaluating the effect of gas hydrates on seafloor strength which, given the widespread occurrence of gas hydrates in the submarine environment, may require a reevaluation of slope stability following future climate-forced variation in bottom-water temperature.

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.

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.

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

Directory of Open Access Journals (Sweden)

Beatrice Castellani

2014-09-01

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

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

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...

Report on the research and development achievements in fiscal 1999 on the international research cooperation project for comprehensive development and utilization technologies for gas hydrate resources; 1999 nendo gas hydrate shigen no energy sogo kaihatsu riyo gijutsu no kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

This paper reports the achievements in fiscal 1999 on development of gas hydrate resources. As a result of synthesizing gas hydrates in deposit systems, identifying stability zones in compositions, and studying thermal conductivity and dielectric constant of the deposits, the estimation accuracy has been enhanced steadily in estimating hydrate existing areas in actual frost areas. In the collecting technologies, a proposal was presented for a system by which carbon dioxide is introduced into ground beds at the same time as recovering gases, and gas hydrates are displaced with carbon dioxide hydrates. The displacement phenomenon was verified experimentally by controlling temperatures and pressures. Even below the freezing point, the production rate of the carbon dioxide hydrates is fast if it is above minus 4 degrees C. Salt diffusion behavior important in control of the production and decomposition, and action mechanisms of production and suppression agents were made clear microscopically. Experimental and theoretical discussions were given on dynamics of the production and decomposition. The cage occupation rate of methane hydrates was quantitatively measured successfully by using the Raman spectroscopy. Hydrates of gas mixture were utilized to have verified the possibility of separating the gas mixture constituents. (NEDO)

Hydration and nutrition knowledge in adolescent swimmers. Does water intake affect urine hydration markers after swimming?

Directory of Open Access Journals (Sweden)

Cesare Altavilla

2017-12-01

Full Text Available Little data exists regarding nutritional knowledge and hydration in adolescent swimmers. The aim of this study was to assess the level of nutrition and hydration knowledge and to describe the fluid balance in adolescent swimmers during training. A study was carried out with a cross-sectional descriptive part and a longitudinal part with repeated measurements over five swimming sessions. Eighty-six adolescent swimmers completed a questionnaire to assess their sport nutrition and hydration knowledge. Fluid balance and urine hydration markers were studied during training. Swimmers showed a limited nutrition knowledge (33.26 % ± SD 12.59 and meagre hydration knowledge (28.61 % ± SD 28.59. Females showed lower scores than male swimmers in nutrition and hydration knowledge. Based on urine specific gravity, swimmers started the training close to the euhydrated threshold (1.019 g/mL ± SD 0.008. Although urine specific gravity and urine colour were reduced after the training, there were minimal changes in body mass (-0.12 Kg ± SD 0.31. Sweat loss (2.67 g/min ± SD 3.23 and the net changes in the fluid balance (-0.22 % ± SD 0.59 were low. The poor knowledge in nutrition and hydration encountered in the swimmers can justify the development of a strategy to incorporate nutritional education programmes for this group. Body water deficit from swimming activity seems to be easily replaced with the water intake to maintain hydration. After the training, the urine of swimmers was diluted regardless of their water intake. Dilution of urine did not reflect real hydration state in swimming.

Methane hydrates in nature - Current knowledge and challenges

Science.gov (United States)

Collett, Timothy S.

2014-01-01

Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance

Geologic implications of gas hydrates in the offshore of India: results of the National Gas Hydrate Program Expedition 01

Science.gov (United States)

Collett, Timothy S.; Boswell, Ray; Cochran, J.R.; Kumar, Pushpendra; Lall, Malcolm; Mazumdar, Aninda; Ramana, Mangipudi Venkata; Ramprasad, Tammisetti; Riedel, Michael; Sain, Kalachand; Sathe, Arun Vasant; Vishwanath, Krishna

2014-01-01

The Indian National Gas Hydrate Program Expedition 01 (NGHP-01) is designed to study the occurrence of gas hydrate along the passive continental margin of the Indian Peninsula and in the Andaman convergent margin, with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. The NGHP-01 expedition established the presence of gas hydrates in the Krishna-Godavari and Mahanadi Basins, and the Andaman Sea. The expedition discovered in the Krishna-Godavari Basin one of the thickest gas hydrate accumulations ever documented, in the Andaman Sea one of the thickest and deepest gas hydrate stability zones in the world, and established the existence of a fully developed gas hydrate petroleum system in all three basins.

Modeling the hydration process of bean grains coated with carnauba wax

Directory of Open Access Journals (Sweden)

Aline Almeida da Paixão

2017-08-01

Full Text Available Edible waxes are widely used to maintain foodstuff until they are consumed. However, some products may be subjected to industrial procedures, such as hydration, prior to their consumption. Hydration of a material is a complex process, which aims to reconstitute the original characteristics of a product when in contact with a liquid phase. An important agricultural product that requires this procedure is beans. Thus, the purpose of this work is to study the hydration process of beans (cultivar BRSMG Majestoso in different temperatures and concentrations of carnauba wax, which is applied on the product surface. Beans with initial moisture content of 0.2015, 0.1972 and 0.1745 (d.b. corresponding to treatments 0 (witness, 1 (wax diluted in water in the ratio 1:1, and 2 (carnauba wax, without dilution were used. Later, these samples were imbibed in distilled water at temperatures of 20, 30 and 40 ºC, for 15 h. The temperature and the carnauba wax influenced the water absorption rate. The Peleg model described satisfactory experimental data and the Mitscherlich model presented biased residual distribution. The constants C1 and C2 of the Peleg model exhibited opposite behaviors with increasing temperatures in the hydration process.

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

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

Mapping the Fluid Pathways and Permeability Barriers of a Large Gas Hydrate Reservoir

Science.gov (United States)

Campbell, A.; Zhang, Y. L.; Sun, L. F.; Saleh, R.; Pun, W.; Bellefleur, G.; Milkereit, B.

2012-12-01

An understanding of the relationship between the physical properties of gas hydrate saturated sedimentary basins aids in the detection, exploration and monitoring one of the world's upcoming energy resources. A large gas hydrate reservoir is located in the MacKenzie Delta of the Canadian Arctic and geophysical logs from the Mallik test site are available for the gas hydrate stability zone (GHSZ) between depths of approximately 850 m to 1100 m. The geophysical data sets from two neighboring boreholes at the Mallik test site are analyzed. Commonly used porosity logs, as well as nuclear magnetic resonance, compressional and Stoneley wave velocity dispersion logs are used to map zones of elevated and severely reduced porosity and permeability respectively. The lateral continuity of horizontal permeability barriers can be further understood with the aid of surface seismic modeling studies. In this integrated study, the behavior of compressional and Stoneley wave velocity dispersion and surface seismic modeling studies are used to identify the fluid pathways and permeability barriers of the gas hydrate reservoir. The results are compared with known nuclear magnetic resonance-derived permeability values. The aim of investigating this heterogeneous medium is to map the fluid pathways and the associated permeability barriers throughout the gas hydrate stability zone. This provides a framework for an understanding of the long-term dissociation of gas hydrates along vertical and horizontal pathways, and will improve the knowledge pertaining to the production of such a promising energy source.

Adsorption of zirconium from nitric acid solutions on hydrated tin dioxide

Energy Technology Data Exchange (ETDEWEB)

Tret' yakov, S Ya; Sharygin, L M; Egorov, Yu V

1977-01-01

Adsorption of zirconium from nitric acid solutions has been studied with the use of the labeled atom method on hydrated tin dioxide depending on the sorbate concentration, pH and prehistory of the solution. It has been found that adsorption behavior of zirconium essentially depends on its state in the solution.

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.

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.

Gas Hydrate Storage of Natural Gas

Energy Technology Data Exchange (ETDEWEB)

Rudy Rogers; John Etheridge

2006-03-31

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

Modeling of Oceanic Gas Hydrate Instability and Methane Release in Response to Climate Change

Energy Technology Data Exchange (ETDEWEB)

Reagan, Matthew; Reagan, Matthew T.; Moridis, George J.

2008-04-15

Paleooceanographic evidence has been used to postulate that methane from oceanic hydrates may have had a significant role in regulating global climate, implicating global oceanic deposits of methane gas hydrate as the main culprit in instances of rapid climate change that have occurred in the past. However, the behavior of contemporary oceanic methane hydrate deposits subjected to rapid temperature changes, like those predicted under future climate change scenarios, is poorly understood. To determine the fate of the carbon stored in these hydrates, we performed simulations of oceanic gas hydrate accumulations subjected to temperature changes at the seafloor and assessed the potential for methane release into the ocean. Our modeling analysis considered the properties of benthic sediments, the saturation and distribution of the hydrates, the ocean depth, the initial seafloor temperature, and for the first time, estimated the effect of benthic biogeochemical activity. The results show that shallow deposits--such as those found in arctic regions or in the Gulf of Mexico--can undergo rapid dissociation and produce significant methane fluxes of 2 to 13 mol/yr/m{sup 2} over a period of decades, and release up to 1,100 mol of methane per m{sup 2} of seafloor in a century. These fluxes may exceed the ability of the seafloor environment (via anaerobic oxidation of methane) to consume the released methane or sequester the carbon. These results will provide a source term to regional or global climate models in order to assess the coupling of gas hydrate deposits to changes in the global climate.

DuraLith geopolymer waste form for Hanford secondary waste: Correlating setting behavior to hydration heat evolution

International Nuclear Information System (INIS)

Xu, Hui; Gong, Weiliang; Syltebo, Larry; Lutze, Werner; Pegg, Ian L.

2014-01-01

Highlights: • Quantitative correlations firstly established for cementitious waste forms. • Quantitative correlations firstly established for geopolymeric materials. • Ternary DuraLith geopolymer waste forms for Hanford radioactive wastes. • Extended setting times which improve workability for geopolymer waste forms. • Reduced hydration heat release from DuraLith geopolymer waste forms. - Abstract: The binary furnace slag-metakaolin DuraLith geopolymer waste form, which has been considered as one of the candidate waste forms for immobilization of certain Hanford secondary wastes (HSW) from the vitrification of nuclear wastes at the Hanford Site, Washington, was extended to a ternary fly ash-furnace slag-metakaolin system to improve workability, reduce hydration heat, and evaluate high HSW waste loading. A concentrated HSW simulant, consisting of more than 20 chemicals with a sodium concentration of 5 mol/L, was employed to prepare the alkaline activating solution. Fly ash was incorporated at up to 60 wt% into the binder materials, whereas metakaolin was kept constant at 26 wt%. The fresh waste form pastes were subjected to isothermal calorimetry and setting time measurement, and the cured samples were further characterized by compressive strength and TCLP leach tests. This study has firstly established quantitative linear relationships between both initial and final setting times and hydration heat, which were never discovered in scientific literature for any cementitious waste form or geopolymeric material. The successful establishment of the correlations between setting times and hydration heat may make it possible to efficiently design and optimize cementitious waste forms and industrial wastes based geopolymers using limited testing results

Distinguishing between hydrated, partially hydrated or unhydrated clinker in hardened concrete using microscopy

NARCIS (Netherlands)

Valcke, S.L.A.; Rooij, M.R. de; Visser, J.H.M.; Nijland, T.G.

2010-01-01

Hydration of clinker particles is since long a topic of interest in both designing and optimizing cement composition and its quantity used in concrete. The interest for carefully observing and also quantifying the type or stage of clinker hydration in hardened cement paste is twofold. Firstly, the

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

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

Simulation of microwave stimulation for the production of gas from methane hydrate sediment

International Nuclear Information System (INIS)

Zhao, Jiafei; Fan, Zhen; Wang, Bin; Dong, Hongsheng; Liu, Yu; Song, Yongchen

2016-01-01

Graphical abstract: Schematic diagram illustrating the process of gas production in hydrate-bearing sediment induced by microwave stimulation. Temperature gradients caused by the drop of microwave penetration depth appear in the sediment, leading to a rapid dissociation rate at the upper part of reservoir. - Highlights: • Hydrate dissociation behavior was analyzed in porous media by microwave stimulation. • Microwave stimulation provides sufficient energy conversion for hydrate dissociation. • Hydrate saturation and specific heat capacity of sediment mainly affect efficiency. • Heat conduction decreases temperature gradients promoting homogeneous dissociation. - Abstract: Natural gas hydrates dissociate via an endothermic process. One of the key requirements for any production technique is to supply the heat necessary for this dissociation. In this study, first, a microwave stimulation model for the production of gas from methane hydrate sediment is developed, which includes mass transport, energy conversion and conservation, and intrinsic kinetic reactions as the governing equations. In addition, the theoretical mixing rule of Lichtenecker and Rother is introduced for calculating the average dielectric data of the sediment containing methane hydrates, which affects the penetration of microwaves into the sediment. Next, simulations are performed for investigating gas production, as well as effects of initial water saturation, initial hydrate saturation, and sediment thermal properties induced by microwave stimulation. Moreover, the energy efficiency ratio is employed in the simulation. The simulation results show that microwave stimulation provides timely energy conversion sufficient for promoting the dissociation of hydrates, with rapid, continuous gas production. Temperature gradients caused by the decrease of the microwave penetration depth appear in the reservoir, leading to a rapid dissociation rate in the upper part of the sediment. The energy

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...

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)

Study of cements silicate phases hydrated under high pressure and high temperature; Etude des phases silicatees du ciment hydrate sous haute pression et haute temperature

Energy Technology Data Exchange (ETDEWEB)

Meducin, F.

2001-10-01

{alpha}-C{sub 2}SH is also produced. Compression tests are done to correlate macroscopic behavior and physico chemical properties of the products. With super-plasticizers, samples porosity is lower and the 28-day aged samples recover the Young modulus they had at the early stage of hydration. (author)

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.

Evaluation of Three Hydration Strategies in Detection Dogs Working in a Hot Environment

Directory of Open Access Journals (Sweden)

Cynthia M. Otto

2017-10-01

Full Text Available Physical activity in hot environments can increase the risk of heat stress or heat stroke in dogs. Heat tolerance is influenced by acclimatization to the environment, physical fitness, and hydration state. Three common strategies to promote hydration in working dogs are free access to water (W, oral electrolyte solutions (OESs, and administration of subcutaneous fluids (SQs. None of these methods have been compared for safety or efficacy in a working environment. In a cross-over design, seven vehicle-screening canines were randomly assigned to each of the three hydration strategies during working shifts at the Sarita, TX checkpoint. Physical, behavioral, and biochemical parameters were collected before, during, and after a work shift (mean 5.7 ± 0.8 h. Dogs were given 10 mL/kg oral W, 10 mL/kg chicken flavored OES, or 15 mL/kg of SQs initially followed by controlled access to W or OES. The dogs drank 15.61 ± 4.47 mL/kg/h of W and OES when in the OES group, compared to 7.04 ± 3.42 and 5.56 ± 4.40 mL of W, for the W and SQ groups, respectively. The median environmental temperature was 84.8°F (29.3°C. The median humidity was 70%. Based on mixed effects linear modeling, dogs in the OES and SQ groups had significantly higher total CO2, and lower packed cell volume and total plasma protein at the end of the day. Creatinine increased a small but significant amount in the SQ group and decreased in the OES group. Searching behaviors were independent of hydration strategy but highly related to the dog specific factors of sex, breed, and activity level. Under conditions of controlled activity in moderate heat and humidity, dogs accustomed to the work and the environment were more likely to increase fluid consumption and hydration when provided a flavored OES. Potential benefits of OES and SQ were indirect and no adverse effects were documented for any of the hydration strategies tested.

Anti-Agglomerator of Tetra-n-Butyl Ammonium Bromide Hydrate and Its Effect on Hydrate-Based CO2 Capture

Directory of Open Access Journals (Sweden)

Rong Li

2018-02-01

Full Text Available Tetra-n-butyl ammonium bromide (TBAB was widely used in the research fields of cold storage and CO2 hydrate separation due to its high phase change latent heat and thermodynamic promotion for hydrate formation. Agglomeration always occurred in the process of TBAB hydrate generation, which led to the blockage in the pipeline and the separation apparatus. In this work, we screened out a kind of anti-agglomerant that can effectively solve the problem of TBAB hydrate agglomeration. The anti-agglomerant (AA is composed of 90% cocamidopropyl dimethylamine and 10% glycerol, which can keep TBAB hydrate of 19.3–29.0 wt. % in a stable state of slurry over 72 h. The microscopic observation of the morphology of the TBAB hydrate particles showed that the addition of AA can greatly reduce the size of the TBAB hydrate particles. CO2 gas separation experiments found that the addition of AA led to great improvement on gas storage capacity, CO2 split fraction and separation factor, due to the increasing of contact area between gas phase and hydrate particles. The CO2 split fraction and separation factor with AA addition reached up to 70.3% and 42.8%, respectively.

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...

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

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)

Changes in structure and preferential cage occupancy of ethane hydrate and ethane-methane mixed gas hydrate under high pressure

International Nuclear Information System (INIS)

Hirai, H; Takahara, N; Kawamura, T; Yamamoto, Y; Yagi, T

2010-01-01

Structural changes and preferential cage occupancies were examined for ethane hydrate and ethane-methane mixed gas hydrates with five compositions in a pressure range of 0.2 to 2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed the following structural changes. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions, where sII and sH appeared. Above 2.1 GPa ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it was thought that ethane molecules were contained only in the large cage.

High-temperature stability of the hydrate shell of a Na+ cation in a flat nanopore with hydrophobic walls

Science.gov (United States)

Shevkunov, S. V.

2017-11-01

The effect of elevated temperature has on the hydrate shell of a singly charged sodium cation inside a flat nanopore with smooth walls is studied using the Monte Carlo method. The free energy and the entropy of vapor molecule attachment are calculated by means of a bicanonical statistical ensemble using a detailed model of interactions. The nanopore has a stabilizing effect on the hydrate shell with respect to fluctuations and a destabilizing effect with respect to complete evaporation. At the boiling point of water, behavior is observed that is qualitatively similar to behavior at room temperature, but with a substantial shift in the vapor pressure and shell size.

Numerical Simulations for Enhanced Methane Recovery from Gas Hydrate Accumulations by Utilizing CO2 Sequestration

Science.gov (United States)

Sridhara, Prathyusha

In 2013, the International Energy Outlook (EIA, 2013) projected that global energy demand will grow by 56% between 2010 and 2040. Despite strong growth in renewable energy supplies, much of this growth is expected to be met by fossil fuels. Concerns ranging from greenhouse gas emissions and energy security are spawning new interests for other sources of energy including renewable and unconventional fossil fuel such as shale gas and oil as well as gas hydrates. The production methods as well as long-term reservoir behavior of gas hydrate deposits have been under extensive investigation. Reservoir simulators can be used to predict the production potentials of hydrate formations and to determine which technique results in enhanced gas recovery. In this work, a new simulation tool, Mix3HydrateResSim (Mix3HRS), which accounts for complex thermodynamics of multi-component hydrate phase comprised of varying hydrate solid crystal structure, is used to perform the CO2-assisted production technique simulations from CH4 hydrate accumulations. The simulator is one among very few reservoir simulators which can simulate the process of CH4 substitution by CO2 (and N2 ) in the hydrate lattice. Natural gas hydrate deposits around the globe are categorized into three different classes based on the characteristics of the geological sediments present in contact with the hydrate bearing deposits. Amongst these, the Class 2 hydrate accumulations predominantly confirmed in the permafrost and along seashore, are characterized by a mobile aqueous phase underneath a hydrate bearing sediment. The exploitation of such gas hydrate deposits results in release of large amounts of water due to the presence of permeable water-saturated sediments encompassing the hydrate deposits, thus lowering the produced gas rates. In this study, a suite of numerical simulation scenarios with varied complexity are considered which aimed at understanding the underlying changes in physical, thermodynamic and

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.

Rheological properties of hydrate suspensions in asphaltenic crude oils; Proprietes rheologiques de suspensions d'hydrate dans des bruts asphalteniques

Energy Technology Data Exchange (ETDEWEB)

Marques de Toledo Camargo, R.

2001-03-01

The development of offshore oil exploitation under increasing water depths has forced oil companies to increase their understanding of gas hydrate formation and transportation in multiphase flow lines in which a liquid hydrocarbon phase is present. This work deals with the flow behaviour of hydrate suspensions in which a liquid hydrocarbon is the continuous phase. Three different liquid hydrocarbons are used: an asphaltenic crude oil, a condensate completely free of asphaltenes and a mixture between the asphaltenic oil and heptane. The rheological characterisation of hydrate suspensions is the main tool employed. Two original experimental devices are used: a PVT cell adapted to operate as a Couette type rheometer and a semi-industrial flow loop. Hydrate suspensions using the asphaltenic oil showed shear-thinning behaviour and thixotropy. This behaviour is typically found in flocculated systems, in which the particles attract each other forming flocs of aggregated particles at low shear rates. The suspensions using the condensate showed Newtonian behaviour. Their relative viscosities were high, which suggests that an aggregation process between hydrate particles takes. place during hydrate formation. Finally, hydrate suspensions using the mixture asphaltenic oil-heptane showed shear-thinning behaviour, thixotropy and high relative viscosity. From these results it can be inferred that, after the achievement of the hydrate formation process, the attractive forces between hydrate particles are weak. making unlikely pipeline obstruction by an aggregation process. Nevertheless, during the hydrate formation, these attractive forces can be sufficiently high. It seems that the hydrate surface wettability is an important parameter in this phenomena. (author)

Micromechanical investigation of sand migration in gas hydrate-bearing sediments

Science.gov (United States)

Uchida, S.; Klar, A.; Cohen, E.

2017-12-01

Past field gas production tests from hydrate bearing sediments have indicated that sand migration is an important phenomenon that needs to be considered for successful long-term gas production. The authors previously developed the continuum based analytical thermo-hydro-mechanical sand migration model that can be applied to predict wellbore responses during gas production. However, the model parameters involved in the model still needs to be calibrated and studied thoroughly and it still remains a challenge to conduct well-defined laboratory experiments of sand migration, especially in hydrate-bearing sediments. Taking the advantage of capability of micromechanical modelling approach through discrete element method (DEM), this work presents a first step towards quantifying one of the model parameters that governs stresses reduction due to grain detachment. Grains represented by DEM particles are randomly removed from an isotropically loaded DEM specimen and statistical analyses reveal that linear proportionality exists between the normalized volume of detached solids and normalized reduced stresses. The DEM specimen with different porosities (different packing densities) are also considered and statistical analyses show that there is a clear transition between loose sand behavior and dense sand behavior, characterized by the relative density.

Amorphous-crystalline transition studied in hydrated MoO3

International Nuclear Information System (INIS)

Camacho-Lopez, M.A.; Haro-Poniatowski, E.; Lartundo-Rojas, L.; Livage, J.; Julien, C.M.

2006-01-01

In this work we study the thermal behavior of hydrated MoO 3 synthesized via acidification of sodium molybdate. MoO 3 .nH 2 O (n = 1.4) amorphous compound was heated in air at increasing temperatures in order to obtain the crystalline MoO 3 phase. We have studied the structural changes as a function of annealing temperature by Raman spectroscopy. A statistical study to determine the average size of the crystallites at each annealing step has been realized by scanning electron microscopy. Results show that the hydrated MoO 3 .1.4H 2 O glass transforms in an amorphous MoO 3 .0.7H 2 O phase prior to its crystallization, while the sample heated at 500 deg. C crystallizes into the orthorhombic α-MoO 3 phase with micro-crystallites having an average size of 6.8 μm

Experimental Determination of Refractive Index of Gas Hydrates

DEFF Research Database (Denmark)

Bylov, Martin; Rasmussen, Peter

1997-01-01

. For methane hydrate (structure I) the refractive index was found to be 1.346 and for natural gas hydrate (structure II) it was found to be 1.350. The measurements further suggest that the gas hydrate growth rate increases if the water has formed hydrates before. The induction time, on the other hand, seems......The refractive indexes of methane hydrate and natural gas hydrate have been experimentally determined. The refractive indexes were determined in an indirect manner making use of the fact that two non-absorbing materials will have the same refractive index if they cannot be distinguished visually...

Nuclear magnetic resonance study of diffusion and relaxation in hydrating white cement pastes of different water content

International Nuclear Information System (INIS)

Nestle, Nikolaus; Galvosas, Petrik; Geier, Oliver; Zimmermann, Christian; Dakkouri, Marwan; Karger, Jorg

2001-01-01

While the nuclear spin relaxation time changes in hydrating cement materials have been widely studied by various groups during the last 20 years, data on the self-diffusion behavior of the pore water during hydration of a cement paste are much scarcer. Taking advantage of improved spectrometer hardware for pulsed field gradient diffusometry and a specialized pulse sequence which is designed to compensate the detrimental effects of inner magnetic field gradients in the sample we have studied the water self-diffusion behavior in pastes prepared from white cement at various water/cement ratios. For the same mixtures, studies of the transverse spin relaxation behavior were also conducted. A comparison of the results from both techniques shows that the diffusion coefficient starts to decrease only much later than the relaxation times for all pastes studied. [copyright] 2001 American Institute of Physics

Measurements of relevant parameters in the formation of clathrate hydrates by a novel experimental apparatus

Energy Technology Data Exchange (ETDEWEB)

Arca, S.; Di Profio, P.; Germani, R.; Savelli, G. [Perugia Univ., CEMIN, Perugia (Italy). Dept. of Chemistry

2008-07-01

There is a growing interest in understanding the thermodynamics and kinetics of clathrate hydrate formation. This paper presented a study that involved the design, construction, calibration, and testing of a new apparatus that could obtain as many parameters as possible in a single formation batch and that could measure unexplored clathrate hydrate parameters. The apparatus was capable of measuring equilibrium phases involving gaseous components. The paper described the conceptual design as well as the chamber, pressure line, temperature control, liquid addition line, and conductometric probe. The paper also discussed data acquisition, stirring, measurement examples, and internal illumination and video monitoring. It was concluded that refining measurements, particularly those concerning kinetic characterizations, is important in order to clarify several uncertain kinetic behaviors of clathrate hydrates. 6 refs., 16 figs.

Comparison on Heat of Hydration between Current Concrete for NPP and High Fluidity Concrete including Pozzolan Powders

International Nuclear Information System (INIS)

Noh, Jea Myoung; Cho, Myung Sug

2010-01-01

Nuclear power plant (NPP) concrete structures are exposed to many construction factors that lower the quality of concrete due to densely packed reinforcements and heat of hydration since they are mostly constructed with mass concrete. The concrete currently being used in Korean NPPs is mixed with Type I cement and fly ash. However, there is a demand to improve the performance of concrete with reduced heat of hydration and superior constructability. Many advantages such as improving workability and durability of concrete and decreasing heat of hydration are introduced by replacing cement with pozzolan binders. Therefore, the manufacturing possibility of high fluidity concrete should be investigated through applying multi-component powders blended with pozzolan binders to the concrete structure of NPPs, while the researches on properties, characteristic of hydration, durability and long-term behavior of high fluidity concrete using multi-component cement should be carried out. High fluidity concrete which is made using portland cement and pozzlonan powders such as fly ash and blast furnace slag has better properties on heat of hydration than the concrete currently in use for NPPs

Relationship between diffusivity of water molecules inside hydrating tablets and their drug release behavior elucidated by magnetic resonance imaging.

Science.gov (United States)

Kikuchi, Shingo; Onuki, Yoshinori; Kuribayashi, Hideto; Takayama, Kozo

2012-01-01

We reported previously that sustained release matrix tablets showed zero-order drug release without being affected by pH change. To understand drug release mechanisms more fully, we monitored the swelling and erosion of hydrating tablets using magnetic resonance imaging (MRI). Three different types of tablets comprised of polyion complex-forming materials and a hydroxypropyl methylcellulose (HPMC) were used. Proton density- and diffusion-weighted images of the hydrating tablets were acquired at intervals. Furthermore, apparent self-diffusion coefficient maps were generated from diffusion-weighted imaging to evaluate the state of hydrating tablets. Our findings indicated that water penetration into polyion complex tablets was faster than that into HPMC matrix tablets. In polyion complex tablets, water molecules were dispersed homogeneously and their diffusivity was relatively high, whereas in HPMC matrix tablets, water molecule movement was tightly restricted within the gel. An optimal tablet formulation determined in a previous study had water molecule penetration and diffusivity properties that appeared intermediate to those of polyion complex and HPMC matrix tablets; water molecules were capable of penetrating throughout the tablets and relatively high diffusivity was similar to that in the polyion complex tablet, whereas like the HPMC matrix tablet, it was well swollen. This study succeeded in characterizing the tablet hydration process. MRI provides profound insight into the state of water molecules in hydrating tablets; thus, it is a useful tool for understanding drug release mechanisms at a molecular level.

A rigorous mechanistic model for predicting gas hydrate formation kinetics: The case of CO2 recovery and sequestration

International Nuclear Information System (INIS)

ZareNezhad, Bahman; Mottahedin, Mona

2012-01-01

Highlights: ► A mechanistic model for predicting gas hydrate formation kinetics is presented. ► A secondary nucleation rate model is proposed for the first time. ► Crystal–crystal collisions and crystal–impeller collisions are distinguished. ► Simultaneous determination of nucleation and growth kinetics are established. ► Important for design of gas hydrate based energy storage and CO 2 recovery systems. - Abstract: A rigorous mechanistic model for predicting gas hydrate formation crystallization kinetics is presented and the special case of CO 2 gas hydrate formation regarding CO 2 recovery and sequestration processes has been investigated by using the proposed model. A physical model for prediction of secondary nucleation rate is proposed for the first time and the formation rates of secondary nuclei by crystal–crystal collisions and crystal–impeller collisions are formulated. The objective functions for simultaneous determination of nucleation and growth kinetics are presented and a theoretical framework for predicting the dynamic behavior of gas hydrate formation is presented. Predicted time variations of CO 2 content, total number and surface area of produced hydrate crystals are in good agreement with the available experimental data. The proposed approach can have considerable application for design of gas hydrate converters regarding energy storage and CO 2 recovery processes.

Raman studies of methane-ethane hydrate metastability.

Science.gov (United States)

Ohno, Hiroshi; Strobel, Timothy A; Dec, Steven F; Sloan, E Dendy; Koh, Carolyn A

2009-03-05

The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement). The kinetic hydrate inhibitor increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable) but retards the rate at 93% methane in ethane (sII is thermodynamically stable), implying there is a complex interaction between the polymer, water, and hydrate guests at crystal surfaces.

Methane Hydrate Field Program: Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

Energy Technology Data Exchange (ETDEWEB)

Myers, Greg [Consortium for Ocean Leadership, Washington, DC (United States)

2014-02-01

This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report: Historical Methane Hydrate Project Review Report; Methane Hydrate Workshop Report; Topical Report: Marine Methane Hydrate Field Research Plan; and Final Scientific/Technical Report.

An effective medium inversion algorithm for gas hydrate quantification and its application to laboratory and borehole measurements of gas hydrate-bearing sediments

Science.gov (United States)

Chand, S.; Minshull, T.A.; Priest, J.A.; Best, A.I.; Clayton, C.R.I.; Waite, W.F.

2006-01-01

The presence of gas hydrate in marine sediments alters their physical properties. In some circumstances, gas hydrate may cement sediment grains together and dramatically increase the seismic P- and S-wave velocities of the composite medium. Hydrate may also form a load-bearing structure within the sediment microstructure, but with different seismic wave attenuation characteristics, changing the attenuation behaviour of the composite. Here we introduce an inversion algorithm based on effective medium modelling to infer hydrate saturations from velocity and attenuation measurements on hydrate-bearing sediments. The velocity increase is modelled as extra binding developed by gas hydrate that strengthens the sediment microstructure. The attenuation increase is modelled through a difference in fluid flow properties caused by different permeabilities in the sediment and hydrate microstructures. We relate velocity and attenuation increases in hydrate-bearing sediments to their hydrate content, using an effective medium inversion algorithm based on the self-consistent approximation (SCA), differential effective medium (DEM) theory, and Biot and squirt flow mechanisms of fluid flow. The inversion algorithm is able to convert observations in compressional and shear wave velocities and attenuations to hydrate saturation in the sediment pore space. We applied our algorithm to a data set from the Mallik 2L–38 well, Mackenzie delta, Canada, and to data from laboratory measurements on gas-rich and water-saturated sand samples. Predictions using our algorithm match the borehole data and water-saturated laboratory data if the proportion of hydrate contributing to the load-bearing structure increases with hydrate saturation. The predictions match the gas-rich laboratory data if that proportion decreases with hydrate saturation. We attribute this difference to differences in hydrate formation mechanisms between the two environments.

Impact of pressure on the dynamic behavior of CO2 hydrate slurry in a stirred tank reactor applied to cold thermal energy storage

International Nuclear Information System (INIS)

Dufour, Thomas; Hoang, Hong Minh; Oignet, Jérémy; Osswald, Véronique; Clain, Pascal; Fournaison, Laurence; Delahaye, Anthony

2017-01-01

Highlights: •CO 2 hydrate storage was studied in a stirred tank reactor under pressure. •CO 2 hydrates can store three times more energy than water during the same time. •Increasing CO 2 hydrate pressure decreases charge time for the same stored energy. •CO 2 hydrate storage allow average power exchange to be maintained along the process. -- Abstract: Phase change material (PCM) slurries are considered as high-performance fluids for secondary refrigeration and cold thermal energy storage (CTES) systems thanks to their high energy density. Nevertheless, the efficiency of such system is limited by storage dynamic. In fact, PCM charging or discharging rate is governed by system design (storage tank, heat exchanger), heat transfer fluid temperature and flow rate (cold or hot source), and PCM temperature. However, with classical PCM (ice, paraffin…), phase change temperature depends only on material/fluid nature and composition. In the case of gas hydrates, phase change temperature is also controlled by pressure. In the current work, the influence of pressure on cold storage with gas hydrates was studied experimentally using a stirred tank reactor equipped with a cooling jacket. A tank reactor model was also developed to assess the efficiency of this storage process. The results showed that pressure can be used to adjust phase change temperature of CO 2 hydrates, and consequently charging/discharging time. For the same operating conditions and during the same charging time, the amount of stored energy using CO 2 hydrates can be three times higher than that using water. By increasing the initial pressure from 2.45 to 3.2 MPa (at 282.15 K), it is also possible to decrease the charging time by a factor of 3. Finally, it appears that the capacity of pressure to increase CO 2 -hydrate phase-change temperature can also improve system efficiency by decreasing thermal losses.

Sedimentological Properties of Natural Gas Hydrates-Bearing Sands in the Nankai Trough and Mallik Areas

Science.gov (United States)

Uchida, T.; Tsuji, T.; Waseda, A.

2009-12-01

The Nankai Trough parallels the Japanese Island, where extensive BSRs have been interpreted from seismic reflection records. High resolution seismic surveys have definitely indicated gas hydrate distributions, and drilling the MITI Nankai Trough wells in 2000 and the METI Tokai-oki to Kumano-nada wells in 2004 have revealed subsurface gas hydrate in the eastern part of Nankai Trough. In 1998 and 2002 Mallik wells were drilled at Mackenzie Delta in the Canadian Arctic that also clarified the characteristics of gas hydrate-dominant sandy layers at depths from 890 to 1110 m beneath the permafrost zone. During the field operations, the LWD and wire-line well log data were continuously obtained and plenty of gas hydrate-bearing sand cores were recovered. Subsequence sedimentological and geochemical analyses performed on those core samples revealed the crucial geologic controls on the formation and preservation of natural gas hydrate in sediments. Pore-space gas hydrates reside in sandy sediments mostly filling intergranular porosity. Pore waters chloride anomalies, core temperature depression and core observations on visible gas hydrates confirm the presence of pore-space gas hydrates within moderate to thick sandy layers, typically 10 cm to a meter thick. Sediment porosities and pore-size distributions were obtained by mercury porosimetry, which indicate that porosities of gas hydrate-bearing sandy strata are approximately 45 %. According to grain size distribution curves, gas hydrate is dominant in fine- to very fine-grained sandy strata. Gas hydrate saturations are typically up to 80 % in pore volume throughout most of the hydrate-dominant sandy layers, which are estimated by well log analyses as well as pore water chloride anomalies. It is necessary for investigating subsurface fluid flow behaviors to evaluate both porosity and permeability of gas hydrate-bearing sandy sediments, and the measurements of water permeability for them indicated that highly saturated

Hydrate bearing clayey sediments: Formation and gas production concepts

KAUST Repository

Jang, Jaewon; Santamarina, Carlos

2016-01-01

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

Hydrate bearing clayey sediments: Formation and gas production concepts

KAUST Repository

Jang, Jaewon

2016-06-20

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

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.

Elastic wave speeds and moduli in polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate

Science.gov (United States)

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

2009-01-01

We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from -20 to 15??C and 22.4 to 32.8 MPa for ice Ih, -20 to 15??C and 30.5 to 97.7 MPa for si methane hydrate, and -20 to 10??C and 30.5 to 91.6 MPa for sll methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates ?? 2009.

Gas hydrate exploration activities in Korea

Energy Technology Data Exchange (ETDEWEB)

Keun-Pil Park, K.P. [Korea Inst. of Geoscience and Mineral Resources, Gas Hydrate R and D Organization, Ministry of Knowledge Economy, Yuseong-gu, Daejeon (Korea, Republic of)

2008-07-01

Korea's first gas hydrate research project was launched in 1996 to study the gas hydrate potential in the Ulleung Basin of the East Sea. It involved a series of laboratory experiments followed by a preliminary offshore seismic survey and regional reconnaissance geophysical and marine geological surveys. The bottom simulating reflector (BSR) was interpreted to show wide area distribution in the southern part of the Ulleung Basin, and its average burial depth was 187 m below the sea floor in the East Sea. A three-phase 10-year National Gas Hydrate Development Program was launched in 2004 to estimate the potential reserves in the East Sea. It will involve drilling to identify natural gas hydrates and to determine the most optimized production methods. Drilling sites were proposed based on five indicators that imply gas hydrate occurrence, notably BSR, gas vent, enhanced seismic reflection, acoustic blanking and gas seeping structure. The UBGH-X-01 gas hydrate expedition in the East Sea Ulleung Basin involved 5 logging while drilling (LWD) surveys at three high priority sites. One wire line logging was implemented at the site of the UBGH09. A total 334 m of non-pressurized conventional cores and 16 pressure cores were obtained in late 2007. The UBGH-X-01 was successfully completed, recovering many natural samples of gas hydrate from 3 coring sites in the East Sea. 7 refs., 12 figs.

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.

Methane Hydrate Field Program. Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

Energy Technology Data Exchange (ETDEWEB)

Collett, Tim [U.S. Geological Survey, Boulder, CO (United States); Bahk, Jang-Jun [Korea Inst. of Geoscience and Mineral Resources, Daejeon (Korea); Frye, Matt [U.S. Bureau of Ocean Energy Management, Sterling, VA (United States); Goldberg, Dave [Lamont-Doherty Earth Observatory, Palisades, NY (United States); Husebo, Jarle [Statoil ASA, Stavenger (Norway); Koh, Carolyn [Colorado School of Mines, Golden, CO (United States); Malone, Mitch [Texas A & M Univ., College Station, TX (United States); Shipp, Craig [Shell International Exploration and Production Inc., Anchorage, AK (United States); Torres, Marta [Oregon State Univ., Corvallis, OR (United States); Myers, Greg [Consortium For Ocean Leadership Inc., Washington, DC (United States); Divins, David [Consortium For Ocean Leadership Inc., Washington, DC (United States); Morell, Margo [Consortium For Ocean Leadership Inc., Washington, DC (United States)

2013-12-31

This topical report represents a pathway toward better understanding of the impact of marine methane hydrates on safety and seafloor stability and future collection of data that can be used by scientists, engineers, managers and planners to study climate change and to assess the feasibility of marine methane hydrate as a potential future energy resource. Our understanding of the occurrence, distribution and characteristics of marine methane hydrates is incomplete; therefore, research must continue to expand if methane hydrates are to be used as a future energy source. Exploring basins with methane hydrates has been occurring for over 30 years, but these efforts have been episodic in nature. To further our understanding, these efforts must be more regular and employ new techniques to capture more data. This plan identifies incomplete areas of methane hydrate research and offers solutions by systematically reviewing known methane hydrate “Science Challenges” and linking them with “Technical Challenges” and potential field program locations.

Energy from gas hydrates - assessing the opportunities and challenges for Canada: report of the expert panel on gas hydrates

International Nuclear Information System (INIS)

2008-09-01

Gas hydrates form when water and natural gas combine at low temperatures and high pressures in regions of permafrost and in marine subseafloor sediments. Estimates suggest that the total amount of natural gas bound in hydrate form may exceed all conventional gas resources, or even the amount of all combined hydrocarbon energy. Gas from gas hydrate could provide a potentially vast new source of energy to offset declining supplies of conventional natural gas in North America and to provide greater energy security for countries such as Japan and India that have limited domestic sources. However, complex issues would need to be addressed if gas hydrate were to become a large part of the energy future of Canada. Natural Resources Canada asked the Council of Canadian Academies to assemble a panel of experts to examine the challenges for an acceptable operational extraction of gas hydrates in Canada. This report presented an overview of relevant contextual background, including some basic science; the medium-term outlook for supply and demand in markets for natural gas; broad environmental issues related to gas hydrate in its natural state and as a fuel; and an overview of Canada's contribution to knowledge about gas hydrate in the context of ongoing international research activity. The report also presented current information on the subject and what would be required to delineate and quantify the resource. Techniques for extracting gas from gas hydrate were also outlined. The report also addressed safety issues related to gas hydrate dissociation during drilling operations or release into the atmosphere; the environmental issues associated with potential leakage of methane into the atmosphere and with the large volumes of water produced during gas hydrate dissociation; and jurisdictional and local community issues that would need to be resolved in order to proceed with the commercial exploitation of gas hydrate. It was concluded that there does not appear to be

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.

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.

Protein Hydration Thermodynamics: The Influence of Flexibility and Salt on Hydrophobin II Hydration.

Science.gov (United States)

Remsing, Richard C; Xi, Erte; Patel, Amish J

2018-04-05

The solubility of proteins and other macromolecular solutes plays an important role in numerous biological, chemical, and medicinal processes. An important determinant of protein solubility is the solvation free energy of the protein, which quantifies the overall strength of the interactions between the protein and the aqueous solution that surrounds it. Here we present an all-atom explicit-solvent computational framework for the rapid estimation of protein solvation free energies. Using this framework, we estimate the hydration free energy of hydrophobin II, an amphiphilic fungal protein, in a computationally efficient manner. We further explore how the protein hydration free energy is influenced by enhancing flexibility and by the addition of sodium chloride, and find that it increases in both cases, making protein hydration less favorable.

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.

Standardization and software infrastructure for gas hydrate data communications

Energy Technology Data Exchange (ETDEWEB)

Kroenlein, K.; Chirico, R.D.; Kazakov, A.; Frenkel, M. [National Inst. of Standards and Technology, Boulder, CO (United States). Physical and Chemical Properties Div.; Lowner, R. [GeoForschungsZentrum Potsdam (Germany); Wang, W. [Chinese Academy of Science, Beijing (China). Computer Network Information Center; Smith, T. [MIT Systems, Flushing, NY (United States); Sloan, E.D. [Colorado School of Mines, Golden, CO (United States). Centre for Hydrate Research

2008-07-01

The perceived value of gas hydrates as an energy resource for the future has led to extensive hydrate research studies and experiments. The hydrate deposits are widely dispersed throughout the world, and many countries are now investigating methods of extracting gas hydrate resources. This paper described a gas hydrates markup language (GHML) developed as an international standard for data transfer and storage within the gas hydrates community. The language is related to a hydrates database developed to facilitate a greater understanding of naturally occurring hydrate interactions with geophysical processes, and aid in the development of hydrate technologies for resource recovery and storage. Recent updates to the GHML included the addition of ThermoML, a communication standard for thermodynamic data into the GHML schema. The standard will be used to represent all gas hydrates thermodynamic data. A new element for the description of crystal structures has also been developed, as well as a guided data capture tool. The tool is available free of charge and is publicly licensed for use by gas hydrate data producers. A web service has also been provided to ensure that access to GHML files for gas hydrates and data files are available for users. It was concluded that the tool will help to ensure data quality assurance for the conversion of data and meta-data within the database. 28 refs., 9 figs.

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)

A new aluminium-hydrate species in hydrated Portland cements characterized by 27Al and 29Si MAS NMR spectroscopy

International Nuclear Information System (INIS)

Andersen, Morten Daugaard; Jakobsen, Hans J.; Skibsted, Jorgen

2006-01-01

Recent 27 Al MAS NMR studies of hydrated Portland cements and calcium-silicate-hydrate (C-S-H) phases have shown a resonance from Al in octahedral coordination, which cannot be assigned to the well-known aluminate species in hydrated Portland cements. This resonance, which exhibits the isotropic chemical shift δ iso = 5.0 ppm and the quadrupole product parameter P Q = 1.2 MHz, has been characterized in detail by 27 Al MAS and 27 Al{ 1 H} CP/MAS NMR for different hydrated white Portland cements and C-S-H phases. These experiments demonstrate that the resonance originates from an amorphous or disordered aluminate hydrate which contains Al(OH) 6 3- or O x Al(OH) 6-x (3+x)- units. The formation of the new aluminate hydrate is related to the formation of C-S-H at ambient temperatures, however, it decomposes by thermal treatment at temperatures of 70-90 o C. From the experiments in this work it is proposed that the new aluminate hydrate is either an amorphous/disordered aluminate hydroxide or a calcium aluminate hydrate, produced as a separate phase or as a nanostructured surface precipitate on the C-S-H phase. Finally, the possibilities of Al 3+ for Ca 2+ substitution in the principal layers and interlayers of the C-S-H structure are discussed

LABORATORY STRATEGIES FOR HYDRATE FORMATION IN FINE-GRAINED SEDIMENTS

KAUST Repository

Lei, L.; Santamarina, Carlos

2018-01-01

Fine‐grained sediments limit hydrate nucleation, shift the phase boundary and hinder gas supply. Laboratory experiments in this study explore different strategies to overcome these challenges, including the use of a more soluble guest molecule rather than methane, grain‐scale gas‐storage within porous diatoms, ice‐to‐hydrate transformation to grow lenses at predefined locations, forced gas injection into water saturated sediments, and long‐term guest molecule transport. Tomographic images, thermal and pressure data provide rich information on hydrate formation and morphology. Results show that hydrate formation is inherently displacive in fine‐grained sediments; lenses are thicker and closer to each other in compressible, high specific surface area sediments subjected to low effective stress. Temperature and pressure trajectories follow a shifted phase boundary that is consistent with capillary effects. Exo‐pore growth results in freshly formed hydrate with a striped and porous structure; this open structure becomes an effective pathway for gas transport to the growing hydrate front. Ice‐to‐hydrate transformation goes through a liquid stage at pre‐melt temperatures; then, capillarity and cryogenic suction compete, and some water becomes imbibed into the sediment faster than hydrate reformation. The geometry of hydrate lenses and the internal hydrate structure continue evolving long after the exothermal response to hydrate formation has completely decayed. Multiple time‐dependent processes occur during hydrate formation, including gas, water and heat transport, sediment compressibility, reaction rate and the stochastic nucleation process. Hydrate formation strategies conceived for this study highlight the inherent difficulties in emulating hydrate formation in fine‐grained sediments within the relatively short time‐scale available for laboratory experiments.

LABORATORY STRATEGIES FOR HYDRATE FORMATION IN FINE-GRAINED SEDIMENTS

KAUST Repository

Lei, L.

2018-04-02

Fine‐grained sediments limit hydrate nucleation, shift the phase boundary and hinder gas supply. Laboratory experiments in this study explore different strategies to overcome these challenges, including the use of a more soluble guest molecule rather than methane, grain‐scale gas‐storage within porous diatoms, ice‐to‐hydrate transformation to grow lenses at predefined locations, forced gas injection into water saturated sediments, and long‐term guest molecule transport. Tomographic images, thermal and pressure data provide rich information on hydrate formation and morphology. Results show that hydrate formation is inherently displacive in fine‐grained sediments; lenses are thicker and closer to each other in compressible, high specific surface area sediments subjected to low effective stress. Temperature and pressure trajectories follow a shifted phase boundary that is consistent with capillary effects. Exo‐pore growth results in freshly formed hydrate with a striped and porous structure; this open structure becomes an effective pathway for gas transport to the growing hydrate front. Ice‐to‐hydrate transformation goes through a liquid stage at pre‐melt temperatures; then, capillarity and cryogenic suction compete, and some water becomes imbibed into the sediment faster than hydrate reformation. The geometry of hydrate lenses and the internal hydrate structure continue evolving long after the exothermal response to hydrate formation has completely decayed. Multiple time‐dependent processes occur during hydrate formation, including gas, water and heat transport, sediment compressibility, reaction rate and the stochastic nucleation process. Hydrate formation strategies conceived for this study highlight the inherent difficulties in emulating hydrate formation in fine‐grained sediments within the relatively short time‐scale available for laboratory experiments.

Suspension hydration of C3S [tricalcium silicate] at constant pH. II. Effect of previously formed hydrates and of additives

NARCIS (Netherlands)

McCurdy, K.G.; Stein, H.N.

1973-01-01

A retardation shown by the hydration of C3S at pH=11.5 can be prevented if before the addition of C3S there are present hydrate particles in the aqueous medium. These hydrate particles probably have the composition CSHn. This indicates a hydrate CSHn, precipitated from solution, as the retarding

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

Science.gov (United States)

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

2009-10-22

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

Mechanical Performance of Asphalt Mortar Containing Hydrated Lime and EAFSS at Low and High Temperatures.

Science.gov (United States)

Moon, Ki Hoon; Falchetto, Augusto Cannone; Wang, Di; Riccardi, Chiara; Wistuba, Michael P

2017-07-03

In this paper, the possibility of improving the global response of asphalt materials for pavement applications through the use of hydrated lime and Electric Arc-Furnace Steel Slag (EAFSS) was investigated. For this purpose, a set of asphalt mortars was prepared by mixing two different asphalt binders with fine granite aggregate together with hydrated lime or EAFSS at three different percentages. Bending Beam Rheometer (BBR) creep tests and Dynamic Shear Rheometer (DSR) complex modulus tests were performed to evaluate the material response both at low and high temperature. Then, the rheological Huet model was fitted to the BBR creep results for estimating the impact of filler content on the model parameters. It was found that an addition of hydrated lime and EAFSS up to 10% and 5%, respectively, results in satisfactory low-temperature performance with a substantial improvement of the high-temperature behavior.

The U.S. Geological Survey’s Gas Hydrates Project

Science.gov (United States)

Ruppel, Carolyn D.

2018-01-17

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

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.

Gas Hydrates | Alaska Division of Geological & Geophysical Surveys

Science.gov (United States)

Preliminary Report - Cascadia Margin Gas Hydrates, Volume 204 Initial Report Mallik 2002 GSC Bulletin 585 : Scientific results from the Mallik 2002 gas hydrate production well program Offshore gas hydrate sample

Use of Computed X-ray Tomographic Data for Analyzing the Thermodynamics of a Dissociating Porous Sand/Hydrate Mixture

Science.gov (United States)

Freifeld, Barry M.; Kneafsey, Timothy J.; Tomutsa, Liviu; Stern, Laura A.; Kirby, Stephen H.

2002-02-28

X-ray computed tomography (CT) is a method that has been used extensively in laboratory experiments for measuring rock properties and fluid transport behavior. More recently, CT scanning has been applied successfully to detect the presence and study the behavior of naturally occurring hydrates. In this study, we used a modified medical CT scanner to image and analyze the progression of a dissociation front in a synthetic methane hydrate/sand mixture. The sample was initially scanned under conditions at which the hydrate is stable (atmospheric pressure and liquid nitrogen temperature, 77 K). The end of the sample holder was then exposed to the ambient air, and the core was continuously scanned as dissociation occurred in response to the rising temperature. CT imaging captured the advancing dissociation front clearly and accurately. The evolved gas volume was monitored as a function of time. Measured by CT, the advancing hydrate dissociation front was modeled as a thermal conduction problem explicitly incorporating the enthalpy of dissociation, using the Stefan moving-boundary-value approach. The assumptions needed to perform the analysis consisted of temperatures at the model boundaries. The estimated value for thermal conductivity of 2.6 W/m K for the remaining water ice/sand mixture is higher than expected based on conduction alone; this high value may represent a lumped parameter that incorporates the processes of heat conduction, methane gas convection, and any kinetic effects that occur during dissociation. The technique presented here has broad implications for future laboratory and field testing that incorporates geophysical techniques to monitor gas hydrate dissociation.

Use of computed X-ray tomographic data for analyzing the thermodynamics of a dissociating porous sand/hydrate mixture

International Nuclear Information System (INIS)

Freifeld, Barry M.; Kneafsey, Timothy J.; Tomutsa, Liviu; Stern, Laura A.; Kirby, Stephen H.

2002-01-01

X-ray computed tomography (CT) is a method that has been used extensively in laboratory experiments for measuring rock properties and fluid transport behavior. More recently, CT scanning has been applied successfully to detect the presence and study the behavior of naturally occurring hydrates. In this study, we used a modified medical CT scanner to image and analyze the progression of a dissociation front in a synthetic methane hydrate/sand mixture. The sample was initially scanned under conditions at which the hydrate is stable (atmospheric pressure and liquid nitrogen temperature, 77 K). The end of the sample holder was then exposed to the ambient air, and the core was continuously scanned as dissociation occurred in response to the rising temperature. CT imaging captured the advancing dissociation front clearly and accurately. The evolved gas volume was monitored as a function of time. Measured by CT, the advancing hydrate dissociation front was modeled as a thermal conduction problem explicitly incorporating the enthalpy of dissociation, using the Stefan moving-boundary-value approach. The assumptions needed to perform the analysis consisted of temperatures at the model boundaries. The estimated value for thermal conductivity of 2.6 W/m K for the remaining water ice/sand mixture is higher than expected based on conduction alone; this high value may represent a lumped parameter that incorporates the processes of heat conduction, methane gas convection, and any kinetic effects that occur during dissociation. The technique presented here has broad implications for future laboratory and field testing that incorporates geophysical techniques to monitor gas hydrate dissociation

Thermodynamic description of the solubility of C-S-H gels in hydrated Portland cement. Literature review

International Nuclear Information System (INIS)

Soler, J.M.

2007-11-01

The objective of this study is to compile the available information published in the scientific literature regarding the solubility of C-S-H (calcium silica hydrate) gels, which are the main components of hydrated Portland cement. Modeling the thermodynamic properties of C-S-H, including its incongruent dissolution behavior, is an important requirement to understand the evolution and degradation of hydrated cement and concrete. The thermodynamic modeling of C-S-H started with the use of empirical or semi-empirical models and evolved to the application of solid solution models. Most of the experimental work has been performed at or near 25 deg C and the models are in principle applicable to temperatures near 25 deg C. One of the models provides an explicit dependence on temperature. (orig.)

Comparative Assessment of Advanced Gay Hydrate Production Methods

Energy Technology Data Exchange (ETDEWEB)

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

2009-06-30

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

Terahertz Time Domain Spectroscopy for Structure-II Gas Hydrates

DEFF Research Database (Denmark)

Takeya, Kei; Zhang, Caihong; Kawayama, Iwao

2009-01-01

For the nondestructive inspection of gas hydrates, terahertz (THz) time-domain spectroscopy (TDS) was applied to tetrahydrofuran (THF) hydrate and propane hydrate. The absorption of propane hydrate monotonically increases with frequency, similar to the case of ice, while THF hydrate has...... a characteristic broad absorption peak at 0.5 THz corresponding to the dipole moment of THF molecules. The refractive indices of THF and propane hydrates are 1.725 and 1.775 at 1 THz, respectively, and show a slight but clear difference from the refractive index of ice (1.79). THz-TDS is a potentially useful...... technique for the ondestructive inspection of gas hydrates. # 2009 The Japan Society of Applied Physics...

Thermodynamics of hydration of MX80-Na. What are the best approaches for evaluating the thermodynamic properties of hydration?

International Nuclear Information System (INIS)

Vieillard, P.; Lassin, A.; Blanc, P.; Gailhanou, H.; Gaboreau, S.; Gaucher, E.C.; Denoyel, R.; Bloch, E.; Fialips, C.; Giffaut, E.

2012-01-01

Document available in extended abstract form only. In the context of a waste disposal within clayey formations (Callovian-Oxfordian argillite) or using clayey barriers, the prediction of the long-term behavior requires the thermodynamic properties of clay minerals. It has been shown by Gailhanou et al. (submitted) that hydration reactions may have some dramatic consequences on the thermodynamic properties of clay minerals. Different theoretical models exist for extracting thermodynamic properties from water adsorption/desorption isotherms. The present work aims at investigating and comparing these methods, because they can provide very different results based on the assumptions of each models. First, three types of models are compared: 1) the Hill (1949) model based on heat of adsorption combined with adsorption isotherm, 2) the Jura and Hill (1951) model, based on the Clausius-Clapeyron relation, and 3) the BET theory. Both have been designed in order to describe surface sorption phenomena. For instance, they suppose that the number of sorption sites is constant during all the vapor sorption process (and at any relative humidity, P/P 0 ). The hydration reaction approach can also be used. Compared to the three previous models, it is not structurally constrained, except for mass balance considerations on the H 2 O component. It had been especially developed by Tardy and Touret, (1985) and modified into a solid solution model, first by Ransom and Helgeson, (1994). It relies simply on the reaction: Clay(dehydrated) + nH 2 O = Clay(hydrated).nH 2 O. The different families of models have been compared to experimental measurements performed on a sodic smectite MX80. The set of experiments includes a series of three adsorption/desorption isotherms obtained at 25, 45 and 60 C and a heat of adsorption combined with a adsorption isotherm obtained at 25 C. The heat of adsorption was derived from the 3 adsorption/desorption isotherms by using the different models. Then

A New Approach to Modeling Densities and Equilibria of Ice and Gas Hydrate Phases

Science.gov (United States)

Zyvoloski, G.; Lucia, A.; Lewis, K. C.

2011-12-01

The Gibbs-Helmholtz Constrained (GHC) equation is a new cubic equation of state that was recently derived by Lucia (2010) and Lucia et al. (2011) by constraining the energy parameter in the Soave form of the Redlich-Kwong equation to satisfy the Gibbs-Helmholtz equation. The key attributes of the GHC equation are: 1) It is a multi-scale equation because it uses the internal energy of departure, UD, as a natural bridge between the molecular and bulk phase length scales. 2) It does not require acentric factors, volume translation, regression of parameters to experimental data, binary (kij) interaction parameters, or other forms of empirical correlations. 3) It is a predictive equation of state because it uses a database of values of UD determined from NTP Monte Carlo simulations. 4) It can readily account for differences in molecular size and shape. 5) It has been successfully applied to non-electrolyte mixtures as well as weak and strong aqueous electrolyte mixtures over wide ranges of temperature, pressure and composition to predict liquid density and phase equilibrium with up to four phases. 6) It has been extensively validated with experimental data. 7) The AAD% error between predicted and experimental liquid density is 1% while the AAD% error in phase equilibrium predictions is 2.5%. 8) It has been used successfully within the subsurface flow simulation program FEHM. In this work we describe recent extensions of the multi-scale predictive GHC equation to modeling the phase densities and equilibrium behavior of hexagonal ice and gas hydrates. In particular, we show that radial distribution functions, which can be determined by NTP Monte Carlo simulations, can be used to establish correct standard state fugacities of 1h ice and gas hydrates. From this, it is straightforward to determine both the phase density of ice or gas hydrates as well as any equilibrium involving ice and/or hydrate phases. A number of numerical results for mixtures of N2, O2, CH4, CO2, water

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.

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

Influence of chemical and physical characteristics of cement kiln dusts (CKDs) on their hydration behavior and potential suitability for soil stabilization

International Nuclear Information System (INIS)

Peethamparan, Sulapha; Olek, Jan; Lovell, Janet

2008-01-01

The interaction of CKDs with a given soil depends on the chemical and physical characteristics of the CKDs. Hence, the characterization of CKDs and their hydration products may lead to better understanding of their suitability as soil stabilizers. In the present article, four different CKD powders are characterized and their hydration products are evaluated. A detailed chemical (X-ray diffraction), thermogravimetric and morphological (scanning electron microscope) analyses of both the CKD powders and the hydrated CKD pastes are presented. In general, high free-lime content (∼ 14-29%) CKDs, when reacted with water produced significant amounts of calcium hydroxide, ettringite and syngenite. These CKDs also developed higher unconfined compressive strength and higher temperature of hydration compared to CKDs with lower amounts of free-lime. An attempt was made to qualitatively correlate the performance of CKD pastes with the chemical and physical characteristics of the original CKD powders and to determine their potential suitability as soil stabilizers. To that effect a limited unconfined compressive strength testing of CKD-treated kaolinite clays was performed. The results of this study suggest that both the compressive strength and the temperature of hydration of the CKD paste can give early indications of the suitability of particular CKD for soil stabilization

Advanced Gas Hydrate Reservoir Modeling Using Rock Physics

Energy Technology Data Exchange (ETDEWEB)

McConnell, Daniel

2017-12-30

Prospecting for high saturation gas hydrate deposits can be greatly aided with improved approaches to seismic interpretation and especially if sets of seismic attributes can be shown as diagnostic or direct hydrocarbon indicators for high saturation gas hydrates in sands that would be of most interest for gas hydrate production.

A large 3D seismic data set in the deep water Eastern Gulf of Mexico was screened for gas hydrates using a set of techniques and seismic signatures that were developed and proven in the Central deepwater Gulf of Mexico in the DOE Gulf of Mexico Joint Industry Project JIP Leg II in 2009 and recently confirmed with coring in 2017.

A large gas hydrate deposit is interpreted in the data where gas has migrated from one of the few deep seated faults plumbing the Jurassic hydrocarbon source into the gas hydrate stability zone. The gas hydrate deposit lies within a flat-lying within Pliocene Mississippi Fan channel that was deposited outboard in a deep abyssal environment. The uniform architecture of the channel aided the evaluation of a set of seismic attributes that relate to attenuation and thin-bed energy that could be diagnostic of gas hydrates. Frequency attributes derived from spectral decomposition also proved to be direct hydrocarbon indicators by pseudo-thickness that could be only be reconciled by substituting gas hydrate in the pore space. The study emphasizes that gas hydrate exploration and reservoir characterization benefits from a seismic thin bed approach.

Experimental Setup to Characterize Bentonite Hydration Processes

International Nuclear Information System (INIS)

Bru, A.; Casero, D.; Pastor, J. M.

2001-01-01

We present an experimental setup to follow-up the hydration process of a bentonite. Clay samples, of 2 cm x 12 cm x 12 cm, were made and introduced in a Hele-Shaw cell with two PMM windows and two steel frames. In hydration experiments, a fluid enters by an orifice in the frame, located both at the top and the bottom of the cell, to perform hydration in both senses. To get a uniform hydration we place a diffuser near the orifice. Volume influxes in hydration cells are registered in time. The evolution of the developed interface was recorded on a videotape. The video cameras was fixed to a holder so that the vertical direction in the monitor was the same as the direction of the larger extension of the cell. (Author) 6 refs

Marine Gas Hydrates - An Untapped Non-conventional Energy ...

Indian Academy of Sciences (India)

Table of contents. Marine Gas Hydrates - An Untapped Non-conventional Energy Resource · Slide 2 · Slide 3 · Slide 4 · Gas Hydrate Stability Zone · Slide 6 · Slide 7 · Exploration of gas hydrates (seismic) · Characteristics of BSR · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Distribution of Gas Hydrates in KG ...

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.

Adsorption of water and carbon dioxide on hematite and consequences for possible hydrate formation.

Science.gov (United States)

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

2012-04-07

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-01-28

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

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.

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

With the completion of scientific studies undertaken as part of the 1998 Mallik 2L-38 gas hydrate research well, an international research site was established for the study of Arctic natural gas hydrates in the Mackenzie Delta of northwestern Canada. Quantitative well log analysis and core studies reveal multiple gas hydrate layers from 890 m to 1106 m depth, exceeding 110 m in total thickness. High gas hydrate saturation values, which in some cases exceed 80% of the pore volume, establish the Mallik gas hydrate field as one of the most concentrated gas hydrate reservoirs in the world. Beginning in December 2001 and continuing to the middle of March 2002, two 1188 m deep science observation wells were drilled and instrumented and a 1166 m deep production research well program was carried out. The program participants include 8 partners; The Geological Survey of Canada (GSC), The Japan National Oil Corporation (JNOC), GeoForschungsZentrum Potsdam (GFZ), United States Geological Survey (USGS), United States Department of the Energy (USDOE), India Ministry of Petroleum and Natural Gas (MOPNG)/Gas Authority of India (GAIL) and the Chevron-BP-Burlington joint venture group. In addition the project has been accepted as part of the International Scientific Continental Drilling Program. The Geological Survey of Canada is coordinating the science program for the project and JAPEX Canada Ltd. acted as the designated operator for the fieldwork. Primary objectives of the research program are to advance fundamental geological, geophysical and geochemical studies of the Mallik gas hydrate field and to undertake advanced production testing of a concentrated gas hydrate reservoir. Full-scale field experiments in the production well monitored the physical behavior of the hydrate deposits in response to depressurization and thermal stimulation. The observation wells facilitated cross-hole tomography and vertical seismic profile experiments (before and after production) as well as

Hydration shells exchange charge with their protein

DEFF Research Database (Denmark)

Abitan, Haim; Lindgård, Per-Anker; Nielsen, Bjørn Gilbert

2010-01-01

. In our experiments, the amplitude of an ultrasonic pressure wave is gradually increased (0–20 atm) while we simultaneously measure the Raman spectra from the hydrated protein (β-lactoglobulin and lysozyme). We detected two types of spectral changes: first, up to 70% increase in the intensity......Investigation of the interaction between a protein and its hydration shells is an experimental and theoretical challenge. Here, we used ultrasonic pressure waves in aqueous solutions of a protein to explore the conformational states of the protein and its interaction with its hydration shells...... the presence of an ultrasonic pressure, a protein and its hydration shells are in thermodynamic and charge equilibrium, i.e. a protein and its hydration shells exchange charges. The ultrasonic wave disrupts these equilibria which are regained within 30–45 min after the ultrasonic pressure is shut off....

Oceanic hydrates: more questions than answers

International Nuclear Information System (INIS)

Laherrere, Jean

2000-01-01

Methane hydrates create problems by blocking pipelines and casing; they are also accused of contributing to environmental problems (e.g. global warming). Methane hydrates are also found in permafrost areas and in oceanic sediments where the necessary temperature and pressure for stability occur. Claims for the widespread occurrence in thick oceanic deposits are unfounded: apparently indirect evidence from seismic reflectors, seismic hydrocarbon indicators, logs and free samples is unreliable. At one time, hydrate was seen as a static, biogenic, continuous, huge resource but that view is changing to one of a dynamic, overpressurised, discontinuous and unreliable resource. Only Japan and India are currently showing any serious interest in hydrates. Academic research has raised more questions than answers. It is suggested that more hard exploratory evidence rather than theoretical study is required

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 ...

Carbon dioxide hydrate formation in a fixed-bed reactor

Energy Technology Data Exchange (ETDEWEB)

Fan, S.; Lang, X. [South China Univ. of Technology, Guangzhou (China). Key Laboratory of Enhanced Heat Transfer and Energy Conservation; Wang, Y.; Liang, D. [Chinese Academy of Sciences, Guangzhou (China). Guangzhou Inst. of Energy Conversion and Guangzhou Center of Natural Gas Hydrate; Sun, X.; Jurcik, B. [Air Liquide Laboratories, Tsukuba (Japan)

2008-07-01

Gas hydrates are thermodynamically stable at high pressures and near the freezing temperature of pure water. Methane hydrates occur naturally in sediments in the deep oceans and permafrost regions and constitute an extensive hydrocarbon reservoir. Carbon dioxide (CO{sub 2}) hydrates are of interest as a medium for marine sequestration of anthropogenic carbon dioxide. Sequestering CO{sub 2} as hydrate has potential advantages over most methods proposed for marine CO{sub 2} sequestration. Because this technique requires a shallower depth of injection when compared with other ocean sequestration methods, the costs of CO{sub 2} hydrate sequestration may be lower. Many studies have successfully used different continuous reactor designs to produce CO{sub 2} hydrates in both laboratory and field settings. This paper discussed a study that involved the design and construction of a fixed-bed reactor for simulation of hydrate formation system. Water, river sands and carbon dioxide were used to simulate the seep kind of hydrate formation. Carbon dioxide gas was distributed as small bubbles to enter from the bottom of the fixed-bed reactor. The paper discussed the experimental data and presented a diagram of the gas hydrate reactor system. The morphology as well as the reaction characters of CO{sub 2} hydrate was presented in detail. The results were discussed in terms of experimental phenomena and hydrate formation rate. A mathematical model was proposed for describing the process. 17 refs., 7 figs.

Structural and hydration properties of amorphous tricalcium silicate

International Nuclear Information System (INIS)

Mori, K.; Fukunaga, T.; Shiraishi, Y.; Iwase, K.; Xu, Q.; Oishi, K.; Yatsuyanagi, K.; Yonemura, M.; Itoh, K.; Sugiyama, M.; Ishigaki, T.; Kamiyama, T.; Kawai, M.

2006-01-01

Mechanical milling was carried out to synthesize amorphous tricalcium silicate (Ca 3 SiO 5 ) sample, where Ca 3 SiO 5 is the most principal component of Portland cement. The partial phase transformation from the crystalline to the amorphous state was observed by X-ray and neutron diffractions. Moreover, it was found that the structural distortion on the Ca-O correlation exists in the milled Ca 3 SiO 5 . The hydration of the milled Ca 3 SiO 5 with D 2 O proceeds as follows: the formation of hydration products such as Ca(OD) 2 rapidly occurs in the early hydration stage, and then proceeds slowly after about 15 h. The induction time for the hydration of the milled Ca 3 SiO 5 is approximately one half shorter than that for the hydration of the unmilled one. This result means that the mechanical milling brings about the chemical activity of Ca 3 SiO 5 for hydration, and may be particularly useful for increasing the reactivity in the early hydration stage

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.

Mechanical Performance of Asphalt Mortar Containing Hydrated Lime and EAFSS at Low and High Temperatures

Directory of Open Access Journals (Sweden)

Ki Hoon Moon

2017-07-01

Full Text Available In this paper, the possibility of improving the global response of asphalt materials for pavement applications through the use of hydrated lime and Electric Arc-Furnace Steel Slag (EAFSS was investigated. For this purpose, a set of asphalt mortars was prepared by mixing two different asphalt binders with fine granite aggregate together with hydrated lime or EAFSS at three different percentages. Bending Beam Rheometer (BBR creep tests and Dynamic Shear Rheometer (DSR complex modulus tests were performed to evaluate the material response both at low and high temperature. Then, the rheological Huet model was fitted to the BBR creep results for estimating the impact of filler content on the model parameters. It was found that an addition of hydrated lime and EAFSS up to 10% and 5%, respectively, results in satisfactory low-temperature performance with a substantial improvement of the high-temperature behavior.

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

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

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

Structural determinants of hydration, mechanics and fluid flow in freeze-dried collagen scaffolds.

Science.gov (United States)

Offeddu, G S; Ashworth, J C; Cameron, R E; Oyen, M L

2016-09-01

Freeze-dried scaffolds provide regeneration templates for a wide range of tissues, due to their flexibility in physical and biological properties. Control of structure is crucial for tuning such properties, and therefore scaffold functionality. However, the common approach of modeling these scaffolds as open-cell foams does not fully account for their structural complexity. Here, the validity of the open-cell model is examined across a range of physical characteristics, rigorously linking morphology to hydration and mechanical properties. Collagen scaffolds with systematic changes in relative density were characterized using Scanning Electron Microscopy, X-ray Micro-Computed Tomography and spherical indentation analyzed in a time-dependent poroelastic framework. Morphologically, all scaffolds were mid-way between the open- and closed-cell models, approaching the closed-cell model as relative density increased. Although pore size remained constant, transport pathway diameter decreased. Larger collagen fractions also produced greater volume swelling on hydration, although the change in pore diameter was constant, and relatively small at ∼6%. Mechanically, the dry and hydrated scaffold moduli varied quadratically with relative density, as expected of open-cell materials. However, the increasing pore wall closure was found to determine the time-dependent nature of the hydrated scaffold response, with a decrease in permeability producing increasingly elastic rather than viscoelastic behavior. These results demonstrate that characterizing the deviation from the open-cell model is vital to gain a full understanding of scaffold biophysical properties, and provide a template for structural studies of other freeze-dried biomaterials. Freeze-dried collagen sponges are three-dimensional microporous scaffolds that have been used for a number of exploratory tissue engineering applications. The characterization of the structure-properties relationships of these scaffolds is

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

Nuclear Well Log Properties of Natural Gas Hydrate Reservoirs

Science.gov (United States)

Burchwell, A.; Cook, A.

2015-12-01

Characterizing gas hydrate in a reservoir typically involves a full suite of geophysical well logs. The most common method involves using resistivity measurements to quantify the decrease in electrically conductive water when replaced with gas hydrate. Compressional velocity measurements are also used because the gas hydrate significantly strengthens the moduli of the sediment. At many gas hydrate sites, nuclear well logs, which include the photoelectric effect, formation sigma, carbon/oxygen ratio and neutron porosity, are also collected but often not used. In fact, the nuclear response of a gas hydrate reservoir is not known. In this research we will focus on the nuclear log response in gas hydrate reservoirs at the Mallik Field at the Mackenzie Delta, Northwest Territories, Canada, and the Gas Hydrate Joint Industry Project Leg 2 sites in the northern Gulf of Mexico. Nuclear logs may add increased robustness to the investigation into the properties of gas hydrates and some types of logs may offer an opportunity to distinguish between gas hydrate and permafrost. For example, a true formation sigma log measures the thermal neutron capture cross section of a formation and pore constituents; it is especially sensitive to hydrogen and chlorine in the pore space. Chlorine has a high absorption potential, and is used to determine the amount of saline water within pore spaces. Gas hydrate offers a difference in elemental composition compared to water-saturated intervals. Thus, in permafrost areas, the carbon/oxygen ratio may vary between gas hydrate and permafrost, due to the increase of carbon in gas hydrate accumulations. At the Mallik site, we observe a hydrate-bearing sand (1085-1107 m) above a water-bearing sand (1107-1140 m), which was confirmed through core samples and mud gas analysis. We observe a decrease in the photoelectric absorption of ~0.5 barnes/e-, as well as an increase in the formation sigma readings of ~5 capture units in the water-bearing sand as

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

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 continental margins. The behavior shall be explored in response to two warming scenarios: longer term change due to sea level rise (e.g. 20 thousand years) and shorter term due to atmospheric warming by anthropogenic forcing (decadal time scale). 1.2. Project Objectives During the first budget period, the objectives are to review and categorize the stability state of existing well-studied hydrate reservoirs, develop conceptual and numerical models of the melting process, and to design and conduct laboratory experiments that dissociate methane hydrate in a model sediment column by systematically controlling the temperature profile along the column. The final objective of the first budget period shall be to validate the models against the experiments. In the second budget period, the objectives are to develop a model of gas flow into sediment in which hydrate is thermodynamically stable, and conduct laboratory experiments of this process to validate the model. The developed models shall be used to quantify the rate and volume of gas that escapes from dissociating hydrate accumulations. In addition, specific scaled simulations characteristic of Arctic regions and regions near the stability limit at continental margins shall be performed. 1.3. Project Background and Rationale The central hypothesis proposed is that hydrate melting (dissociation) due to climate change generates free gas that can, under certain conditions, propagate through the gas hydrate stability

First-principles elasticity of monocarboaluminate hydrates

KAUST Repository

Moon, J.; Yoon, S.; Wentzcovitch, R. M.; Monteiro, P. J. M.

2014-01-01

The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

First-principles elasticity of monocarboaluminate hydrates

KAUST Repository

Moon, J.

2014-07-01

The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

Water Dynamics in the Hydration Shells of Biomolecules

Science.gov (United States)

2017-01-01

The structure and function of biomolecules are strongly influenced by their hydration shells. Structural fluctuations and molecular excitations of hydrating water molecules cover a broad range in space and time, from individual water molecules to larger pools and from femtosecond to microsecond time scales. Recent progress in theory and molecular dynamics simulations as well as in ultrafast vibrational spectroscopy has led to new and detailed insight into fluctuations of water structure, elementary water motions, electric fields at hydrated biointerfaces, and processes of vibrational relaxation and energy dissipation. Here, we review recent advances in both theory and experiment, focusing on hydrated DNA, proteins, and phospholipids, and compare dynamics in the hydration shells to bulk water. PMID:28248491

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

Science.gov (United States)

Grim, R. Gary

-guest molecule. Finally, for all of the collective research on gas hydrates since their discovery in 1810 by Sir Humphrey Davy, the one common theme that unites them is the assumption that guest molecules are trapped at the center (or near center) of the host water cages that makes up the respective crystal structure. For the first time, this work provides evidence suggesting that this definition of clathrate hydrate guest occupancy is possibly incomplete, and should include the addition of interstitial sites within the water crystal lattice. Specifically, H2 is found within the shared heptagonal faces of the large (4 3596273) cage and in cavities formed from the disruption of smaller (445 4) water cages in structure VI hydrates. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 in solids and reveals new insight into guest-guest and guest-host interactions in clathrate hydrates with potential implications in increasing overall energy storage properties.

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.

Hydration of swelling clays: multi-scale sequence of hydration and determination of macroscopic energies from microscopic properties; Hydratation des argiles gonflantes: sequence d'hydratation multi-echelle determination des energies macroscopiques a partir des proprietes microscopiques

Energy Technology Data Exchange (ETDEWEB)

Salles, F

2006-10-15

Smectites have interesting properties which make them potential candidates for engineered barriers in deep geological nuclear waste repository: low permeability, swelling and cations retention. The subject of this thesis consists in the determination of the relationship between hydration properties, swelling properties and cations mobility in relation with confinement properties of clayey materials. The aim is to understand and to predict the behaviour of water in smectites, following two research orientations: the mechanistic aspects and the energetic aspects of the hydration of smectites. We worked on the Na-Ca montmorillonite contained in the MX80 bentonite, with the exchanged homo ionic structure (saturated with alkaline cations and calcium cations). The approach crosses the various scales (microscopic, mesoscopic and macroscopic) and implied the study of the various components of the system (layer-cation-water), by using original experimental methods (thermo-poro-metry and electric conductivity for various relative humidities (RH) and electrostatic calculations. Initially, the dry state is defined by SCTA (scanning calorimetry thermal analysis). Then a classical characterization of the smectite porosity for the dry state is carried out using mercury intrusion and nitrogen adsorption. We evidenced the existence of a meso-porosity which radius varies from 2 to 10 nm depending on the compensating cation. The thermo-poro-metry and conductivity experiments performed at various hydration states made it possible to follow the increase in the pore sizes and the cations mobility as a function of the hydration state. We highlight in particular the existence of an osmotic mesoscopic swelling for low RH (approximately 50-60%RH for Li and Na). By combining the results of thermo-poro-metry, X-ray diffraction and electric conductivity, we are able to propose a complete hydration sequence for each cation, showing the crucial role of the compensating cation in the hydration of

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.

Constraining gas hydrate occurrence in the northern Gulf of Mexico continental slope : fine scale analysis of grain-size in hydrate-bearing sediments

Energy Technology Data Exchange (ETDEWEB)

Hangsterfer, A.; Driscoll, N.; Kastner, M. [Scripps Inst. of Oceanography, La Jolla, CA (United States). Geosciences Research Division

2008-07-01

Methane hydrates can form within the gas hydrate stability zone (GHSZ) in sea beds. The Gulf of Mexico (GOM) contains an underlying petroleum system and deeply buried, yet dynamic salt deposits. Salt tectonics and fluid expulsion upward through the sediment column result in the formation of fractures, through which high salinity brines migrate into the GHSZ, destabilizing gas hydrates. Thermogenic and biogenic hydrocarbons also migrate to the seafloor along the GOMs northern slope, originating from the thermal and biogenic degradation of organic matter. Gas hydrate occurrence can be controlled by either primary permeability, forming in coarse-grained sediment layers, or by secondary permeability, forming in areas where hydrofracture and faulting generate conduits through which hydrocarbon-saturated fluids flow. This paper presented a study that attempted to determine the relationship between grain-size, permeability, and gas hydrate distribution. Grain-size analyses were performed on cores taken from Keathley Canyon and Atwater Valley in the GOM, on sections of cores that both contained and lacked gas hydrate. Using thermal anomalies as proxies for the occurrence of methane hydrate within the cores, samples of sediment were taken and the grain-size distributions were measured to see if there was a correlation between gas hydrate distribution and grain-size. The paper described the methods, including determination of hydrate occurrence and core analysis. It was concluded that gas hydrate occurrence in Keathley Canyon and Atwater Valley was constrained by secondary permeability and was structurally controlled by hydrofractures and faulting that acted as conduits through which methane-rich fluids flowed. 11 refs., 2 tabs., 5 figs.

Methane Recycling During Burial of Methane Hydrate-Bearing Sediments

Science.gov (United States)

You, K.; Flemings, P. B.

2017-12-01

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

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)

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.

On the hydration of subnanometric antifouling organosilane adlayers: a molecular dynamics simulation.

Science.gov (United States)

Sheikh, Sonia; Blaszykowski, Christophe; Nolan, Robert; Thompson, Damien; Thompson, Michael

2015-01-01

The connection between antifouling and surface hydration is a fascinating but daunting question to answer. Herein, we use molecular dynamics (MD) computer simulations to gain further insight into the role of surface functionalities in the molecular-level structuration of water (surface kosmotropicity)--within and atop subnanometric organosilane adlayers that were shown in previous experimental work to display varied antifouling behavior. Our simulations support the hypothesized intimate link between surface hydration and antifouling, in particular the importance of both internal and interfacial hydrophilicity and kosmotropicity. The antifouling mechanism is also discussed in terms of surface dehydration energy and water dynamicity (lability and mobility), notably the crucial requirement for clustered water molecules to remain tightly bound for extensive periods of time--i.e. exhibit slow exchange dynamics. A substrate effect on surface hydration, which would also participate in endowing antifouling adlayers with hydrogel-like characteristics, is also proposed. In contrast, the role of adlayer flexibility, if any, is assigned a secondary role in these ultrathin structures made of short building blocks. The conclusions from this work are well in line with those previously drawn in the literature. Copyright © 2014 Elsevier Inc. All rights reserved.

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.

Nasogastric Hydration in Infants with Bronchiolitis Less Than 2 Months of Age.

Science.gov (United States)

Oakley, Ed; Bata, Sonny; Rengasamy, Sharmila; Krieser, David; Cheek, John; Jachno, Kim; Babl, Franz E

2016-11-01

To determine whether nasogastric hydration can be used in infants less than 2 months of age with bronchiolitis, and characterize the adverse events profile of these infants compared with infants given intravenous (IV) fluid hydration. A descriptive retrospective cohort study of children with bronchiolitis under 2 months of age admitted for hydration at 3 centers over 3 bronchiolitis seasons was done. We determined type of hydration (nasogastric vs IV fluid hydration) and adverse events, intensive care unit admission, and respiratory support. Of 491 infants under 2 months of age admitted with bronchiolitis, 211 (43%) received nonoral hydration: 146 (69%) via nasogastric hydration and 65 (31%) via IV fluid hydration. Adverse events occurred in 27.4% (nasogastric hydration) and 23.1% (IV fluid hydration), difference of 4.3%; 95%CI (-8.2 to 16.9), P = .51. The majority of adverse events were desaturations (21.9% nasogastric hydration vs 21.5% IV fluid hydration, difference 0.4%; [-11.7 to 12.4], P = .95). There were no pulmonary aspirations in either group. Apneas and bradycardias were similar in each group. IV fluid hydration use was positively associated with intensive care unit admission (38.5% IV fluid hydration vs 19.9% nasogastric hydration; difference 18.6%, [5.1-32.1], P = .004); and use of ventilation support (27.7% IV fluid hydration vs 15.1% nasogastric hydration; difference 12.6 [0.3-23], P = .03). Fewer infants changed from nasogastric hydration to IV fluid hydration than from IV fluid hydration to nasogastric hydration (12.3% vs 47.7%; difference -35.4% [-49 to -22], P hydration can be used in the majority of young infants admitted with bronchiolitis. Nasogastric hydration and IV fluid hydration had similar rates of complications. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Amorphous-crystalline transition studied in hydrated MoO{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Camacho-Lopez, M.A. [Facultad de Quimica, Universidad Autonoma del Estado de Mexico, Paseo Colon y Tollocan, Toluca Edo. de Mexico 50110 (Mexico); Haro-Poniatowski, E. [Departamento de Fisica, Laboratorio de Optica Cuantica, Universidad Autonoma Metropolitana-Iztapalapa, Apdo. Postal 55-534, Mexico, D.F. 09340 (Mexico); Lartundo-Rojas, L. [Laboratorio de Microscopia, Universidad Autonoma Metropolitana-Iztapalapa, Apdo. Postal 55-534, Mexico, D.F. 09340 (Mexico); Livage, J. [Chimie de la Matiere Condensee, Universite Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05 (France); Julien, C.M. [Institut des Nano-Sciences de Paris, UMR 7588, Universite Pierre et Marie Curie, Campus Boucicaut, 140 rue de Lourmel, 75015 Paris (France)]. E-mail: Christian.Julien@insp.jussieu.fr

2006-11-25

In this work we study the thermal behavior of hydrated MoO{sub 3} synthesized via acidification of sodium molybdate. MoO{sub 3}.nH{sub 2}O (n = 1.4) amorphous compound was heated in air at increasing temperatures in order to obtain the crystalline MoO{sub 3} phase. We have studied the structural changes as a function of annealing temperature by Raman spectroscopy. A statistical study to determine the average size of the crystallites at each annealing step has been realized by scanning electron microscopy. Results show that the hydrated MoO{sub 3}.1.4H{sub 2}O glass transforms in an amorphous MoO{sub 3}.0.7H{sub 2}O phase prior to its crystallization, while the sample heated at 500 deg. C crystallizes into the orthorhombic {alpha}-MoO{sub 3} phase with micro-crystallites having an average size of 6.8 {mu}m.

Thermal conductivity measurements in unsaturated hydrate-bearing sediments

Science.gov (United States)

Dai, Sheng; Cha, Jong-Ho; Rosenbaum, Eilis J.; Zhang, Wu; Seol, Yongkoo

2015-08-01

Current database on the thermal properties of hydrate-bearing sediments remains limited and has not been able to capture their consequential changes during gas production where vigorous phase changes occur in this unsaturated system. This study uses the transient plane source (TPS) technique to measure the thermal conductivity of methane hydrate-bearing sediments with various hydrate/water/gas saturations. We propose a simplified method to obtain thermal properties from single-sided TPS signatures. Results reveal that both volume fraction and distribution of the pore constituents govern the thermal conductivity of unsaturated specimens. Thermal conductivity hysteresis is observed due to water redistribution and fabric change caused by hydrate formation and dissociation. Measured thermal conductivity increases evidently when hydrate saturation Sh > 30-40%, shifting upward from the geometric mean model prediction to a Pythagorean mixing model. These observations envisage a significant drop in sediment thermal conductivity when residual hydrate/water saturation falls below ~40%, hindering further gas production.

Effect of Gemini-type surfactant on methane hydrate formation

Energy Technology Data Exchange (ETDEWEB)

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

2008-07-01

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

Volume of hydration in terminal cancer patients.

Science.gov (United States)

Bruera, E; Belzile, M; Watanabe, S; Fainsinger, R L

1996-03-01

In this retrospective study we reviewed the volume and modality of hydration of consecutive series of terminal cancer patients in two different settings. In a palliative care unit 203/290 admitted patients received subcutaneous hydration for 12 +/- 8 days at a daily volume of 1015 +/- 135 ml/day. At the cancer center, 30 consecutive similar patients received intravenous hydration for 11.5 +/- 5 days (P > 0.2) but at a daily volume of 2080 +/- 720 ml/day (P palliative care unit patients required discontinuation of hydration because of complications. Hypodermoclysis was administered mainly as a continuous infusion, an overnight infusion, or in one to three 1-h boluses in 62 (31%), 98 (48%) and 43 (21%) patients, respectively. Our findings suggest that, in some settings, patients may be receiving excessive volumes of hydration by less comfortable routes such as the intravenous route. Increased education and research in this area are badly needed.

Life Origination Hydrate Theory (LOH-Theory) and Mitosis and Replication Hydrate Theory (MRH-Theory): three-dimensional PC validation

Science.gov (United States)

Kadyshevich, E. A.; Dzyabchenko, A. V.; Ostrovskii, V. E.

2014-04-01

Size compatibility of the CH4-hydrate structure II and multi-component DNA fragments is confirmed by three-dimensional simulation; it is validation of the Life Origination Hydrate Theory (LOH-Theory).

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

Vibrational dynamics of hydration water in amylose

CERN Document Server

Cavatorta, F; Albanese, G; Angelini, N

2002-01-01

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

Separation of water through gas hydrate formation

DEFF Research Database (Denmark)

Boch Andersen, Torben; Thomsen, Kaj

2009-01-01

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

Enclathration of CO2 as a co-guest of structure H hydrates and its implications for CO2 capture and sequestration

International Nuclear Information System (INIS)

Lee, Yohan; Lee, Dongyoung; Lee, Jong-Won; Seo, Yongwon

2016-01-01

Highlights: • We examine sH hydrates with CO 2 + N 2 + neohexane for CO 2 capture and sequestration. • The structural transition occurs in the CO 2 (40%) + N 2 (60%) + neohexane system. • CO 2 molecules are enclathrated into sH hydrates in the N 2 -rich systems. • CO 2 selectivity in sH hydrates is slightly lower than that in sI hydrates. • ΔH d values provide information on the structural transition of sH to sI hydrates. - Abstract: In this study, the thermodynamic behaviors, cage-specific guest distributions, structural transition, and dissociation enthalpies of sH hydrates with CO 2 + N 2 gas mixtures were investigated for their potential applications to hydrate-based CO 2 capture and sequestration. The stability conditions of the CO 2 + N 2 + water systems and the CO 2 + N 2 + neohexane (2,2-dimethylbutane, NH) + water systems indicated that the gas mixtures in the range of flue gas compositions could form sH hydrates, thereby mitigating the pressure and temperature required for gas hydrate formation. Structure identification using powder X-ray diffraction (PXRD) revealed the coexistence of sI and sH hydrates in the CO 2 (40%) + N 2 (60%) + NH system and the hydrate structure transformed from sH into sI as the CO 2 concentration increased. In addition, the Raman analysis clearly demonstrated that CO 2 molecules were enclathrated into the cages of sH hydrates in the N 2 -rich systems. It was found from direct CO 2 composition measurements that CO 2 selectivity in the sH hydrate phase was slightly lower than that in the corresponding sI hydrate phase. Dissociation enthalpy (ΔH d ) measurements using a high-pressure micro-differential scanning calorimeter (HP μ-DSC) indicated that the ΔH d values could also provide valuable information on the structural transition of sH to sI hydrates with respect to the CO 2 concentration in the feed gas. This study provides a better understanding of the thermodynamic and physicochemical background for CO 2

Spectral Decomposition and Other Seismic Attributes for Gas Hydrate Prospecting

Energy Technology Data Exchange (ETDEWEB)

McConnell, Dan

2018-02-25

Studying the sediments at the base of gas hydrate stability is ideal for determining the seismic response to gas hydrate saturation. First, assuming gas migration to the shallow section, this area is more likely to have concentrated gas hydrate because it encompasses the zone in which upward moving buoyant gas transitions to form immobile gas hydrate deposits. Second, this zone is interesting because these areas have the potential to show a hydrate filled zone and a gas filled zone within the same sediments. Third, the fundamental measurement within seismic data is impedance contrasts between velocity*density layers. High saturation gas hydrates and free gas inhabit opposite ends of these measurements making the study of this zone ideal for investigating the seismic characteristics of gas hydrate and, hence, the investigation of other seismic attributes that may indicate gas hydrate fill.

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

Energy Technology Data Exchange (ETDEWEB)

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

1997-02-01

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

A new educational tool to learn about hydration: taste workshops for children.

Science.gov (United States)

Valero Gaspar, Teresa; Rodríguez-Alonso, Paula; Ruiz Moreno, Emma; Del Pozo de la Calle, Susana; Ávila Torres, José Manuel; Varela Moreiras, Gregorio

2016-07-13

Nutrition education contributes to children´s understanding and practice of healthy lifestyles behaviors. Having a well hydration status is an essential topic, especially since children are a vulnerable population who are much more  prone to dehydration than adults are. The approval of the Report on the European Gastronomic Heritage: Cultural and Educational Aspects in 2014 served as starting point to work on innovative audio-visual and multimedia materials for children. The Spanish Nutrition Foundation (FEN) and the Royal Academy of Gastronomy (RAG), in collaboration with the Ministry of Education, Culture and Sport in Spain (MECD),  developed educational videos for schoolchildren to learn about food, nutrition and gastronomy, specially, the importance of being hydrated. To develop a serial of videos for children between 3 and 9 years old with nutrition and cooking lessons to be used as educational resources in the official curricula. Fourteen chapters related to food, nutrition, gastronomy, physical activity and hydration to be used to record videos were designed and tested. A nutritionist, a chef and two puppets were the main characters acting in the videos.  The chapters were assembled in nine videos that included five sections: introduction, video lesson, recipes -in case of hydration, recipes with different water content foods were recorded-, what have you learntand check your knowledge. A summary of the new educational material was officially presented at the Spain Pavilion during the Expo Milano 2015. Moreover, they are included as education  tool for teachers in the new PANGEI Programme (Food, Nutrition and Gastronomy for Infantile Education) conjointly launched by FEN, RAG and MEDC. Taste workshops are useful as innovative nutrition education tools to reinforce language, listening and motor skills as well as food and nutrition concepts, and specially, the importance of being well hydrated.

Dynamic morphology of gas hydrate on a methane bubble in water: Observations and new insights for hydrate film models

Science.gov (United States)

Warzinski, Robert P.; Lynn, Ronald; Haljasmaa, Igor; Leifer, Ira; Shaffer, Frank; Anderson, Brian J.; Levine, Jonathan S.

2014-10-01

Predicting the fate of subsea hydrocarbon gases escaping into seawater is complicated by potential formation of hydrate on rising bubbles that can enhance their survival in the water column, allowing gas to reach shallower depths and the atmosphere. The precise nature and influence of hydrate coatings on bubble hydrodynamics and dissolution is largely unknown. Here we present high-definition, experimental observations of complex surficial mechanisms governing methane bubble hydrate formation and dissociation during transit of a simulated oceanic water column that reveal a temporal progression of deep-sea controlling mechanisms. Synergistic feedbacks between bubble hydrodynamics, hydrate morphology, and coverage characteristics were discovered. Morphological changes on the bubble surface appear analogous to macroscale, sea ice processes, presenting new mechanistic insights. An inverse linear relationship between hydrate coverage and bubble dissolution rate is indicated. Understanding and incorporating these phenomena into bubble and bubble plume models will be necessary to accurately predict global greenhouse gas budgets for warming ocean scenarios and hydrocarbon transport from anthropogenic or natural deep-sea eruptions.

Influence of Lithium Carbonate on C3A Hydration

Directory of Open Access Journals (Sweden)

Weiwei Han

2018-01-01

Full Text Available Lithium salts, known to ameliorate the effects of alkali-silica reaction, can make significant effects on cement setting. However, the mechanism of effects on cement hydration, especially the hydration of C3A which is critical for initial setting time of cement, is rarely reported. In this study, the development of pH value of pore solution, conductivity, thermodynamics, and mineralogical composition during hydration of C3A with or without Li2CO3 are investigated. The results demonstrate that Li2CO3 promotes C3A hydration through high alkalinity, due to higher activity of lithium ion than that of calcium ion in the solution and carbonation of C3A hydration products resulted from Li2CO3. Li2CO3 favors the C3A hydration in C3A-CaSO4·2H2O-Ca(OH2-H2O hydration system and affects the mineralogical variation of the ettringite phase(s.

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.

Gas hydrate inhibition by perturbation of liquid water structure

Science.gov (United States)

Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Lee, Kun-Hong

2015-06-01

Natural gas hydrates are icy crystalline materials that contain hydrocarbons, which are the primary energy source for this civilization. The abundance of naturally occurring gas hydrates leads to a growing interest in exploitation. Despite their potential as energy resources and in industrial applications, there is insufficient understanding of hydrate kinetics, which hinders the utilization of these invaluable resources. Perturbation of liquid water structure by solutes has been proposed to be a key process in hydrate inhibition, but this hypothesis remains unproven. Here, we report the direct observation of the perturbation of the liquid water structure induced by amino acids using polarized Raman spectroscopy, and its influence on gas hydrate nucleation and growth kinetics. Amino acids with hydrophilic and/or electrically charged side chains disrupted the water structure and thus provided effective hydrate inhibition. The strong correlation between the extent of perturbation by amino acids and their inhibition performance constitutes convincing evidence for the perturbation inhibition mechanism. The present findings bring the practical applications of gas hydrates significantly closer, and provide a new perspective on the freezing and melting phenomena of naturally occurring gas hydrates.

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....

Reflective terahertz (THz) imaging: system calibration using hydration phantoms

Science.gov (United States)

Bajwa, Neha; Garritano, James; Lee, Yoon Kyung; Tewari, Priyamvada; Sung, Shijun; Maccabi, Ashkan; Nowroozi, Bryan; Babakhanian, Meghedi; Sanghvi, Sajan; Singh, Rahul; Grundfest, Warren; Taylor, Zachary

2013-02-01

Terahertz (THz) hydration sensing continues to gain traction in the medical imaging community due to its unparalleled sensitivity to tissue water content. Rapid and accurate detection of fluid shifts following induction of thermal skin burns as well as remote corneal hydration sensing have been previously demonstrated in vivo using reflective, pulsed THz imaging. The hydration contrast sensing capabilities of this technology were recently confirmed in a parallel 7 Tesla Magnetic Resonance (MR) imaging study, in which burn areas are associated with increases in local mobile water content. Successful clinical translation of THz sensing, however, still requires quantitative assessments of system performance measurements, specifically hydration concentration sensitivity, with tissue substitutes. This research aims to calibrate the sensitivity of a novel, reflective THz system to tissue water content through the use of hydration phantoms for quantitative comparisons of THz hydration imagery.Gelatin phantoms were identified as an appropriate tissue-mimicking model for reflective THz applications, and gel composition, comprising mixtures of water and protein, was varied between 83% to 95% hydration, a physiologically relevant range. A comparison of four series of gelatin phantom studies demonstrated a positive linear relationship between THz reflectivity and water concentration, with statistically significant hydration sensitivities (p hydration). The THz-phantom interaction is simulated with a three-layer model using the Transfer Matrix Method with agreement in hydration trends. Having demonstrated the ability to accurately and noninvasively measure water content in tissue equivalent targets with high sensitivity, reflective THz imaging is explored as a potential tool for early detection and intervention of corneal pathologies.

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.

An experimental point of view on hydration/solvation in halophilic proteins.

Science.gov (United States)

Talon, Romain; Coquelle, Nicolas; Madern, Dominique; Girard, Eric

2014-01-01

Protein-solvent interactions govern the behaviors of proteins isolated from extreme halophiles. In this work, we compared the solvent envelopes of two orthologous tetrameric malate dehydrogenases (MalDHs) from halophilic and non-halophilic bacteria. The crystal structure of the MalDH from the non-halophilic bacterium Chloroflexus aurantiacus (Ca MalDH) solved, de novo, at 1.7 Å resolution exhibits numerous water molecules in its solvation shell. We observed that a large number of these water molecules are arranged in pentagonal polygons in the first hydration shell of Ca MalDH. Some of them are clustered in large networks, which cover non-polar amino acid surface. The crystal structure of MalDH from the extreme halophilic bacterium Salinibacter ruber (Sr) solved at 1.55 Å resolution shows that its surface is strongly enriched in acidic amino acids. The structural comparison of these two models is the first direct observation of the relative impact of acidic surface enrichment on the water structure organization between a halophilic protein and its non-adapted counterpart. The data show that surface acidic amino acids disrupt pentagonal water networks in the hydration shell. These crystallographic observations are discussed with respect to halophilic protein behaviors in solution.

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

An international effort to compare gas hydrate reservoir simulators

Energy Technology Data Exchange (ETDEWEB)

Wilder, J.W. [Akron Univ., Akron, OH (United States). Dept. of Theoretical and Applied Math; Moridis, G.J. [California Univ., Berkely, CA (United States). Earth Sciences Div., Lawrence Berkely National Lab.; Wilson, S.J. [Ryder Scott Co., Denver, CO (United States); Kurihara, M. [Japan Oil Engineering Co. Ltd., Tokyo (Japan); White, M.D. [Pacific Northwest National Laboratory Hydrology Group, Richland, WA (United States); Masuda, Y. [Tokyo Univ., Tokyo (Japan). Dept. of Geosystem Engineering; Anderson, B.J. [National Energy Technology Lab., Morgantown, WV (United States)]|[West Virginia Univ., Morgantown, WV (United States). Dept. of Chemical Engineering; Collett, T.S. [United States Geological Survey, Denver, CO (United States); Hunter, R.B. [ASRC Energy Services, Anchorage, AK (United States); Narita, H. [National Inst. of Advanced Industrial Science and Technology, MEthane hydrate Research Lab., Sapporo (Japan); Pooladi-Darvish, M. [Fekete Associates Inc., Calgary, AB (Canada); Rose, K.; Boswell, R. [National Energy Technology Lab., Morgantown, WV (United States)

2008-07-01

In this study, 5 different gas hydrate production scenarios were modeled by the CMG STARS, HydateResSim, MH-21 HYDRES, STOMP-HYD and the TOUGH+HYDRATE reservoir simulators for comparative purposes. The 5 problems ranged in complexity from 1 to 3 dimensional with radial symmetry, and in horizontal dimensions of 20 meters to 1 kilometer. The scenarios included (1) a base case with non-isothermal multi-fluid transition to equilibrium, (2) a base case with gas hydrate (closed-domain hydrate dissociation), (3) dissociation in a 1-D open domain, (4) gas hydrate dissociation in a one-dimensional radial domain, similarity solutions, (5) gas hydrate dissociation in a two-dimensional radial domain. The purpose of the study was to compare the world's leading gas hydrate reservoir simulators in an effort to improve the simulation capability of experimental and naturally occurring gas hydrate accumulations. The problem description and simulation results were presented for each scenario. The results of the first scenario indicated very close agreement among the simulators, suggesting that all address the basics of mass and heat transfer, as well as overall process of gas hydrate dissociation. The third scenario produced the initial divergence among the simulators. Other differences were noted in both scenario 4 and 5, resulting in significant corrections to algorithms within several of the simulators. The authors noted that it is unlikely that these improvements would have been identified without this comparative study due to a lack of real world data for validation purposes. It was concluded that the solution for gas hydrate production involves a combination of highly coupled fluid, heat and mass transport equations combined with the potential for formation or disappearance of multiple solid phases in the system. The physical and chemical properties of the rocks containing the gas hydrate depend on the amount of gas hydrate present in the system. Each modeling and

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

[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.

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.

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.

Dynamics of proteins and of their hydration layer studied by neutron scattering and additional biophysical methods

International Nuclear Information System (INIS)

Gallat, Francois-Xavier

2011-01-01

This thesis work focused on the dynamics of proteins, surrounded by their hydration layer, a water shell around the protein vital for its biological function. Each of these components is accompanied by a specific dynamics which union reforms the complex energy landscape of the system. The joint implementation of selective deuteration, incoherent neutron scattering and tera-hertz spectroscopy allowed to explore the dynamics of proteins and that of the hydration shell. The influence of the folding state of protein on its dynamics has been studied by elastic neutron scattering. Globular proteins were less dynamic than its intrinsically disordered analogues. Themselves appear to be stiffer than non-physiological unfolded proteins. The oligomerization state and the consequences on the dynamics were investigated. Aggregates of a globular protein proved to be more flexible than the soluble form. In contrast, aggregates of a disordered protein showed lower average dynamics compared to the soluble form. These observations demonstrate the wide range of dynamics among the proteome. Incoherent neutron scattering experiences on the hydration layer of globular and disordered proteins have yielded information on the nature of water motion around these proteins. The measurements revealed the presence of translational motions concomitant with the onset of the transition dynamics of hydration layers, at 220 K. Measurements have also shown a stronger coupling between a disordered protein and its hydration water, compared to a globular protein and its hydration shell. The nature of the hydration layer and its influence on its dynamics has been explored with the use of polymers that mimic the water behavior and that act as a source of flexibility for the protein. Eventually, the dynamics of methyl groups involved in the dynamical changes observed at 150 and 220 K, was investigated. (author) [fr

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.

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.

Direct phase coexistence molecular dynamics study of the phase equilibria of the ternary methane-carbon dioxide-water hydrate system.

Science.gov (United States)

Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

2016-09-14

Molecular dynamics simulation is used to predict the phase equilibrium conditions of a ternary hydrate system. In particular, the direct phase coexistence methodology is implemented for the determination of the three-phase coexistence temperature of the methane-carbon dioxide-water hydrate system at elevated pressures. The TIP4P/ice, TraPPE-UA and OPLS-UA forcefields for water, carbon dioxide and methane respectively are used, in line with our previous studies of the phase equilibria of the corresponding binary hydrate systems. The solubility in the aqueous phase of the guest molecules of the respective binary and ternary systems is examined under hydrate-forming conditions, providing insight into the predictive capability of the methodology as well as the combination of these forcefields to accurately describe the phase behavior of the ternary system. The three-phase coexistence temperature is calculated at 400, 1000 and 2000 bar for two compositions of the methane-carbon dioxide mixture. The predicted values are compared with available calculations with satisfactory agreement. An estimation is also provided for the fraction of the guest molecules in the mixed hydrate phase under the conditions examined.

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.

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.

A DFT-based comparative equilibrium study of thermal dehydration and hydrolysis of CaCl2 hydrates and MgCl2 hydrates for seasonal 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

Salt hydrates store solar energy in chemical form via a reversible dehydration–hydration reaction. However, as a side reaction to dehydration, hydrolysis (HCl formation) may occur in chloride based salt hydrates (specially in MgCl2 hydrates), affecting the durability of the storage system. The

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.

Precise structural analysis of methane hydrate by neutron diffraction

International Nuclear Information System (INIS)

Igawa, Naoki; Hoshikawa, Akinori; Ishii, Yoshinobu

2006-01-01

Methane hydrate has attracted great interest as an energy resource to replace natural gas since this material is deposited in the seafloor and the deposits are estimated to exceed those of natural gas. Understanding the physical proprieties, such as the temperature dependence of the crystal structure, helps to specify the optimum environmental temperature and pressure during drilling, transport, and storage of methane hydrate. Clathrate hydrates consisted of encaging atomic and/or molecular species as a guest and host water formed by a hydrogen bonding. Although many studies on the clathrate hydrate including methane hydrate were reported, no detailed crystallographic property has yet been cleared. We focused on the motion of methane in the clathrate hydrate by the neutron diffraction. The crystal structure of the methane hydrate was analyzed by the applying the combination of the Rietveld refinement and the maximum entropy method (MEM) to neutron powder diffraction. Temperature dependence of the scattering-length density distribution maps revealed that the motion of methane molecules differs between the shapes of dodecahedron and tetrakaidecahedron. (author)

National Gas Hydrate Program Expedition 01 offshore India; gas hydrate systems as revealed by hydrocarbon gas geochemistry

Science.gov (United States)

Lorenson, Thomas; Collett, Timothy S.

2018-01-01

The National Gas Hydrate Program Expedition 01 (NGHP-01) targeted gas hydrate accumulations offshore of the Indian Peninsula and along the Andaman convergent margin. The primary objectives of coring were to understand the geologic and geochemical controls on the accumulation of methane hydrate and their linkages to underlying petroleum systems. Four areas were investigated: 1) the Kerala-Konkan Basin in the eastern Arabian Sea, 2) the Mahanadi and 3) Krishna-Godavari Basins in the western Bay of Bengal, and 4) the Andaman forearc Basin in the Andaman Sea.Upward flux of methane at three of the four of the sites cored during NGHP-01 is apparent from the presence of seafloor mounds, seismic evidence for upward gas migration, shallow sub-seafloor geochemical evidence of methane oxidation, and near-seafloor gas composition that resembles gas from depth.The Kerala-Konkan Basin well contained only CO2 with no detectable hydrocarbons suggesting there is no gas hydrate system here. Gas and gas hydrate from the Krishna-Godavari Basin is mainly microbial methane with δ13C values ranging from −58.9 to −78.9‰, with small contributions from microbial ethane (−52.1‰) and CO2. Gas from the Mahanadi Basin was mainly methane with lower concentrations of C2-C5 hydrocarbons (C1/C2 ratios typically >1000) and CO2. Carbon isotopic compositions that ranged from −70.7 to −86.6‰ for methane and −62.9 to −63.7‰ for ethane are consistent with a microbial gas source; however deeper cores contained higher molecular weight hydrocarbon gases suggesting a small contribution from a thermogenic gas source. Gas composition in the Andaman Basin was mainly methane with lower concentrations of ethane to isopentane and CO2, C1/C2 ratios were mainly >1000 although deeper samples were compositions range from −65.2 to −80.7‰ for methane, −53.1 to −55.2‰ for ethane is consistent with mainly microbial gas sources, although one value recorded of −35.4‰ for propane

The influence of Na2O on the hydration of C3A II. Suspension hydration

NARCIS (Netherlands)

Spierings, G.A.C.M.; Stein, H.N.

1976-01-01

The influence of Na2O on the hydration of C3A was studied in suspensions from the start of the reaction onwards. The heat evolution rate in very early stages of the hydration, measured at varying NaOH concentrations, and SEM, indicate that at NaOH concentrations larger then 0.1 M the reaction

Estimating pore-space gas hydrate saturations from well log acoustic data

Science.gov (United States)

Lee, Myung W.; Waite, William F.

2008-07-01

Relating pore-space gas hydrate saturation to sonic velocity data is important for remotely estimating gas hydrate concentration in sediment. In the present study, sonic velocities of gas hydrate-bearing sands are modeled using a three-phase Biot-type theory in which sand, gas hydrate, and pore fluid form three homogeneous, interwoven frameworks. This theory is developed using well log compressional and shear wave velocity data from the Mallik 5L-38 permafrost gas hydrate research well in Canada and applied to well log data from hydrate-bearing sands in the Alaskan permafrost, Gulf of Mexico, and northern Cascadia margin. Velocity-based gas hydrate saturation estimates are in good agreement with Nuclear Magneto Resonance and resistivity log estimates over the complete range of observed gas hydrate saturations.

Material Research on Salt Hydrates for Seasonal Heat Storage Application in a Residential Environment

Energy Technology Data Exchange (ETDEWEB)

Ferchaud, C.J.; Zondag, H.A.; De Boer, R. [ECN Biomass and Energy Efficiency, Petten (Netherlands)

2013-09-15

Water vapor sorption in salt hydrates is a promising method to realize seasonal solar heat storage in the residential sector. Several materials already showed promising performance for this application. However, the stability of these materials needs to be improved for long-term (30 year) application in seasonal solar heat storages. The purpose of this article is to identify the influence of the material properties of the salt hydrates on the performance and the reaction kinetics of the sorption process. The experimental investigation presented in this article shows that the two salt hydrates Li2SO4.H2O and CuSO4.5H2O can store and release heat under the operating conditions of a seasonal solar heat storage in a fully reversible way. However, these two materials show differences in terms of energy density and reaction kinetics. Li2SO4.H2O can release heat with an energy density of around 0.80 GJ/m{sup 3} within 4 hours of rehydration at 25C, while CuSO4.5H2O needs around 130 hours at the same temperature to be fully rehydrated and reaches an energy density of 1.85 GJ/m{sup 3}. Since the two salts are dehydrated and hydrated under the same conditions, this difference in behavior is directly related to the intrinsic properties of the materials.

Lattice constants of pure methane and carbon dioxide hydrates at low temperatures. Implementing quantum corrections to classical molecular dynamics studies

Energy Technology Data Exchange (ETDEWEB)

Costandy, Joseph; Michalis, Vasileios K.; Economou, Ioannis G., E-mail: i.tsimpanogiannis@qatar.tamu.edu, E-mail: ioannis.economou@qatar.tamu.edu [Chemical Engineering Program, Texas A& M University at Qatar, P.O. Box 23874, Doha (Qatar); Tsimpanogiannis, Ioannis N., E-mail: i.tsimpanogiannis@qatar.tamu.edu, E-mail: ioannis.economou@qatar.tamu.edu [Chemical Engineering Program, Texas A& M University at Qatar, P.O. Box 23874, Doha (Qatar); Environmental Research Laboratory, National Center for Scientific Research NCSR “Demokritos,” 15310 Aghia Paraskevi, Attikis (Greece); Stubos, Athanassios K. [Environmental Research Laboratory, National Center for Scientific Research NCSR “Demokritos,” 15310 Aghia Paraskevi, Attikis (Greece)

2016-03-28

We introduce a simple correction to the calculation of the lattice constants of fully occupied structure sI methane or carbon dioxide pure hydrates that are obtained from classical molecular dynamics simulations using the TIP4PQ/2005 water force field. The obtained corrected lattice constants are subsequently used in order to obtain isobaric thermal expansion coefficients of the pure gas hydrates that exhibit a trend that is significantly closer to the experimental behavior than previously reported classical molecular dynamics studies.

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

, regardless of the consolidation history with hydrate in place, the consolidation behavior after dissociation will first return to, then follow, the original normal consolidation curve for the hydrate-free host sediment.

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.)

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)

Hydration of swelling clays: multi-scale sequence of hydration and determination of macroscopic energies from microscopic properties

International Nuclear Information System (INIS)

Salles, F.

2006-10-01

Smectites have interesting properties which make them potential candidates for engineered barriers in deep geological nuclear waste repository: low permeability, swelling and cations retention. The subject of this thesis consists in the determination of the relationship between hydration properties, swelling properties and cations mobility in relation with confinement properties of clayey materials. The aim is to understand and to predict the behaviour of water in smectites, following two research orientations: the mechanistic aspects and the energetic aspects of the hydration of smectites. We worked on the Na-Ca montmorillonite contained in the MX80 bentonite, with the exchanged homo ionic structure (saturated with alkaline cations and calcium cations). The approach crosses the various scales (microscopic, mesoscopic and macroscopic) and implied the study of the various components of the system (layer-cation-water), by using original experimental methods (thermo-poro-metry and electric conductivity for various relative humidities (RH) and electrostatic calculations. Initially, the dry state is defined by SCTA (scanning calorimetry thermal analysis). Then a classical characterization of the smectite porosity for the dry state is carried out using mercury intrusion and nitrogen adsorption. We evidenced the existence of a meso-porosity which radius varies from 2 to 10 nm depending on the compensating cation. The thermo-poro-metry and conductivity experiments performed at various hydration states made it possible to follow the increase in the pore sizes and the cations mobility as a function of the hydration state. We highlight in particular the existence of an osmotic mesoscopic swelling for low RH (approximately 50-60%RH for Li and Na). By combining the results of thermo-poro-metry, X-ray diffraction and electric conductivity, we are able to propose a complete hydration sequence for each cation, showing the crucial role of the compensating cation in the hydration of

India National Gas Hydrate Program Expedition 02 Technical Contributions

Science.gov (United States)

Collett, T. S.; Kumar, P.; Shukla, K. M.; Nagalingam, J.; Lall, M. V.; Yamada, Y.; Schultheiss, P. J.; Holland, M.; Waite, W. F.

2017-12-01

The National Gas Hydrate Program Expedition 02 (NGHP-02) was conducted from 3-March-2015 to 28-July-2015 off the eastern coast of India. The primary objective of this expedition was the exploration and discovery of highly saturated gas hydrate occurrences in sand reservoirs that would be targets of future production testing. The first 2 months of the expedition were dedicated to logging while drilling (LWD) operations with a total of 25 holes being drilled and logged. The next 3 months were dedicated to coring operations at 10 of the most promising sites. NGHP-02 downhole logging, coring and formation pressure testing have confirmed the presence of large, highly saturated, gas hydrate accumulations in coarse-grained sand-rich depositional systems throughout the Krishna-Godavari Basin within the regions defined during NGHP-02 as Area-B, Area-C, and Area-E. The nature of the discovered gas hydrate occurrences closely matched pre-drill predictions, confirming the project developed depositional models for the sand-rich depositional facies in the Krishna-Godavari and Mahanadi Basins. The existence of a fully developed gas hydrate petroleum system was established in Area-C of the Krishna-Godavari Basin with the discovery of a large slope-basin interconnected depositional system, including a sand-rich, gas-hydrate-bearing channel-levee prospect at Sites NGHP-02-08 and -09. The acquisition of closely spaced LWD and core holes in the Area-B L1 Block gas hydrate accumulation have provided one of the most complete three-dimensional petrophysical-based views of any known gas hydrate reservoir system in the world. It was concluded that Area-B and Area-C in the area of the greater Krishna-Godavari Basin contain important world-class gas hydrate accumulations and represent ideal sites for consideration of future gas hydrate production testing.

Experimental Investigation into the Combustion Characteristics of Propane Hydrates in Porous Media

Directory of Open Access Journals (Sweden)

Xiang-Ru Chen

2015-02-01

Full Text Available The combustion characteristics of both pure propane hydrates and the mixtures of hydrates and quartz sands were investigated by combustion experiments. The flame propagation, flame appearance, burning time and temperature in different hydrate layers were studied. For pure propane hydrate combustion, the initial flame falls in the “premixed” category. The flame propagates very rapidly, mainly as a result of burnt gas expansion. The flame finally self-extinguishes with some proportion of hydrates remaining unburned. For the hydrate-sand mixture combustion, the flame takes the form of many tiny discontinuous flames appearing and disappearing at different locations. The burn lasts for a much shorter amount of time than pure hydrate combustion. High porosity and high hydrate saturation is beneficial to the combustion. The hydrate combustion is the combustion of propane gas resulting from the dissociation of the hydrates. In both combustion test scenarios, the hydrate-dissociated water plays a key role in the fire extinction, because it is the main resistance that restrains the heat transfer from the flame to the hydrates and that prevents the hydrate-dissociated gas from releasing into the combustion zone.

Kinetic Hydration Heat Modeling for High-Performance Concrete Containing Limestone Powder

Directory of Open Access Journals (Sweden)

Xiao-Yong Wang

2017-01-01

Full Text Available Limestone powder is increasingly used in producing high-performance concrete in the modern concrete industry. Limestone powder blended concrete has many advantages, such as increasing the early-age strength, reducing the setting time, improving the workability, and reducing the heat of hydration. This study presents a kinetic model for modeling the hydration heat of limestone blended concrete. First, an improved hydration model is proposed which considers the dilution effect and nucleation effect due to limestone powder addition. A degree of hydration is calculated using this improved hydration model. Second, hydration heat is calculated using the degree of hydration. The effects of water to binder ratio and limestone replacement ratio on hydration heat are clarified. Third, the temperature history and temperature distribution of hardening limestone blended concrete are calculated by combining hydration model with finite element method. The analysis results generally agree with experimental results of high-performance concrete with various mixing proportions.

Natural gas storage in hydrates with the presence of promoters

International Nuclear Information System (INIS)

Sun Zhigao; Wang Ruzhu; Ma Rongsheng; Guo Kaihua; Fan Shuanshi

2003-01-01

Hydrate technology is being developed for the storage and transport of natural gas. Micellar surfectant solutions were found to increase the gas hydrate formation rate and storage capacity. An anionic surfactant, a nonionic surfactant, their mixtures and cyclopentane were used to improve the hydrate formation of a synthetic natural gas (methane=92.05 mol%, ethane=4.96 mol%, propane=2.99 mol%) in a quiescent system in this work. The effect of an anionic surfactant (sodium dodecyl sulfate) on natural gas storage in hydrates is more pronounced compared to the effect of a nonionic surfactant (dodecyl polysaccharide glycoside). Cyclopentane could reduce hydrate formation induction time but could not improve the hydrate formation rate and storage capacity

Thermodynamic of hydration of a Wyoming montmorillonite saturated with Ca, Mg, Na and K

International Nuclear Information System (INIS)

Vieillard, P.; Blanc, P.; Gailhanou, H.; Gaboreau, S.; Giffaut, E.

2010-01-01

Document available in extended abstract form only. In the context of a disposal within clayey formations (Callovo-Oxfordian argillite) or using clayey barriers, the assessment of the long-term behavior of clay materials by geochemical modeling, requires thermodynamic properties of clay minerals. The Thermochimie database has been created by ANDRA in 1996 in order to provide coherent thermodynamic data of many minerals of interests with regards to this context, such as clay minerals. However, the thermodynamic properties of clay minerals, which govern the stability of these minerals in solution are still poorly understood. Indeed, there is little experimental data available in the literature concerning the hydration of smectites. On the other hand, it is not possible to acquire all the experimental thermodynamic hydration properties of clay minerals involved in natural systems or likely to be in the implementation of a deep disposal. In this study, we propose a method to estimate the thermodynamic hydration properties of a clay mineral. By considering the following reaction: Smectite nm H 2 O Smectite (0 H 2 O) + nm H 2 O (l), the hydration of smectite is calculated from an equilibrium condition involving anhydrous and hydrous components in which nm is the maximal number of moles of water in the fully hydrated end-member. By using a solid-solution formalism, the variation of the hydration state of a smectite with temperature or [H 2 O] can be possible. Analysis of experimental data indicates that solid solutions of hydrous and anhydrous smectite components at 25 deg. C and 1 bar are not ideal but can be expressed in terms of regular solution theory by considering the excess molal enthalpy of mixing (Hxs), the excess molal entropy of mixing (Sxs) and excess molal Gibbs free energy of mixing (Gxs) for binary solid solutions of homologous hydrous and anhydrous smectite components expressed in terms of Margules parameters W1 and W2. A compilation of measurements of

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...

DNA under Force: Mechanics, Electrostatics, and Hydration

Directory of Open Access Journals (Sweden)

Jingqiang Li

2015-02-01

Full Text Available Quantifying the basic intra- and inter-molecular forces of DNA has helped us to better understand and further predict the behavior of DNA. Single molecule technique elucidates the mechanics of DNA under applied external forces, sometimes under extreme forces. On the other hand, ensemble studies of DNA molecular force allow us to extend our understanding of DNA molecules under other forces such as electrostatic and hydration forces. Using a variety of techniques, we can have a comprehensive understanding of DNA molecular forces, which is crucial in unraveling the complex DNA functions in living cells as well as in designing a system that utilizes the unique properties of DNA in nanotechnology.

Irrigation port hydration in phacoemulsification surgery

Directory of Open Access Journals (Sweden)

Suzuki H

2018-01-01

Full Text Available Hisaharu Suzuki,1 Yoichiro Masuda,2 Yuki Hamajima,1 Hiroshi Takahashi3 1Department of Ophthalmology, Nippon Medical School Musashikosugi Hospital, Kawasaki City, Kanagawa, 2Department of Ophthalmology, The Jikei University, Katsushika Medical Center, Tokyo, 3Department of Ophthalmology, Nippon Medical School, Tokyo, Japan Background: In most cases, hydration is performed by water injection into the stromal tissue with a needle. The technique is simple, however it is sometimes troublesome.Purpose: We describe a simple technique for hydrating the corneal stroma in cataract surgery using an irrigation port.Patients and methods: The technique began by pushing the irrigation port against the corneal stroma for a few seconds during phacoemulsification, which generated edema in the corneal incision that subsequently prevented leakage. This procedure is called the hydration using irrigation port (HYUIP technique. A total of 60 eyes were randomized and placed in two groups, 30 eyes underwent surgeries using the HYUIP technique (HYUIP group and 30 eyes underwent surgeries without the HYUIP technique (control. The three points evaluated during each surgery included 1 the occurrence of anterior chamber collapse during the pulling out of the I/A tip after inserting the intraocular lens, 2 the need for conventional hydration, and 3 watertight completion at the end stage of surgery.Results: The anterior chamber collapse and the need for conventional hydration were significantly smaller in the HYUIP group compared to the control group. Regarding the self-sealing completion, no significant difference was observed between the two groups.Conclusion: The HYUIP technique is an effective method for creating self-sealing wound. In addition, this technique helps to prevent anterior chamber collapse. Keywords: cataract surgery, hydration, irrigation and aspiration, phacoemulsification, wound, self-sealing 

Sedative effect of oral diazepam and chloral hydrate in the dental treatment of children

Directory of Open Access Journals (Sweden)

Kantovitz Kamila

2007-06-01

Full Text Available Purpose : The purpose was to evaluate two sedation protocols during dental sessions in anxious children. Materials and Methods : It was a randomized and double-blind study, with each individual being his/her own control within each protocol. Furthermore, the two protocols were compared. Twenty children (36 to 84 months old who exhibited "definitely negative" behavior according to the Frankl scale were assigned to receive oral chloral hydrate (40 mg/kg (Group I or Diazepamβ (5 mg (Group II. Behavior during local anesthesia, application of rubber dam, cavity preparation, restorative procedures was evaluated, considering the degree of sleep, body movement, crying and overall behavior. Vital signs were assessed at three different times. The Wilcoxon, Mann-Whitney, Exact Fisher′s and Spearman correlation tests were used to analyze the data. Results : Group I presented higher scores for sleep during the CH session than placebo session during rubber dam application ( P = 0.0431 and restoration ( P = 0.0431. In Group II there was no statistically significant difference ( p > 0.05. There were no statistically significant differences between sessions and groups in the evaluation of body movement, crying and vital signs. Overall behavior in the placebo session was better than in the CH session during local anesthesia, but there was no difference between the two drug regimens. There was influence of age during anesthesia and cavity preparation in Group I and during rubber dam application in Group II. It was concluded that oral diazepam and chloral hydrate had no influence on the behavior management for dental treatment with the studied sample.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-12-30

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

Hydration for the prevention of contrast medium-induced nephropathy. An update

International Nuclear Information System (INIS)

Heinrich, M.; Uder, M.

2006-01-01

Contrast medium-induced nephropathy (CIN) continues to be one of the most common causes of hospital-acquired acute renal failure. Since most of the clinical studies on the prophylactic use of different drugs to prevent CIN produced disappointing results, hydration remains the mainstay of prophylaxis. A number of recent prospective randomized trials provided further evidence of the effectiveness of hydration and relevant information regarding the optimization of hydration protocols. It was shown that a bolus hydration solely during examination is not sufficient to prevent CIN. In addition, isotonic 0.9% saline was superior to the commonly used halfisotonic 0.45% saline in another trial. An outpatient hydration protocol including oral hydration before the examination followed by forced intravenous hydration over 6 hrs. beginning 30 to 60 min. prior to examination seems to be comparable to the usual hydration over 24 hrs. Another hydration protocol, which could also be very attractive especially for outpatients, included the infusion of sodium bicarbonate. In a recent trial, hydration with sodium bicarbonate, given as a bolus for 1 hr. prior to examination followed by an infusion for 6 hrs. after examination, was more effective than hydration with sodium chloride for the prophylaxis of CIN. However, there is still a lack of large-scale, multi-center trials comparing different hydration protocols and investigating their influence on clinically relevant endpoints such as mortality or the need for dialysis. (orig.)

The effect of hydrate promoters on gas uptake.

Science.gov (United States)

Xu, Chun-Gang; Yu, Yi-Song; Ding, Ya-Long; Cai, Jing; Li, Xiao-Sen

2017-08-16

Gas hydrate technology is considered as a promising technology in the fields of gas storage and transportation, gas separation and purification, seawater desalination, and phase-change thermal energy storage. However, to date, the technology is still not commercially used mainly due to the low gas hydrate formation rate and the low gas uptake. In this study, the effect of hydrate promoters on gas uptake was systematically studied and analyzed based on hydrate-based CH 4 storage and CO 2 capture from CO 2 /H 2 gas mixture experiments. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and gas chromatography (GC) were employed to analyze the microstructures and gas compositions. The results indicate that the effect of the hydrate promoter on the gas uptake depends on the physical and chemical properties of the promoter and gas. A strong polar ionic promoter is not helpful towards obtaining the ideal gas uptake because a dense hydrate layer is easily formed at the gas-liquid interface, which hinders gas diffusion from the gas phase to the bulk solution. For a weak polar or non-polar promoter, the gas uptake depends on the dissolution characteristics among the different substances in the system. The lower the mutual solubility among the substances co-existing in the system, the higher the independence among the substances in the system; this is so that each phase has an equal chance to occupy the hydrate cages without or with small interactions, finally leading to a relatively high gas uptake.

Enzyme hydration, activity and flexibility : A neutron scattering approach

International Nuclear Information System (INIS)

Kurkal-Siebert, V.; Finney, J.L.; Daniel, R.M.; Smith, Jeremy C.

2006-01-01

Recent measurements have demonstrated enzyme activity at hydrations as low as 3%. The question of whether the hydration-induced enzyme flexibility is important for activity is addressed by performing picosecond dynamic neutron scattering experiments on pig liver esterase powders at various temperatures as well as solutions. At all temperatures and hydrations investigated here, significant quasielastic scattering intensity is found in the protein, indicating the presence of anharmonic, diffusive motion. As the hydration increases a temperature-dependent dynamical transition appears and strengthens involving additional diffusive motion. At low temperature, increasing hydration resulted in lower flexibility of the enzyme. At higher temperatures, systems containing sufficient number of water molecules interacting with the protein exhibit increased flexibility. The implication of these results is that, although the additional hydration-induced diffusive motion and flexibility at high temperatures in the enzyme detected here may be related to increased activity, they are not required for the enzyme to function

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

Tapping methane hydrates for unconventional natural gas

Science.gov (United States)

Ruppel, Carolyn

2007-01-01

Methane hydrate is an icelike form of concentrated methane and water found in the sediments of permafrost regions and marine continental margins at depths far shallower than conventional oil and gas. Despite their relative accessibility and widespread occurrence, methane hydrates have never been tapped to meet increasing global energy demands. With rising natural gas prices, production from these unconventional gas deposits is becoming economically viable, particularly in permafrost areas already being exploited for conventional oil and gas. This article provides an overview of gas hydrate occurrence, resource assessment, exploration, production technologies, renewability, and future challenges.

Hydrates plugs dissociation in pipelines; Dissociation des bouchons d'hydrates de gaz dans les conduites petrolieres sous-marines

Energy Technology Data Exchange (ETDEWEB)

Nguyen Hong, D.

2005-03-15

Natural gas hydrates plugs cause problems during drilling, well operations, production, transportation and processing of oil and gas. Especially, it is a very serious problem in off-shore oil transportation where low temperature and high pressure become more and more favourable to gas hydrate formation as the new production wells are more and more deeper. Up to now, although many studies have been developed concerning the possibility of preventing pipe plugging, there is limited information in open literature on hydrate plugs dissociation and all models in literature are numerically complicated. In this study, hydrate plugs are formed from water in n-dodecane mixture with addition of a dispersant E102B in two different experimental apparatus in order to obtain hydrates plugs with different sizes (diameter of 7, 10.75 and 12 cm). Then, the plugs are dissociated by the method of two-sided depressurization. In this paper, we propose a numerical model which describes the dissociation of gas hydrate plugs in pipelines. The numerical model, which is constructed for cylindrical coordinates and for two-sided pressurization, is based on enthalpy method. We present also an approximate analytical model which has an average error 2.7 % in comparison with the numerical model. The excellent agreement between our experimental results, literature data and the two models shows that the models give a good prediction independently of the pipeline diameter, plug porosity and gas. The simplicity of the analytical model will make it easier in industrial applications. (author)

Ultrasonic sound speed of hydrating calcium sulphate hemihydrate; part 2, the correlation of sound velocity to hydration degree

NARCIS (Netherlands)

de Korte, A.C.J.; Brouwers, Jos; Fischer, H.B; Matthes, C.; Beuthan, C.

2011-01-01

In this article the sound velocity through a mix is correlated to the hydration degree of the mix. Models are presented predicting the sound velocity through fresh slurries and hardened products. These two states correspond to the starting and finishing point of the hydration process. The present

Ultrasonic sound speed of hydrating calcium sulphate hemihydrate; Part 2, The correlation of sound velocity to hydration degree

NARCIS (Netherlands)

Korte, de A.C.J.; Brouwers, H.J.H.; Fischer, H.B.; Mattes, Chr.; Beutha, C.

2011-01-01

In this article the sound velocity through a mix is correlated to the hydration degree of the mix. Models are presented predicting the sound velocity through fresh slurries and hardened products. These two states correspond to the starting and finishing point of the hydration process. The present

Towards understanding the role of amines in the SO2 hydration and the contribution of the hydrated product to new particle formation in the Earth's atmosphere.

Science.gov (United States)

Lv, Guochun; Nadykto, Alexey B; Sun, Xiaomin; Zhang, Chenxi; Xu, Yisheng

2018-08-01

By theoretical calculations, the gas-phase SO 2 hydration reaction assisted by methylamine (MA) and dimethylamine (DMA) was investigated, and the potential contribution of the hydrated product to new particle formation (NPF) also was evaluated. The results show that the energy barrier for aliphatic amines (MA and DMA) assisted SO 2 hydration reaction is lower than the corresponding that of water and ammonia assisted SO 2 hydration. In these hydration reactions, nearly barrierless reaction (only a barrier of 0.1 kcal mol -1 ) can be found in the case of SO 2  + 2H 2 O + DMA. These lead us to conclude that the SO 2 hydration reaction assisted by MA and DMA is energetically facile. The temporal evolution for hydrated products (CH 3 NH 3 + -HSO 3 - -H 2 O or (CH 3 ) 2 NH 2 + -HSO 3 - -H 2 O) in molecular dynamics simulations indicates that these complexes can self-aggregate into bigger clusters and can absorb water and amine molecules, which means that these hydrated products formed by the hydration reaction may serve as a condensation nucleus to initiate the NPF. Copyright © 2018 Elsevier Ltd. All rights reserved.

Stages of Gas-Hydrate Evolution on the Northern Cascadia Margin

Directory of Open Access Journals (Sweden)

the IODP Expedition 311 Scientists

2006-09-01

Full Text Available Natural gas hydrate occurs beneath many continental slopes and in arctic permafrost areas. Recent studies have indicated that the largest deposits of gas hydrate might lie in nearly horizontal layers several hundred meters beneath the seafloor of continental slopes, especially in the large, accretionary sedimentary prisms of subduction zones. Expedition 311 of the Integrated Ocean Drilling Program (IODP investigated the formation of gas hydrate in the accretionary prism of the Cascadia subduction zone (Fig. 1. The primary objectives of Expedition 311 were to test and constraingeological models of gas hydrate formation by upward fluidand methane transport in accretionary prisms. We specifi -cally sought to (a determine the mechanisms that controlthe nature, magnitude, and distribution of the gas hydrate,(b find the pathways of the fluid migration required to formlarge concentrations of gas hydrate, (c examine the effectsof gas hydrate on the physical properties of the host sediment,and (d investigate the microbiology and geochemistryassociated with the occurrence of gas hydrate. Furthermore,we concentrated on the contrast between methane transportby focused fl ow in fault zones and by dispersed pervasiveupward flow at various scales of permeability.

Spectroscopic determination of optimal hydration time of zircon surface

Energy Technology Data Exchange (ETDEWEB)

Ordonez R, E. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Garcia R, G. [Instituto Tecnologico de Toluca, Division de Estudios del Posgrado, Av. Tecnologico s/n, Ex-Rancho La Virgen, 52140 Metepec, Estado de Mexico (Mexico); Garcia G, N., E-mail: eduardo.ordonez@inin.gob.m [Universidad Autonoma del Estado de Mexico, Facultad de Quimica, Av. Colon y Av. Tollocan, 50180 Toluca, Estado de Mexico (Mexico)

2010-07-01

When a mineral surface is immersed in an aqueous solution, it develops and electric charge produced by the amphoteric dissociation of hydroxyl groups created by the hydration of the solid surface. This is one influential surface property. The complete hydration process takes a time which is specific for each mineral species. The knowledge of the aqueous solution contact time for complete surface hydration is mandatory for further surface phenomena studies. This study deals with the optimal hydration time of the raw zircon (ZrSiO{sub 4}) surface comparing the classical potentiometric titrations with a fluorescence spectroscopy technique. The latter is easy and rea liable as it demands only one sample batch to determine the optimal time to ensure a total hydration of the zircon surface. The analytical results of neutron activation analysis showed the presence of trace quantities of Dy{sup 3+}, Eu{sup 3+} and Er{sup 3} in the bulk of zircon. The Dy{sup 3+} is structured in the zircon crystalline lattice and undergoes the same chemical reactions as zircon. Furthermore, the Dy{sup 3+} has a good fluorescent response whose intensity is enhanced by hydration molecules. The results show that, according to the potentiometric analysis, the hydration process for each batch (at least 8 sample batches) takes around 2 h, while the spectrometric method indicates only 5 minutes from only one batch. Both methods showed that the zircon surface have a 16 h optimal hydration time. (Author)

Spectroscopic determination of optimal hydration time of zircon surface

International Nuclear Information System (INIS)

Ordonez R, E.; Garcia R, G.; Garcia G, N.

2010-01-01

When a mineral surface is immersed in an aqueous solution, it develops and electric charge produced by the amphoteric dissociation of hydroxyl groups created by the hydration of the solid surface. This is one influential surface property. The complete hydration process takes a time which is specific for each mineral species. The knowledge of the aqueous solution contact time for complete surface hydration is mandatory for further surface phenomena studies. This study deals with the optimal hydration time of the raw zircon (ZrSiO 4 ) surface comparing the classical potentiometric titrations with a fluorescence spectroscopy technique. The latter is easy and rea liable as it demands only one sample batch to determine the optimal time to ensure a total hydration of the zircon surface. The analytical results of neutron activation analysis showed the presence of trace quantities of Dy 3+ , Eu 3+ and Er 3 in the bulk of zircon. The Dy 3+ is structured in the zircon crystalline lattice and undergoes the same chemical reactions as zircon. Furthermore, the Dy 3+ has a good fluorescent response whose intensity is enhanced by hydration molecules. The results show that, according to the potentiometric analysis, the hydration process for each batch (at least 8 sample batches) takes around 2 h, while the spectrometric method indicates only 5 minutes from only one batch. Both methods showed that the zircon surface have a 16 h optimal hydration time. (Author)

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.

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.

Free energy landscape and molecular pathways of gas hydrate nucleation

Energy Technology Data Exchange (ETDEWEB)

Bi, Yuanfei; Porras, Anna; Li, Tianshu, E-mail: tsli@gwu.edu [Department of Civil and Environmental Engineering, George Washington University, Washington DC 20052 (United States)

2016-12-07

Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p{sub B} histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the p{sub B} histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

Free energy landscape and molecular pathways of gas hydrate nucleation

International Nuclear Information System (INIS)

Bi, Yuanfei; Porras, Anna; Li, Tianshu

2016-01-01

Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p B histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the p B histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

Free energy landscape and molecular pathways of gas hydrate nucleation.

Science.gov (United States)

Bi, Yuanfei; Porras, Anna; Li, Tianshu

2016-12-07

Despite the significance of gas hydrates in diverse areas, a quantitative knowledge of hydrate formation at a molecular level is missing. The impediment to acquiring this understanding is primarily attributed to the stochastic nature and ultra-fine scales of nucleation events, posing a great challenge for both experiment and simulation to explore hydrate nucleation. Here we employ advanced molecular simulation methods, including forward flux sampling (FFS), p B histogram analysis, and backward flux sampling, to overcome the limit of direct molecular simulation for exploring both the free energy landscape and molecular pathways of hydrate nucleation. First we test the half-cage order parameter (H-COP) which we developed for driving FFS, through conducting the p B histogram analysis. Our results indeed show that H-COP describes well the reaction coordinates of hydrate nucleation. Through the verified order parameter, we then directly compute the free energy landscape for hydrate nucleation by combining both forward and backward flux sampling. The calculated stationary distribution density, which is obtained independently of nucleation theory, is found to fit well against the classical nucleation theory (CNT). Subsequent analysis of the obtained large ensemble of hydrate nucleation trajectories show that although on average, hydrate formation is facilitated by a two-step like mechanism involving a gradual transition from an amorphous to a crystalline structure, there also exist nucleation pathways where hydrate crystallizes directly, without going through the amorphous stage. The CNT-like free energy profile and the structural diversity suggest the existence of multiple active transition pathways for hydrate nucleation, and possibly also imply the near degeneracy in their free energy profiles among different pathways. Our results thus bring a new perspective to the long standing question of how hydrates crystallize.

Multicomponent modelling of Portland cement hydration reactions

NARCIS (Netherlands)

Ukrainczyk, N.; Koenders, E.A.B.; Van Breugel, K.

2012-01-01

The prospect of cement and concrete technologies depends on more in depth understanding of cement hydration reactions. Hydration reaction models simulate the development of the microstructures that can finally be used to estimate the cement based material properties that influence performance and

The dynamics of water in hydrated white bread investigated using quasielastic neutron scattering

International Nuclear Information System (INIS)

Sjoestroem, J; Kargl, F; Fernandez-Alonso, F; Swenson, J

2007-01-01

The dynamics of water in fresh and in rehydrated white bread is studied using quasielastic neutron scattering (QENS). A diffusion constant for water in fresh bread, without temperature gradients and with the use of a non-destructive technique, is presented here for the first time. The self-diffusion constant for fresh bread is estimated to be D s = 3.8 x 10 -10 m 2 s -1 and the result agrees well with previous findings for similar systems. It is also suggested that water exhibits a faster dynamics than previously reported in the literature using equilibration of a hydration-level gradient monitored by vibrational spectroscopy. The temperature dependence of the dynamics of low hydration bread is also investigated for T = 280-350 K. The average relaxation time at constant momentum transfer (Q) shows an Arrhenius behavior in the temperature range investigated

Meiotic changes in Vicia faba L. subsequent to treatments of hydrazine hydrate and maleic hydrazide

Directory of Open Access Journals (Sweden)

Shaheen Husain

2013-01-01

Full Text Available Assessing the impact of mutagens for creating variations in crops like faba bean (Vicia faba L. is an important criterion in the contemporary world where food insecurity and malnutrition is alarming at the doors of various nations. Impact of two chemical mutagens viz. hydrazine hydrate (HZ and maleic hydrazide (MH on the two varieties (NDF-1 and HB-405 of Vicia faba were analysed in terms of meiotic behavior and pollen sterility. Since there are not enough data about the effect of these mutagens on the chromosomal behaviors of Vicia faba, this study presents the role of hydrazine hydrate and maleic hydrazide as well as various types of chromosomal aberrations in crop improvement. The lower concentration of mutagens showed less pollen sterility compared to the higher concentrations. Manipulation of plant structural component to induce desirable alternations provides valuable material for the breeders and could be used favorably for increasing mutation rate and obtaining a desirable spectrum of mutation in faba beans based on preliminary studies of cell division.

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.

The structural response of the cornea to changes in stromal hydration.

Science.gov (United States)

Hayes, Sally; White, Tomas; Boote, Craig; Kamma-Lorger, Christina S; Bell, James; Sorenson, Thomas; Terrill, Nick; Shebanova, Olga; Meek, Keith M

2017-06-01

The primary aim of this study was to quantify the relationship between corneal structure and hydration in humans and pigs. X-ray scattering data were collected from human and porcine corneas equilibrated with polyethylene glycol (PEG) to varying levels of hydration, to obtain measurements of collagen fibril diameter, interfibrillar spacing (IFS) and intermolecular spacing. Both species showed a strong positive linear correlation between hydration and IFS 2 and a nonlinear, bi-phasic relationship between hydration and fibril diameter, whereby fibril diameter increased up to approximately physiological hydration, H = 3.0, with little change thereafter. Above H = 3.0, porcine corneas exhibited a larger fibril diameter than human corneas ( p < 0.001). Intermolecular spacing also varied with hydration in a bi-phasic manner but reached a maximum value at a lower hydration ( H = 1.5) than fibril diameter. Human corneas displayed a higher intermolecular spacing than porcine corneas at all hydrations ( p < 0.0001). Human and porcine corneas required a similar PEG concentration to reach physiological hydration, suggesting that the total fixed charge that gives rise to the swelling pressure is the same. The difference in their structural responses to hydration can be explained by variations in molecular cross-linking and intra/interfibrillar water partitioning. © 2017 The Authors.

Influence of limestone on the hydration of Portland cements

International Nuclear Information System (INIS)

Lothenbach, Barbara; Le Saout, Gwenn; Gallucci, Emmanuel; Scrivener, Karen

2008-01-01

The influence of the presence of limestone on the hydration of Portland cement was investigated. Blending of Portland cement with limestone was found to influence the hydrate assemblage of the hydrated cement. Thermodynamic calculations as well as experimental observations indicated that in the presence of limestone, monocarbonate instead of monosulfate was stable. Thermodynamic modelling showed that the stabilisation of monocarbonate in the presence of limestone indirectly stabilised ettringite leading to a corresponding increase of the total volume of the hydrate phase and a decrease of porosity. The measured difference in porosity between the 'limestone-free' cement, which contained less than 0.3% CO 2 , and a cement containing 4% limestone, however, was much smaller than calculated. Coupling of thermodynamic modelling with a set of kinetic equations which described the dissolution of the clinker, predicted quantitatively the amount of hydrates. The quantities of ettringite, portlandite and amorphous phase as determined by TGA and XRD agreed well with the calculated amounts of these phases after different periods of time. The findings in this paper show that changes in the bulk composition of hydrating cements can be followed by coupled thermodynamic models. Comparison between experimental and modelled data helps to understand in more detail the dominating processes during cement hydration

Relaxation mechanism of the hydrated electron.

Science.gov (United States)

Elkins, Madeline H; Williams, Holly L; Shreve, Alexander T; Neumark, Daniel M

2013-12-20

The relaxation dynamics of the photoexcited hydrated electron have been subject to conflicting interpretations. Here, we report time-resolved photoelectron spectra of hydrated electrons in a liquid microjet with the aim of clarifying ambiguities from previous experiments. A sequence of three ultrashort laser pulses (~100 femtosecond duration) successively created hydrated electrons by charge-transfer-to-solvent excitation of dissolved anions, electronically excited these electrons via the s→p transition, and then ejected them into vacuum. Two distinct transient signals were observed. One was assigned to the initially excited p-state with a lifetime of ~75 femtoseconds, and the other, with a lifetime of ~400 femtoseconds, was attributed to s-state electrons just after internal conversion in a nonequilibrated solvent environment. These assignments support the nonadiabatic relaxation model.

Gas hydrate drilling transect across northern Cascadia margin - IODP Expedition 311

Science.gov (United States)

Riedel, M.; Collett, T.; Malone, M.J.; Collett, T.S.; Mitchell, M.; Guerin, G.; Akiba, F.; Blanc-Valleron, M.; Ellis, M.; Hashimoto, Y.; Heuer, V.; Higashi, Y.; Holland, M.; Jackson, P.D.; Kaneko, M.; Kastner, M.; Kim, J.-H.; Kitajima, H.; Long, P.E.; Malinverno, A.; Myers, Gwen E.; Palekar, L.D.; Pohlman, J.; Schultheiss, P.; Teichert, B.; Torres, M.E.; Trehu, A.M.; Wang, Jingyuan; Worthmann, U.G.; Yoshioka, H.

2009-01-01

A transect of four sites (U1325, U1326, U1327 and U1329) across the northern Cascadia margin was established during Integrated Ocean Drilling Program Expedition 311 to study the occurrence and formation of gas hydrate in accretionary complexes. In addition to the transect sites, a fifth site (U1328) was established at a cold vent with active fluid flow. The four transect sites represent different typical geological environments of gas hydrate occurrence across the northern Cascadia margin from the earliest occurrence on the westernmost first accreted ridge (Site U1326) to the eastward limit of the gas hydrate occurrence in shallower water (Site U1329). Expedition 311 complements previous gas hydrate studies along the Cascadia accretionary complex, especially ODP Leg 146 and Leg 204 by extending the aperture of the transect sampled and introducing new tools to systematically quantify the gas hydrate content of the sediments. Among the most significant findings of the expedition was the occurrence of up to 20 m thick sand-rich turbidite intervals with gas hydrate concentrations locally exceeding 50% of the pore space at Sites U1326 and U1327. Moreover, these anomalous gas hydrate intervals occur at unexpectedly shallow depths of 50-120 metres below seafloor, which is the opposite of what was expected from previous models of gas hydrate formation in accretionary complexes, where gas hydrate was predicted to be more concentrated near the base of the gas hydrate stability zone just above the bottom-simulating reflector. Gas hydrate appears to be mainly concentrated in turbidite sand layers. During Expedition 311, the visual correlation of gas hydrate with sand layers was clearly and repeatedly documented, strongly supporting the importance of grain size in controlling gas hydrate occurrence. The results from the transect sites provide evidence for a structurally complex, lithology-controlled gas hydrate environment on the northern Cascadia margin. Local shallow

Theoretical description of biomolecular hydration - Application to A-DNA

International Nuclear Information System (INIS)

Garcia, A.E.; Hummer, G.; Soumpasis, D.M.

1994-01-01

The local density of water molecules around a biomolecule is constructed from calculated two- and three-points correlation functions of polar solvents in water using a Potential-of-Mean-Force (PMF) expansion. As a simple approximation, the hydration of all polar (including charged) groups in a biomolecule is represented by the hydration of water oxygen in bulk water, and the effect of non-polar groups on hydration are neglected, except for excluded volume effects. Pair and triplet correlation functions are calculated by molecular dynamics simulations. We present calculations of the structural hydration for ideal A-DNA molecules with sequences [d(CG) 5 ] 2 and [d(C 5 G 5 )] 2 . We find that this method can accurately reproduce the hydration patterns of A-DNA observed in neutron diffraction experiments on oriented DNA fibers

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

75 FR 9886 - Methane Hydrate Advisory Committee

Science.gov (United States)

2010-03-04

... DEPARTMENT OF ENERGY Methane Hydrate Advisory Committee AGENCY: Department of Energy, Office of Fossil Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane... the Committee: The purpose of the Methane Hydrate Advisory Committee is to provide advice on potential...

Geologic implications of gas hydrates in the offshore of India: Results of the National Gas Hydrate Program Expedition 01

Digital Repository Service at National Institute of Oceanography (India)

Collett, T.S.; Boswell, R.; Cochran, J.R.; Kumar, P.; Lall, M.; Mazumdar, A.; Ramana, M.V.; Ramprasad, T.; Riedel, M.; Sain, K.; Sathe, A.V.; Vishwanath, K.; NGHP Expedition 01 Scientific Party

in Japan (Tsujii et al., 2009) and in the Gulf of Mexico (Boswell et al., 2012a) and the pace of gas-hydrate energy-assessment projects continues to accelerate. Beyond a future energy resource, gas hydrates may in some cases represent a significant...

Effect of overpressure on gas hydrate distribution

Energy Technology Data Exchange (ETDEWEB)

Bhatnagar, G.; Chapman, W.G.; Hirasaki, G.J. [Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering; Dickens, G.R.; Dugan, B. [Rice Univ., Houston, TX (United States). Dept. of Earth Sciences

2008-07-01

Natural gas hydrate systems can be characterized by high sedimentation rates and/or low permeability sediments, which can lead to pore pressure higher than hydrostatic. This paper discussed a study that examined this effect of overpressure on gas hydrate and free gas distribution in marine sediments. A one-dimensional numerical model that coupled sedimentation, fluid flow, and gas hydrate formation was utilized. In order to quantify the relative importance of sedimentation rates and low permeability sediments, a dimensionless sedimentation-compaction group (scN) was defined, that compared the absolute permeability of the sediments to the sedimentation rate. Higher values of scN mean higher permeability or low sedimentation rate which generally yield hydrostatic pore pressure while lower values of scN normally create pore pressure greater than hydrostatic. The paper discussed non-hydrostatic consolidation in gas hydrate systems, including mass balances; constitutive relationships; normalized variables; and dimensionless groups. A numerical solution to the problem was presented. It was concluded that simulation results demonstrated that decreasing scN not only increased pore pressure above hydrostatic values, but also lowered the lithostatic stress gradient and gas hydrate saturation. This occurred because overpressure resulted in lower effective stress, causing higher porosity and lower bulk density of the sediment. 16 refs., 5 figs., 1 appendix.

Blue LED irradiation to hydration of skin

Science.gov (United States)

Menezes, Priscila F. C.; Requena, Michelle B.; Lizarelli, Rosane F., Z.; Bagnato, Vanderlei S.

2015-06-01

Blue LED system irradiation shows many important properties on skin as: bacterial decontamination, degradation of endogenous skin chromophores and biostimulation. In this clinical study we prove that the blue light improves the skin hydration. In the literature none authors reports this biological property on skin. Then this study aims to discuss the role of blue light in the skin hydration. Twenty patients were selected to this study with age between 25-35 years old and phototype I, II and III. A defined area from forearm was pre determined (A = 4.0 cm2). The study was randomized in two treatment groups using one blue light device (power of 5.3mW and irradiance of 10.8mW/cm2). The first treatment group was irradiated with 3J/cm2 (277seconds) and the second with 6J/cm2 (555 seconds). The skin hydration evaluations were done using a corneometer. The measurements were collected in 7, 14, 21 and 30 days, during the treatment. Statistical test of ANOVA, Tukey and T-Student were applied considering 5% of significance. In conclusion, both doses were able to improve the skin hydration; however, 6J/cm2 has kept this hydration for 30 days.

Methane hydrates. A possible energy source in the twenty-first century

International Nuclear Information System (INIS)

Sorassi, S.

1998-01-01

The morphological characteristics of particular crystal structures, to be found in nature both in arctic and Antarctic regions and under seas and oceans, and consisting of water and gas molecules, the so-called 'gas hydrates', are dealt with. Technical problems related to gas recovery (methane in particular) from hydrates, above all under sea level, mainly due to their reduced stability, are examined. On the ground of these considerations, various gas recovery methods from hydrate fields are described. An overall evaluation of methane availability as hydrates all over the world, as well as a comparison between extraction costs from hydrate and well as a comparison between extraction costs from hydrate and conventional fields, are made. Finally, short-term programmes on research and development of methane hydrate fields in some areas of the Earth are described [it

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.

Confocal spectroscopic imaging measurements of depth dependent hydration dynamics in human skin in-vivo

Science.gov (United States)

Behm, P.; Hashemi, M.; Hoppe, S.; Wessel, S.; Hagens, R.; Jaspers, S.; Wenck, H.; Rübhausen, M.

2017-11-01

We present confocal spectroscopic imaging measurements applied to in-vivo studies to determine the depth dependent hydration profiles of human skin. The observed spectroscopic signal covers the spectral range from 810 nm to 2100 nm allowing to probe relevant absorption signals that can be associated with e.g. lipid and water-absorption bands. We employ a spectrally sensitive autofocus mechanism that allows an ultrafast focusing of the measurement spot on the skin and subsequently probes the evolution of the absorption bands as a function of depth. We determine the change of the water concentration in m%. The water concentration follows a sigmoidal behavior with an increase of the water content of about 70% within 5 μm in a depth of about 14 μm. We have applied our technique to study the hydration dynamics of skin before and after treatment with different concentrations of glycerol indicating that an increase of the glycerol concentration leads to an enhanced water concentration in the stratum corneum. Moreover, in contrast to traditional corneometry we have found that the application of Aluminium Chlorohydrate has no impact to the hydration of skin.

Confocal spectroscopic imaging measurements of depth dependent hydration dynamics in human skin in-vivo

Directory of Open Access Journals (Sweden)

P. Behm

2017-11-01

Full Text Available We present confocal spectroscopic imaging measurements applied to in-vivo studies to determine the depth dependent hydration profiles of human skin. The observed spectroscopic signal covers the spectral range from 810 nm to 2100 nm allowing to probe relevant absorption signals that can be associated with e.g. lipid and water-absorption bands. We employ a spectrally sensitive autofocus mechanism that allows an ultrafast focusing of the measurement spot on the skin and subsequently probes the evolution of the absorption bands as a function of depth. We determine the change of the water concentration in m%. The water concentration follows a sigmoidal behavior with an increase of the water content of about 70% within 5 μm in a depth of about 14 μm. We have applied our technique to study the hydration dynamics of skin before and after treatment with different concentrations of glycerol indicating that an increase of the glycerol concentration leads to an enhanced water concentration in the stratum corneum. Moreover, in contrast to traditional corneometry we have found that the application of Aluminium Chlorohydrate has no impact to the hydration of skin.

Effect of hydration on the organo-noble gas molecule HKrCCH: role of krypton in the stabilization of hydrated HKrCCH complexes.

Science.gov (United States)

Biswas, Biswajit; Singh, Prashant Chandra

2015-11-11

The effect of hydration on the fluorine free organo-noble gas compound HKrCCH and the role of krypton in the stabilization of the hydrated HKrCCH complexes have been investigated using the quantum chemical calculations on the HKrCCH-(H2O)n=1-6 clusters. Structure and energetics calculations show that water stabilizes HKrCCH through the π hydrogen bond in which the OH group of water interacts with the C[triple bond, length as m-dash]C group of HKrCCH. A maximum of four water molecules can directly interact with the C[triple bond, length as m-dash]C of HKrCCH and after that only inter-hydrogen bonding takes place between the water molecules indicating that the primary hydration shell contains four water molecules. Atom in molecule analysis depicts that π hydrogen bonded complexes of the hydrated HKrCCH are cyclic structures in which the OKr interaction cooperates in the formation of strong O-HC[triple bond, length as m-dash]C interaction. Structure, energetics and charge analysis clearly established that krypton plays an important role in the stabilization as well as the formation of the primary hydration shell of hydrated HKrCCH complexes.

Characteristics of Methane Hydrate Formation in Artificial and Natural Media

Directory of Open Access Journals (Sweden)

Qingbai Wu

2013-03-01

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

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.

Raman Spectroscopic Studies of Methane Gas Hydrates

DEFF Research Database (Denmark)

Hansen, Susanne Brunsgaard; Berg, Rolf W.

2009-01-01

A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory.......A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory....

Small angle neutron scattering from hydrated cement pastes

International Nuclear Information System (INIS)

Sabine, T.M.; Bertram, W.K.; Aldridge, L.P.

1996-01-01

Small angle neutron scattering (SANS) was used to study the microstructure of hydrating cement made with, and without silica fume. Some significant differences were found between the SANS spectra of pastes made from OPC (ordinary Portland cement) and DSP (made with silica fume and superplasticiser). The SANS spectra are interpreted in terms of scattering from simple particles. Particle growth was monitored during hydration and it was found that the growth correlated with the heat of hydration of the cement

Observation of microstructure of hydrated Ca3SiO5

International Nuclear Information System (INIS)

Mori, Kazuhiro; Sato, Takashi; Fukunaga, Toshiharu; Oishi, Koji; Kimura, Katsuhiko; Iwase, Kenji; Sugiyama, Masaaki; Itoh, Keiji; Shikanai, Fumihito; Wuernisha, Tuerxun; Yonemura, Masao; Sulistyanintyas, Dyah; Tsukushi, Itaru; Takata, Shinich; Otomo, Toshiya; Kamiyma, Takashi; Kawai, Masayoshi

2006-01-01

Quasi-elastic neutron scattering experiments were carried out to evaluate the hydration rate of tricalcium silicate (Ca 3 SiO 5 ). Furthermore, in the early hydration period, a variation in surface roughness of Ca 3 SiO 5 was observed in nano-scale by the small-angle neutron scattering. From these results, it was found that the hydration rate of Ca 3 SiO 5 is suppressed when the surface of Ca 3 SiO 5 becomes rough through the creation of hydration products C-S-H gel and Ca(OH) 2 , and this roughness is associated with changes in the Ca 3 SiO 5 hydration rate

MORPHOLOGY OF METHANE HYDRATE HOST SEDIMENTS

International Nuclear Information System (INIS)

JONES, K.W.; FENG, H.; TOMOV, S.; WINTER, W.J.; EATON, M.; MAHAJAN, D.

2004-01-01

Results from simulated experiments in several laboratories show that host sediments influence hydrate formation in accord with known heterogeneity of host sediments at sites of gas hydrate occurrence (1). For example, in Mackenzie Delta, NWT Canada (Mallik 2L-38 well), coarser-grained units (pore-filling model) are found whereas in the Gulf of Mexico, the found hydrate samples do not appear to be lithologically controlled. We have initiated a systematic study of sediments, initially focusing on samples from various depths at a specific site, to establish a correlation with hydrate occurrence (or variations thereof) to establish differences in their microstructure, porosity, and other associated properties. The synchrotron computed microtomography (CMT) set-up at the X-27A tomography beam line at the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory was used as a tool to study sediments from Blake Ridge at three sub bottom depths of 0.2, 50, and 667 meters. Results from the tomographic analysis of the deepest sample (667 m) are presented here to illustrate how tomography can be used to obtain new insights into the structures of methane hydrate host sediments. The investigation shows the internal grain/pore space resolution in the microstructure and a 3-D visualization of the connecting pathways obtained following data segmentation into pore space and grains within the sediment sample. The analysis gives the sample porosity, specific surface area, mean particle size, and tortuosity, as well. An earlier report on the experimental program has been given by Mahajan et al. (2)

Modelling the incongruent dissolution of hydrated cement minerals

International Nuclear Information System (INIS)

Berner, U.R.

1988-01-01

Hydrated calciumsilicates are the main constituents of hydrated portland cements. Their chemistry will strongly influence the longterm behaviour of a concrete system envisioned in use in radioactive waste repositories. Experimental data show that hydrated calciumsilicates dissolve incongruently, depending on the calcium/silicon ratio of the solid. A model that simulates the incongruent dissolution behaviour of these hydrated calciumsilicates is presented. In the model the hydrated calciumcilicates are represented as a mixture of two congruently soluble components. The dissolution of the particular components is described using the concept of variable activities in the solid state. Each component's activity in the solid state is obtained from a large body of solubility data by applying the Gibbs-Duhem equation for nonideal mixtures. Using this approach a simplified set of equations, which describe the solubility of the components as a function of the calcium/silicon ratio of the solid, is derived. As an application, the degradation of a standard portland cement in pure water and in a carbonate-rich groundwater is modelled. (orig.)

Theoretical description of biomolecular hydration - Application to A-DNA

Energy Technology Data Exchange (ETDEWEB)

Garcia, A.E.; Hummer, G. [Los Alamos National Laboratory, NM (United States); Soumpasis, D.M. [Max Planck Inst. for Biophysical Chemistry, Goettingen (Germany)

1994-12-31

The local density of water molecules around a biomolecule is constructed from calculated two- and three-points correlation functions of polar solvents in water using a Potential-of-Mean-Force (PMF) expansion. As a simple approximation, the hydration of all polar (including charged) groups in a biomolecule is represented by the hydration of water oxygen in bulk water, and the effect of non-polar groups on hydration are neglected, except for excluded volume effects. Pair and triplet correlation functions are calculated by molecular dynamics simulations. We present calculations of the structural hydration for ideal A-DNA molecules with sequences [d(CG){sub 5}]{sub 2} and [d(C{sub 5}G{sub 5})]{sub 2}. We find that this method can accurately reproduce the hydration patterns of A-DNA observed in neutron diffraction experiments on oriented DNA fibers.

BSR and methane hydrates: New challenges for geophysics and rock physics

Energy Technology Data Exchange (ETDEWEB)

Nur, A. [Stanford Univ., CA (United States). Dept. of Geophysics

1996-12-31

It is generally accepted that solid gas hydrates which form within the uppermost few hundred meters of the sea floor are responsible for so-called Bottom Simulating Reflectors (BSRs) at continental margins. Gas to solid volumetric ratio in recovered hydrate samples may be as large as 170. Consequently, huge amounts of compressed methane (more than twice all recoverable and nonrecoverable oil, gas, and coal on earth) may exist under earth`s oceans. These hydrates are a potential energy resource, they influence global warming and effect seafloor mechanical stability. It is possible, in principle, to obtain a quantitative estimate of the amount and state of existing hydrates by relating seismic velocity to the volume of gas hydrate in porous sediments. This can be done by linking the elastic properties of hydrated sediments to their internal structure. The authors approach this problem by examining two micromechanical models of hydrate deposition in the pore space: (1) the hydrate cements grain contacts and thus significantly stiffens the sediment; and (2) the hydrate is located away from grain contacts and only weakly affects the stiffness of the sediment frame. To discriminate between the two models the authors use the Amplitude Versus Offset (AVO) technique of seismic data processing. This approach allows them to estimate the amount of gas hydrates in the pore space, and also to tell whether the permeability of the hydrated sediment is high or low. The latter is important for determining whether free methane can be trapped underneath a BSR.

A novel assay reveals hygrotactic behavior in Drosophila.

Directory of Open Access Journals (Sweden)

Feiteng Ji

Full Text Available Humidity is one of the most important factors that determines the geographical distribution and survival of terrestrial animals. The ability to detect variation in humidity is conserved across many species. Here, we established a novel behavioral assay that revealed the thirsty Drosophila exhibits strong hygrotactic behavior, and it can locate water by detecting humidity gradient. In addition, exposure to high levels of moisture was sufficient to elicit proboscis extension reflex behavior in thirsty flies. Furthermore, we found that the third antennal segment was necessary for hygrotactic behavior in thirsty flies, while arista was required for the avoidance of moist air in hydrated flies. These results indicated that two types of hygroreceptor cells exist in Drosophila: one located in the third antennal segment that mediates hygrotactic behavior in thirst status, and the other located in arista which is responsible for the aversive behavior toward moist air in hydration status. Using a neural silencing screen, we demonstrated that synaptic output from the mushroom body α/β surface and posterior neurons was required for both hygrotactic behavior and moisture-aversive behavior.

Numerical modeling of the simulated gas hydrate production test at Mallik 2L-38 in the pilot scale pressure reservoir LARS - Applying the "foamy oil" model

Science.gov (United States)

Abendroth, Sven; Thaler, Jan; Klump, Jens; Schicks, Judith; Uddin, Mafiz

2014-05-01

In the context of the German joint project SUGAR (Submarine Gas Hydrate Reservoirs: exploration, extraction and transport) we conducted a series of experiments in the LArge Reservoir Simulator (LARS) at the German Research Centre of Geosciences Potsdam. These experiments allow us to investigate the formation and dissociation of hydrates at large scale laboratory conditions. We performed an experiment similar to the field-test conditions of the production test in the Mallik gas hydrate field (Mallik 2L-38) in the Beaufort Mackenzie Delta of the Canadian Arctic. The aim of this experiment was to study the transport behavior of fluids in gas hydrate reservoirs during depressurization (see also Heeschen et al. and Priegnitz et al., this volume). The experimental results from LARS are used to provide details about processes inside the pressure vessel, to validate the models through history matching, and to feed back into the design of future experiments. In experiments in LARS the amount of methane produced from gas hydrates was much lower than expected. Previously published models predict a methane production rate higher than the one observed in experiments and field studies (Uddin et al. 2010; Wright et al. 2011). The authors of the aforementioned studies point out that the current modeling approach overestimates the gas production rate when modeling gas production by depressurization. They suggest that trapping of gas bubbles inside the porous medium is responsible for the reduced gas production rate. They point out that this behavior of multi-phase flow is not well explained by a "residual oil" model, but rather resembles a "foamy oil" model. Our study applies Uddin's (2010) "foamy oil" model and combines it with history matches of our experiments in LARS. Our results indicate a better agreement between experimental and model results when using the "foamy oil" model instead of conventional models of gas flow in water. References Uddin M., Wright J.F. and Coombe D

Comparing the sensitivity of permafrost and marine gas hydrate to climate warming

International Nuclear Information System (INIS)

Taylor, A.E.; Dallimore, S.R.; Hyndman, R.D.; Wright, F.

2005-01-01

The sensitivity of Arctic subpermafrost gas hydrate at the Mallik borehole was compared to temperate marine gas hydrate located offshore southwestern Canada. In particular, a finite element geothermal model was used to determine the sensitivity to the end of the ice age, and contemporary climate warming of a 30 m thick methane hydrate layer lying at the base of a gas hydrate stability zone prior to 13.5 kiloannum (ka) before present (BP). It was suggested that the 30 m gas-hydrate-bearing layer would have disappeared by now, according to the thermal signal alone. However, the same gas-hydrate-bearing layer underlying permafrost would persist until at least 4 ka after present, even with contemporary climate warming. The longer time for subpermafrost gas hydrate comes from the thawing pore ice at the base of permafrost, at the expense of dissociation of the deeper gas hydrate. The dissociation of underlying gas hydrate from climate surface warming is buffered by the overlying permafrost

Thermal conductivity measurements in porous mixtures of methane hydrate and quartz sand

Science.gov (United States)

Waite, W.F.; deMartin, B.J.; Kirby, S.H.; Pinkston, J.; Ruppel, C.D.

2002-01-01

Using von Herzen and Maxwell's needle probe method, we measured thermal conductivity in four porous mixtures of quartz sand and methane gas hydrate, with hydrate composing 0, 33, 67 and 100% of the solid volume. Thermal conductivities were measured at a constant methane pore pressure of 24.8 MPa between -20 and +15??C, and at a constant temperature of -10??C between 3.5 and 27.6 MPa methane pore pressure. Thermal conductivity decreased with increasing temperature and increased with increasing methane pore pressure. Both dependencies weakened with increasing hydrate content. Despite the high thermal conductivity of quartz relative to methane hydrate, the largest thermal conductivity was measured in the mixture containing 33% hydrate rather than in hydrate-free sand. This suggests gas hydrate enhanced grain-to-grain heat transfer, perhaps due to intergranular contact growth during hydrate synthesis. These results for gas-filled porous mixtures can help constrain thermal conductivity estimates in porous, gas hydrate-bearing systems.

Permafrost-associated natural gas hydrate occurrences on the Alaska North Slope

Science.gov (United States)

Collett, T.S.; Lee, M.W.; Agena, W.F.; Miller, J.J.; Lewis, K.A.; Zyrianova, M.V.; Boswell, R.; Inks, T.L.

2011-01-01

In the 1960s Russian scientists made what was then a bold assertion that gas hydrates should occur in abundance in nature. Since this early start, the scientific foundation has been built for the realization that gas hydrates are a global phenomenon, occurring in permafrost regions of the arctic and in deep water portions of most continental margins worldwide. In 1995, the U.S. Geological Survey made the first systematic assessment of the in-place natural gas hydrate resources of the United States. That study suggested that the amount of gas in the gas hydrate accumulations of northern Alaska probably exceeds the volume of known conventional gas resources on the North Slope. Researchers have long speculated that gas hydrates could eventually become a producible energy resource, yet technical and economic hurdles have historically made gas hydrate development a distant goal. This view began to change in recent years with the realization that this unconventional resource could be developed with existing conventional oil and gas production technology. One of the most significant developments was the completion of the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well on the Alaska North Slope, which along with the Mallik project in Canada, have for the first time allowed the rational assessment of gas hydrate production technology and concepts. Almost 40 years of gas hydrate research in northern Alaska has confirmed the occurrence of at least two large gas hydrate accumulations on the North Slope. We have also seen in Alaska the first ever assessment of how much gas could be technically recovered from gas hydrates. However, significant technical concerns need to be further resolved in order to assess the ultimate impact of gas hydrate energy resource development in northern Alaska. ?? 2009 Elsevier Ltd.

Major factors influencing the generation of natural gas hydrate in porous media

Directory of Open Access Journals (Sweden)

V.N. Khlebnikov

2017-11-01

Full Text Available Current researches related to natural gas hydrate mainly focus on its physical and chemical properties, as well as the approaches to the production (decomposition of hydrate. Physical modeling of the flow process in hydrate deposits is critical to the study on the exploitation or decomposition of hydrate. However, investigation of the dynamic hydrate process by virtue of porous media like sand-packed tubes which are widely used in petroleum production research is rarely reported in literature. In this paper, physical simulation of methane hydrate generation process was conducted using river sand-packed tubes in the core displacement apparatus. During the simulation, the influences of parameters such as reservoir temperature, methane pressure and reservoir model properties on the process of hydrate generation were investigated. The following results are revealed. First, the use of ice-melted water as the immobile water in the reservoir model can significantly enhance the rate of methane hydrate generation. Second, the process driving force in porous media (i.e., extents to which the experimental pressure or temperature deviating those corresponding to the hydrate phase equilibrium plays a key role in the generation of methane hydrate. Third, the induction period of methane hydrate generation almost does not change with temperature or pressure when the methane pressure is above 1.4 folds of the hydrate phase equilibrium pressure or the laboratory temperature is lower than the phase equilibrium temperature by 3 °C or more. Fourth, the parameters such as permeability, water saturation and wettability don't have much influence on the generation of methane hydrate.

Dissociation heat of mixed-gas hydrate composed of methane and ethane

Energy Technology Data Exchange (ETDEWEB)

Hachikubo, A.; Nakagawa, R.; Kubota, D.; Sakagami, H.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan)

2008-07-01

Formation and dissociation processes of natural gas hydrates in permafrost, marine and lake sediments are highly controlled by their thermal properties. Dissociation heat of gas hydrates can be estimated from phase equilibrium data using the Clausius-Clapeyron equation. However, this method is applicable for pure gas hydrate and at a temperature of 0 degrees Celsius. Direct calorimetric measurements on gas hydrates using a calorimeter have been developed to obtain thermal properties of gas hydrates, including dissociation heat and heat capacity. Studies have shown that a structure 2 gas hydrate appears in appropriate gas composition of methane and ethane. This paper investigated the effect of ethane concentration on dissociation heat of mixed-gas (methane and ethane) hydrate. Raman spectroscopy was used to confirm the appearance of a structure 2 gas hydrate. The paper identified the experimental procedure and discussed sample preparation, Raman spectroscopy, and calorimetric measurements. A schematic diagram of the calorimeter was also presented. It was concluded that in most cases, two stages of dissociation were found at the dissociation process. 15 refs., 6 figs.

Small angle X-ray scattering from hydrating tricalcium silicate

International Nuclear Information System (INIS)

Vollet, D.

1983-01-01

The small-angle X-ray scattering technique was used to study the structural evolution of hydrated tricalcium silicate at room temperature. The changes in specific area of the associated porosity and the evolution of density fluctuations in the solid hydrated phase were deduced from the scattering data. A correlation of these variations with the hydration mechanism is tried. (Author) [pt

On the electrolytic generation of hydrated electron

International Nuclear Information System (INIS)

Ghosh Mazumdar, A.S.; Guha, S.N.

1975-01-01

Investigations on the electrolytic generation of hydrated electron in oxygenated as well as oxygen-free solutions at different pH were undertaken. Since sup(-e)aq is known to react rapidly with O 2 yielding the transient O 2 - ion, the latter was looked for through its interaction with phosphite ions resulting in their oxidation near the cathode. It appears from the results that in electrolytic processes, the primary electron (esup(-)sub(cathode)) probably reacts directly with reactive solutes like oxygen, bypassing the hydration step. Data obtained in oxygen-free solutions, however, support the possible formation of hydrated electron at least in alkaline solutions. (author)

The analysis of magnesium oxide hydration in three-phase reaction system

Energy Technology Data Exchange (ETDEWEB)

Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin, E-mail: ntp@dlmu.edu.cn

2014-05-01

In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.

Methane hydrates and the future of natural gas

Science.gov (United States)

Ruppel, Carolyn

2011-01-01

For decades, gas hydrates have been discussed as a potential resource, particularly for countries with limited access to conventional hydrocarbons or a strategic interest in establishing alternative, unconventional gas reserves. Methane has never been produced from gas hydrates at a commercial scale and, barring major changes in the economics of natural gas supply and demand, commercial production at a large scale is considered unlikely to commence within the next 15 years. Given the overall uncertainty still associated with gas hydrates as a potential resource, they have not been included in the EPPA model in MITEI’s Future of Natural Gas report. Still, gas hydrates remain a potentially large methane resource and must necessarily be included in any consideration of the natural gas supply beyond two decades from now.

Giordano Bruno crater on the Moon: Detection and Mapping of Hydration Features of Endogenic and/or Exogenic Nature

Science.gov (United States)

Saran Bhiravarasu, Sriram; Bhattacharya, Satadru; Chauhan, Prakash

2017-10-01

We analyze high resolution spectral and spatial data from the recent lunar missions and report the presence of strong hydration features within the inner flank, hummocky floor, ejecta and impact melt deposits of crater Giordano Bruno. Hydroxyl-bearing lithologies at Giordano Bruno are characterized primarily by a prominent absorption feature near 2800 nm, the band minima of which goes beyond 3000 nm. The hydration features are found to be associated with low-Ca pyroxene-bearing noritic lithologies along the inner crater flanks, whereas similar features are also seen within the hummocky crater floor in association with shocked plagioclase-bearing anorthositic lithology. Interestingly, the ejecta blanket is characterized by sharp, narrow features centered near 2800 nm similar to the features previously reported from Compton-Belkovich volcanic complex and central peak of crater Theophilus. The low-Ca pyroxene-bearing rock exposures within the crater inner flanks are characterized by both presence and absence of the hydration features. Enhanced hydration is also seen within the ejecta blanket covering the nearby Harkhebi K and J craters. We also analyze the impact melts and ejecta using radar images at regions interior and exterior to the Giordano Bruno crater rim.Anomalous behaviors of hydration feature associated with low-Ca pyroxene-rich exposures, its nature and occurrences within the impact melt sheets inside the crater along with the ejecta blankets could possibly indicate endogenic and/or exogenic nature of the observed hydration feature. Initial results indicate the presence of strongest hydration feature in the partially shadowed pole-facing slopes (with low-Ca pyroxene-bearing exposures) and its complete absence in the equator-facing sun-lit slopes. This hints at a possible exogenic origin, whereas the same feature occurring (with same mineral) under both sun-lit and shadowed conditions suggest it to be of magmatic origin. We propose that the heterogeneous

Medical chilling device designed for hypothermic hydration graft storage system: Design, thermohydrodynamic modeling, and preliminary testing

Energy Technology Data Exchange (ETDEWEB)

Seo, Jung Hwan [Hongik University, Seoul (Korea, Republic of)

2015-02-15

Hypothermic hydration graft storage is essential to reduce the metabolic demand of cells in vitro. The alleviated metabolic demands reduce the emergence rate of anaerobic metabolism generating adenosine triphosphate (ATP) energy that creates free radicals. The cessive free radicals can damage cells and tissues due to their highly oxidative power with molecules. Current cooling systems such as a conventional air cooling system and an ice pack system are inappropriate for chilling cell tissues in vitro because of inconvenience in use and inconsistent temperature sustainability caused by large size and progressive melting, respectively. Here, we develop a medical chilling device (MCD) for hypothermic hydration graft storage based on thermo-hydrodynamic modeling and thermal electric cooling technology. Our analysis of obtained hydrodynamic thermal behavior of the MCD revealed that the hypothermic condition of 4 .deg. C was continuously maintained, which increased the survival rates of cells in vitro test by reduced free radicals. The validated performance of the MCD promises future development of an optimal hypothermic hydration graft storage system designed for clinical use.

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.

Analysis of Decomposition for Structure I Methane Hydrate by Molecular Dynamics Simulation

Science.gov (United States)

Wei, Na; Sun, Wan-Tong; Meng, Ying-Feng; Liu, An-Qi; Zhou, Shou-Wei; Guo, Ping; Fu, Qiang; Lv, Xin

2018-05-01

Under multi-nodes of temperatures and pressures, microscopic decomposition mechanisms of structure I methane hydrate in contact with bulk water molecules have been studied through LAMMPS software by molecular dynamics simulation. Simulation system consists of 482 methane molecules in hydrate and 3027 randomly distributed bulk water molecules. Through analyses of simulation results, decomposition number of hydrate cages, density of methane molecules, radial distribution function for oxygen atoms, mean square displacement and coefficient of diffusion of methane molecules have been studied. A significant result shows that structure I methane hydrate decomposes from hydrate-bulk water interface to hydrate interior. As temperature rises and pressure drops, the stabilization of hydrate will weaken, decomposition extent will go deep, and mean square displacement and coefficient of diffusion of methane molecules will increase. The studies can provide important meanings for the microscopic decomposition mechanisms analyses of methane hydrate.

Microstructure of hydrated cement pastes as determined by SANS

International Nuclear Information System (INIS)

Sabine, T.; Bertram, W.; Aldridge, L.

1999-01-01

Full text: Technologists have known how to make concrete for over 2000 years but despite painstaking research no one has been able to show how and why concrete sets. Part of the problem is that the calcium silicate hydrate (the gel produced by hydrating cement) is amorphous and cannot be characterised by x-ray crystallographic techniques. Small angle neutron scattering on instrument V12a at BENSC was used to characterise the hydration reactions and show the growth of the calcium silicate hydrates during initial hydration and the substantial differences in the rate of growth and structure as different additives are used. SANS spectra were measured as a function of the hydration from three different types of cement paste: 1) Ordinary Portland Cement made with a water to cement ratio of about 0.4; 2) A blend of Ordinary Portland Cement(25%) and Ground Granulated Blast Furnace Slag (75%) with a water to cement ration of about 0.4; 3) A dense paste made from silica fume(24%), Ordinary Portland Cement (76%) at a water to powder ratio of 0.18. The differences in the spectra are interpreted in terms of differences between the microstructure of the pastes

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.

Exergy analysis of a gas-hydrate cool storage system

International Nuclear Information System (INIS)

Bi, Yuehong; Liu, Xiao; Jiang, Minghe

2014-01-01

Based on exergy analysis of charging and discharging processes in a gas-hydrate cool storage system, the formulas for exergy efficiency at the sensible heat transfer stage and the phase change stage corresponding to gas-hydrate charging and discharging processes are obtained. Furthermore, the overall exergy efficiency expressions of charging, discharging processes and the thermodynamic cycle of the gas-hydrate cool storage system are obtained. By using the above expressions, the effects of number of transfer units, the inlet temperatures of the cooling medium and the heating medium on exergy efficiencies of the gas-hydrate cool storage system are emphatically analyzed. The research results can be directly used to evaluate the performance of gas-hydrate cool storage systems and design more efficient energy systems by reducing the sources of inefficiency in gas-hydrate cool storage systems. - Highlights: • Formulas for exergy efficiency at four stages are obtained. • Exergy efficiency expressions of two processes and one cycle are obtained. • Three mainly influencing factors on exergy efficiencies are analyzed. • With increasing the inlet temperature of cooling medium, exergy efficiency increases. • With decreasing the inlet temperature of heating medium, exergy efficiency increases

A millimeter-wave reflectometer for whole-body hydration sensing

Science.gov (United States)

Zhang, W.-D.; Brown, E. R.

2016-05-01

This paper demonstrates a non-invasive method to determine the hydration level of human skin by measuring the reflectance of W-band (75-110 GHz) and Ka-band (26-40 GHz) radiation. Ka-band provides higher hydration accuracy ( 1 mm), thereby allowing access to the important dermis layer of skin. W-band provides less depth of penetration but finer spatial resolution (~2 mm). Both the hydration sensing concept and experimental results are presented here. The goal is to make a human hydration sensor that is 1% accurate or better, operable by mechanically scanning, and fast enough to measure large areas of the human body in seconds.

Effects of various vehicles on skin hydration in vivo.

Science.gov (United States)

Wiedersberg, S; Leopold, C S; Guy, R H

2009-01-01

The stratum corneum, the outermost layer of the skin, regulates the passive loss of water to the environment. Furthermore, it is well accepted that drug penetration is influenced by skin hydration, which may be manipulated by the application of moisturizing or oleaginous vehicles. Measurements of transepidermal water loss (TEWL), and of skin hydration using a corneometer, were used to assess the effect of different vehicles on stratum corneum barrier function in vivo in human volunteers. A microemulsion significantly increased skin hydration relative to a reference vehicle based on medium chain triglycerides; in contrast, Transcutol(R) lowered skin hydration. TEWL measurements confirmed these observations. Copyright 2009 S. Karger AG, Basel.

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

Focus on the Development of Natural Gas Hydrate in China

Directory of Open Access Journals (Sweden)

Zhongfu Tan

2016-05-01