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Sample records for hydrate formation temperature

  1. 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.

  2. 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.

  3. 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.

  4. Prediction of hydrate formation temperature by both statistical models and artificial neural network approaches

    International Nuclear Information System (INIS)

    Zahedi, Gholamreza; Karami, Zohre; Yaghoobi, Hamed

    2009-01-01

    In this study, various estimation methods have been reviewed for hydrate formation temperature (HFT) and two procedures have been presented. In the first method, two general correlations have been proposed for HFT. One of the correlations has 11 parameters, and the second one has 18 parameters. In order to obtain constants in proposed equations, 203 experimental data points have been collected from literatures. The Engineering Equation Solver (EES) and Statistical Package for the Social Sciences (SPSS) soft wares have been employed for statistical analysis of the data. Accuracy of the obtained correlations also has been declared by comparison with experimental data and some recent common used correlations. In the second method, HFT is estimated by artificial neural network (ANN) approach. In this case, various architectures have been checked using 70% of experimental data for training of ANN. Among the various architectures multi layer perceptron (MLP) network with trainlm training algorithm was found as the best architecture. Comparing the obtained ANN model results with 30% of unseen data confirms ANN excellent estimation performance. It was found that ANN is more accurate than traditional methods and even our two proposed correlations for HFT estimation.

  5. 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

  6. Formation of submarine gas hydrates

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    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.)

  7. The temperature hydration kinetics

    Directory of Open Access Journals (Sweden)

    Mircea Oroian

    2017-07-01

    Full Text Available The aim of this study is to evaluate the hydration kinetics of lentil seeds (Lens culinaris in water at different temperatures (25, 32.5, 40, 55, 70 and 80 °C for assessing the adequacy of models for describing the absorption phenomena during soaking. The diffusion coefficient values were calculated using Fick’s model for spherical and hemispherical geometries and the values were in the range of 10−6 m2/s. The experimental data were fitted to Peleg, Sigmoidal, Weibull and Exponential models. The models adequacy was determined using regression coefficients (R2, root mean square error (RMSE and reduced chi-square (χ2. The Peleg model is the suitable one for predicting the experimental data. Temperature had a positive and significant effect on the water absorption capacities and absorption was an endothermic process.

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

    DEFF Research Database (Denmark)

    Daraboina, Nagu; von Solms, Nicolas

    2015-01-01

    ) hydrate formation using a rocking cell apparatus. Hydrate formation and decomposition kinetics were investigated by constant cooling (hydrate nucleation temperature) and isothermal (hydrate nucleation time) methods. Improved (synergistic) hydrate formation kinetics (hydrate nucleation and growth) were...... of these two promoters is favorable both thermodynamically and kinetically for hydrate formation from flue gas....

  9. 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

  10. Effect of temperature dependence of the Langmuir constant molecular pair potentials on gas hydrates formation mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtari, B.; Enayati, M. [Iranian Offshore Oil Co., Tehran (Iran, Islamic Republic of); Heidaryan, E. [Islamic Azad Univ., Tehran (Iran, Islamic Republic of). Masjidosolayman Branch

    2008-07-01

    Theoretical methods show that crystalline hydrates can form from single-phase systems consisting of both vapor water with gaseous hydrate former and liquid water with dissolved hydrate former. Two phase systems consist of both liquid water with gaseous hydrate former and with liquid hydrate former on the surface. This paper presented a Langmuir constant related model for the prediction of equilibrium pressures and cage occupancies of pure component hydrates. Intermolecular potentials were fit to quantum mechanical energies to obtain the Langmuir constants, which differed from the procedure utilized with the vdWP model. The paper described the experimental method and model calculations. This included the Fugacity model and Van der Waals and Platteeuw model. The paper also discussed pair potential of non-spherical molecules, including the multicentre (site-site) potential; Gaussian overlap potential; Lennard-Jones potential; and Kihara generalized pair potential. It was concluded that fraction of occupied cavities is a function of pair potentials between hard core and empty hydrate lattice. These pair potentials could be calculated from some model as Kihara cell potential, Gaussian potential, Lennard-Jones potential and multicentre pair potential. 49 refs., 3 figs.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Formation of nitric acid hydrates - A chemical equilibrium approach

    Science.gov (United States)

    Smith, Roland H.

    1990-01-01

    Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

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

    Science.gov (United States)

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

    2018-02-01

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

  20. 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.

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

    Directory of Open Access Journals (Sweden)

    Yanli Guo

    2016-09-01

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

  2. 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

  3. Synergistic kinetic inhibition of natural gas hydrate formation

    DEFF Research Database (Denmark)

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

    2013-01-01

    Rocking cells were used to investigate the natural gas hydrate formation and decomposition in the presence of kinetic inhibitor, Luvicap. In addition, the influence of poly ethylene oxide (PEO) and NaCl on the performance of Luvicap was investigated using temperature ramping and isothermal...

  4. Experimental and modeling investigation on structure H hydrate formation kinetics

    International Nuclear Information System (INIS)

    Mazraeno, M. Seyfi; Varaminian, F.; Vafaie sefti, M.

    2013-01-01

    Highlights: • Applying affinity model for the formation kinetics of sH hydrate and two stage kinetics. • Performing the experiments of hydrate formation of sH with MCP. • A unique path for the SH hydrate formation. - Abstract: In this work, the kinetics of crystal H hydrate and two stage kinetics formation is modeled by using the chemical affinity model for the first time. The basic idea is that there is a unique path for each experiment by which the crystallization process decays the affinity. The experiments were performed at constant temperatures of 274.15, 275.15, 275.65, 276.15 and 277.15 K. The initial pressure of each experiment is up to 25 bar above equilibrium pressure of sI. Methylcyclohexane (MCH), methylcyclopentane (MCP) and tert-butyl methyl ether (TBME) are used as sH former and methane is used as a help gas. The parameters of the affinity model (A r and t k ) are determined and the results show that the parameter of (A r )/(RT) has not a constant value when temperature changes in each group of experiments. The results indicate that this model can predict experimental data very well at several conditions

  5. 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

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    Gas hydrate formation in multi phase mixtures containing an aqueous phase (with dissolved salts), reservoir fluid (crude oil) and natural gas phase was investigated by using a standard rocking cell (RC-5) apparatus. The hydrate formation temperature was reduced in the presence of crude oils...... can contribute to the safe operation of sub sea pipelines in the oil and gas industry....

  7. 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.

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

    Science.gov (United States)

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

    2018-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  10. Investigation of the Methane Hydrate Formation by Cavitation Jet

    Science.gov (United States)

    Morita, H.; Nagao, J.

    2015-12-01

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

  11. 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.

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

    International Nuclear Information System (INIS)

    Tajima, Hideo; Yamasaki, Akihiro; Kiyono, Fumio

    2004-01-01

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

  13. 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.

  14. 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.

  15. Characteristics of Methane Hydrate Formation in Artificial and Natural Media

    OpenAIRE

    Peng Zhang; Qingbai Wu; Yuzhong Yang

    2013-01-01

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

  16. 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.

  17. Synthesis, formation mechanism and sensing properties of WO3 hydrate nanowire netted-spheres

    International Nuclear Information System (INIS)

    Yan, Aihua; Xie, Changsheng; Zeng, Dawen; Cai, Shuizhou; Hu, Mulin

    2010-01-01

    Tungsten oxide hydrate nanowire netted-spheres were successfully synthesized in the glycol solution using a facile solvothermal approach. The nanowires with uniform diameter of 4-6 nm are actually a kind of tungsten oxide hydrate/surfactant hybrid materials. The influence of surfactant, solvent, time and temperature on tailoring morphology was investigated in detail. The possible formation process of WO 3 hydrate nanowire netted-sphere was proposed. Sensing properties of such WO 3 hydrate sensor show that the desirable sensing characteristics towards 100 ppm ammonia gas at 320 o C were obtained, such as rapid response (18.3 s), high sensitivity, good reproducibility and stability.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

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

    Directory of Open Access Journals (Sweden)

    Yousheng Deng

    2011-08-01

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

  20. Basin-Wide Temperature Constraints On Gas Hydrate Stability In The Gulf Of Mexico

    Science.gov (United States)

    MacDonald, I. R.; Reagan, M. T.; Guinasso, N. L.; Garcia-Pineda, O. G.

    2012-12-01

    Gas hydrate deposits commonly occur at the seafloor-water interface on marine margins. They are especially prevalent in the Gulf of Mexico where they are associated with natural oil seeps. The stability of these deposits is potentially challenged by fluctuations in bottom water temperature, on an annual time-scale, and under the long-term influence of climate change. We mapped the locations of natural oil seeps where shallow gas hydrate deposits are known to occur across the entire Gulf of Mexico basin based on a comprehensive review of synthetic aperture radar (SAR) data (~200 images). We prepared a bottom water temperature map based on the archive of CTD casts from the Gulf (~6000 records). Comparing the distribution of gas hydrate deposits with predicted bottom water temperature, we find that a broad area of the upper slope lies above the theoretical stability horizon for structure 1 gas hydrate, while all sites where gas hydrate deposits occur are within the stability horizon for structure 2 gas hydrate. This is consistent with analytical results that structure 2 gas hydrates predominate on the upper slope (Klapp et al., 2010), where bottom water temperatures fluctuate over a 7 to 10 C range (approx. 600 m depth), while pure structure 1 hydrates are found at greater depths (approx. 3000 m). Where higher hydrocarbon gases are available, formation of structure 2 gas hydrate should significantly increase the resistance of shallow gas hydrate deposits to destabilizing effects variable or increasing bottom water temperature. Klapp, S.A., Bohrmann, G., Kuhs, W.F., Murshed, M.M., Pape, T., Klein, H., Techmer, K.S., Heeschen, K.U., and Abegg, F., 2010, Microstructures of structure I and II gas hydrates from the Gulf of Mexico: Marine and Petroleum Geology, v. 27, p. 116-125.Bottom temperature and pressure for Gulf of Mexico gas hydrate outcrops and stability horizons for sI and sII hydrate.

  1. Dehydration of hydrated low-temperature tar

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, T

    1949-01-01

    Yoshida examined the mechanism of the dehydration of hydrated low-temperature tar with a microscope. The tar containing free carbon and coal dust is so stable that the removal of the above substances and water by a physical method is very difficult. Addition of light oil produced by fractionation of low-temperature tar facilitates the operations. Yoshida tried using the separate acid, neutral, and basic components of the light oil; the acid oil proved to be most effective. For many reasons it is convenient to use light oil as it is. In this method the quantity of light oil required is 2 to 3 times that of tar. But in supplementing the centrifugal method, the quantity of light oil needed might be only half the amount of tar.

  2. Determining the mechanism and parameters of hydrate formation and loss in glucose.

    Science.gov (United States)

    Scholl, Sarah K; Schmidt, Shelly J

    2014-11-01

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

  3. Tetrafluoroethane (R134a) hydrate formation within variable volume reactor accompanied by evaporation and condensation

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, K.; Choo, Y. S.; Hong, H. J.; Yoon, Y. S.; Song, M. H., E-mail: songm@dgu.edu [Department of Mechanical, Robotics, and Energy Engineering, Dongguk University, Seoul 100-715 (Korea, Republic of)

    2015-03-15

    Vast size hydrate formation reactors with fast conversion rate are required for the economic implementation of seawater desalination utilizing gas hydrate technology. The commercial target production rate is order of thousand tons of potable water per day per train. Various heat and mass transfer enhancement schemes including agitation, spraying, and bubbling have been examined to maximize the production capacities in scaled up design of hydrate formation reactors. The present experimental study focused on acquiring basic knowledge needed to design variable volume reactors to produce tetrafluoroethane hydrate slurry. Test vessel was composed of main cavity with fixed volume of 140 ml and auxiliary cavity with variable volume of 0 ∼ 64 ml. Temperatures at multiple locations within vessel and pressure were monitored while visual access was made through front window. Alternating evaporation and condensation induced by cyclic volume change provided agitation due to density differences among water and vapor, liquid and hydrate R134a as well as extended interface area, which improved hydrate formation kinetics coupled with latent heat release and absorption. Influences of coolant temperature, piston stroke/speed, and volume change period on hydrate formation kinetics were investigated. Suggestions of reactor design improvement for future experimental study are also made.

  4. Tetrafluoroethane (R134a) hydrate formation within variable volume reactor accompanied by evaporation and condensation

    International Nuclear Information System (INIS)

    Jeong, K.; Choo, Y. S.; Hong, H. J.; Yoon, Y. S.; Song, M. H.

    2015-01-01

    Vast size hydrate formation reactors with fast conversion rate are required for the economic implementation of seawater desalination utilizing gas hydrate technology. The commercial target production rate is order of thousand tons of potable water per day per train. Various heat and mass transfer enhancement schemes including agitation, spraying, and bubbling have been examined to maximize the production capacities in scaled up design of hydrate formation reactors. The present experimental study focused on acquiring basic knowledge needed to design variable volume reactors to produce tetrafluoroethane hydrate slurry. Test vessel was composed of main cavity with fixed volume of 140 ml and auxiliary cavity with variable volume of 0 ∼ 64 ml. Temperatures at multiple locations within vessel and pressure were monitored while visual access was made through front window. Alternating evaporation and condensation induced by cyclic volume change provided agitation due to density differences among water and vapor, liquid and hydrate R134a as well as extended interface area, which improved hydrate formation kinetics coupled with latent heat release and absorption. Influences of coolant temperature, piston stroke/speed, and volume change period on hydrate formation kinetics were investigated. Suggestions of reactor design improvement for future experimental study are also made

  5. Clathrate hydrates - the energy of the future an overview and a postulated formation mechanism

    International Nuclear Information System (INIS)

    Pratt, R.M.

    2000-01-01

    Clathrate hydrates are non-stoichiometric compounds that form when water and certain low molecular weight hydrocarbons coexist at high pressures and low temperatures. The majority of the earth hydrocarbons are in the hydrate phase and are primarily located along the ocean bottoms and to a lesser degree in the permafrost regions. In addition, hydrate formation is induced in undersea gas transmission lines and causes costly pipeline plugs and requires expensive inhibition measures to be taken. Therefore, both a stick and a carrot motivate hydrate research. They are a costly and dangerous nuisance to the oil and gas industry and represent a tremendous, untapped energy resource of the future. The formation mechanism of clathrate hydrate formation has always been shrouded in mystery, and an ongoing debate has ensued as to whether their formation is a bulk or surface phenomenon. Molecular dynamics simulation and fractal modeling suggest that this may be an irrelevant issue and that two independent factors contribute to the symmetrical ordered structure of clathrate hydrates: hydrophobic hydration of hydrocarbon molecules in water and formation of linked cavities as these small clusters aggregate. (Author)

  6. 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...

  7. 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.

  8. 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

  9. Experimental flowloop study on methane hydrate formation and agglomeration in high water cut emulsion systems

    OpenAIRE

    Pham , Trung-Kien; Cameirao , Ana ,; Herri , Jean-Michel

    2016-01-01

    Thème de cette communication: International Conference on Integrated Petroleum Engineering (IPE); International audience; hydrate risk also increases. Especially in the offshore systems, operating at low temperature and high pressure, conditions are favourable to the formation of gas hydrate, from the combination of liquid water and gas molecules, under the form of a solid phase. It is a serious issue in the flow assurance; it may cause many troubles, up to plugging.This work brings new under...

  10. Gas Hydrate Formation Probability Distributions: The Effect of Shear and Comparisons with Nucleation Theory.

    Science.gov (United States)

    May, Eric F; Lim, Vincent W; Metaxas, Peter J; Du, Jianwei; Stanwix, Paul L; Rowland, Darren; Johns, Michael L; Haandrikman, Gert; Crosby, Daniel; Aman, Zachary M

    2018-03-13

    Gas hydrate formation is a stochastic phenomenon of considerable significance for any risk-based approach to flow assurance in the oil and gas industry. In principle, well-established results from nucleation theory offer the prospect of predictive models for hydrate formation probability in industrial production systems. In practice, however, heuristics are relied on when estimating formation risk for a given flowline subcooling or when quantifying kinetic hydrate inhibitor (KHI) performance. Here, we present statistically significant measurements of formation probability distributions for natural gas hydrate systems under shear, which are quantitatively compared with theoretical predictions. Distributions with over 100 points were generated using low-mass, Peltier-cooled pressure cells, cycled in temperature between 40 and -5 °C at up to 2 K·min -1 and analyzed with robust algorithms that automatically identify hydrate formation and initial growth rates from dynamic pressure data. The application of shear had a significant influence on the measured distributions: at 700 rpm mass-transfer limitations were minimal, as demonstrated by the kinetic growth rates observed. The formation probability distributions measured at this shear rate had mean subcoolings consistent with theoretical predictions and steel-hydrate-water contact angles of 14-26°. However, the experimental distributions were substantially wider than predicted, suggesting that phenomena acting on macroscopic length scales are responsible for much of the observed stochastic formation. Performance tests of a KHI provided new insights into how such chemicals can reduce the risk of hydrate blockage in flowlines. Our data demonstrate that the KHI not only reduces the probability of formation (by both shifting and sharpening the distribution) but also reduces hydrate growth rates by a factor of 2.

  11. 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.

  12. Formation and dissociation of CO{sub 2} and CO{sub 2}-THF hydrates compared to CH{sub 4} and CH{sub 4}-THF hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Giavarini, C.; Maccioni, F.; Broggi, A. [Roma Univ. La Sapienza, Roma (Italy). Dept. of Chemical Engineering; Politi, M. [ENEL-RICERCHE, Brindisi (Italy)

    2008-07-01

    Carbon sequestration involves the removal of greenhouse gases from industrial or utility plant streams and their long term storage so that they cannot interact with the climate system. Different methods for selective carbon dioxide (CO{sub 2}) removal are in commercial use and are based on, gas absorption, membrane process, and cryogenic fractionation. In addition, disposal of captured CO{sub 2} in the ocean and in geological reservoirs has been proposed by researchers. Another challenge is to take advantage of the properties of CO{sub 2} hydrates for carbon sequestration since it could have a number of uses such as chemical production. As such, it is important to understand the hydrate decomposition kinetics during storage, transportation, and disposal. This paper presented a project that involved the separation of carbon dioxide from the flue gases of powers plants, in the form of hydrate. The project also involved the storage, use, and disposal of the hydrate. The purpose of the study was to evaluate the decomposition kinetics of CO{sub 2} hydrate containing different quantities of ice, at low pressures and temperatures between -3 and 0 degrees Celsius. In addition, in order to evaluate the tetrahydrofuran (THF) stabilization effect, the study examined the influence of THF on the formation and decomposition kinetics of mixed THF-methane (CH{sub 4}) and THF-CO{sub 2} hydrates. Preservation tests were conducted to determine the best pressure and temperature conditions for the mixed-hydrates conservation, with reference to the simple hydrates. The paper described the apparatus for the formation and dissociation tests which consisted of a jacketed stainless steel reactor, equipped with stirrer. The paper also described the hydrate formation procedure as well as hydrate characterization. Last, the paper discussed the hydrate dissociation tests that were conducted immediately after hydrate formation in the reactor. It was concluded that the hydrophilic and hydrophobic

  13. Experimental Study on Methane Hydrate Formation and Transport from Emulsions in a “Gas Lift” Riser in a Flowloop

    OpenAIRE

    Pham , Trung-Kien; Cameirao , Ana ,; Herri , Jean-Michel; Glenat , Philippe

    2017-01-01

    Session : Flow Assurance: Transportability Strategies - GasHyDyn : Logiciel de simulation de la composition et de la stabilité des hydrates de gaz; International audience; Production of crude oil with natural gas and water at low temperature and high pressure favours conditions for gas hydrate formation which can cause many troubles, up to blockage of pipelines. This work deals with hydrate kinetics of crystallization and agglomeration together with slurry transport and deposition under flowi...

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

    Science.gov (United States)

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

    2008-08-28

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

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

    Directory of Open Access Journals (Sweden)

    Carollina de M. Molinari O. Antunes

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

  16. Study on the Promotion Effect of Ionic Liquid on CH4 Hydrate Formation

    International Nuclear Information System (INIS)

    Shin, Ju-Young; Mun, Sungyong; Kang, Seong-Pil; Kim, Kisub

    2013-01-01

    In this study, we investigated the kinetics of gas hydrate formation in the presence of ionic liquid (IL). Hydroxyethyl-methyl-morpholinium chloride (HEMM-Cl) was chosen as a material for the promotion effect test. Phase equilibrium curve for CH 4 hydrate with aqueous IL solution was obtained and its induction time and consumed amount of CH 4 gas were also measured. Aqueous solutions containing 20-20,000 ppm of HEMM-Cl was prepared and studied at 70 bar and 274.15 K. To compare the measured results to those of the conventional promoter, sodium dodecyl sulfate was also tested at the same condition. Result showed that the hydrate equilibrium curve was shifted toward higher pressure and lower temperature region. In addition, the induction time on CH 4 hydrate formation in the presence of IL was not shown. The amount of consumed CH 4 was increased with the whole range of tested concentration of IL and the highest consumption of CH 4 happened at 1,000 ppm of HEMM-Cl. HEMM-Cl induced and enhanced the CH 4 hydrate formation with a small amount of addition. Obtained result is expected to be applied for the development of technologies such as gas storage and transport using gas hydrates

  17. Gas hydrate formation process for pre-combustion capture of carbon dioxide

    International Nuclear Information System (INIS)

    Lee, Hyun Ju; Lee, Ju Dong; Linga, Praveen; Englezos, Peter; Kim, Young Seok; Lee, Man Sig; Kim, Yang Do

    2010-01-01

    In this study, gas hydrate from CO 2 /H 2 gas mixtures with the addition of tetrahydrofuran (THF) was formed in a semi-batch stirred vessel at various pressures and temperatures to investigate the CO 2 separation/recovery properties. This mixture is of interest to CO 2 separation and recovery from Integrated Gasification Combine Cycle (IGCC) power plants. During hydrate formation the gas uptake was determined and composition changes in the gas phase were obtained by gas chromatography. The impact of THF on hydrate formation from the CO 2 /H 2 was observed. The addition of THF significantly reduced the equilibrium formation conditions. 1.0 mol% THF was found to be the optimum concentration for CO 2 capture based on kinetic experiments. The present study illustrates the concept and provides thermodynamic and kinetic data for the separation/recovery of CO 2 (pre-combustion capture) from a fuel gas (CO 2 /H 2 ) mixture.

  18. 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

  19. The role of hydrophobic interactions for the formation of gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, R.H.; Wang, J.; Eriksson, J.C. [Virginia Polytech Inst. and State Univ., Blacksburg, VA (United States). Center for Advanced Separation Technologies; Sum, A.K. [Colorado School of Mines, Golden, CO (United States). Dept. of Chemical Engineering

    2008-07-01

    The process of hydrate formation remains largely unexplained due to a lack of evidence for the water molecules around the hydrophobic solute such as methane, and the nucleation process leading to the clustering that induces hydrate growth. However, the water structure is known to play a major role in the mechanism for hydrate nucleation. This paper presented evidence that hydrophobic solutes promote the structuring of water. Water molecules at room temperature tend to form ice structures around the hydrocarbon chains of surfactant molecules dissolved in water. An atomic force microscope (AFM) was used in this study to measure the surface forces between thiolated gold surfaces. The purpose was to better understand the structure of the thin films of water between hydrophobic surfaces. The water molecules tended to reorganize themselves to form ordered structures, which may be related to the nucleation of hydrates. The entropy reduction associated with the ice structure can be considered as the net driving force for self-assembly. Recent studies have revealed that long-range attractive forces exist between hydrophobic surfaces, which are likely to result from structuring of the water molecules in the vicinity of the hydrophobic surfaces. Similarly, the hydrophobic nature of most gas hydrate formers may induce ordering of water molecules in the vicinity of dissolved solutes. It was concluded that the results of this study may be used to develop a new mechanism for the formation of gas hydrates, including methane. 20 refs., 2 figs.

  20. How Sodium Chloride Salt Inhibits the Formation of CO2 Gas Hydrates.

    Science.gov (United States)

    Holzammer, Christine; Finckenstein, Agnes; Will, Stefan; Braeuer, Andreas S

    2016-03-10

    We present an experimental Raman study on how the addition of sodium chloride to CO2-hydrate-forming systems inhibits the hydrate formation thermodynamically. For this purpose, the molar enthalpy of reaction and the molar entropy of reaction for the reaction of weakly hydrogen-bonded water molecules to strongly hydrogen bonded water molecules are determined for different salinities from the Raman spectrum of the water-stretching vibration. Simultaneously, the influence of the salinity on the solubility of CO2 in the liquid water-rich phase right before the start of hydrate formation is analyzed. The results demonstrate that various mechanisms contribute to the inhibition of gas hydrate formation. For the highest salt concentration of 20 wt % investigated, the temperature of gas hydrate formation is lowered by 12 K. For this concentration the molar enthalpy and entropy of reaction become smaller by 50 and 20%, respectively. Concurrently, the solubility of carbon dioxide is reduced by 70%. These results are compared with data in literature for systems of sodium chloride in water (without carbon dioxide).

  1. 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.

  2. Low temperature X-ray diffraction studies of natural gas hydrate samples from the Gulf of Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Rawn, C.J. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Materials Science and Technology Div.; Sassen, R. [Texas A and M Univ., College Station, TX (United States). Geochemical and Environmental Research Group; Ulrich, S.M.; Phelps, T.J. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Biosciences Div.; Chakoumakos, B.C. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Neutron Scattering Science Div.; Payzant, E.A. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Center for Nanophase Materials Science

    2008-07-01

    Quantitative studies of natural clathrate hydrates are hampered by the difficulties associated with obtaining pristine samples for the sea floor without comprising their integrity. This paper discussed X-ray power diffraction studies conducted to measure natural gas hydrate samples obtained from the Green Canyon in the Gulf of Mexico. Data on the hydrate deposits were initially collected in 2002. The X-ray diffraction data were collected in order to examine the structure 2 (s2) gas hydrates as functions of temperature and time. A diffractometer with a theta-theta goniometer modified with a helium closed cycle refrigerator and temperature controller was used. Aragonite, quartz and halite phases were determined in the decomposed sample. Refined phase fractions for both the ice and the s2 hydrate were obtained as a function of temperature. Results of the study demonstrated that the amount of hydrates decreased with increasing temperatures and amounts of time. Large pieces of the hydrate showed heterogenous ice content. Dissociation rates were higher at lower temperatures. It was concluded that unusual trends observed for the smaller lattice parameter of the hydrates resulted from the formation of ice layers that acted as barriers to the released gases and caused increased isostatic pressures around the hydrate core. 9 refs., 6 figs.

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

    International Nuclear Information System (INIS)

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

    2010-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-12-15

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

  5. 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

  6. Gas hydrate formation and accumulation potential in the Qiangtang Basin, northern Tibet, China

    International Nuclear Information System (INIS)

    Fu, Xiugen; Wang, Jian; Tan, Fuwen; Feng, Xinglei; Wang, Dong; He, Jianglin

    2013-01-01

    Highlights: • Qiangtang Basin is the biggest residual petroleum-bearing basin in Tibet Plateau. • The Late Triassic Tumen Gela Formation is the most important gas source rock. • Seventy-one potential anticline structural traps have been found. • A favorable geothermal condition for gas hydrate formation. • A large number of mud volcanoes were discovered in the basin. - Abstract: The Qiangtang Basin is the biggest residual petroleum-bearing basin in the Qinghai–Tibet Plateau, and is also an area of continuous permafrost in southwest China with strong similarities to other known gas-hydrate-bearing regions. Permafrost thickness is typically 60–180 m; average surface temperature ranges from −0.2 to −4.0 °C, and the geothermal gradient is about 2.64 °C/100 m. In the basin, the Late Triassic Tumen Gela Formation is the most important gas source rock for gas, and there are 34.3 × 10 8 t of gas resources in the Tumen Gela Formation hydrocarbon system. Seventy-one potential anticline structural traps have been found nowadays covering an area of more than 30 km 2 for each individual one, five of them are connected with the gas source by faults. Recently, a large number of mud volcanoes were discovered in the central Qiangtang Basin, which could be indicative of the formation of potential gas hydrate. The North Qiangtang depression should be delineated as the main targets for the purpose of gas hydrate exploration

  7. Ultrasonic experiment on hydrate formation of a synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Shicai; Fan, Shuanshi; Liang, Deqing; Zhang, Junshe; Feng, Ziping

    2005-07-01

    The effect of ultrasonic on the induction time and formation rate of natural gas hydrates was investigated in a stainless steel cell in this study. The results show that the induction time with ultrasonic was about 1/6 of that without ultrasonic and only about 1/10 if rehydration after decomposition in water-gas system. In sodium dodecyl sulfate (SDS) solution-gas system, the critical micellar concentration (CMC) was not identified with ultrasonic. The formation rate and storage capacity of hydrate increased with increasing SDS concentration at a range of 0 to 800ppm. However, the increase was insignificant as the SDS concentration increased from 600 to 800ppm, (Author)

  8. Temperature controlled 'void' formation

    International Nuclear Information System (INIS)

    Dasgupta, P.; Sharma, B.D.

    1975-01-01

    The nucleation and growth of voids in structural materials during high temperature deformation or irradiation is essentially dependent upon the existence of 'vacancy supersaturation'. The role of temperature dependent diffusion processes in 'void' formation under varying conditions, and the mechanical property changes associated with this microstructure are briefly reviewed. (author)

  9. Formation and Transformation Behavior of Sodium Dehydroacetate Hydrates

    Directory of Open Access Journals (Sweden)

    Xia Zhang

    2016-04-01

    Full Text Available The effect of various controlling factors on the polymorphic outcome of sodium dehydroacetate crystallization was investigated in this study. Cooling crystallization experiments of sodium dehydroacetate in water were conducted at different concentrations. The results revealed that the rate of supersaturation generation played a key role in the formation of the hydrates. At a high supersaturation generation rate, a new sodium dehydroacetate dihydrate needle form was obtained; on the contrary, a sodium dehydroacetate plate monohydrate was formed at a low supersaturation generation rate. Furthermore, the characterization and transformation behavior of these two hydrated forms were investigated with the combined use of microscopy, powder X-ray diffraction (PXRD, Raman spectroscopy, Fourier transform infrared (FTIR, thermal gravimetric analysis (TGA, scanning electron microscopy (SEM and dynamic vapor sorption (DVS. It was found that the new needle crystals were dihydrated and hollow, and they eventually transformed into sodium dehydroacetate monohydrate. In addition, the mechanism of formation of sodium dehydroacetate hydrates was discussed, and a process growth model of hollow crystals in cooling crystallization was proposed.

  10. Formation of Sclerotic Hydrate Deposits in a Pipe for Extraction of a Gas from a Dome Separator

    Science.gov (United States)

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

    2017-09-01

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

  11. Influence of Physical Activity and Ambient Temperature on Hydration: The European Hydration Research Study (EHRS

    Directory of Open Access Journals (Sweden)

    Ricardo Mora-Rodriguez

    2016-04-01

    Full Text Available This study explored the effects of physical activity (PA and ambient temperature on water turnover and hydration status. Five-hundred seventy three healthy men and women (aged 20–60 years from Spain, Greece and Germany self-reported PA, registered all food and beverage intake, and collected 24-h urine during seven consecutive days. Fasting blood samples were collected at the onset and end of the study. Food moisture was assessed using nutritional software to account for all water intake which was subtracted from daily urine volume to allow calculation of non-renal water loss (i.e., mostly sweating. Hydration status was assessed by urine and blood osmolality. A negative association was seen between ambient temperature and PA (r = −0.277; p < 0.001. Lower PA with high temperatures did not prevent increased non-renal water losses (i.e., sweating and elevated urine and blood osmolality (r = 0.218 to 0.163 all p < 0.001. When summer and winter data were combined PA was negatively associated with urine osmolality (r = −0.153; p = 0.001. Our data suggest that environmental heat acts to reduce voluntary PA but this is not sufficient to prevent moderate dehydration (increased osmolality. On the other hand, increased PA is associated with improved hydration status (i.e., lower urine and blood osmolality.

  12. Hydration and temperature in tennis - a practical review.

    Science.gov (United States)

    Kovacs, Mark S

    2006-03-01

    Competitive tennis is typically played in warm and hot environments. Because hypohydration will impair tennis performance and increases the risk of heat injury, consumption of appropriate fluid levels is necessary to prevent dehydration and enhance performance. The majority of research in this area has focused on continuous aerobic activity - unlike tennis, which has average points lasting less than ten seconds with rest periods dispersed between each work period. For this reason, hydration and temperature regulation methods need to be specific to the activity. Tennis players can sweat more than 2.5 L·h(-1) and replace fluids at a slower rate during matches than in practice. Latter stages of matches and tournaments are when tennis players are more susceptible to temperature and hydration related problems. Sodium (Na(+)) depletion, not potassium (K(+)), is a key electrolyte in tennis related muscle cramps. However, psychological and competitive factors also contribute. CHO drinks have been shown to promote fluid absorption to a greater degree than water alone, but no performance benefits have been shown in tennis players in short matches. It is advisable to consume a CHO beverage if practice or matches are scheduled longer than 90-120 minutes. Key PointsAlthough substantial research has been performed on temperature and hydration concerns in aerobic activities, there is little information with regard to tennis performance and safetyTennis athletes should be on an individualized hydration schedule, consuming greater than 200ml of fluid every changeover (approximately 15 minutes).Optimum hydration and temperature regulation will reduce the chance of tennis related muscle cramps and performance decrements.

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

    Directory of Open Access Journals (Sweden)

    Kumar Saw V.

    2015-11-01

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

  14. Communication: Quantitative Fourier-transform infrared data for competitive loading of small cages during all-vapor instantaneous formation of gas-hydrate aerosols

    Science.gov (United States)

    Uras-Aytemiz, Nevin; Abrrey Monreal, I.; Devlin, J. Paul

    2011-10-01

    A simple method has been developed for the measurement of high quality FTIR spectra of aerosols of gas-hydrate nanoparticles. The application of this method enables quantitative observation of gas hydrates that form on subsecond timescales using our all-vapor approach that includes an ether catalyst rather than high pressures to promote hydrate formation. The sampling method is versatile allowing routine studies at temperatures ranging from 120 to 210 K of either a single gas or the competitive uptake of different gas molecules in small cages of the hydrates. The present study emphasizes hydrate aerosols formed by pulsing vapor mixtures into a cold chamber held at 160 or 180 K. We emphasize aerosol spectra from 6 scans recorded an average of 8 s after "instantaneous" hydrate formation as well as of the gas hydrates as they evolve with time. Quantitative aerosol data are reported and analyzed for single small-cage guests and for mixed hydrates of CO2, CH4, C2H2, N2O, N2, and air. The approach, combined with the instant formation of gas hydrates from vapors only, offers promise with respect to optimization of methods for the formation and control of gas hydrates.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

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

    Science.gov (United States)

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

    2018-05-01

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

  17. Effect of temperature on the hydration of Portland cement blended with siliceous fly ash

    Energy Technology Data Exchange (ETDEWEB)

    Deschner, Florian, E-mail: florian.deschner@gmail.com [Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Concrete and Construction Chemistry, Überlandstrasse 129, 8600 Dübendorf (Switzerland); Lothenbach, Barbara; Winnefeld, Frank [Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Concrete and Construction Chemistry, Überlandstrasse 129, 8600 Dübendorf (Switzerland); Neubauer, Jürgen [GeoZentrum Nordbayern, Mineralogy, University of Erlangen-Nuremberg, 91054 Erlangen (Germany)

    2013-10-15

    The effect of temperature on the hydration of Portland cement pastes blended with 50 wt.% of siliceous fly ash is investigated within a temperature range of 7 to 80 °C. The elevation of temperature accelerates both the hydration of OPC and fly ash. Due to the enhanced pozzolanic reaction of the fly ash, the change of the composition of the C–S–H and the pore solution towards lower Ca and higher Al and Si concentrations is shifted towards earlier hydration times. Above 50 °C, the reaction of fly ash also contributes to the formation of siliceous hydrogarnet. At 80 °C, ettringite and AFm are destabilised and the released sulphate is partially incorporated into the C–S–H. The observed changes of the phase assemblage in dependence of the temperature are confirmed by thermodynamic modelling. The increasingly heterogeneous microstructure at elevated temperatures shows an increased density of the C–S–H and a higher coarse porosity. -- Highlights: •The reaction of quartz powder at 80 °C strongly enhances the compressive strength. •Almost no strength increase of fly ash blended OPC at 80 °C was found after 2 days. •Siliceous hydrogarnet is formed upon the reaction of fly ash at high temperatures. •Temperature dependent change of the system was simulated by thermodynamic modelling. •Destabilisation of ettringite above 50 °C correlates with sulphate content of C–S–H.

  18. Effect of temperature on the hydration of Portland cement blended with siliceous fly ash

    International Nuclear Information System (INIS)

    Deschner, Florian; Lothenbach, Barbara; Winnefeld, Frank; Neubauer, Jürgen

    2013-01-01

    The effect of temperature on the hydration of Portland cement pastes blended with 50 wt.% of siliceous fly ash is investigated within a temperature range of 7 to 80 °C. The elevation of temperature accelerates both the hydration of OPC and fly ash. Due to the enhanced pozzolanic reaction of the fly ash, the change of the composition of the C–S–H and the pore solution towards lower Ca and higher Al and Si concentrations is shifted towards earlier hydration times. Above 50 °C, the reaction of fly ash also contributes to the formation of siliceous hydrogarnet. At 80 °C, ettringite and AFm are destabilised and the released sulphate is partially incorporated into the C–S–H. The observed changes of the phase assemblage in dependence of the temperature are confirmed by thermodynamic modelling. The increasingly heterogeneous microstructure at elevated temperatures shows an increased density of the C–S–H and a higher coarse porosity. -- Highlights: •The reaction of quartz powder at 80 °C strongly enhances the compressive strength. •Almost no strength increase of fly ash blended OPC at 80 °C was found after 2 days. •Siliceous hydrogarnet is formed upon the reaction of fly ash at high temperatures. •Temperature dependent change of the system was simulated by thermodynamic modelling. •Destabilisation of ettringite above 50 °C correlates with sulphate content of C–S–H

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-07-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-07-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Herri, J M

    1996-02-02

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

  3. Thermogravimetric study on the hydration of reactive magnesia and silica mixture at room temperature

    International Nuclear Information System (INIS)

    Jin, Fei; Al-Tabbaa, Abir

    2013-01-01

    Highlights: • The characteristics of reactive MgO vary significantly in terms of their impurity content and reactivity depending on their sources and calcination conditions. • The synthesis of magnesium silicate hydrate (MSH) is affected by the characteristics of the precursors, i.e., MgO and silica. • The reaction process in the MgO–SiO 2 –H 2 O system can be followed by TGA, and is essential to develop MSH-based materials. - Abstract: The synthesis of magnesium silicate hydrate (MSH), which has wide applications in both construction and environmental fields, has been studied for decades. However, it is known that the characteristics of magnesia (MgO) vary significantly depending on their calcination conditions, which is expected to affect their performance in the MgO–SiO 2 –H 2 O system. This paper investigated the effect of different MgO and silica sources on the formation of magnesium silicate hydrate (MSH) at room temperature. The hydration process was studied by mixing commercial reactive MgO and silica powders with water and curing for 1, 7 and 28 days. The hydration products were analysed with the help of X-ray diffraction (XRD) and thermogravimatric analysis (TGA). The results showed the continuous consumption of MgO and the existence of MSH and brucite and other minor phases such as magnesite and calcite. It is found that the Mg and Si sources have significant effect on the hydration process of MgO–SiO 2 –H 2 O system. The reaction degree is controlled by the availability of dissolved Mg and Si in the solution. The former is determined by the reactivity of MgO and the latter is related to the reactivity of the silica as well as the pH of the system

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  5. 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.

  6. 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

  7. The phase equilibria of multicomponent gas hydrate in methanol/ethylene glycol solution based formation water

    International Nuclear Information System (INIS)

    Xu, Shurui; Fan, Shuanshi; Yao, Haiyuan; Wang, Yanhong; Lang, Xuemei; Lv, Pingping; Fang, Songtian

    2017-01-01

    Highlights: • The equilibrium data in THI solution based formation water is first investigated. • The 0.55 mass fraction concentration of EG 0.55 mass fraction fills the vacancy of this area. • The testing pressure range from 4.22 MPa to 34.72 MPa was rare in published data. - Abstract: In this paper, the three-phase coexistence points are generated for multicomponent gas hydrate in methanol (MeOH) solution for (0.05, 0.10, 0.15, and 0.35) mass fraction and ethylene glycol (EG) solution for (0.05, 0.10, 0.15, 0.35, 0.40 and 0.55) mass fraction. The phase equilibrium curves of different system were obtained by an isochoric pressure-search method on high pressure apparatus. The phase equilibrium regions of multicomponent gas hydrate were measured using the same composition of natural gas distributed in the South China Sea. And the different concentration solutions were prepared based formation water. The experimental data were measured in a wide range temperature from 267.74 to 298.53 K and a wide range pressure from 4.22 MPa to 34.72 MPa. The results showed that the hydrate phase equilibrium curves shifted to the inhibition region in accordance with the increased inhibitor concentration. In addition, the equilibrium temperature would decrease about 2.7 K when the concentration of MeOH increased 0.05 mass fraction. Besides, the suppression temperature was 1.25 K with the 0.05 mass fraction increase of EG concentration in the range of 0.05 mass fraction to 0.15 mass fraction. While in high EG concentration region, the suppression temperature was 3.3 K with the same increase of EG concentration (0.05 mass fraction).

  8. Hydration and temperature interdependence of protein picosecond dynamics.

    Science.gov (United States)

    Lipps, Ferdinand; Levy, Seth; Markelz, A G

    2012-05-14

    We investigate the nature of the solvent motions giving rise to the rapid temperature dependence of protein picoseconds motions at 220 K, often referred to as the protein dynamical transition. The interdependence of picoseconds dynamics on hydration and temperature is examined using terahertz time domain spectroscopy to measure the complex permittivity in the 0.2-2.0 THz range for myoglobin. Both the real and imaginary parts of the permittivity over the frequency range measured have a strong temperature dependence at >0.27 h (g water per g protein), however the permittivity change is strongest for frequencies 1 THz, and 0.27 h for frequencies <1 THz. The data are consistent with the dynamical transition solvent fluctuations requiring only clusters of ~5 water molecules, whereas the enhancement of lowest frequency motions requires a fully spanning water network. This journal is © the Owner Societies 2012

  9. HYDRATION AND TEMPERATURE IN TENNIS - A PRACTICAL REVIEW

    Directory of Open Access Journals (Sweden)

    Mark S. Kovacs

    2006-03-01

    Full Text Available Competitive tennis is typically played in warm and hot environments. Because hypohydration will impair tennis performance and increases the risk of heat injury, consumption of appropriate fluid levels is necessary to prevent dehydration and enhance performance. The majority of research in this area has focused on continuous aerobic activity - unlike tennis, which has average points lasting less than ten seconds with rest periods dispersed between each work period. For this reason, hydration and temperature regulation methods need to be specific to the activity. Tennis players can sweat more than 2.5 L·h-1 and replace fluids at a slower rate during matches than in practice. Latter stages of matches and tournaments are when tennis players are more susceptible to temperature and hydration related problems. Sodium (Na+ depletion, not potassium (K+, is a key electrolyte in tennis related muscle cramps. However, psychological and competitive factors also contribute. CHO drinks have been shown to promote fluid absorption to a greater degree than water alone, but no performance benefits have been shown in tennis players in short matches. It is advisable to consume a CHO beverage if practice or matches are scheduled longer than 90-120 minutes.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-05-15

    The aim of this work is to study the modeling of the thermal evolution inside an hydrate forming system which is submitted to an imposed steady cooling. The study system is a w/o emulsion where the formulation considers the CCl{sub 3}F as the hydrate forming molecule dissolved in the oil phase. The hydrate formation occurs in the aqueous phase of the emulsion, i.e. in the dispersed phase. The model equation is based on the resolution of the continuity equation in terms of a heat balance for the dispersed phase. The crystallization of the CCl{sub 3}F hydrate occurs at supercooling conditions (T{sub c}temperature around the system. Thus, the inclusion of the heat source term has to be considered in order to take into account the influence of crystallization. The rate of heat released during the crystallization is governed by the probability of nucleation J(T). Previous experimental measurements allowed to derive the corresponding function J(T) of the w/o emulsion. The results provided by the model equation subjected to boundary conditions allow to depict the evolution of temperature in the dispersed phase. The most singular point in the temperature-time curve is the onset time of hydrate crystallization. Three time intervals characterize the evolution of temperature during the steady cooling of the w/o emulsion: (1) steady cooling, (2) hydrate formation with a release of heat, (3) a last interval of steady cooling. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-01

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

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

    African Journals Online (AJOL)

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

  13. Experimental and theoretical investigations on the carbon dioxide gas hydrate formation kinetics at the onset of turbidity regarding CO2 capture and sequestration processes

    International Nuclear Information System (INIS)

    ZareNezhad, Bahman; Mottahedin, Mona; Varaminian, Farshad

    2013-01-01

    The carbon dioxide gas hydrate formation kinetics at the onset of turbidity is experimentally and theoretically investigated. It is shown that the time-dependent heterogeneous nucleation and growth kinetics are simultaneously governing the hydrate formation process at the onset of turbidity. A new approach is also presented for determination of gas hydrate-liquid interfacial tension. The CO 2 hydrate-liquid interfacial tension according to the suggested heterogeneous nucleation mechanism is found to be about 12.7 mJ/m 2 . The overall average absolute deviation between predicted and measured CO 2 molar consumption is about 0.61%, indicating the excellent accuracy of the proposed model for studying the hydrate-based CO 2 capture and sequestration processes over wide ranges of pressures and temperatures

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

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  15. Thermodynamic simulations of hydrate formation from gas mixtures in batch operations

    International Nuclear Information System (INIS)

    Kobayashi, Takehito; Mori, Yasuhiko H.

    2007-01-01

    This paper deals with the hydrate formation from mixed hydrate-forming gases such as natural gas to be converted to hydrates for the purpose of its storage and biogases from which carbon dioxide is to be separated by hydrate formation. When a batch operation is selected for processing such a gas mixture in a closed reactor, we need to predict the evolution of the thermodynamic and compositional states inside the reactor during the operation. We have contrived a simulation scheme that allows us to estimate the simultaneous changes in the composition of the residual gas, the structure of the hydrate formed and the guest composition in the hydrate, in addition to the change in the system pressure, with the progress of hydrate formation during each operation. This scheme assumes the transient hydrate forming process in a reactor during each operation to be a series of numerous equilibrium states, each slightly deviating from the preceding state. That is, a thermodynamic system composed of the contents of the reactor is assumed to be subjected to a quasi-static, irreversible change in state, instantaneously keeping itself in thermodynamic equilibrium. The paper demonstrates a simulation of a process of hydrate formation from a methane + propane mixture and compares its results to relevant experimental results reported by Uchida et al. [Uchida T, Morikawa M, Takeya S, Ikeda IY, Ohmura R, Nagao J, et al. Two-step formation of methane-propane mixed gas hydrates in a batch-type reactor. AIChE J 2004;50(2):518-23

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

    OpenAIRE

    Niu, Jing

    2012-01-01

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

  17. Comparison of setting time and temperature hydration in mortar with substituent ceramic

    International Nuclear Information System (INIS)

    Rodrigues, R.A.; Alves, L.S.; Evangelista, A.C.J.; Almeida, V.C.

    2011-01-01

    The workability of mortar is determined mainly by the kinetics of hydration of the hydraulic binder, the process of gelation / hydration of this material in aqueous solutions is significantly influenced by the presence of additives. As a result, this work aims at studying changes in setting time and temperature of hydration of mortars with 10, 15 and 30% of Portland cement replaced by residues of porcelain and ceramic bricks. The influence of these residues in the cement hydration process was studied by testing takes time, temperature, hydration and X-ray diffraction. The results indicate that the mortar setting time not changed significantly since the temperature of hydration has a minor variation on what is preferred because it reduces the microcracks created in mortar during drying.(author)

  18. Hydration kinetics modeling of Portland cement considering the effects of curing temperature and applied pressure

    International Nuclear Information System (INIS)

    Lin Feng; Meyer, Christian

    2009-01-01

    A hydration kinetics model for Portland cement is formulated based on thermodynamics of multiphase porous media. The mechanism of cement hydration is discussed based on literature review. The model is then developed considering the effects of chemical composition and fineness of cement, water-cement ratio, curing temperature and applied pressure. The ultimate degree of hydration of Portland cement is also analyzed and a corresponding formula is established. The model is calibrated against the experimental data for eight different Portland cements. Simple relations between the model parameters and cement composition are obtained and used to predict hydration kinetics. The model is used to reproduce experimental results on hydration kinetics, adiabatic temperature rise, and chemical shrinkage of different cement pastes. The comparisons between the model reproductions and the different experimental results demonstrate the applicability of the proposed model, especially for cement hydration at elevated temperature and high pressure.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

  20. Electron migration in hydrated biopolymers following pulsed irradiation at low temperatures

    International Nuclear Information System (INIS)

    Lith, D. van.

    1987-01-01

    Charge migration in biopolymer-water mixtures and the effect of water concentration on the charge migration is investigated by measuring the electrical conductivity and the light emission with the pulse radiolysis technique. A preliminary account of the microwave conductivity observed in hydrated DNA and collagen at low temperature after pulsed irradiation is given. The results show that when hydrated DNA or collagen are irradiated at low temperatures, conductivity transients with microsecond lifetime are observed. It is tentatively concluded that these transients are due to the highly mobile dry electron. The effect of water concentration on mobility, lifetime and migration distance of the electron is discussed. The effect of additives to the hydrated systems on the behaviour of the electron is described. It is shown that the observed effects of the additives confirm the earlier conclusions that the dry electron is the species responsible for the radiation induced conductivity. The water concentration in the DNA- and collagen-systems could be varied only between zero and approximately fifty percent, due to inhomogeneities which occur at higher water concentrations. Experiments on gelatin, a biopolymer which forms homogeneous samples with levels of hydration varying from almost zero to 100% water (ice) are described. Both the radiation induced and the dark microwave conductivity have been studied as a function of water content. Preliminary results of a study of the light emission from pulse irradiated DNA-water mixtures are reported in an attempt to establish a relation between the observed electron migration and the formation of excited states via charge neutralization. (Auth.)

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

    Directory of Open Access Journals (Sweden)

    Dvorkin Leonid

    2018-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-01

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

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

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  4. Low frequency enzyme dynamics as a function of temperature and hydration: A neutron scattering study

    Energy Technology Data Exchange (ETDEWEB)

    Kurkal, V. [Interdisciplinary Center for Scientific Computing (IWR), University of Heidelberg, Im Neuenheimer Feld 368, D-69120 Heidelberg (Germany); Daniel, R.M. [Department of Biological Sciences, University of Waikato, Private Bag 3105, Hamilton (New Zealand); Finney, John L. [Department of Physics and Astronomy, University college, London, Gower Street, London WC1E 6BT, England (United Kingdom); Tehei, M. [Department of Biological Sciences, University of Waikato, Private Bag 3105, Hamilton (New Zealand); Dunn, R.V. [Department of Biological Sciences, University of Waikato, Private Bag 3105, Hamilton (New Zealand); Smith, Jeremy C. [Interdisciplinary Center for Scientific Computing (IWR), University of Heidelberg, Im Neuenheimer Feld 368, D-69120 Heidelberg (Germany)], E-mail: biocomputing@iwr.uni-heidelberg.de

    2005-10-31

    The effect of hydration and temperature on the low-frequency dynamics of the enzyme Pig liver esterase has been investigated with incoherent neutron scattering experiments. The results suggest that at low temperature, increasing hydration results in lower flexibility of the protein. At higher temperatures, systems containing sufficient number of water molecules interacting with the protein exhibit increased flexibility. The environmental force constants indicate that the environment of the protein is more rigid below than it is above the dynamical transition temperature.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

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

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

    DEFF Research Database (Denmark)

    Jensen, Lars; Ramløv, Hans; Thomsen, Kaj

    2010-01-01

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

  7. Carbon dioxide storage in marine sediments - dissolution, transport and hydrate formation kinetics from high-pressure experiments

    Science.gov (United States)

    Bigalke, N. K.; Savy, J. P.; Pansegrau, M.; Aloisi, G.; Kossel, E.; Haeckel, M.

    2009-12-01

    By satisfying thermodynamic framework conditions for CO2 hydrate formation, pressures and temperatures of the deep marine environment are unique assets for sequestering CO2 in clathrates below the seabed. However, feasibility and safety of this storage option require an accurate knowledge of the rate constants governing the speed of physicochemical reactions following the injection of the liquefied gas into the sediments. High-pressure experiments designed to simulate the deep marine environment open the possibility to obtain the required parameters for a wide range of oceanic conditions. In an effort to constrain mass transfer coefficients and transport rates of CO2 in(to) the pore water of marine sediments first experiments were targeted at quantifying the rate of CO2 uptake by de-ionized water and seawater across a two-phase interface. The nature of the interface was controlled by selecting p and T to conditions within and outside the hydrate stability field (HSF) while considering both liquid and gaseous CO2. Concentration increase and hydrate growth were monitored by Raman spectroscopy. The experiments revealed anomalously fast transport rates of dissolved CO2 at conditions both inside and outside the HSF. While future experiments will further elucidate kinetics of CO2 transport and hydrate formation, these first results could have major significance to safety-related issues in the discussion of carbon storage in the marine environment.

  8. Development of an offshore gas field - investigation of hydrate and paraffin formation potential with regard to flow assurance; Entwicklung eines Offshore-Gasfeldes: Hydrat- und Paraffinuntersuchungen zur Sicherstellung der kontinuierlichen Produktion

    Energy Technology Data Exchange (ETDEWEB)

    Zettlitzer, M.; Busch, M. [RWE Dea AG, Wietze (Germany)

    2005-11-01

    During the production of offshore gas fields, raw gas from a number of production wells is usually led to a platform or - for reservoirs located close to shore - even transported as wet gas to an onshore gas treatment plant. The pipelines are located at the sea bottom, resulting in significant cooling of the raw gas with subsequent potential for the formation of hydrates and/or precipitation of paraffin on the pipeline walls. In order to safeguard continuous production, additional installations and/or dosage of chemicals would possibly be required. On the basis of gas and condensate samples from production tests, the formation potential for paraffins was experimentally investigated while the hydrate formation potential was assessed by simulations. The very small volume of condensate available (2-3 ml of each sample) formed a special challenge and limited the number of possible analytical investigations. Nevertheless, wax appearance temperature of five condensates under investigation could successfully be determined by a combination of gas-chromatographic and rheological measurements. Two of the three gas-bearing layers turned out to produce dry gas so that paraffin problems can be excluded. However, according to the simulations, hydrate formation at temperatures {<=}+20 C has to be expected under the formation pressure of about 200 bars. The third layer contains a gas condensate, causing paraffin precipitation at {<=}0 C and forming hydrate in a temperature range similar to that of the other two sands. Hence, precautions have to taken to prevent hydrate formation in all field lines containing wet gas. Furthermore, the paraffin precipitation potential has to be taken into account in the subsequent low-temperature gas-treatment plant. (orig.)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-05-11

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

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

    DEFF Research Database (Denmark)

    Airaksinen, Sari; Luukkonen, Pirjo; Jørgensen, Anna

    2003-01-01

    its dissolution rate. The aim of this study was to investigate whether excipients, such as alpha-lactose monohydrate or the highly water absorbing silicified microcrystalline cellulose (SMCC) can influence the hydrate formation of theophylline. In particular, the aim was to study if SMCC offers...... protection against the formation of theophylline monohydrate relative to alpha-lactose monohydrate in wet masses after an overnight equilibration and the stability of final granules during controlled storage. In addition, the aim was to study the use of spectroscopic methods to identify hydrate formation...... in the formulations containing excipients. Off-line evaluation of materials was performed using X-ray powder diffractometry, near infrared and Raman spectroscopy. alpha-Lactose monohydrate with minimal water absorbing potential was not able to prevent but enhanced hydrate formation of theophylline. Even though SMCC...

  11. Equivalent formation strength as a proxy tool for exploring the existence and distribution of gas hydrates

    Science.gov (United States)

    Hamada, Y.; Yamada, Y.; Sanada, Y.; Nakamura, Y.; Kido, Y. N.; Moe, K.

    2017-12-01

    Gas hydrates bearing layer can be normally identified by a basement simulating reflector (BSR) or well logging because of their high acoustic- and electric impedance compared to the surrounding formation. These characteristics of the gas hydrate can also represent contrast of in-situ formation strength. We here attempt to describe gas hydrate bearing layers based on the equivalent strength (EST). The Indian National Gas Hydrate Program (NGHP) Expedition 02 was executed 2015 off the eastern margin of the Indian Peninsula to investigate distribution and occurrence of gas hydrates. From 25 drill sites, downhole logging data, cored samples, and drilling performance data were collected. Recorded drilling performance data was converted to the EST, which is a developed mechanical strength calculated only by drilling parameters (top drive torque, rotation per minute , rate of penetration , and drill bit diameter). At a representative site, site 23, the EST shows constant trend of 5 to 10 MPa, with some positive peaks at 0 - 270 mbsf interval, and sudden increase up to 50 MPa above BSR depth (270 - 290 mbsf). Below the BSR, the EST stays at 5-10 MPa down to the bottom of the hole (378 mbsf). Comparison of the EST with logging data and core sample description suggests that the depth profiles of the EST reflect formation lithology and gas hydrate content: the EST increase in the sand-rich layer and the gas hydrate bearing zone. Especially in the gas hydrate zone, the EST curve indicates approximately the same trend with that of P-wave velocity and resistivity measured by downhole logging. Cross plot of the increment of the EST and resistivity revealed the relation between them is roughly logarithmic, indicating the increase and decrease of the EST strongly depend on the saturation factor of gas hydrate. These results suggest that the EST, proxy of in-situ formation strength, can be an indicator of existence and amount of the gas-hydrate layer. Although the EST was calculated

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

  14. A sample cell to study hydrate formation with x-ray scattering

    International Nuclear Information System (INIS)

    Conrad, Heiko; Lehmkuehler, Felix; Sternemann, Christian; Feroughi, Omid; Tolan, Metin; Simonelli, Laura; Huotari, Simo

    2009-01-01

    We present a new sample cell for measuring nonresonant inelastic x-ray scattering spectra of a tetrahydrofuran (THF)-water liquid mixture and THF hydrate. The hydrate is formed inside the cell after nucleation seeds have been offered by a special magnetic stirring mechanism. Hydrate formation was verified by wide angle x-ray scattering and nonresonant x-ray Raman scattering spectra at the oxygen K-edge. A broad range of scattering angles can be studied with this cell which is necessary for momentum transfer dependent inelastic x-ray scattering. This cell is ideal to examine other liquid hydrate formers or other liquid samples, which have to be mixed in situ during the measurements.

  15. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-06-01

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

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

    DEFF Research Database (Denmark)

    Jørgensen, Anna; Rantanen, Jukka; Karjalainen, Milja

    2002-01-01

    PURPOSE: The aim was to follow hydrate formation of two structurally related drugs, theophylline and caffeine, during wet granulation using fast and nondestructive spectroscopic methods. METHODS: Anhydrous theophylline and caffeine were granulated with purified water. Charge-coupled device (CCD......) Raman spectroscopy was compared with near-infrared spectroscopy (NIR) in following hydrate formation of drugs during wet granulation (off-line). To perform an at-line process analysis, the effect of water addition was monitored by NIR spectroscopy and principal components analysis (PCA). The changes...

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

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

    Science.gov (United States)

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

    1987-01-01

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

  20. Towards an understanding of the propensity for crystalline hydrate formation by molecular compounds

    Directory of Open Access Journals (Sweden)

    Alankriti Bajpai

    2016-11-01

    Full Text Available Hydrates are technologically important and ubiquitous yet they remain a poorly understood and understudied class of molecular crystals. In this work, we attempt to rationalize propensity towards hydrate formation through crystallization studies of molecules that lack strong hydrogen-bond donor groups. A Cambridge Structural Database (CSD survey indicates that the statistical occurrence of hydrates in 124 molecules that contain five- and six-membered N-heterocyclic aromatic moieties is 18.5%. However, hydrate screening experiments on a library of 11 N-heterocyclic aromatic compounds with at least two acceptor moieties and no competing hydrogen-bond donors or acceptors reveals that over 70% of this group form hydrates, suggesting that extrapolation from CSD statistics might, at least in some cases, be deceiving. Slurrying in water and exposure to humidity were found to be the most effective discovery methods. Electrostatic potential maps and/or analysis of the crystal packing in anhydrate structures was used to rationalize why certain molecules did not readily form hydrates.

  1. Diagnosing solubility limitations – the example of hydrate formation

    Directory of Open Access Journals (Sweden)

    Joerg Berghausen

    2014-07-01

    Full Text Available Solubility is regarded as one of the key challenges in many drug discovery projects. Thus, it’s essential to support the lead finding and optimization efforts by appropriate solubility data. In silico solubility prediction remains challenging and therefore a screening assay is used as a first filter, followed by selected follow-up assays to reveal what causes the low solubility of a specific compound or chemotype. Results from diagnosing the underlying reason for solubility limitation are discussed. As lipophilicity and crystal lattice forces are regarded as main contributors to limiting solubility, changes in solid state are important to be recognized. Solubility limitation by various factors will be presented and the impact of the solid-state is exemplified by compounds that are able to form hydrates.

  2. Kinetics of the Formation and Dissociation of Gas Hydrates from CO2-CH4 Mixtures

    Directory of Open Access Journals (Sweden)

    Devinder Mahajan

    2012-07-01

    Full Text Available Sequestration of carbon dioxide (CO2 in the form of its hydrates in natural methane (CH4 hydrate reservoirs, via CO2/CH4 exchange, is an attractive pathway that also yields valuable CH4 gas as product. In this paper, we describe a macroscale experiment to form CO2 and CH4-CO2 hydrates, under seafloor-mimic conditions, in a vessel fitted with glass windows that provides visualization of hydrates throughout formation and dissociation processes. Time resolved pressure and temperature data as well as images of hydrates are presented. Quantitative gas conversions with pure CO2, calculated from gas chromatographic measurements yielded values that range from 23 – 59% that correspond to the extent of formed hydrates. In CH4-rich CH4-CO2 mixed gas systems, CH4 hydrates were found to form preferentially.

  3. 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

    This study concerns the durability of oil-well cementing. Indeed, in oil well cementing a cement slurry is pumped down the steel casing of the well up the annular space between it and the surrounding rock to support and protect the casing. The setting conditions of pressure and temperature may be very high (up to 1000 bar and 250 deg C at the bottom of the oil-well). In this research, the hydration of the main constituent of cement, synthetic tri-calcium silicate Ca{sub 3}SiO{sub 2}, often called C{sub 3}S (C = CaO; S = SiO{sub 2} and H H{sub 2}O), is studied. Calcium Silicate hydrates are prepared in high-pressure cells to complete their phase diagram (P,T) and obtain the stability conditions for each species. Indeed, the phases formed in these conditions are unknown and the study consists in the hydration of C{sub 3}S at different temperatures, pressures, and during different times to simulate the oil-well conditions. In a first step (until 120 deg C at ambient pressure) the C-S-H, a not well crystallized and non-stoichiometric phase, is synthesized: it brings adhesion and mechanical properties., Then, when pressure and temperature increase, crystallized phases appear such as jaffeite (Ca{sub 6}(Si{sub 2}O{sub 7})(OH){sub 6}) and hillebrandite (Ca{sub 2}(SiO{sub 3})(OH){sub 2}). Silicon {sup 29}Si Nuclear Magnetic Resonance (using standard sequences MAS, CPMAS) allow us to identify all the silicates hydrates formed. Indeed, {sup 29}Si NMR is a valuable tool to determine the structure of crystallized or not-well crystallized phases of cement. The characterization of the hydrated samples is completed by other techniques: X- Ray Diffraction and Scanning Electron Microscopy. The following results are found: jaffeite is the most stable phase at C/S=3. To simulate the hydration of real cement, hydration of C{sub 3}S with ground quartz and with or without super-plasticizers is done. In those cases, new phases appear: kilchoanite mainly, and xonotlite. A large amount of

  4. Pore Effect on the Occurrence and Formation of Gas Hydrate in Permafrost of Qilian Mountain, Qinghai-Tibet Plateau, China

    Science.gov (United States)

    Gao, H.; Lu, H.; Lu, Z.

    2014-12-01

    Gas hydrates were found in the permafrost of Qilian Mountain, Qinghai- Tibet Plateau, China in 2008. It has been found that gas hydrates occur in Jurassic sedimentary rocks, and the hydrated gases are mainly thermogenic. Different from the gas hydrates existing in loose sands in Mallik, Mackenzie Delta, Canada and North Slope, Alaska, USA, the gas hydrates in Qilian Mountain occurred in hard rocks. For understanding the occurrence and formation mechanism of gas hydrate in hard rcok, extensive experimental investigations have been conducted to study the pore features and hydrate formation in the rocks recovered from the hydrate layers in Qilian Mountain. The structures of sedimentary rock were observed by high-resolution X-ray CT, and pore size distribution of a rock specimen was measured with the mercury-injection method. Methane hydrate was synthesized in water-saturated rocks, and the saturations of hydrate in sedimentary rocks of various types were estimated from the amount of gas released from certain volume of rock. X-ray CT observation revealed that fractures were developed in the rocks associated with faults, while those away from faults were generally with massive structure. The mercury-injection analysis of pore features found that the porosities of the hydrate-existing rocks were generally less than 3%, and the pore sizes were generally smaller than 100 nm. The synthesizing experiments found that the saturation of methane hydrate were generally lower than 6% of pore space in rocks, but up to 16% when fractures developed. The low hydrate saturation in Qilian sedimentary rocks has been found mainly due to the small pore size of rock. The low hydrate saturation in the rocks might be the reason for the failure of regional seismic and logging detections of gas hydrates in Qilian Mountain.

  5. Complex formation constant and hydration number change of aqua-rare earth ions

    International Nuclear Information System (INIS)

    Kanno, H.

    1998-01-01

    Full text: It is now well established that the inner-sphere hydration number of aqua-rare earth ions changes from nine to eight in the middle of the rare earth series. This hydration number change greatly affects the complex formation of rare earth ions as we observe irregular variations in most series behaviours of the complex formation constant (K) in aqueous solution systems when K being plotted against 1/r or r (r is ionic radius of rare earth ion). Furthermore, it shows very anomalous concentration dependence in the sense that nona-aqua Ln 3+ ion increases in number with increase in salt concentration in aqueous rare earth salt solution (salt chloride, perchlorate). In this report, a theoretical derivation of the formation constant (K) for the inner-sphere complex formation of rare earth ions with a monodentate ligand was made by taking account of both the hydration number change in the middle of the series and its anomalous salt concentration dependence. The series behaviour of the formation constant against 1/r (or r) is successfully explained with using the empirical finding that K varies almost linearly with 1/r (or r) in the region where only one hydration number dominates. This success is also taken as evidence that the anomalous salt concentration dependence of the hydration number change is caused by the outer-sphere complex formation of rare earth ions with the condition that nona-aqua rare earth ions form outer-sphere complexes more easily than octa-aqua ions

  6. HYDRATION AND TEMPERATURE IN TENNIS - A PRACTICAL REVIEW

    OpenAIRE

    Mark S. Kovacs

    2006-01-01

    Competitive tennis is typically played in warm and hot environments. Because hypohydration will impair tennis performance and increases the risk of heat injury, consumption of appropriate fluid levels is necessary to prevent dehydration and enhance performance. The majority of research in this area has focused on continuous aerobic activity - unlike tennis, which has average points lasting less than ten seconds with rest periods dispersed between each work period. For this reason, hydration a...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  8. Influence of polymeric excipient properties on crystal hydrate formation kinetics of caffeine in aqueous slurries.

    Science.gov (United States)

    Gift, Alan D; Southard, Leslie A; Riesberg, Amanda L

    2012-05-01

    The influence of polymeric excipients on the hydrate transformation of caffeine (CAF) was studied. Anhydrous CAF was added to aqueous solutions containing different additives and the transformation to the hydrate form was monitored using in-line Raman spectroscopy. Various properties of two known inhibitors of CAF hydrate formation, polyacrylic acid (PAA) and polyvinyl alcohol (PVA), were investigated. For inhibition by PAA, a pH dependence was observed: at low pH, the inhibition was greatest, whereas no inhibitory effects were observed at pH above 6.5. For PVA, grades with high percent hydrolysis were the most effective at inhibiting the transformation. In addition, PVA with higher molecular weight showed slightly more inhibition than the shorter chain PVA polymers. A variety of other hydroxyl containing compounds were examined but none inhibited the CAF anhydrate-to-hydrate transformation. The observed inhibitory effects of PAA and PVA are attributed to the large number of closely spaced hydrogen bond donating groups of the polymer molecule, which can interact with the CAF hydrate crystal. Copyright © 2012 Wiley Periodicals, Inc.

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

    Science.gov (United States)

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

    2017-12-01

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

  10. Hydration of Rhyolitic Glasses: Comparison Between High- and Low-Temperature Processes

    Science.gov (United States)

    Anovitz, L.; Fayek, M.; Cole, D. R.; Carter, T.

    2012-12-01

    While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is more obscure. Comparisons between high- and low-temperature diffusive studies suggest that several factors play an important role under lower-temperatures conditions that are not significant at higher temperatures. Surface concentrations, which equilibrate quickly at high temperature, change far more slowly as temperatures decrease, and may not equilibrate at room temperature for hundreds or thousands of years. Coupled with temperature-dependent diffusion coefficients this complicates calculation of diffusion profiles as a function of time. A key factor in this process appears to be the inability of "self-stress", caused by the in-diffusing species, to relax at lower temperatures, a result expected below the glass transition. Regions of the glass hydrated at low temperatures are strongly optically anisotropic, and preliminary calculations suggest that the magnitude of stress involved may be very high. On the microstuctural scale, extrapolations of high-temperature FTIR data to lower temperatures suggests there should be little or no hydroxyl present in glasses "hydrated" at low temperatures. Analyses of both block and powder samples suggest that this is generally true in the bulk of the hydrated glass, excluding hydroxyl groups that formed during the initial cooling of the melt. However, hydroxyl do groups appear to be present at the glass surface, where both SIMS and neutron reflectometry data suggest hydration levels may be higher than projected from the bulk of the glass. Isotopic exchange experiments also suggest that bonding is relatively weak, as hydration water exchanges readily with the enviroment. All of these observations lead to the conclusion that the observed stress is due to the presence of interstructural, rather than bonded, water. This likely explains the

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Peytavy J. L.

    2006-12-01

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

  13. A systematic multi-step screening of numerous salt hydrates for low temperature thermochemical energy storage

    International Nuclear Information System (INIS)

    N’Tsoukpoe, Kokouvi Edem; Schmidt, Thomas; Rammelberg, Holger Urs; Watts, Beatriz Amanda; Ruck, Wolfgang K.L.

    2014-01-01

    Highlights: • We report an evaluation of the potential of salt hydrates for thermochemical storage. • Both theoretical calculations and experimental measurements using TGA/DSC are used. • Salt hydrates offer very low potential for thermochemical heat storage. • The efficiency of classical processes using salt hydrates is very low: typically 25%. • New processes are needed for the use of salt hydrates in thermochemical heat storage. - Abstract: In this paper, the potential energy storage density and the storage efficiency of salt hydrates as thermochemical storage materials for the storage of heat generated by a micro-combined heat and power (micro-CHP) have been assessed. Because salt hydrates used in various thermochemical heat storage processes fail to meet the expectations, a systematic evaluation of the suitability of 125 salt hydrates has been performed in a three-step approach. In the first step general issues such as toxicity and risk of explosion have been considered. In the second and third steps, the authors implement a combined approach consisting of theoretical calculations and experimental measurements using Thermogravimetric Analysis (TGA). Thus, application-oriented comparison criteria, among which the net energy storage density of the material and the thermal efficiency, have been used to evaluate the potential of 45 preselected salt hydrates for a low temperature thermochemical heat storage application. For an application that requires a discharging temperature above 60 °C, SrBr 2 ·6H 2 O and LaCl 3 ·7H 2 O appear to be the most promising, only from thermodynamic point of view. However, the maximum net energy storage density including the water in the water storage tank that they offer (respectively 133 kW h m −3 and 89 kW h m −3 ) for a classical thermochemical heat storage process are not attractive for the intended application. Furthermore, the thermal efficiency that would result from the storage process based on salt hydrates

  14. 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.

  15. 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.

  16. Hydration of the sulfuric acid-methylamine complex and implications for aerosol formation.

    Science.gov (United States)

    Bustos, Danielle J; Temelso, Berhane; Shields, George C

    2014-09-04

    The binary H2SO4-H2O nucleation is one of the most important pathways by which aerosols form in the atmosphere, and the presence of ternary species like amines increases aerosol formation rates. In this study, we focus on the hydration of a ternary system of sulfuric acid (H2SO4), methylamine (NH2CH3), and up to six waters to evaluate its implications for aerosol formation. By combining molecular dynamics (MD) sampling with high-level ab initio calculations, we determine the thermodynamics of forming H2SO4(NH2CH3)(H2O)n, where n = 0-6. Because it is a strong acid-base system, H2SO4-NH2CH3 quickly forms a tightly bound HSO4(-)-NH3CH3(+) complex that condenses water more readily than H2SO4 alone. The electronic binding energy of H2SO4-NH2CH3 is -21.8 kcal mol(-1) compared with -16.8 kcal mol(-1) for H2SO4-NH3 and -12.8 kcal mol(-1) for H2SO4-H2O. Adding one to two water molecules to the H2SO4-NH2CH3 complex is more favorable than adding to H2SO4 alone, yet there is no systematic difference for n ≥ 3. However, the average number of water molecules around H2SO4-NH2CH3 is consistently higher than that of H2SO4, and it is fairly independent of temperature and relative humidity.

  17. CALCIUM ORTHOPHOSPHATES HYDRATES: FORMATION, STABILITY AND INFLUENCE ON STANDARD PROPERTIES OF PORTLAND CEMENT

    Directory of Open Access Journals (Sweden)

    Kaziliunas A.

    2013-12-01

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

  18. 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.

  19. 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

  20. Numerical modeling of hydration process and temperature evolution in early age concrete

    NARCIS (Netherlands)

    Caggiano, A.; Pepe, M.; Koenders, E.A.B.; Martinelli, E.; Etse, G.J.

    2012-01-01

    Heat production induced by the hydration reaction and the resulting temperature evolution in the early phases of setting and hardening processes are critical phenomena, often leading to premature cracking of concrete members. However, the interest for simulating such phenomena is also related to the

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  2. Changes in the solid state of anhydrous and hydrated forms of sodium naproxen under different grinding and environmental conditions: Evidence of the formation of new hydrated forms.

    Science.gov (United States)

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

    2015-05-01

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

  3. The method of predicting the process of condensation of moisture and hydrate formation in the gas pipeline

    OpenAIRE

    Хвостова, Олена Вікторівна

    2014-01-01

    The problem of ensuring the required value of one of the natural gas quality indicators during its transportation to the consumer - moisture content is considered in the paper. The method for predicting possible moisture condensation and hydrate formation processes in gas pipelines considering mixing gas flows with different moisture content was developed.Predicting the moisture condensation and hydrate formation in gas pipelines is an actual task since a timely prevention of these processes ...

  4. Effects of C3H8 on hydrate formation and dissociation for integrated CO2 capture and desalination technology

    International Nuclear Information System (INIS)

    Yang, Mingjun; Zheng, Jianan; Liu, Weiguo; Liu, Yu; Song, Yongchen

    2015-01-01

    Hydrate-based technology has been developing for decades to meet the demands in industrial applications. With the global demands for reduced carbon dioxide (CO 2 ) emissions and more fresh water, CHBD (CO 2 hydrate-based desalination) was proposed and has developed rapidly. In this study, to provide basic data for the improvement of CHBD, the thermodynamic and kinetic characteristics of CO 2 and propane (C 3 H 8 ) mixed-gas hydrates in salt solution were experimentally investigated in which C 3 H 8 was chosen as the hydrate formation promoter. We studied nine experimental cases (54 cycles) with different C 3 H 8 proportions (ranging from 0 to 13%) and different initial solution saturations (30%, 40% and 50%). The hydrate phase equilibrium data were generated using the isochoric method, and the hydrate formation saturations were calculated using the relative gas uptake equation. The results indicated that the increase in the C 3 H 8 proportion significantly decreases the gas mixture hydrate equilibrium pressure. Additionally, the relative gas uptake was reduced as the C 3 H 8 proportion increased. A lower relative gas uptake was obtained at a lower gas pressure for the same gas mixture. The initial solution saturation exhibited an insignificant effect on the hydrate phase equilibrium conditions. When the initial solution saturations increased from 30% to 50%, the relative gas uptake decreased. - Highlights: • C 3 H 8 improves the thermodynamics and kinetics of CO 2 hydrates formation. • Hydrates equilibrium pressure decreases with the increase of C 3 H 8 proportion. • Higher C 3 H 8 proportion and/or solution saturation decrease relative gas uptake. • Initial pressure and solution saturation has interactive effect on gas uptake.

  5. Formation temperatures of thermogenic and biogenic methane

    Science.gov (United States)

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

    2014-01-01

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

  6. 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.

  7. Hydration products of lime-metakaolin pastes at ambient temperature with ageing

    Energy Technology Data Exchange (ETDEWEB)

    Gameiro, A., E-mail: agameiro@lnec.pt [National Laboratory of Civil Engineering, Materials Department, Av. do Brasil, 101, 1700 Lisbon (Portugal); Santos Silva, A., E-mail: ssilva@lnec.pt [National Laboratory of Civil Engineering, Materials Department, Av. do Brasil, 101, 1700 Lisbon (Portugal); Veiga, R., E-mail: rveiga@lnec.pt [National Laboratory of Civil Engineering, Buildings Department, Av. do Brasil, 101, 1700 Lisbon (Portugal); Velosa, A., E-mail: avelosa@ua.pt [Department of Civil Engineering, Geobiotec, University of Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro (Portugal)

    2012-05-10

    Highlights: Black-Right-Pointing-Pointer We study the compounds formed in lime/MK blended pastes and their stability over time. Black-Right-Pointing-Pointer Different mixes of lime/MK pastes show different reaction kinetics during curing time, being the pozzolanic compounds formed directly proportional to the lime by MK replacement. Black-Right-Pointing-Pointer Some pozzolanic products are found to be unstable during the hydration reaction employed in our study. - Abstract: Mortars constituted of lime mixtures with pozzolanic additions have been extensively used in the past for the construction of historic and traditional buildings. This paper presents the results of blended pastes of lime and metakaolin (MK), namely compounds formed and their stability over time. This research is part of an extensive study aiming at the formulation of lime based mortars for restoration purposes. It has been shown for several years that MK has been applied in inorganic binders due to its capacity to react vigorously with calcium hydroxide (CH). In the presence of water originating a series of major hydrated phases, namely tetra calcium aluminate hydrate (C{sub 4}AH{sub 13}), calcium silicates hydrates (CSH) and calcium aluminium silicate hydrates (stratlingite - C{sub 2}ASH{sub 8}). Several blended pastes of lime and MK, with different substitution rates of lime by MK (wt%) were prepared and cured at a temperature of 20 Degree-Sign C and relative humidity RH > 95%. The phase composition of the formed hydrated phases was determined by X-ray diffraction (XRD) and simultaneous thermal analysis (TG-DTA). The obtained results showed that lime/MK pastes compositions displayed different reaction kinetics during curing time, being the pozzolanic products content directly proportional to the substitution rate of lime by MK. Also, a relationship between the increase stratlingite content and the MK substitution rate of lime by MK was found.

  8. Comparison of Freezing and Hydrate Formation Methods in Removing Chloride and Bromide Ions from Brine

    Directory of Open Access Journals (Sweden)

    Marzieh Fattahi

    2018-01-01

    Full Text Available The growing population and enhanced industrial activities coupled with limitations on freshwater availability have led to efforts to desalinate salt water from the seas. Membrane and thermal technologies are the two commonly used for this purpose. In this study, the direct freezing and hydrate formation techniques were used for salt water desalination. Materials and Methods: Distilled water, sodium chloride, and sodium bromide were used as raw materials in the experiments. The experimental setup included a stationary reactor with two coaxial cylinders, in which ice crystals were deposited outside the cool inner cylinder to increase the salt concentration in the residual brine. An electrical conductivity instrument was used to measure sal removal. Results: Salt removal was shown to decrease with increasing salt concentration in the direct freeze method. A different trend was, however, observed in the hydrate formation method; salt removal was negligible at low concentrations in this method but increased at high concentrations before a constant value was reached. Overall, the hydrate formation recorded a higher salt removal efficiency than the other method. To investigate the effect of anion size on salt removal efficiency, experiments were carried out using NaCl and NaBr, which have the same cation but different anion sizes. Result showed that removal efficiency increased with increasing anion size. Conclusion: It was found that increasing ion radius leads to the lower likelihood of ion presence in the crystal lattice, thereby reducing salt removal efficiency. On the other hand, low concentrations of salt serve as site for the generation of cores, which naturally serve as removal accelerators.

  9. Research on the nanolevel influence of surfactants on structure formation of the hydrated Portland cement compositions

    Directory of Open Access Journals (Sweden)

    Guryanov Alexander

    2016-01-01

    Full Text Available The research of the structure formation process on a nanolevel of the samples of hydrated Portland cement compositions containing the modifying additives has been conducted with the help of small angle neutron scattering method. Carbonate and aluminum alkaline slimes as well as the complex additives containing surfactants were used as additives. The influence of slimes and surfactants on structural parameters change of Portland cement compositions of the average size of the disseminating objects, fractal dimension samples is considered. These Portland cement compositions are shown to be fractal clusters.

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

    Directory of Open Access Journals (Sweden)

    Behar E.

    2006-11-01

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

  11. Hydrothermal Formation Of Hemi-hydrate Calcium Sulfate Whiskers In The Presence Of Additives

    International Nuclear Information System (INIS)

    Luo, K. B.; Li, C. M.; Li, H. P.; Ning, P.; Xiang, L.

    2010-01-01

    The influence of addictives on the hydrothermal formation of hemi-hydrate calcium sulfate (CaSO 4 ·0.5H 2 O) whiskers were discussed in this paper, using CaCl 2 and Na 2 SO 4 as the reactants. The presence of NaCl, CaCl 2 or Na 2 SO 4 increased the concentrations of Ca 2+ and SO 4 2- , leading to the formation of CaSO 4 ·0.5H 2 O whiskers with aspect ratio lower than 50. The one dimensional growth of CaSO 4 ·0.5H 2 O whiskers was enhanced in water with no additives owing to the low super-saturation, leading to the formation of uniform whiskers with a length of 200-2000 μm and an aspect ratio higher than 100.

  12. The Temperature Dependence of the Partition of CH4 and C2H6 in Structure I Hydrates

    Science.gov (United States)

    Cheng, H.; Lu, W.

    2017-12-01

    At present, we mainly use hydrocarbon gas and carbon isotope composition to determine the gas source of natural gas hydrate. Judging the type of gas source plays a key role in the evaluation of hydrate reservoirs, but there is still controversy over this approach. Considering the crystal properties of hydrate, the process of aggregation and decomposition of natural gas hydrates may have an important effect on the gas composition. We used CH4 (C1), C2H6 (C2) and their mixture as gas sources to synthesize hydrates from aqueous solution in high-pressure capillary tubes. Gas concentration in hydrates grew at different temperatures was measured with quantitative Raman spectroscopy. The results show that concentrations of gas in pure methane and pure ethane hydrates increase with temperature. The results of the mixture are similar to pure gas below 288.15 K, the concentration of C1 in small cages (SC, 512) slowly increased, but the competitive relationship between methane and ethane in large cages (LC, 51262) become obvious after 288.15 K. From 278.15 K to 294.15 K, the value of C1/C2 decreased from 26.38 to 6.61, gradually closing to the original gas composition of 4. We find that gas hydrates are more likely to gather C1 when they accumulate. The lower the temperature is, the more obvious it will be, and the closer the value of C1/C2 is to the microbial gases.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kharrat, M.

    2004-10-15

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

  14. 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.

  15. 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.

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

    Science.gov (United States)

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

    2017-12-01

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

  17. Non-spherical particle formation induced by repulsive hydration forces during spray drying

    Energy Technology Data Exchange (ETDEWEB)

    Suh, Yong Jae; Lee, Jin-Woo; Chang, Hankwon; Jang, Hee-Dong, E-mail: hdjang@kigam.re.kr; Cho, Kuk, E-mail: kukcho@pusan.ac.kr [Korea Institute of Geoscience and Mineral Resources (Korea, Republic of)

    2013-09-15

    Non-spherical particles were produced during a spray-drying process, but the exact mechanism of their formation was unknown. The non-spherical particles form when the strength of the colloidal droplets is exceeded by external stress stemming from drag in the velocity gradient. Here, we show that repulsive hydration forces reduce the mechanical strength of the droplets; this is critical to the formation of non-spherical particles. Toroidal or ellipsoidal particles were prepared from low-concentration hydrophilic SiO{sub 2}, TiO{sub 2}, and CuO colloidal solutions, but not from hydrophobic ZnO colloidal solutions. The surface properties of the solid particulates are crucial for the morphology of particles formed during spray drying.

  18. Non-spherical particle formation induced by repulsive hydration forces during spray drying

    International Nuclear Information System (INIS)

    Suh, Yong Jae; Lee, Jin-Woo; Chang, Hankwon; Jang, Hee-Dong; Cho, Kuk

    2013-01-01

    Non-spherical particles were produced during a spray-drying process, but the exact mechanism of their formation was unknown. The non-spherical particles form when the strength of the colloidal droplets is exceeded by external stress stemming from drag in the velocity gradient. Here, we show that repulsive hydration forces reduce the mechanical strength of the droplets; this is critical to the formation of non-spherical particles. Toroidal or ellipsoidal particles were prepared from low-concentration hydrophilic SiO 2 , TiO 2 , and CuO colloidal solutions, but not from hydrophobic ZnO colloidal solutions. The surface properties of the solid particulates are crucial for the morphology of particles formed during spray drying

  19. 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

  20. Study on Characteristic of Self-preservation Effect of CO2 Hydrate according to Temperature, Particle Diameter and Shape

    International Nuclear Information System (INIS)

    Kim, Yeon-Soo; Kang, Seong-Pil; Park, So-Jin

    2013-01-01

    Gas hydrate studies are attracting attention of many researchers as an innovative, economic and environmentally friendly technology when it is applied to CO 2 capture, transport, and storage. In this study, we investigated whether CO 2 hydrate shows the self-preservation effect or not, that is the key property for developing a novel CO 2 transport/storage method. Especially the degree of self-preservation effect for CO 2 hydrate was studied according to the particle size of CO 2 hydrate samples. We prepared three kinds of CO 2 hydrate samples varying their particle diameter as millimeter, micron and nano size and measured their change of weight at -15 - -30 .deg. C under atmospheric pressure during 3 weeks. According to our experimental result, the lower temperature, larger particle size, and compact structure for higher density are the better conditions for obtaining self-preservation effect

  1. Effect of temperature on hydration kinetics and polymerization of tricalcium silicate in stirred suspensions of CaO-saturated solutions

    International Nuclear Information System (INIS)

    Grant, Steven A.; Boitnott, Ginger E.; Korhonen, Charles J.; Sletten, Ronald S.

    2006-01-01

    Tricalcium silicate was hydrated at 274, 278, 283, 298, and 313 K in stirred suspensions of saturated CaO solutions under a nitrogen-gas atmosphere until the end of deceleratory period. The suspension conductivities and energy flows were measured continuously. The individual reaction rates for tricalcium silicate dissolution, calcium silicate hydrate precipitation, and calcium hydroxide precipitation were calculated from these measurements. The results suggest that the proportion of tricalcium silicate dissolved was determined by the rate of tricalcium silicate dissolution and the time to very rapid calcium hydroxide precipitation. The time to very rapid calcium hydroxide precipitation was more sensitive to changes in temperature than was the rate of tricalcium silicate dissolution, so that the proportion of tricalcium silicate hydration dissolved by the deceleratory period increased with decreasing temperature. The average chain length of the calcium silicate hydrate ascertained by magic-angle spinning nuclear magnetic resonance spectroscopy increased with increasing temperature

  2. Temperature and hydration effects on absorbance spectra and radiation sensitivity of a radiochromic medium

    Energy Technology Data Exchange (ETDEWEB)

    Rink, Alexandra; Lewis, David F.; Varma, Sangya; Vitkin, I. Alex; Jaffray, David A. [Princess Margaret Hospital/Ontario Cancer Institute, Department of Medical Biophysics and Radiation Oncology, University of Toronto, Toronto, Ontario M5G 2M9 (Canada); Advanced Materials Group, International Specialty Products, Inc., Wayne, New Jersey 07470 (United States); Princess Margaret Hospital/Ontario Cancer Institute, Department of Medical Biophysics and Radiation Oncology, University of Toronto, Toronto, Ontario M5G 2M9 (Canada)

    2008-10-15

    The effects of temperature on real time changes in optical density ({Delta}OD) of GAFCHROMIC EBT film were investigated. The spectral peak of maximum change in absorbance ({lambda}{sub max}) was shown to downshift linearly when the temperature of the film was increased from 22 to 38 degree sign C. The {Delta}OD values were also shown to decrease linearly with temperature, and this decrease could not be attributed to the shift in {lambda}{sub max}. A compensation scheme using {lambda}{sub max} and a temperature-dependent correction factor was investigated, but provided limited improvement. Part of the reason may be the fluctuations in hydration of the active component, which were found to affect both position of absorbance peaks and the sensitivity of the film. To test the effect of hydration, laminated and unlaminated films were desiccated. This shifted both the major and minor absorbance peaks in the opposite direction to the change observed with temperature. The desiccated film also exhibited reduced sensitivity to ionizing radiation. Rehydration of the desiccated films did not reverse the effects, but rather gave rise to another form of the polymer with absorbance maxima upshifted further 20 nm. Hence, the spectral characteristics and sensitivity of the film can be dependent on its history, potentially complicating both real-time and conventional radiation dosimetry.

  3. Formation of hydrated layers in PMMA thin films in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Akers, Peter W. [School of Chemical Sciences, University of Auckland, Auckland (New Zealand); Nelson, Andrew R.J. [The Bragg Institute, Australian Nuclear Science and Technology Organisation, Menai, NSW (Australia); Williams, David E. [School of Chemical Sciences, University of Auckland, Auckland (New Zealand); MacDiarmid Institute of Advanced Materials and Nanotechnology, Wellington (New Zealand); McGillivray, Duncan J., E-mail: d.mcgillivray@auckland.ac.nz [School of Chemical Sciences, University of Auckland, Auckland (New Zealand); MacDiarmid Institute of Advanced Materials and Nanotechnology, Wellington (New Zealand)

    2015-10-30

    Graphical abstract: - Highlights: • Homogeneous thin PMMA films prepared on Si/SiOx substrates and measured in air and water. • Reproducible formation of highly hydrated layer containing 50% water at the PMMA/SiOx interface. • When heated the films swell at 50 °C without loss of material. • Upon re-cooling to 25 °C the surface roughens and material is lost. - Abstract: Neutron reflectometry (NR) measurements have been made on thin (70–150 Å) poly(methylmethacrylate) (PMMA) films on Si/SiOx substrates in aqueous conditions, and compared with parameters measured using ellipsometry and X-Ray reflectometry (XRR) on dry films. All techniques show that the thin films prepared using spin-coating techniques were uniform and had low roughness at both the silicon and subphase interfaces, and similar surface energetics to thicker PMMA films. In aqueous solution, NR measurements at 25 °C showed that PMMA forms a partially hydrated layer at the SiOx interface 10 Å under the film, while the bulk film remains intact and contains around 4% water. Both the PMMA film layer and the sublayer showed minimal swelling over a period of 24 h. At 50 °C, PMMA films in aqueous solution roughen and swell, without loss of PMMA material at the surface. After cooling back to 25 °C, swelling and roughening increases further, with loss of material from the PMMA layer.

  4. Formation of hydrated layers in PMMA thin films in aqueous solution

    International Nuclear Information System (INIS)

    Akers, Peter W.; Nelson, Andrew R.J.; Williams, David E.; McGillivray, Duncan J.

    2015-01-01

    Graphical abstract: - Highlights: • Homogeneous thin PMMA films prepared on Si/SiOx substrates and measured in air and water. • Reproducible formation of highly hydrated layer containing 50% water at the PMMA/SiOx interface. • When heated the films swell at 50 °C without loss of material. • Upon re-cooling to 25 °C the surface roughens and material is lost. - Abstract: Neutron reflectometry (NR) measurements have been made on thin (70–150 Å) poly(methylmethacrylate) (PMMA) films on Si/SiOx substrates in aqueous conditions, and compared with parameters measured using ellipsometry and X-Ray reflectometry (XRR) on dry films. All techniques show that the thin films prepared using spin-coating techniques were uniform and had low roughness at both the silicon and subphase interfaces, and similar surface energetics to thicker PMMA films. In aqueous solution, NR measurements at 25 °C showed that PMMA forms a partially hydrated layer at the SiOx interface 10 Å under the film, while the bulk film remains intact and contains around 4% water. Both the PMMA film layer and the sublayer showed minimal swelling over a period of 24 h. At 50 °C, PMMA films in aqueous solution roughen and swell, without loss of PMMA material at the surface. After cooling back to 25 °C, swelling and roughening increases further, with loss of material from the PMMA layer.

  5. Experimental study and thermodynamic modeling of CO2 gas hydrate formation in presence of zinc oxide nanoparticles

    International Nuclear Information System (INIS)

    Mohammadi, Mohsen; Haghtalab, Ali; Fakhroueian, Zahra

    2016-01-01

    Highlights: • Nanofluids enhance heat and mass transfer and affect on kinetic and thermodynamics. • The ZnO nanoparticles in liquid affect on kinetics and P-T curve of CO 2 hydrate. • ZnO nanoparticles enhance the growth rate and gas storage in CO 2 hydrate. • A thermodynamic modeling of CO 2 hydrate proposed in the presence of nanoparticles. • Water activity in ZnO + nanofluid was affected by enhancement of the CO 2 solubility. - Abstract: The effect of synthesized zinc oxide (ZnO) nanoparticles was investigated on the kinetic and thermodynamic equilibrium conditions of CO 2 hydrate formation. The amount of the gas consumption was measured and compared for the four sample fluids: pure water, aqueous solution of sodium dodecyl sulfate (SDS), water-based ZnO-nanofluid and water-based ZnO-nanofluid in the presence of SDS (0.001 mass fraction). The time of hydrate growth decreased and the amount of the storage gas enhanced in the presence of nanoparticles. Moreover, the nanoparticles size effect besides the CO 2 solubility enhancement in ZnO-nanofluid led to the reduction of water activity, so that the equilibrium curve of hydrate formation was shifted to higher pressures. A new correlation for Henry’s law constant was obtained using CO 2 -solubility data in ZnO-nanofluid. Finally using this correlation, the water activity was calculated through the Chen–Guo approach to propose a thermodynamic method for prediction of the equilibrium hydrate formation conditions in the presence of the nanoparticles.

  6. Kinetics of CO2 and methane hydrate formation : an experimental analysis in the bulk phase

    NARCIS (Netherlands)

    He, Y.; Rudolph, E.S.J.; Zitha, P.L.J.; Golombok, M.

    2011-01-01

    Gas resources captured in the form of gas hydrates are by an order of magnitude larger than the resources available from conventional resources. In order to keep the CO2CO2 footprint in the world as small as possible, the idea is to produce methane hydrates and sequestrate CO2CO2 into hydrates in

  7. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-07-01

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

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

    DEFF Research Database (Denmark)

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

    2004-01-01

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

  10. Determination of hydration numbers of electrolytes from temperature dependence of PMR chemical shifts

    International Nuclear Information System (INIS)

    Subramanian, N.

    1979-01-01

    The method proposed by Malinowski et al. for the determination of effective hydration numbers (h) of electrolytes leads to a consistent incrrease in the observed values of 'h' with increase in solution concentration. An attempt is made to rationalize the experimental results by cosidering the simultaneous effects of temperature and concentration on the proton chemical shift. It is suggested that Malinowski's technique might yeld 'h' values very close to the true value for those ions for which there is a fortuitous cancellation of structure-making and structure-breaking properties. (Author) [pt

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

    Directory of Open Access Journals (Sweden)

    Xiangjun Liu

    2016-03-01

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

  12. The investigation of lithium formate hydrate, sodium dithionate and N-methyl taurine as clinical EPR dosimeters

    International Nuclear Information System (INIS)

    Lelie, S.; Hole, E.O.; Duchateau, M.; Schroeyers, W.; Schreurs, S.; Verellen, D.

    2013-01-01

    Introduction: EPR-dosimetry using L-α-alanine is an established method for measuring high doses of ionizing radiation. However, since a minimum dose of approximately 4 Gy is required to achieve sufficient low uncertainties (1–2%) for clinical application, alternative dosimeter materials are being inquired. Lithium formate (LiFo) monohydrate has been studied by several groups and has revealed several promising properties in the low dose region (<4 Gy). The fading properties, however, are somewhat unpredictable, and depend on properties not yet fully uncovered. This paper reports the results from a study of lithium formate hydrate and N-methyl taurine as potential low dose EPR dosimeters. Methods and materials: Pellet shaped dosimeters of lithium formate monohydrate, lithium formate hydrate, sodium dithionate and N-methyl taurine were produced using a manual Weber press, L-α-alanine was obtained from Harwell dosimeters and irradiated using 60 kV and 6 MV X-ray beams, and Co-60 gamma-rays to a dose of 30 Gy and dose ranges of 0.5–100 Gy and 2–20 Gy respectively. The dosimeters were measured using an Electron Paramagnetic Resonance (EPR)-spectrometer. The detector responses for 6 MV and Co-60 radiation beams, the fading behaviors and signal shape in time were investigated. Results: Lithium formate monohydrate and lithium formate hydrate are apparently associated with near identical EPR-spectra (mainly one broad line), and the same spectrum arises for all radiation energies investigated. The shape of the EPR resonance remains constant with time, but the intensities decreases, and the fading is more prominent for the monohydrate than for the hydrate. The EPR resonance associated with N-methyl taurine is more complex than the resonance associated with LiFo and it changes with time, implying radical transitions and growth. Conclusions: The study showed that lithium formate hydrate is a strong candidate for EPR dosimetry with slightly better fading characteristics

  13. 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 ...

  14. Borehole Stability in High-Temperature Formations

    Science.gov (United States)

    Yan, Chuanliang; Deng, Jingen; Yu, Baohua; Li, Wenliang; Chen, Zijian; Hu, Lianbo; Li, Yang

    2014-11-01

    In oil and gas drilling or geothermal well drilling, the temperature difference between the drilling fluid and formation will lead to an apparent temperature change around the borehole, which will influence the stress state around the borehole and tend to cause borehole instability in high geothermal gradient formations. The thermal effect is usually not considered as a factor in most of the conventional borehole stability models. In this research, in order to solve the borehole instability in high-temperature formations, a calculation model of the temperature field around the borehole during drilling is established. The effects of drilling fluid circulation, drilling fluid density, and mud displacement on the temperature field are analyzed. Besides these effects, the effect of temperature change on the stress around the borehole is analyzed based on thermoelasticity theory. In addition, the relationships between temperature and strength of four types of rocks are respectively established based on experimental results, and thermal expansion coefficients are also tested. On this basis, a borehole stability model is established considering thermal effects and the effect of temperature change on borehole stability is also analyzed. The results show that the fracture pressure and collapse pressure will both increase as the temperature of borehole rises, and vice versa. The fracture pressure is more sensitive to temperature. Temperature has different effects on collapse pressures due to different lithological characters; however, the variation of fracture pressure is unrelated to lithology. The research results can provide a reference for the design of drilling fluid density in high-temperature wells.

  15. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-07-01

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

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

    Science.gov (United States)

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

    2017-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-12-15

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

  19. Effects of Agitation and Storage Temperature on Measurements of Hydration Status.

    Science.gov (United States)

    Adams, Heather M; Eberman, Lindsey E; Yeargin, Susan W; Niemann, Andrew J; Mata, Heather L; Dziedzicki, David J

    2015-12-01

    Hypohydration can have significant implications on normal physiological functions of the body. This study aimed to determine the impact of agitation, storage temperature, and storage time on urine osmolality compared to the criterion control. We used a descriptive diagnostic validity test design. To investigate agitation, we recruited 75 healthy individuals (males = 41, females = 34; mean age = 22 ± 5 years; mean self-reported height = 172 ± 23 cm and mass = 77 ± 17 kg) who provided one or more samples (total = 81). The independent variables were agitation (vortex, hand shaken, no agitation) and temperature (room temperature, freezer, and refrigerator) type. Participants completed informed consent, a health questionnaire and were asked to provide a urine sample, which was split and labeled according to agitation type or storage temperature. Urine osmolality was used to determine hydration status at two time points (within 2 hours [control], 48 hours). We used t-tests to determine the difference between each condition and the control and calculated percent error for each condition. No significant differences for no agitation (t79 = -0.079, P = 0.937), hand shaken (t79 = 1.395, P = 0.167) or vortex mixed (t79 = -0.753, P = 0.453) were identified when compared to the criterion control. No significant differences for room temperature (t82 = -0.720, P = 0.474), refrigerator (t82 = -2.697, P = 0.008) or freezer (t82 = 2.576, P = 0.012) were identified when compared to the criterion control. Our findings suggest agitation of urine specimen is not necessary and samples do not require refrigeration or freezing if assessed within 48 hours. Analysis within two hours of collection is not necessary and samples can be stored for up to 48 hours without impacting the hydration status of the sample.

  20. 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

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

    OpenAIRE

    Tzirakis, Fragkiskos; Kontogeorgis, Georgios; Coquelet, Christophe; von Solms, Nicolas; Stringari, Paolo

    2016-01-01

    Hydrate krystallisering kan blive en vigtig kulstofopsamling metode, forudsat at denne teknologi undergår yderligere forskning. Med henblik på dette mål, forsøger denne undersøgelse at kaste lys over en helt nyt emne for forskning: hydrat forfremmelse.Hydrate forfremmelse indebærer produktion af hydrat ved lavere tryk (og dermed lavere supplerende driftsomkostninger) ved brug af specielle kemikalier (promotore). I første omgang har et omfattende litteraturstudie vist at både eksperimentelle d...

  2. Heating tar sands formations to visbreaking temperatures

    Science.gov (United States)

    Karanikas, John Michael [Houston, TX; Colmenares, Tulio Rafael [Houston, TX; Zhang, Etuan [Houston, TX; Marino, Marian [Houston, TX; Roes, Augustinus Wilhelmus Maria [Houston, TX; Ryan, Robert Charles [Houston, TX; Beer, Gary Lee [Houston, TX; Dombrowski, Robert James [Houston, TX; Jaiswal, Namit [Houston, TX

    2009-12-22

    Methods for treating a tar sands formation are described herein. Methods may include heating at least a section of a hydrocarbon layer in the formation from a plurality of heaters located in the formation. The heat may be controlled so that at least a majority of the section reaches an average temperature of between 200.degree. C. and 240.degree. C., which results in visbreaking of at least some hydrocarbons in the section. At least some visbroken hydrocarbon fluids may be produced from the formation.

  3. Structural studies of aqueous solutions at high temperatures. Critical opalescence and hydration

    International Nuclear Information System (INIS)

    Sullivan, D.M.

    2000-09-01

    Neutron scattering techniques were used to study aspects of the static, or equilibrium, structure at microscopic scales in a number of aqueous solutions at non ambient conditions (Temperature, T > 300 K, and pressure, P > 1 bar). Critical opalescence was observed in both pure D 2 O and a NaCI-D 2 O mixture by means of small-angle neutron scattering (SANS), as described in Part I. The dependence of the correlation length, ξ, and the long wavelength limit, S(0), was measured at a number of state points on the critical isochore. The results are interpreted in terms of theories of critical phenomena; in particular the expected power law behaviour of ξ and S(0) with respect to reduced temperature, t, on the critical isochore. In the case of D 2 O, we observe the expected 3d-Ising behaviour with exponents (ν = 0.623 ± 0.030, γ = 1.14 ± 0.05) and amplitudes in agreement with theoretical and semi-empirical predictions. We performed measurements on aqueous sodium chloride, equivalent to those on pure 020, with the intention of classifying the critical behaviour. Although strong power-law divergence of the quantities ξ and S(0) was not observed, we find that the value of S(0) for a given ξ is strongly reduced in the ionic solution with respect to the pure solvent. Such behaviour is inconsistent with a thermodynamic model of aqueous sodium chloride, based on experimental thermodynamic data and the expected asymptotic 3d-Ising behaviour. Short-range structural correlations between solute and solvent atoms in aqueous solutions were studied by the technique of neutron diffraction and isotopic substitution (NDIS), as described in Part II. The anion hydration structure in 1.5 molal aqueous NaCl, was investigated at (T = 580 K, P = 800 bar) and (T = 380 K, P = 200 bar). Isotopic substitution was performed on the chloride ion, enabling the difference between scattering functions to be interpreted in terms of CI-H and CI-O correlation functions. The results show the chloride

  4. Structural studies of aqueous solutions at high temperatures. Critical opalescence and hydration

    Energy Technology Data Exchange (ETDEWEB)

    Sullivan, D.M

    2000-09-01

    Neutron scattering techniques were used to study aspects of the static, or equilibrium, structure at microscopic scales in a number of aqueous solutions at non ambient conditions (Temperature, T > 300 K, and pressure, P > 1 bar). Critical opalescence was observed in both pure D{sub 2}O and a NaCI-D{sub 2}O mixture by means of small-angle neutron scattering (SANS), as described in Part I. The dependence of the correlation length, {xi}, and the long wavelength limit, S(0), was measured at a number of state points on the critical isochore. The results are interpreted in terms of theories of critical phenomena; in particular the expected power law behaviour of {xi} and S(0) with respect to reduced temperature, t, on the critical isochore. In the case of D{sub 2}O, we observe the expected 3d-Ising behaviour with exponents ({nu} = 0.623 {+-} 0.030, {gamma} = 1.14 {+-} 0.05) and amplitudes in agreement with theoretical and semi-empirical predictions. We performed measurements on aqueous sodium chloride, equivalent to those on pure 020, with the intention of classifying the critical behaviour. Although strong power-law divergence of the quantities {xi} and S(0) was not observed, we find that the value of S(0) for a given {xi} is strongly reduced in the ionic solution with respect to the pure solvent. Such behaviour is inconsistent with a thermodynamic model of aqueous sodium chloride, based on experimental thermodynamic data and the expected asymptotic 3d-Ising behaviour. Short-range structural correlations between solute and solvent atoms in aqueous solutions were studied by the technique of neutron diffraction and isotopic substitution (NDIS), as described in Part II. The anion hydration structure in 1.5 molal aqueous NaCl, was investigated at (T = 580 K, P = 800 bar) and (T = 380 K, P = 200 bar). Isotopic substitution was performed on the chloride ion, enabling the difference between scattering functions to be interpreted in terms of CI-H and CI-O correlation functions

  5. 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)

  6. 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.

  7. Effect of temperature on the microstructure of calcium silicate hydrate (C-S-H)

    Energy Technology Data Exchange (ETDEWEB)

    Gallucci, E., E-mail: gallucci.emmanuel@ch.sika.com; Zhang, X.; Scrivener, K.L.

    2013-11-15

    Temperature affects the properties of concrete through its effect on the hydration of cement and its associated microstructural development. This paper focuses on the modifications to C-S-H induced by isothermal curing between 5 and 60 °C. The results show that as the temperature increases (within the range studied) the C/S ratio of C-S-H changes only slightly, with a higher degree of polymerisation of silicate chains, but there is a significant decrease in its bound water content and an increase of apparent density of 25%. This increase seems to come from a different packing of C-S-H at the nanoscale. As a consequence of these changes, the microstructure of the cement paste is much coarser and porous, which explains the lower final strengths obtained by curing at elevated temperatures. -- Highlights: •C-S-H structure studied at the atomic level •Multiple analytical techniques used •Studies conducted at temperatures above and below normal temperatures.

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

    NARCIS (Netherlands)

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

    2010-01-01

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

  9. Thermodynamic modelling of the effect of temperature on the hydration and porosity of Portland cement

    International Nuclear Information System (INIS)

    Lothenbach, Barbara; Matschei, Thomas; Moeschner, Goeril; Glasser, Fred P.

    2008-01-01

    The composition of the phase assemblage and the pore solution of Portland cements hydrated between 0 and 60 deg. C were modelled as a function of time and temperature. The results of thermodynamic modelling showed a good agreement with the experimental data gained at 5, 20, and 50 deg. C. At 5 and at 20 deg. C, a similar phase assemblage was calculated to be present, while at approximately 50 deg. C, thermodynamic calculations predicted the conversion of ettringite and monocarbonate to monosulphate. Modelling showed that in Portland cements which have an Al 2 O 3 /SO 3 ratio of > 1.3 (bulk weight), above 50 deg. C monosulphate and monocarbonate are present. In Portland cements which contain less Al (Al 2 O 3 /SO 3 < 1.3), above 50 deg. C monosulphate and small amounts of ettringite are expected to persist. A good correlation between calculated porosity and measured compressive strength was observed

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

    Directory of Open Access Journals (Sweden)

    Doris E. Braun

    2017-12-01

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

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

    DEFF Research Database (Denmark)

    Zuo, You-Xiang; Stenby, Erling Halfdan

    1997-01-01

    In this paper, the extended Patel-Teja equation of state was modified to describe non-ideality of the liquid phase containing water and electrolytes accurately. The modified Patel-Teja equation of state (MPT EOS) was utilized to develop a predictive method for gas hydrate equilibria. The new method...... employs the Barkan and Sheinin hydrate model for the description of the hydrate phase, the original Patel-Teja equation of state for the vapor phase fugacities, and the MPT EOS (instead of the activity coefficient model) for the activity of water in the aqueous phase. The new method has succesfully...

  12. 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.

  13. 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

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

    Science.gov (United States)

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

    2012-06-21

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

  15. Neutron scattering studies of the dynamics of biological systems as a function of hydration, temperature and pressure

    International Nuclear Information System (INIS)

    Trapp, Marcus

    2010-01-01

    Incoherent elastic and quasi-elastic neutron scattering were used to measure membrane and protein dynamics in the nano- to picosecond time and Angstrom length scale. The hydration dependent dynamics of DMPC model membranes was studied using elastic and quasi-elastic neutron scattering. The elastic experiments showed a clear shift of the temperature of the main phase transition to higher temperatures with decreasing hydration level. The performed quasi-elastic measurements demonstrated nicely the influence, hydration has on the diffusive motions of the head lipid groups. Different models are necessary to fit the Q-dependence of the elastic incoherent structure factor and show therefore the reduced mobility as a result of reduced water content. In addition to temperature, pressure as a second thermodynamic variable was used to explore dynamics of DMPC membranes. The ordering introduced by applying pressure has similar effect to decreased hydration, therefore both approaches are complementary. Covering three orders of magnitude in observation time, the dynamics of native AChE and its complexed counterpart in presence of Huperzin A was investigated in the range from 1 ns to 100 ps. The mean square displacements obtained from the elastic data allowed the determination of activation energies and gave evidence that a hierarchy of motions contributes to the enzymatic activity. Diffusion constants and residence times were extracted from the quasi-elastic broadening. (author) [fr

  16. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-12-01

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

  18. Dehydration/hydration of granular beds for thermal storage applications: a combined NMR and temperature study

    NARCIS (Netherlands)

    Donkers, P.A.J.; Pel, L.; Adan, O.C.G.

    For heat/cold storage systems a granular bed of salt hydrates is studied during dehydration/hydration. The water density in these beds are measured with help of NMR. Diffusion based dehydration of a granular bed of Na2SO4·10H2O is shown to be internally limited as larger grains dehydrate faster than

  19. Thermal regime of a continental permafrost associated gas hydrate occurrence a continuous temperature profile record after drilling

    Science.gov (United States)

    Henninges, J.; Huenges, E.; Mallik Working Group

    2003-04-01

    Both the size and the distribution of natural methane hydrate occurrences, as well as the release of gaseous methane through the dissociation of methane hydrate, are affected by the subsurface pressure and temperature conditions. During a field experiment, which was carried out in the Mackenzie Delta, NWT, Canada, within the framework of the Mallik 2002 Production Research Well Program*, the variation of temperature within three 40 m spaced, 1200 m deep wells was measured deploying the Distributed Temperature Sensing (DTS) technology. An innovative experimental design for the monitoring of spatial and temporal variations of temperature along boreholes was developed and successfully applied under extreme arctic conditions. A special feature is the placement of the fibre-optic sensor cable inside the cement annulus between the casing and the wall of the borehole. Temperature profiles were recorded with a sampling interval of 0.25 m and 5 min, and temperatures can be determined with a resolution of 0.3 °C. The observed variation of temperature over time shows the decay of the thermal disturbances caused by the drilling and construction of the wells. An excellent indicator for the location of the base of the ice-bonded permafrost layer, which stands out as a result of the latent heat of the frozen pore fluid, is a sharp rise in temperature at 604 m depth during the period of equilibration. A similar effect can be detected in the depth interval between 1105 m and 1110 m, which is interpreted as an indicator for the depth to the base of the methane hydrate stability zone. Nine months after the completion of the wells the measured borehole temperatures are close to equilibrium. The mean temperature gradient rises from 9.4 K/km inside the permafrost to 25.4 K/km in the ice-free sediment layers underneath. The zone of the gas hydrate occurrences between 900 m and 1100 m shows distinct variations of the geothermal gradient, which locally rises up to 40 K/km. At the lower

  20. Second Hagedorn temperature and glueball formation

    International Nuclear Information System (INIS)

    Dias de Deus, J.; Pimenta, M.

    1984-09-01

    We argue that confinement involving higher representations of SU(N) in singlet Ranti R bound states may occur at higher Hagedorn temperatures. The simplest possibility corresponds to the case when the binding potential is proportional to the quadratic Casimir Csub(R). The lowest Hagedorn temperature Tsub(H1) is the temperature for qanti q meson formation. The next, Tsub(H2), is the temperature for glueball hadronization. Higher representation Ranti R bound states are not likely to occur. The second Hagedorn temperature, separating the physics of hadrons from the physics of QCD plasma, plays the role of the deconfining temperature. Simple effective potential estimates give Tsub(H2)/Tsub(H1)approx.=(Csub(A)/Csub(F))sup(1/2)=3/2, in SU(3), with Tsub(H2)=395 MeV and Tsub(H1)=210 MeV, and for the glueball spin-averaged mass, μsub(G)=1370 MeV. Glueballs, in comparison with normal hadrons, are produced with larger psub(T) and larger multiplicities. (orig.)

  1. Unexpected inhibition of CO2 gas hydrate formation in dilute TBAB solutions and the critical role of interfacial water structure

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Ngoc N.; Nguyen, Anh V.; Nguyen, Khoi T.; Rintoul, Llew; Dang, Liem X.

    2016-12-01

    Gas hydrates formed under moderated conditions open up novel approaches to tackling issues related to energy supply, gas separation, and CO2 sequestration. Several additives like tetra-n-butylammonium bromide (TBAB) have been empirically developed and used to promote gas hydrate formation. Here we report unexpected experimental results which show that TBAB inhibits CO2 gas hydrate formation when used at minuscule concentration. We also used spectroscopic techniques and molecular dynamics simulation to gain further insights and explain the experimental results. They have revealed the critical role of water alignment at the gas-water interface induced by surface adsorption of tetra-n-butylammonium cation (TBA+) which gives rise to the unexpected inhibition of dilute TBAB solution. The water perturbation by TBA+ in the bulk is attributed to the promotion effect of high TBAB concentration on gas hydrate formation. We explain our finding using the concept of activation energy of gas hydrate formation. Our results provide a step toward to mastering the control of gas hydrate formation.

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

    Science.gov (United States)

    Daitoku, Tadafumi; Utaka, Yoshio

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

  3. Effect of the hydration temperature on the microstructure of Class G cement: C-S-H composition and density

    International Nuclear Information System (INIS)

    Bahafid, Sara; Ghabezloo, Siavash; Duc, Myriam; Faure, Pamela; Sulem, Jean

    2017-01-01

    Curing temperature has a significant influence on cement paste microstructure and the properties of its principal hydrate C-S-H. In this paper, the effect of the hydration temperature in the range of 7 °C to 90 °C on the microstructure of a class G oil-well cement is studied. This is done by combining various experimental methods, including X-ray diffraction associated with the Rietveld analysis, thermo-gravimetric analysis, mercury intrusion porosimetry and porosity evaluation by drying. The experimental results show an increase of the capillary porosity and a decrease of the gel porosity by increasing the hydration temperature. This is attributed to a decrease of the C-S-H intrinsic porosity and a corresponding increase of the C-S-H density for higher curing temperatures. The experimental results are used in a simple analysis method to evaluate the density of C-S-H, as well as its C/S ratio and H/S ratio in dry and saturated conditions. The evaluated C-S-H density varies from 1.88 g/cm 3 at 7 °C to 2.10 g/cm 3 at 90 °C. The results also show a decrease of molar C/S ratio with increasing hydration temperature from 1.93 at 7 °C to 1.71 at 90 °C and of the H/S ratio from 5.1 at 7 °C to 2.66 at 90 °C.

  4. 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

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

    Science.gov (United States)

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

    2016-04-01

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

  6. 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.

  7. Hydration, phase separation and nonlinear rheology of temperature-sensitive water-soluble polymers

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Fumihiko; Koga, Tsuyoshi [Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510 (Japan); Kaneda, Isamu [Department of Food Science, Rakuno Gakuen University, Ebetsu, Hokkaido 069-8501 (Japan); Winnik, Francoise M, E-mail: ftanaka@phys.polym.kyoto-u.ac.jp [Department of Chemistry and Faculty of Pharmacy, University of Montreal, Montreal, H3C 3J7 (Canada)

    2011-07-20

    The collapse of a poly(N-isopropylacrylamide) (PNIPAM) chain upon heating and the phase diagrams of aqueous PNIPAM solutions with a very flat lower critical solution temperature (LCST) phase separation line are theoretically studied on the basis of cooperative dehydration (simultaneous dissociation of bound water molecules in a group of correlated sequence), and compared with the experimental observation of temperature-induced coil-globule transition by light scattering methods. The transition becomes sharper with the cooperativity parameter {sigma} of hydration. The reentrant coil-globule-coil transition and cononsolvency in a mixed solvent of water and methanol are also studied from the viewpoint of competitive hydrogen bonds between polymer-water and polymer-methanol. The downward shift of the cloud-point curves (LCST cononsolvency) with the mol fraction of methanol due to the competition is calculated and compared with the experimental data. Aqueous solutions of hydrophobically modified PNIPAM carrying short alkyl chains at both chain ends (telechelic PNIPAM) are theoretically and experimentally studied. The LCST of these solutions is found to shift downward along the sol-gel transition curve as a result of end-chain association (association-induced phase separation), and separate from the coil-globule transition line. Associated structures in the solution, such as flower micelles, mesoglobules, and higher fractal assembly, are studied by ultra small-angle neutron scattering with theoretical modeling of the scattering function. Dynamic-mechanical modulus, nonlinear stationary viscosity, and stress build-up in start-up shear flows of the associated networks are studied on the basis of the affine and non-affine transient network theory. The molecular conditions for thickening, strain hardening, and stress overshoot are found in terms of the nonlinear amplitude A of the chain tension and the tension-dissociation coupling constant g.

  8. Cisplatin enhances the formation of DNA single- and double-strand breaks by hydrated electrons and hydroxyl radicals.

    Science.gov (United States)

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

    2013-03-01

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

  9. 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

  10. Static Formation Temperature Prediction Based on Bottom Hole Temperature

    Directory of Open Access Journals (Sweden)

    Changwei Liu

    2016-08-01

    Full Text Available Static formation temperature (SFT is required to determine the thermophysical properties and production parameters in geothermal and oil reservoirs. However, it is not easy to determine SFT by both experimental and physical methods. In this paper, a mathematical approach to predicting SFT, based on a new model describing the relationship between bottom hole temperature (BHT and shut-in time, has been proposed. The unknown coefficients of the model were derived from the least squares fit by the particle swarm optimization (PSO algorithm. Additionally, the ability to predict SFT using a few BHT data points (such as the first three, four, or five points of a data set was evaluated. The accuracy of the proposed method to predict SFT was confirmed by a deviation percentage less than ±4% and a high regression coefficient R2 (>0.98. The proposed method could be used as a practical tool to predict SFT in both geothermal and oil wells.

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

    International Nuclear Information System (INIS)

    Wu Qingbai; Jiang Guanli; Zhang Peng

    2010-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2000-04-01

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

  14. 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.

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

    International Nuclear Information System (INIS)

    Ostrovskii, Viktor E; Kadyshevich, Elena A

    2007-01-01

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

  16. 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.

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    Crystal structures of Sr4(Sr2Ta2)O11 and Sr4(Sr1.92Ta2.08)O11.12, synthesized by solid state reaction technique in dry and hydrated state have been studied mainly using Transmission Electron Microscopy. Due to the lesser ability of X-rays to probe details in oxygen sublattice, the change in crystal...... and corresponding unit cells of all the perovskites based on the ordering of oxygen vacancies is deduced. Crystal unit cells based on the observations are proposed with ideal atomic coordinates. Finally an attempt is made to explain the water uptake behaviour of these perovskites based on the proposed crystal...

  18. The genetic source and timing of hydrocarbon formation in gas hydrate reservoirs in Green Canyon, Block GC955

    Science.gov (United States)

    Moore, M. T.; Darrah, T.; Cook, A.; Sawyer, D.; Phillips, S.; Whyte, C. J.; Lary, B. A.

    2017-12-01

    Although large volumes of gas hydrates are known to exist along continental slopes and below permafrost, their role in the energy sector and the global carbon cycle remains uncertain. Investigations regarding the genetic source(s) (i.e., biogenic, thermogenic, mixed sources of hydrocarbon gases), the location of hydrocarbon generation, (whether hydrocarbons formed within the current reservoir formations or underwent migration), rates of clathrate formation, and the timing of natural gas formation/accumulation within clathrates are vital to evaluate economic potential and enhance our understanding of geologic processes. Previous studies addressed some of these questions through analysis of conventional hydrocarbon molecular (C1/C2+) and stable isotopic (e.g., δ13C-CH4, δ2H-CH4, δ13C-CO2) composition of gases, water chemistry and isotopes (e.g., major and trace elements, δ2H-H2O, δ18O-H2O), and dissolved inorganic carbon (δ13C-DIC) of natural gas hydrate systems to determine proportions of biogenic and thermogenic gas. However, the effects from contributions of mixing, transport/migration, methanogenesis, and oxidation in the subsurface can complicate the first-order application of these techniques. Because the original noble gas composition of a fluid is preserved independent of microbial activity, chemical reactions, or changes in oxygen fugacity, the integration of noble gas data can provide both a geochemical fingerprint for sources of fluids and an additional insight as to the uncertainty between effects of mixing versus post-genetic modification. Here, we integrate inert noble gases (He, Ne, Ar, and associated isotopes) with these conventional approaches to better constrain the source of gas hydrate formation and the residence time of fluids (porewaters and natural gases) using radiogenic 4He ingrowth techniques in cores from two boreholes collected as part of the University of Texas led UT-GOM2-01 drilling project. Pressurized cores were extracted from

  19. Effect of Temperature on Acidity and Hydration Equilibrium Constants of Delphinidin-3-O- and Cyanidin-3-O-sambubioside Calculated from Uni- and Multiwavelength Spectroscopic Data.

    Science.gov (United States)

    Vidot, Kévin; Achir, Nawel; Mertz, Christian; Sinela, André; Rawat, Nadirah; Prades, Alexia; Dangles, Olivier; Fulcrand, Hélène; Dornier, Manuel

    2016-05-25

    Delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside are the main anthocyanins of Hibiscus sabdariffa calyces, traditionally used to make a bright red beverage by decoction in water. At natural pH, these anthocyanins are mainly in their flavylium form (red) in equilibrium with the quinonoid base (purple) and the hemiketal (colorless). For the first time, their acidity and hydration equilibrium constants were obtained from a pH-jump method followed by UV-vis spectroscopy as a function of temperature from 4 to 37 °C. Equilibrium constant determination was also performed by multivariate curve resolution (MCR). Acidity and hydration constants of cyanidin-3-O-sambubioside at 25 °C were 4.12 × 10(-5) and 7.74 × 10(-4), respectively, and were significantly higher for delphinidin-3-O-sambubioside (4.95 × 10(-5) and 1.21 × 10(-3), respectively). MCR enabled the obtaining of concentration and spectrum of each form but led to overestimated values for the equilibrium constants. However, both methods showed that formations of the quinonoid base and hemiketal were endothermic reactions. Equilibrium constants of anthocyanins in the hibiscus extract showed comparable values as for the isolated anthocyanins.

  20. Relating friction on the human skin to the hydration and temperature of the skin

    NARCIS (Netherlands)

    Veijgen, N.K.; Masen, Marc Arthur; van der Heide, Emile

    2013-01-01

    The human skin is constantly in interaction with materials and products. Therefore, skin friction is relevant to all people. In the literature, the frictional properties of the skin have been linked to a large variety of variables, like age, gender and hydration. The present study compares the data

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1988-12-31

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

  2. 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.

  3. 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)

  4. 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

  5. Ice formation in PEM fuel cells operated isothermally at sub-freezing temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Mukundan, Rangachary [Los Alamos National Laboratory; Luhan, Roger W [Los Alamos National Laboratory; Davey, John R [Los Alamos National Laboratory; Spendelow, Jacob S [Los Alamos National Laboratory; Borup, Rodney L [Los Alamos National Laboratory; Hussey, Daniel S [NIST; Jacobson, David L [NIST; Arif, Muhammad [NIST

    2009-01-01

    The effect of MEA and GDL structure and composition on the performance of single-PEM fuel cells operated isothermally at subfreezing temperatures is presented. The cell performance and durability are not only dependent on the MEA/GDL materials used but also on their interfaces. When a cell is operated isothermally at sub-freezing temperatures in constant current mode, the water formation due to the current density initially hydrates the membrane/ionomer and then forms ice in the catalyst layer/GDL. An increase in high frequency resistance was also observed in certain MEAs where there is a possibility of ice formation between the catalyst layer and GDL leading to a loss in contact area. The total water/ice holding capacity for any MEA was lower at lower temperatures and higher current densities. The durability of MEAs subjected to multiple isothermal starts was better for LANL prepared MEAs as compared to commercial MEAs, and cloth GDLs when compared to paper GDLs. The ice formation was monitored using high-resolution neutron radiography and was found to be concentrated near the cathode catalyst layer. However, there was significant ice formation in the GDLs especially at the higher temperature ({approx} -10 C) and lower current density (0.02 A/cm{sup 2}) operations. These results are consistent with the longer-term durability observations that show more severe degradation at the lower temperatures.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    of hydrate growth. Additionally, hydrate formed in the presence of inhibitor decomposed at higher temperatures compared to pure water, indicating that while hydrate formation is initially inhibited; once hydrates form, they are more stable in the presence of inhibitor. Overall, this method proved a viable......Methane hydrate formation and decomposition were investigated in the presence of the kinetic inhibitor (Luvicap EG) and synergist (polyethylene oxide; PEO) using a high pressure micro-differential scanning calorimeter (HP-μDSC) with both temperature ramping and isothermal temperature programs....... These investigations were performed using small samples in four different capillary tubes in the calorimeter cell. When the isothermal method was employed, it was found that Luvicap EG significantly delays the hydrate nucleation time as compared to water. The results obtained from the ramping method demonstrated...

  7. 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.

  8. The bimolecular reaction of radiolysis product of hydrated electron at temperature up to 473K; Reaksi bimolekular antar produk radiolisis elektron terhidrasi pada temperatur hingga 473K

    Energy Technology Data Exchange (ETDEWEB)

    Sunaryo, G R [Reactor Safety Technology Research Centre, National Atomic Energy Agency, Serpong (Indonesia)

    1996-06-01

    Rate constant from the bimolecular reaction of hydrated electron was determined by using radiolysis method. The methanol solution with concentration of 5 x 10{sup -2} dm{sup 3} mol{sup -1} was used as a scavenger of H and OH radicals. The pH was kept by adding the buffer solution of 1.0 x 10{sup -3} dm{sup 3} mol{sup -1} Na{sub 2}HPO{sub 4} + 1.0 x 10{sup 4} dm{sup 3} mol{sup -1} NaH{sub 2}PO{sub 4}. The irradiation was done by using the electron beam which come from linear accelerator 28 MeV with pulse width 10ns and dose of 80 Gy per pulse. The absorbance of hydrated electron was observed at wavelength of 824 nm. By using the kinetic equation the rate reaction constants were obtained. The bimolecular reaction of hydrated electron increase with temperature up to 423K. The activation energy was 19.3 kJ mol{sup -1} and the 2 k (298K) was 1.1 x 10{sup 10} dm{sup 3} mol{sup -1}. Then this bimolecular reaction decrease at temperature higher than 423K and the rate reaction constant at 473K almost similar with that at 298K. (author)

  9. Personalized Hydration Strategy Attenuates the Rise in Heart Rate and in Skin Temperature Without Altering Cycling Capacity in the Heat

    Directory of Open Access Journals (Sweden)

    Denise de Melo-Marins

    2018-04-01

    Full Text Available The optimal hydration plan [i.e., drink to thirst, ad libitum (ADL, or personalized plan] to be adopted during exercise in recreational athletes has recently been a matter of debate and, due to conflicting results, consensus does not exist. In the present investigation, we tested whether a personalized hydration strategy based on sweat rate would affect cardiovascular and thermoregulatory responses and exercise capacity in the heat. Eleven recreational male cyclists underwent two familiarization cycling sessions in the heat (34°C, 40% RH where sweat rate was also determined. A fan was used to enhance sweat evaporation. Participants then performed three randomized time-to-exhaustion (TTE trials in the heat with different hydration strategies: personalized volume (PVO, where water was consumed, based on individual sweat rate, every 10 min; ADL, where free access to water was allowed; and a control (CON trial with no fluids. Blood osmolality and urine-specific gravity were measured before each trial. Heart rate (HR, rectal, and skin temperatures were monitored throughout trials. Time to exhaustion at 70% of maximal workload was used to define exercise capacity in the heat, which was similar in all trials (p = 0.801. Body mass decreased after ADL (p = 0.008 and CON (p < 0.001 and was maintained in PVO trials (p = 0.171. Participants consumed 0 ml in CON, 166 ± 167 ml in ADL, and 1,080 ± 166 ml in PVO trials. The increase in mean body temperature was similar among trials despite a lower increase in skin temperature during PVO trial in comparison with CON (2.1 ± 0.6 vs. 2.9 ± 0.5°C, p = 0.0038. HR was lower toward the end of TTE in PVO (162 ± 8 bpm in comparison with ADL (168 ± 12 bpm and CON (167 ± 10 bpm, p < 0.001. In conclusion, a personalized hydration strategy can reduce HR during a moderate to high intensity exercise session in the heat and halt the increase in skin

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-11-01

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

  11. High-temperature CO2 capture cycles of hydrated limestone prepared with aluminum (hydr)oxides derived from kaolin

    International Nuclear Information System (INIS)

    Wang, Ke; Zhao, Pengfei; Guo, Xin; Han, Dongtai; Chao, Yang

    2014-01-01

    Highlights: • Hydrated limestone exhibited a higher reactivity and stability. • Microstructure of hydrated limestone was significantly improved. • Hydrated limestone still suffered less loss-incapacity. • Hydrated limestone sorbents with kaolin-based binders were prepared and characterized. • Sorbents prepared from hydrated limestone and Al(OH) 3 binder are a promising sorbent. - Abstract: A simple and convenient process was used to improve the utilization of natural limestone and kaolin for calcium looping technology and environmental applications. The calcined natural limestone modified with the distilled water (denoted as Limestone-W), was systematically studied and compared with the other CaO sorbents (calcium acetate, calcium D-gluconate and calcined natural limestone). These CaO-based sorbents were tested for their CO 2 capture behavior through 20 carbonation/calcination cycles in a thermo-gravimetric analyzer (TGA). Their morphology, pore structure and phase composition before and after carbonation/calcination cycles were determined by scanning electron microscopy, nitrogen adsorption, and X-ray diffraction. The first-cycle and multicycle sorption results revealed that the Limestone-W sorbent exhibited a relatively faster reaction rate and higher cyclic CO 2 capture. The characterization data indicated that the Limestone-W was composed of a special calcium oxide structure with lower crystalline and higher porosity nanoparticles, which appeared to be the main reasons for its higher CO 2 capture capability. However, the Limestone-W still suffered loss of reactivity, even though it was less pronounced than the other CaO sorbent. To avoid this unfavorable effect, a thermally stable inert material (aluminum hydroxide derived from kaolin) was incorporated into the Limestone-W structure. This new sorbent revealed higher stability because the formation of a stable framework of Ca 12 Al 14 O 33 particles hindered densification and sintering of the CaO phase

  12. Geological evolution and analysis of confirmed or suspected gas hydrate localities: Volume 10, Basin analysis, formation and stability of gas hydrates of the Aleutian Trench and the Bering Sea

    Energy Technology Data Exchange (ETDEWEB)

    Krason, J.; Ciesnik, M.

    1987-01-01

    Four major areas with inferred gas hydrates are the subject of this study. Two of these areas, the Navarin and the Norton Basins, are located within the Bering Sea shelf, whereas the remaining areas of the Atka Basin in the central Aleutian Trench system and the eastern Aleutian Trench represent a huge region of the Aleutian Trench-Arc system. All four areas are geologically diverse and complex. Particularly the structural features of the accretionary wedge north of the Aleutian Trench still remain the subjects of scientific debates. Prior to this study, suggested presence of the gas hydrates in the four areas was based on seismic evidence, i.e., presence of bottom simulating reflectors (BSRs). Although the disclosure of the BSRs is often difficult, particularly under the structural conditions of the Navarin and Norton basins, it can be concluded that the identified BSRs are mostly represented by relatively weak and discontinuous reflectors. Under thermal and pressure conditions favorable for gas hydrate formation, the relative scarcity of the BSRs can be attributed to insufficient gas supply to the potential gas hydrate zone. Hydrocarbon gas in sediment may have biogenic, thermogenic or mixed origin. In the four studied areas, basin analysis revealed limited biogenic hydrocarbon generation. The migration of the thermogenically derived gases is probably diminished considerably due to the widespread diagenetic processes in diatomaceous strata. The latter processes resulted in the formation of the diagenetic horizons. The identified gas hydrate-related BSRs seem to be located in the areas of increased biogenic methanogenesis and faults acting as the pathways for thermogenic hydrocarbons.

  13. Personalized Hydration Strategy Attenuates the Rise in Heart Rate and in Skin Temperature Without Altering Cycling Capacity in the Heat.

    Science.gov (United States)

    de Melo-Marins, Denise; Souza-Silva, Ana Angélica; da Silva-Santos, Gabriel Lucas Leite; Freire-Júnior, Francisco de Assis; Lee, Jason Kai Wei; Laitano, Orlando

    2018-01-01

    The optimal hydration plan [i.e., drink to thirst, ad libitum (ADL), or personalized plan] to be adopted during exercise in recreational athletes has recently been a matter of debate and, due to conflicting results, consensus does not exist. In the present investigation, we tested whether a personalized hydration strategy based on sweat rate would affect cardiovascular and thermoregulatory responses and exercise capacity in the heat. Eleven recreational male cyclists underwent two familiarization cycling sessions in the heat (34°C, 40% RH) where sweat rate was also determined. A fan was used to enhance sweat evaporation. Participants then performed three randomized time-to-exhaustion (TTE) trials in the heat with different hydration strategies: personalized volume (PVO), where water was consumed, based on individual sweat rate, every 10 min; ADL, where free access to water was allowed; and a control (CON) trial with no fluids. Blood osmolality and urine-specific gravity were measured before each trial. Heart rate (HR), rectal, and skin temperatures were monitored throughout trials. Time to exhaustion at 70% of maximal workload was used to define exercise capacity in the heat, which was similar in all trials ( p  = 0.801). Body mass decreased after ADL ( p  = 0.008) and CON ( p  skin temperature during PVO trial in comparison with CON (2.1 ± 0.6 vs. 2.9 ± 0.5°C, p  = 0.0038). HR was lower toward the end of TTE in PVO (162 ± 8 bpm) in comparison with ADL (168 ± 12 bpm) and CON (167 ± 10 bpm), p  hydration strategy can reduce HR during a moderate to high intensity exercise session in the heat and halt the increase in skin temperature. Despite these advantages, cycling capacity in the heat remained unchanged.

  14. 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.)

  15. 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.

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

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  17. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1990-01-01

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

  19. 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.

  20. 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.

  1. Temperature Dependence of Logarithmic-like Relaxational Dynamics of Hydrated tRNA.

    Science.gov (United States)

    Chu, Xiang-Qiang; Mamontov, Eugene; O'Neill, Hugh; Zhang, Qiu

    2013-03-21

    The dynamics of RNA within the β-relaxation region of 10 ps to 1 ns is crucial to its biological function. Because of its simpler chemical building blocks and the lack of the side methyl groups, faster relaxational dynamics of RNA compared to proteins can be expected. However, the situation is actually opposite. In this work, the relaxational dynamics of tRNA is measured by quasielastic neutron scattering and analyzed using the mode coupling theory, originally developed for glass-forming liquids. Our results reveal that the dynamics of tRNA follows a log-decay within the β-relaxation region, which is an important trait demonstrated by the dynamics of proteins. The dynamics of hydrated tRNA and lysozyme compared in the time domain further demonstrate that the slower dynamics of tRNA relative to proteins originates from the difference in the folded states of tRNA and proteins, as well as the influence of their hydration water.

  2. 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.

  3. Extensin network formation in Vitis vinifera callus cells is an essential and causal event in rapid and H2O2-induced reduction in primary cell wall hydration

    Science.gov (United States)

    2011-01-01

    Background Extensin deposition is considered important for the correct assembly and biophysical properties of primary cell walls, with consequences to plant resistance to pathogens, tissue morphology, cell adhesion and extension growth. However, evidence for a direct and causal role for the extensin network formation in changes to cell wall properties has been lacking. Results Hydrogen peroxide treatment of grapevine (Vitis vinifera cv. Touriga) callus cell walls was seen to induce a marked reduction in their hydration and thickness. An analysis of matrix proteins demonstrated this occurs with the insolubilisation of an abundant protein, GvP1, which displays a primary structure and post-translational modifications typical of dicotyledon extensins. The hydration of callus cell walls free from saline-soluble proteins did not change in response to H2O2, but fully regained this capacity after addition of extensin-rich saline extracts. To assay the specific contribution of GvP1 cross-linking and other wall matrix proteins to the reduction in hydration, GvP1 levels in cell walls were manipulated in vitro by binding selected fractions of extracellular proteins and their effect on wall hydration during H2O2 incubation assayed. Conclusions This approach allowed us to conclude that a peroxidase-mediated formation of a covalently linked network of GvP1 is essential and causal in the reduction of grapevine callus wall hydration in response to H2O2. Importantly, this approach also indicated that extensin network effects on hydration was only partially irreversible and remained sensitive to changes in matrix charge. We discuss this mechanism and the importance of these changes to primary wall properties in the light of extensin distribution in dicotyledons. PMID:21672244

  4. Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

    Science.gov (United States)

    Braun, Doris E.; Griesser, Ulrich J.

    2018-01-01

    The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS) 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and (form III) differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products. PMID:29520359

  5. Phase changes induced by guest orientational ordering of filled ice Ih methane hydrate under high pressure and low temperature

    International Nuclear Information System (INIS)

    Hirai, H; Tanaka, T; Yagi, T; Matsuoka, T; Ohishi, Y; Ohtake, M; Yamamoto, Y

    2014-01-01

    Low-temperature and high-pressure experiments were performed with filled ice Ih structure of methane hydrate under pressure and temperature conditions of 2.0 to 77.0 GPa and 30 to 300 K, respectively, using diamond anvil cells and a helium-refrigeration cryostat. Distinct changes in the axial ratios of the host framework were revealed by In-situ X-ray diffractometry. Splitting in the CH vibration modes of the guest methane molecules, which was previously explained by the orientational ordering of the guest molecules, was observed by Raman spectroscopy. The pressure and temperature conditions at the split of the vibration modes agreed well with those of the axial ratio changes. The results indicated that orientational ordering of the guest methane molecules from orientational disordered-state occurred at high pressures and low temperatures, and that this guest ordering led to the axial ratio changes in the host framework. Existing regions of the guest disordered-phase and the guest ordered-phase were roughly estimated by the X-ray data. In addition, above the pressure of the guest-ordered phase, another high pressure phase was developed at a low-temperature region. The deuterated-water host samples were also examined and isotopic effects on the guest ordering and phase changes were observed.

  6. Methane Hydrate in Confined Spaces: An Alternative Storage System.

    Science.gov (United States)

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

    2018-03-14

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

  7. Analytical investigation of high temperature 1 kW solid oxide fuel cell system feasibility in methane hydrate recovery and deep ocean power generation

    International Nuclear Information System (INIS)

    Azizi, Mohammad Ali; Brouwer, Jacob; Dunn-Rankin, Derek

    2016-01-01

    Highlights: • A dynamic Solid Oxide Fuel Cell (SOFC) model was developed. • Hydrate bed methane dissociation model was integrated with the SOFC model. • SOFC operated steadily for 120 days at high pressure deep ocean environment. • Burning some of the dissociated gas for SMR heat leads to more net methane produced. • Higher SOFC fuel utilization produces higher integrated system efficiency. - Abstract: Methane hydrates are potential valuable energy resources. However, finding an efficient method for methane gas recovery from hydrate sediments is still a challenge. New challenges arise from increasing environmental protection. This is due in part to the technical difficulties involved in the efficient dissociation of methane hydrates at high pressures. In this study, a new approach is proposed to produce valuable products of: 1. Net methane gas recovery from the methane hydrate sediment, and 2. Deep ocean power generation. We have taken the first steps toward utilization of a fuel cell system in methane gas recovery from deep ocean hydrate sediments. An integrated high pressure and high temperature solid oxide fuel cell (SOFC) and steam methane reformer (SMR) system is analyzed for this application and the recoverable amount of methane from deep ocean sediments is measured. System analysis is accomplished for two major cases regarding system performance: 1. Energy for SMR is provided by the burning part of the methane gas dissociated from the hydrate sediment. 2. Energy for SMR is provided through heat exchange with fuel cell effluent gases. We found that the total production of methane gas is higher in the first case compared to the second case. The net power generated by the fuel cell system is estimated for all cases. The primary goal of this study is to evaluate the feasibility of integrated electrochemical devices to accomplish energy efficient dissociation of methane hydrate gases in deep ocean sediments. Concepts for use of electrochemical devices

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

    DEFF Research Database (Denmark)

    Tzirakis, Fragkiskos

    , the simultaneous combination of these chemicals achieved greater pressure reduction than if they were used separately. Then, experimental uncertainties were measured (for pressure/temperature transducers and gas chromatograph) and calculated (for the inserted quantities of water and chemicals). The uncertainties...

  9. 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.

  10. 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.

  11. Temperature effects on geotechnical and hydraulic properties of bentonite hydrated with inorganic salt solutions

    DEFF Research Database (Denmark)

    Rashid, H. M. A.; Kawamoto, K.; Saito, T.

    2015-01-01

    © 2015, International Journal of GEOMATE. This study investigated the combined effect of temperature and single-species salt solutions on geotechnical properties (swell index and liquid limit) and hydraulic conductivity of bentonite applying different cation types, concentrations, and temperatures...

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  13. Investigating the Metastability of Clathrate Hydrates for Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-18

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

  14. 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.

  15. 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.

  16. Temperature dependence of the rate constant for reactions of hydrated electrons with H, OH and H2O2

    DEFF Research Database (Denmark)

    Christensen, H.; Sehested, K.; Løgager, T.

    1994-01-01

    The temperature dependence of the rate constants, for the reactions of hydrated electrons with H atoms, OH radicals and H2O2 has been determined. The reaction with H atoms, studied in the temperature range 20-250-degrees-C gives k(20-degrees-C) = 2.4 x 10(10) M-1 s-1 and the activation energy E......-1 and E(A) = 15.6 kJ mol-1 (3.7 kcal mol-1) measured from 5-150-degrees-C. Thus, the activation energy for all three fast reactions is close to that expected for diffusion controlled reactions. As phosphates were used as buffer system, the rate constant and activation energy for the reaction......(A) = 14.0 kJ mol-1 (3.3 kcal mol-1). For reaction with OH radicals the corresponding values are, k(20-degrees-C) = 3.1 x 10(10) M-1 s-1 and E(A) = 14.7 kJ mol-1 (3.5 kcal mol-1) determined in the temperature range 5-175-degrees-C. For reaction with H2O2 the values are, k(20-degrees-C) = 1.2 x 10(10) M-1 s...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-02-28

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

  18. The influences of skin visco-elasticity, hydration level and aging on the formation of wrinkles: a comprehensive and objective approach.

    Science.gov (United States)

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

    2013-02-01

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

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

    International Nuclear Information System (INIS)

    Eslamimanesh, Ali

    2012-01-01

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

  20. Gas hydrate formation and dissipation histories in the northern margin of Canada: Beaufort-Mackenzie and the Sverdrup Basins

    Czech Academy of Sciences Publication Activity Database

    Majorowicz, J.; Osadetz, K.; Šafanda, Jan

    2012-01-01

    Roč. 2012, č. 1 (2012), 879393/1-879393/17 ISSN 1687-8833 Institutional research plan: CEZ:AV0Z30120515 Keywords : gas hydrates * Canadian Arctic continental margin * permafrost Subject RIV: DC - Siesmology, Volcanology, Earth Structure

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1988-12-31

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

  2. Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

    Directory of Open Access Journals (Sweden)

    Doris E. Braun

    2018-02-01

    Full Text Available The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis, gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations. Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (dehydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules and (form III differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products.

  3. The Impact of Hydration and Temperature on Bacterial Diversity in Arid Soil Mesocosms

    Directory of Open Access Journals (Sweden)

    Adam Št'ovíček

    2017-06-01

    Full Text Available Hot desert ecosystems experience rare and unpredictable rainfall events that resuscitate the arid flora and fauna. However, the effect of this sudden abundance of water on soil microbial communities is still under debate. We modeled varying rainfall amounts and temperatures in desert soil mesocosms and monitored the microbial community response over a period of 21 days. We studied two different wetting events, simulating heavy (50 mm and light (10 mm rain, as well as three different temperature regimes: constant 25° or 36°C, or a temperature diurnal cycle alternating between 36 and 10 °C. Amplicon sequencing of the bacterial ribosomal RNA revealed that rain intensity affects the soil bacterial community, but the effects are mitigated by temperature. The combination of water-pulse intensity with lower temperature had the greatest effect on the bacterial community. These experiments demonstrated that the soil microbial response to rain events is dependent not only on the intensity of the water pulse but also on the ambient temperature, thus emphasizing the complexity of bacterial responses to highly unpredictable environments.

  4. Temperature controlled formation of lead/acid batteries

    Science.gov (United States)

    Bungardt, M.

    At present, standard formation programs have to accommodate the worst case. This is important, especially in respect of variations in climatic conditions. The standard must be set so that during the hottest weather periods the maximum electrolyte temperature is not exceeded. As this value is defined not only by the desired properties and the recipe of the active mass, but also by type and size of the separators and by the dimensions of the plates, general rules cannot be formulated. It is considered to be advantageous to introduce limiting data for the maximum temperature into a general formation program. The latter is defined so that under normal to good ambient conditions the shortest formation time is achieved. If required, the temperature control will reduce the currents employed in the different steps, according to need, and will extend the formation time accordingly. With computer-controlled formation, these parameters can be readily adjusted to suit each type of battery and can also be reset according to modifications in the preceding processing steps. Such a procedure ensures that: (i) the formation time is minimum under the given ambient conditions; (ii) in the event of malpractice ( e.g. actual program not fitting to size) the batteries will not be destroyed; (iii) the energy consumption is minimized (note, high electrolyte temperature leads to excess gassing). These features are incorporated in the BA/FOS-500 battery formation system developed by Digatron. The operational characteristics of this system are listed in Table 1.

  5. A study on dehydration of rare earth chloride hydrate

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  6. Numerical simulation studies of gas production scenarios from hydrate accumulations at the Mallik Site, McKenzie Delta, Canada

    International Nuclear Information System (INIS)

    Moridis, George J.; Collett, Timothy S.; Dallimore, Scott R.; Satoh, Tohru; Hancock, Stephen; Weatherill, Brian

    2002-01-01

    The Mallik site represents an onshore permafrost-associated gas hydrate accumulation in the Mackenzie Delta, Northwest Territories, Canada. An 1150 m deep gas hydrate research well was drilled at the site in 1998. The objective of this study is the analysis of various gas production scenarios from several gas-hydrate-bearing zones at the Mallik site. The TOUGH2 general-purpose simulator with the EOSHYDR2 module were used for the analysis. EOSHYDR2 is designed to model the non-isothermal CH(sub 4) (methane) release, phase behavior and flow under conditions typical of methane-hydrate deposits by solving the coupled equations of mass and heat balance, and can describe any combination of gas hydrate dissociation mechanisms. Numerical simulations indicated that significant gas hydrate production at the Mallik site was possible by drawing down the pressure on a thin free-gas zone at the base of the hydrate stability field. Gas hydrate zones with underlying aquifers yielded significant gas production entirely from dissociated gas hydrate, but large amounts of produced water. Lithologically isolated gas-hydrate-bearing reservoirs with no underlying free gas or water zones, and gas-hydrate saturations of at least 50% were also studied. In these cases, it was assumed that thermal stimulation by circulating hot water in the well was the method used to induce dissociation. Sensitivity studies indicated that the methane release from the hydrate accumulations increases with gas-hydrate saturation, the initial formation temperature, the temperature of the circulating water in the well, and the formation thermal conductivity. Methane production appears to be less sensitive to the rock and hydrate specific heat and permeability of the formation

  7. Onset and stability of gas hydrates under permafrost in an environment of surface climatic change : past and future

    International Nuclear Information System (INIS)

    Majorowicz, J.A.; Osadetz, K.; Safanda, J.

    2008-01-01

    This paper presented a model designed to simulate permafrost and gas hydrate formation in a changing surface temperature environment in the Beaufort-Mackenzie Basin (BMB). The numerical model simulated surface forcing due to general cooling trends that began in the late Miocene era. This study modelled the onset of permafrost formation and subsequent gas hydrate formation in the changing surface temperature environment for the BMB. Paleoclimatic data were used. The 1-D model was constrained by deep heat flow from well bottom hole temperatures; conductivity; permafrost thickness; and the thickness of the gas hydrates. The model used latent heat effects for the ice-bearing permafrost and hydrate intervals. Surface temperatures for glacial and interglacial histories for the last 14 million years were considered. The model also used a detailed Holocene temperature history as well as a scenario in which atmospheric carbon dioxide (CO 2 ) levels were twice as high as current levels. Two scenarios were considered: (1) the formation of gas hydrates from gas entrapped under geological seals; and (2) the formation of gas hydrates from gas located in free pore spaces simultaneously with permafrost formation. Results of the study showed that gas hydrates may have formed at a depth of 0.9 km only 1 million years ago. Results of the other modelling scenarios suggested that the hydrates formed 6 million years ago, when temperature changes caused the gas hydrate layer to expand both downward and upward. Detailed models of more recent glacial and interglacial histories showed that the gas hydrate zones will persist under the thick body of the BMB permafrost through current interglacial warming as well as in scenarios where atmospheric CO 2 is doubled. 28 refs., 13 figs

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

    Science.gov (United States)

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

    2018-01-01

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

  9. Multicavity SCRF calculation of ion hydration energies

    International Nuclear Information System (INIS)

    Diercksen, B.H.F.; Karelson, M.; Tamm, T.

    1994-01-01

    The hydration energies of the proton, hydroxyl ion, and several inorganic ions were calculated using the multicavity self-consistent reaction field (MCa SCRF) method developed for the quantum-mechanical modeling of rotationally or flexible systems in dielectric media. The ionic complexes H 3 O + (H2O) 4 , OH - (H2O) 4 , NH + 4 (H2O) 4 , and Hal - (H2O) 4 , where Hal = F, Cl, or Br, have been studied. Each complex was divided between five spheres, corresponding to the central ion and four water molecules in their first coordination sphere, respectively. Each cavity was surrounded by a polarizable medium with the dielectric permittivity of water at room temperature (80). The ionic hydration energies of ions were divided into specific and nonspecific parts. After accounting for the cavity-formation energy using scaled particle theory, good agreement between the total calculated and experimental hydration energies was obtained for all ions studied

  10. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-10-15

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

  12. 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.

  13. Catalysis of gas hydrates by biosurfactants in seawater-saturated sand/clay

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, R. E.; Kothapalli, C.; Lee, M.S. [Mississippi State University, Swalm School of Chemical Engineering, MS (United States); Woolsey, J. R. [University of Mississippi, Centre of Marine Resources and Environmental Technology, MS (United States)

    2003-10-01

    Large gas hydrate mounds have been photographed in the seabed of the Gulf of Mexico and elsewhere. According to industry experts, the carbon trapped within gas hydrates is two or three times greater than all known crude oil, natural gas and coal reserves in the world. Gas hydrates, which are ice-like solids formed from the hydrogen bonding of water as water temperature is lowered under pressure to entrap a suitable molecular-size gas in cavities of the developing crystal structure, are found below the ocean floor to depths exhibiting temperature and pressure combinations within the appropriate limits. The experiments described in this study attempt to ascertain whether biosurfactant byproducts of microbial activity in seabeds could catalyze gas hydrate formation. Samples of five possible biosurfactants classifications were used in the experiments. Results showed that biosurfactants enhanced hydrate formation rate between 96 per cent and 288 percent, and reduced hydrate induction time 20 per cent to 71 per cent relative to the control. The critical micellar concentration of rhamnolipid/seawater solution was found to be 13 ppm at hydrate-forming conditions. On the basis of these results it was concluded that minimal microbial activity in sea floor sands could achieve the threshold concentration of biosurfactant that would greatly promote hydrate formation. 28 refs., 2 tabs., 4 figs.

  14. Isothermal martensite formation at sub-zero temperatures

    DEFF Research Database (Denmark)

    Stojko, Allan; Hansen, Mikkel Fougt; Slycke, Jan

    2010-01-01

    austenitized and quenched in oil and thereafter investigated with vibrating sample agnetometry, which allows a quantitative assessment of the fraction of retained austenite as a function of the subzero temperature and time. Isothermal martensite formation was observed on interrupting the continuous cooling (5...... with a continuation of the martensitic transformation. On prolonged isothermal holding a volume reduction was observed for AISI 52100, but not for AISI 1070. A mechanism is proposed that explains the occurrence of isothermal martensite formation....

  15. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-12-31

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

  17. Gas hydrate cool storage system

    Science.gov (United States)

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

    1984-09-12

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

  18. THERMODYNAMIC MODEL OF GAS HYDRATES

    OpenAIRE

    Недоступ, В. И.; Недоступ, О. В.

    2015-01-01

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

  19. Electrical Conductive Mechanism of Gas Hydrate-Bearing Reservoirs in the Permafrost Region of Qilian Mountain

    Science.gov (United States)

    Peng, C.; Zou, C.; Tang, Y.; Liu, A.; Hu, X.

    2017-12-01

    In the Qilian Mountain, gas hydrates not only occur in pore spaces of sandstones, but also fill in fractures of mudstones. This leads to the difficulty in identification and evaluation of gas hydrate reservoir from resistivity and velocity logs. Understanding electrical conductive mechanism is the basis for log interpretation. However, the research is insufficient in this area. We have collected well logs from 30 wells in this area. Well logs and rock samples from DK-9, DK-11 and DK-12 wells were used in this study. The experiments including SEM, thin section, NMR, XRD, synthesis of gas hydrate in consolidated rock cores under low temperature and measurement of their resistivity and others were performed for understanding the effects of pore structure, rock composition, temperature and gas hydrate on conductivity. The results show that the porosity of reservoir of pore filling type is less than 10% and its clay mineral content is high. As good conductive passages, fractures can reduce resistivity of water-saturated rock. If fractures in the mudstone are filled by calcite, resistivity increases significantly. The resistivity of water-saturated rock at 2°C is twice of that at 18°C. The gas hydrate formation process in the sandstone was studied by resistivity recorded in real time. In the early stage of gas hydrate formation, the increase of residual water salinity may lead to the decrease of resistivity. In the late stage of gas hydrate formation, the continuity decrease of water leads to continuity increase of resistivity. In summary, fractures, rock composition, temperature and gas hydrate are important factors influencing resistivity of formation. This study is helpful for more accurate evaluation of gas hydrate from resistivity log. Acknowledgment: We acknowledge the financial support of the National Special Program for Gas Hydrate Exploration and Test-production (GZH201400302).

  20. Remagnetization and Cementation of Unconsolidated Sediments in the Mallik 5L-38 Well (Canadian Arctic) by Solute Exclusion During Gas Hydrate Formation

    Science.gov (United States)

    Hamilton, T. S.; Enkin, R. J.; Esteban, L.

    2007-05-01

    mineralogy. Silt samples are significantly stronger than sand samples in saturation magnetization and magnetic susceptibility. The silt samples have single-domain to pseudo-single domain coercivity ratios whereas the gas hydrate bearing sands have a more multi-domain nature. Sands with current gas hydrate concentrations > 80% have less magnetic material and single domain characteristics. The source of the greigite, carbonates, and other diagenetic minerals was apparently concentrated solutes excluded from formation waters by the freezing and formation of the water dominated gas hydrate. The hydrates served as a cementing agent for the unconsolidated sediments, allowing them to fracture. Some layers have been so inflated by the introduction carbonate and sulfide cements that they resemble hydrothermal tufa and skarns with floating sand grains. In the silts, the magnetic properties reflect the mixture of primary detrital magnetite and diagenetic greigite in various grain sizes and concentrations. At Mallik, the magnetic properties are sensitive to the diagenetic mineralogy and redox state associated with the transport of methane and pore fluids and the creation of gas hydrates. Hypersaline brines, produced by solute exclusion from pore waters, fractured and inflated less permeable sediments and forced rapid disequilibrium growth of greigite without dissolving primary detrital magnetite grains.

  1. Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

    Science.gov (United States)

    Birkner, Nancy; Navrotsky, Alexandra

    2014-04-29

    Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings.

  2. Hydration of Caffeine at High Temperature by Neutron Scattering and Simulation Studies.

    Science.gov (United States)

    Tavagnacco, L; Brady, J W; Bruni, F; Callear, S; Ricci, M A; Saboungi, M L; Cesàro, A

    2015-10-22

    The solvation of caffeine in water is examined with neutron diffraction experiments at 353 K. The experimental data, obtained by taking advantage of isotopic H/D substitution in water, were analyzed by empirical potential structure refinement (EPSR) in order to extract partial structure factors and site-site radial distribution functions. In parallel, molecular dynamics (MD) simulations were carried out to interpret the data and gain insight into the intermolecular interactions in the solutions and the solvation process. The results obtained with the two approaches evidence differences in the individual radial distribution functions, although both confirm the presence of caffeine stacks at this temperature. The two approaches point to different accessibility of water to the caffeine sites due to different stacking configurations.

  3. 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.

  4. Calcium aluminates hydration in presence of amorphous SiO2 at temperatures below 90 deg. C

    International Nuclear Information System (INIS)

    Rivas Mercury, J.M.; Turrillas, X.; Aza, A.H. de; Pena, P.

    2006-01-01

    The hydration behaviour of Ca 3 Al 2 O 6 , Ca 12 Al 14 O 33 and CaAl 2 O 4 with added amorphous silica at 40, 65 and 90 deg. C has been studied for periods ranging from 1 to 31 days. In hydrated samples crystalline phases like katoite (Ca 3 Al 2 (SiO 4 ) 3- x (OH) 4 x ) and gibbsite, Al(OH) 3 , were identified, likewise amorphous phases like Al(OH) x , calcium silicate hydrates, C-S-H, and calcium aluminosilicate hydrates, C-S-A-H, were identified. The stoichiometry of Ca 3 Al 2 (SiO 4 ) 3- x (OH) 4 x (0≤3-x≤0.334), which was the main crystalline product, was established by Rietveld refinement of X-ray and neutron diffraction data and by transmission electron microscopy. - Graphical abstract: Katoite, Ca 3 Al 2 (SiO 4 ) 3- x (OH) 4 x (0≤3-x≤0.334), was identified besides gibbsite, Al(OH) 3 , as a crystalline stable hydration products in Ca 3 Al 2 O 6 , Ca 12 Al 14 O 33 and CaAl 2 O 4 hydrated with added amorphous silica between 40 and 90 deg. C

  5. 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...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  7. Heat Transfer Analysis of Methane Hydrate Sediment Dissociation in a Closed Reactor by a Thermal Method

    Directory of Open Access Journals (Sweden)

    Mingjun Yang

    2012-05-01

    Full Text Available The heat transfer analysis of hydrate-bearing sediment involved phase changes is one of the key requirements of gas hydrate exploitation techniques. In this paper, experiments were conducted to examine the heat transfer performance during hydrate formation and dissociation by a thermal method using a 5L volume reactor. This study simulated porous media by using glass beads of uniform size. Sixteen platinum resistance thermometers were placed in different position in the reactor to monitor the temperature differences of the hydrate in porous media. The influence of production temperature on the production time was also investigated. Experimental results show that there is a delay when hydrate decomposed in the radial direction and there are three stages in the dissociation period which is influenced by the rate of hydrate dissociation and the heat flow of the reactor. A significant temperature difference along the radial direction of the reactor was obtained when the hydrate dissociates and this phenomenon could be enhanced by raising the production temperature. In addition, hydrate dissociates homogeneously and the temperature difference is much smaller than the other conditions when the production temperature is around the 10 °C. With the increase of the production temperature, the maximum of ΔToi grows until the temperature reaches 40 °C. The period of ΔToi have a close relation with the total time of hydrate dissociation. Especially, the period of ΔToi with production temperature of 10 °C is twice as much as that at other temperatures. Under these experimental conditions, the heat is mainly transferred by conduction from the dissociated zone to the dissociating zone and the production temperature has little effect on the convection of the water in the porous media.

  8. Formation of actinide hexafluorides at ambient temperatures with krypton difluoride

    International Nuclear Information System (INIS)

    Asprey, L.B.; Eller, P.G.; Kinkead, S.A.

    1986-01-01

    A second low-temperature agent, krypton difluoride, for generating volatile plutonium hexafluoride is reported (dioxygen difluoride is the only other reported agent). Plutonium hexafluoride is formed at ambient or lower temperature by the treatment of various solid substrates with krypton difluoride. Volatilization of uranium and neptunium from solid substrates using gaseous krypton difluoride is also reported for the first time. The formation of actinide hexafluorides has been confirmed for the reaction of krypton difluoride in anhydrous HF with UO 2 and with uranium and neptunium fluorides at ambient temperatures. Treatment of americium dioxide with krypton difluoride did not yield americium hexafluoride under the conditions studied. 15 references, 2 figures

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

    Science.gov (United States)

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

    2005-11-01

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

  10. Moessbauer and calorimetric studies of portland cement hydration in the presence of black gram pulse

    International Nuclear Information System (INIS)

    Rai, Sarita; Kurian, Sajith; Dwivedi, V. N.; Das, S. S.; Singh, N. B.; Gajbhiye, N. S.

    2009-01-01

    Effect of different concentrations of naturally occurring admixture in the form of fine powder of black gram pulse (BGP) on the hydration of Portland cement was studied by isothermal calorimetry and 57 Fe Moessbauer spectroscopy. The spectra were recorded for anhydrous cement and the hydration products at room temperature and 77 K. In the presence of BGP, the spectra showed superparamagnetic doublets at room temperature and the sextet at 77 K, due to the presence of fine particles of iron containing component. Moessbauer studies of hydration products confirmed the formation of nanosize hydration products containing Fe 3+ . The isomer shift (δ) and the quadrupole splitting (ΔE Q ) values of C 4 AF in the cement confirmed iron in an octahedral and tetrahedral environment with +3 oxidation state. The high value of quadrupole splitting showed the high asymmetry of the electron environment around the iron atom. The overall mechanism of the hydration of cement in presence of BGP is discussed.

  11. 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

  12. 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.

  13. Phase equilibria with hydrate formation in H2O + CO2 mixtures modeled with reference equations of state

    Czech Academy of Sciences Publication Activity Database

    Jäger, A.; Vinš, Václav; Gernert, J.; Span, R.; Hrubý, Jan

    2013-01-01

    Roč. 338, Januar (2013), s. 100-113 ISSN 0378-3812 R&D Projects: GA ČR(CZ) GPP101/11/P046; GA ČR(CZ) GAP101/11/1593 Institutional support: RVO:61388998 Keywords : carbon dioxide * gas hydrate * modeling Subject RIV: BJ - Thermodynamics Impact factor: 2.241, year: 2013 http://www.sciencedirect.com/science/article/pii/S0378381212005158

  14. Manufacture of Methane Hydrate using Carbon Nano Tubes

    International Nuclear Information System (INIS)

    Park, Sung Seek

    2010-02-01

    . Therefore, it is found that NaCl acts as a inhibitor. Also, when the multi wall carbon nanotubes of 0.004 wt% was added to pure water, the amount of consumed gas was about 300% higher than that in pure water and the hydrate formation time decreased at the low subcooling temperature

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

    Science.gov (United States)

    Zhang, Zhengcai; Guo, Guang-Jun

    2017-07-26

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

  16. Late Glacial temperature and precipitation changes in the lowland Neotropics by tandem measurement of δ 18O in biogenic carbonate and gypsum hydration water

    Science.gov (United States)

    Hodell, David A.; Turchyn, Alexandra V.; Wiseman, Camilla J.; Escobar, Jaime; Curtis, Jason H.; Brenner, Mark; Gilli, Adrian; Mueller, Andreas D.; Anselmetti, Flavio; Ariztegui, Daniel; Brown, Erik T.

    2012-01-01

    We applied a new method to reconstruct paleotemperature in the tropics during the last deglaciation by measuring oxygen isotopes of co-occurring gypsum hydration water and biogenic carbonate in sediment cores from two lakes on the Yucatan Peninsula. Oxygen and hydrogen isotope values of interstitial and gypsum hydration water indicate that the crystallization water preserves the isotopic signal of the lake water, and has not undergone post-depositional isotopic exchange with sediment pore water. The estimated lake water δ18O is combined with carbonate δ18O to calculate paleotemperature. Three paired measurements of 1200-yr-old gypsum and gastropod aragonite from Lake Chichancanab, Mexico, yielded a mean temperature of 26 °C (range 23-29.5 °C), which is consistent with the mean and range of mean annual temperatures (MAT) in the region today. Paired measurements of ostracods, gastropods, and gypsum hydration water samples were measured in cores from Lake Petén Itzá, Guatemala, spanning the Late Glacial and early Holocene period (18.5-10.4 ka). The lowest recorded temperatures occurred at the start of Heinrich Stadial (HS) 1 at 18.5 ka. Inferred temperatures from benthic ostracods ranged from 16 to 20 °C during HS 1, which is 6-10 °C cooler than MAT in the region today, whereas temperatures derived from shallow-water gastropods were generally warmer (20-25 °C), reflecting epilimnetic temperatures. The derived temperatures support previous findings of greater tropical cooling on land in Central America during the Late Glacial than indicated by nearby marine records. Temperature increased in two steps during the last deglaciation. The first occurred during the Bolling-Allerod (B-A; from 14.7 to 13 ka) when temperature rose to 20-24 °C towards the end of this period. The second step occurred at 10.4 ka near the beginning of the Holocene when ostracod-inferred temperature rose to 26 °C, reflecting modern hypolimnetic temperature set during winter, whereas

  17. Isothermal martensite formation at sub-zero temperatures

    DEFF Research Database (Denmark)

    Stojko, Allan; Hansen, Mikkel Fougt; Slycke, Jan

    2012-01-01

    , quenched in oil, and thereafter investigated with vibrating sample magnetometry, which allows a quantitative assessment of the fraction of retained austenite as a function of the sub-zero temperature and time. Isothermal martensite formation was observed on interrupting the continuous cooling (5 K...... with a continuation of the martensitic transformation. On prolonged isothermal holding, a volume reduction was observed for AISI 52100, but not for AISI 1070. Copyright © 2011 by ASTM International....

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

    DEFF Research Database (Denmark)

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

    2017-01-01

    Formation of gas hydrates is a problem in the petroleum industry where the gas hydrates can cause blockage of the flowlines. Kinetic hydrate inhibitors (KHIs) are water-soluble polymers, sometimes used in combination synergistically or with non-polymeric synergists, that are used to prevent gas h...... are preferable in KHI polymers as long as they are water-soluble at hydrate-forming temperatures.......Formation of gas hydrates is a problem in the petroleum industry where the gas hydrates can cause blockage of the flowlines. Kinetic hydrate inhibitors (KHIs) are water-soluble polymers, sometimes used in combination synergistically or with non-polymeric synergists, that are used to prevent gas...... hydrate blockages. They have been used in the field successfully since 1995. In this paper, we present the first KHI results for the polymer, poly(3-methylene-2-pyrrolidone) (P(3M2P)), which is structurally similar to poly(N-vinylpyrrolidone) (PVP), one of the first KHIs to be discovered. 3M2P polymers...

  19. Experimental validation of kinetic inhibitor strength on natural gas hydrate nucleation

    DEFF Research Database (Denmark)

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

    2015-01-01

    The kinetics of natural gas hydrate formation in the presence of dissolved salts (NaCl) and crude oil ( a middle east crude with density 851.5 kg/m3 were investigated by using a standard rocking cell (RC-5) apparatus. The hydrate nucleation temperature was reduced in the presence of NaCl and oil...... management in oil and gas facilities. (C) 2014 Elsevier Ltd. All rights reserved....

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

    Science.gov (United States)

    White, M. D.

    2011-12-01

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

  1. Biofilm formation capacity of Salmonella serotypes at different temperature conditions

    Directory of Open Access Journals (Sweden)

    Karen A. Borges

    Full Text Available ABSTRACT: Salmonella spp. are one of the most important agents of foodborne disease in several countries, including Brazil. Poultry-derived products are the most common food products, including meat and eggs, involved in outbreaks of human salmonellosis. Salmonella has the capacity to form biofilms on both biotic and abiotic surfaces. The biofilm formation process depends on an interaction among bacterial cells, the attachment surface and environmental conditions. These structures favor bacterial survival in hostile environments, such as slaughterhouses and food processing plants. Biofilms are also a major problem for public health because breakage of these structures can cause the release of pathogenic microorganisms and, consequently, product contamination. The aim of this study was to determine the biofilm production capacity of Salmonella serotypes at four different temperatures of incubation. Salmonella strains belonging to 11 different serotypes, isolated from poultry or from food involved in salmonellosis outbreaks, were selected for this study. Biofilm formation was investigated under different temperature conditions (37°, 28°, 12° and 3°C using a microtiter plate assay. The tested temperatures are important for the Salmonella life cycle and to the poultry-products process. A total of 92.2% of the analyzed strains were able to produce biofilm on at least one of the tested temperatures. In the testing, 71.6% of the strains produced biofilm at 37°C, 63% at 28°C, 52.3% at 12°C and 39.5% at 3°C, regardless of the serotype. The results indicate that there is a strong influence of temperature on biofilm production, especially for some serotypes, such as S. Enteritidis, S. Hadar and S. Heidelberg. The production of these structures is partially associated with serotype. There were also significant differences within strains of the same serotype, indicating that biofilm production capacity may be strain-dependent.

  2. Gas hydrates in gas storage caverns; Gashydrate bei der Gaskavernenspeicherung

    Energy Technology Data Exchange (ETDEWEB)

    Groenefeld, P. [Kavernen Bau- und Betriebs-GmbH, Hannover (Germany)

    1997-12-31

    Given appropriate pressure and temperature conditions the storage of natural gas in salt caverns can lead to the formation of gas hydrates in the producing well or aboveground operating facilities. This is attributable to the stored gas becoming more or less saturated with water vapour. The present contribution describes the humidity, pressure, and temperature conditions conducive to gas hydrate formation. It also deals with the reduction of the gas removal capacity resulting from gas hydrate formation, and possible measures for preventing hydrate formation such as injection of glycol, the reduction of water vapour absorption from the cavern sump, and dewatering of the cavern sump. (MSK) [Deutsch] Bei der Speicherung von Erdgas in Salzkavernen kann es unter entsprechenden Druck- und Temperaturverhaeltnissen zur Gashydratbildung in den Foerdersonden oder obertaegigen Betriebseinrichtungen kommen, weil sich das eingelagerte Gas mehr oder weniger mit Wasserdampf aufsaettigt. Im Folgenden werden die Feuchtigkeits-, Druck- und Temperaturbedingungen, die zur Hydratbildung fuehren erlaeutert. Ebenso werden die Verringerung der Auslagerungskapazitaet durch die Hydratbildung, Massnahmen zur Verhinderung der Hydratbildung wie die Injektion von Glykol, die Verringerung der Wasserdampfaufnahme aus dem Kavernensumpf und die Entwaesserung der Kavernensumpfs selbst beschrieben.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

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

    Science.gov (United States)

    Collett, T.S.; Ladd, J.

    2000-01-01

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

  5. Formation of carbonate concretions in deep-sea sediment below the CCD and above an active gas hydrate system

    Science.gov (United States)

    Dicus, C. M.; Snyder, G. T.; Dickens, G. R.

    2004-12-01

    Site 1230 of the Ocean Drilling Program targeted the chemistry and microbiology of an active deep-water gas hydrate system in the Peru Trench. The site is noteworthy because, at nearly 6000 m water depth, it lies well below the carbonate compensation depth and the sediments comprise mostly terrigenous clays and biogenic silica. Shipboard work at this site delineated a prominent sulfate-methane transition (SMT) at 8-10 m below seafloor (mbsf) as well as some carbonate horizons. In this study, we present calcium and strontium data for pore waters and sediments at this site, including across the SMT. Concentration profiles show that dissolved Ca2+ diffuses downward from the seafloor toward the SMT, where a sharp inflection indicates consumption of Ca2+ into an authigenic phase. Dissolved Sr2+, on the other hand, diffuses upward from depth toward the SMT. Again, however, a prominent inflection suggests removal of Sr2+ to sediment. The inferences from pore water profiles are borne out by sediment chemistry. Large peaks in the calcium and strontium content of sediment mark the SMT. The calcium and strontium fronts reach ˜2700 and ˜5 mmol/kg, respectively, at 9 mbsf, which are much greater than average background values of ˜10 and ˜1 mmol/kg. These authigenic fronts are primarily composed of carbonate minerals, as determined by acetic acid extractions and x-ray diffraction. Because the calcium and strontium fronts coincide with both the SMT and changes in dissolved chemistry, it is proposed that the carbonates are currently forming as follows: methane rising from the underlying gas hydrate system reacts with dissolved sulfate through anaerobic oxidation of methane which releases HCO3- and alkalinity and causes carbonate precipitation. The overall process has been observed elsewhere; the Peru Trench is interesting, however, because the process leads to carbonate in sediments otherwise devoid of carbonate.

  6. Study on gas hydrate as a new energy resource in the 21th century

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Byeong-Jae; Kwak Young-Hoon; Kim, Won-Sik [Korea Institute of Geology Mining and Materials, Taejon (KR)] (and others)

    1999-12-01

    Natural gas hydrate, a special type of clathrate hydrates, is a metastable solid compound which mainly consists of methane and water, and generally called as gas hydrate. It is stable in the specific low-temperature/high-pressure conditions. Gas hydrates play an important role as major reservoir of methane on the earth. On the other hand, the formation and dissociation of gas hydrates could cause the plugging in pipeline, gas kick during production, atmospheric pollution and geohazard. To understand the formation and dissociation of the gas hydrate, the experimental equilibrium conditions of methane hydrate were measured in pure water, 3 wt.% NaCl and MgCl{sub 2} solutions. The equilibrium conditions of propane hydrates were also measured in pure water. The relationship between methane hydrate formation time and overpressure was also analyzed through the laboratory work. The geophysical surveys using air-gun system and multibeam echo sounder were implemented to develop exploration techniques and to evaluate the gas hydrate potential in the East Sea, Korea. General indicators of submarine gas hydrates on seismic data is commonly inferred from the BSR developed parallel to the see floor, amplitude blanking at the upper part of the BSR, and phase reversal and decrease of the interval velocity at BSR. The field data were processed using Geobit 2.9.5 developed by KIGAM to detect the gas hydrate indicators. The accurate velocity analysis was performed by XVA (X-window based Velocity Analysis). Processing results show that the strong reflector occurred parallel to the sea floor were shown at about 1800 ms two way travel time. The interval velocity decrease at this strong reflector and at the reflection phase reversal corresponding to the reflection at the sea floor. Gas hydrate stability field in the study area was determined using the data of measured hydrate equilibrium condition, hydrothermal gradient and geothermal gradient. The depth of BSR detected in the seismic

  7. 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

  8. Numerical studies of gas production from several CH4 hydrate zones at the Mallik site, Mackenzie Delta, Canada

    Science.gov (United States)

    Moridis, G.J.; Collett, T.S.; Dallimore, S.R.; Satoh, T.; Hancock, S.; Weatherill, B.

    2004-01-01

    The Mallik site represents an onshore permafrost-associated gas hydrate accumulation in the Mackenzie Delta, Northwest Territories, Canada. A 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 five methane hydrate-bearing zones at the Mallik site. In Zone #1, numerical simulations using the EOSHYDR2 model indicated that gas production from hydrates at the Mallik site was possible by depressurizing a thin free gas zone at the base of the hydrate stability field. Horizontal wells appeared to have a slight advantage over vertical wells, while multiwell systems involving a combination of depressurization and thermal stimulation offered superior performance, especially when a hot noncondensible gas was injected. Zone #2, which involved a gas hydrate layer with an underlying aquifer, could yield significant amounts of gas originating entirely from gas hydrates, the volumes of which increased with the production rate. However, large amounts of water were also produced. Zones #3, #4 and #5 were lithologically isolated gas hydrate-bearing deposits with no underlying zones of mobile gas or water. In these zones, thermal stimulation by circulating hot water in the well was used to induce dissociation. Sensitivity studies indicated that the methane release from the hydrate accumulations increased with the 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 specific heat of the rock and of the hydrate, and to the permeability of the formation. ?? 2004 Published by Elsevier B.V.

  9. Prediction of Austenite Formation Temperatures Using Artificial Neural Networks

    International Nuclear Information System (INIS)

    Schulze, P; Schmidl, E; Grund, T; Lampke, T

    2016-01-01

    For the modeling and design of heat treatments, in consideration of the development/ transformation of the microstructure, different material data depending on the chemical composition, the respective microstructure/phases and the temperature are necessary. Material data are, e.g. the thermal conductivity, heat capacity, thermal expansion and transformation data etc. The quality of thermal simulations strongly depends on the accuracy of the material data. For many materials, the required data - in particular for different microstructures and temperatures - are rare in the literature. In addition, a different chemical composition within the permitted limits of the considered steel alloy cannot be predicted. A solution for this problem is provided by the calculation of material data using Artificial Neural Networks (ANN). In the present study, the start and finish temperatures of the transformation from the bcc lattice to the fcc lattice structure of hypoeutectoid steels are calculated using an Artificial Neural Network. An appropriate database containing different transformation temperatures (austenite formation temperatures) to train the ANN is selected from the literature. In order to find a suitable feedforward network, the network topologies as well as the activation functions of the hidden layers are varied and subsequently evaluated in terms of the prediction accuracy. The transformation temperatures calculated by the ANN exhibit a very good compliance compared to the experimental data. The results show that the prediction performance is even higher compared to classical empirical equations such as Andrews or Brandis. Therefore, it can be assumed that the presented ANN is a convenient tool to distinguish between bcc and fcc phases in hypoeutectoid steels. (paper)

  10. Prediction of Austenite Formation Temperatures Using Artificial Neural Networks

    Science.gov (United States)

    Schulze, P.; Schmidl, E.; Grund, T.; Lampke, T.

    2016-03-01

    For the modeling and design of heat treatments, in consideration of the development/ transformation of the microstructure, different material data depending on the chemical composition, the respective microstructure/phases and the temperature are necessary. Material data are, e.g. the thermal conductivity, heat capacity, thermal expansion and transformation data etc. The quality of thermal simulations strongly depends on the accuracy of the material data. For many materials, the required data - in particular for different microstructures and temperatures - are rare in the literature. In addition, a different chemical composition within the permitted limits of the considered steel alloy cannot be predicted. A solution for this problem is provided by the calculation of material data using Artificial Neural Networks (ANN). In the present study, the start and finish temperatures of the transformation from the bcc lattice to the fcc lattice structure of hypoeutectoid steels are calculated using an Artificial Neural Network. An appropriate database containing different transformation temperatures (austenite formation temperatures) to train the ANN is selected from the literature. In order to find a suitable feedforward network, the network topologies as well as the activation functions of the hidden layers are varied and subsequently evaluated in terms of the prediction accuracy. The transformation temperatures calculated by the ANN exhibit a very good compliance compared to the experimental data. The results show that the prediction performance is even higher compared to classical empirical equations such as Andrews or Brandis. Therefore, it can be assumed that the presented ANN is a convenient tool to distinguish between bcc and fcc phases in hypoeutectoid steels.

  11. 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

  12. Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K.

    Science.gov (United States)

    Akhgarnusch, Amou; Tang, Wai Kit; Zhang, Han; Siu, Chi-Kit; Beyer, Martin K

    2016-09-14

    The recombination reactions of gas-phase hydrated electrons (H2O)n˙(-) with CO2 and O2, as well as the charge exchange reaction of CO2˙(-)(H2O)n with O2, were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry in the temperature range T = 80-300 K. Comparison of the rate constants with collision models shows that CO2 reacts with 50% collision efficiency, while O2 reacts considerably slower. Nanocalorimetry yields internally consistent results for the three reactions. Converted to room temperature condensed phase, this yields hydration enthalpies of CO2˙(-) and O2˙(-), ΔHhyd(CO2˙(-)) = -334 ± 44 kJ mol(-1) and ΔHhyd(O2˙(-)) = -404 ± 28 kJ mol(-1). Quantum chemical calculations show that the charge exchange reaction proceeds via a CO4˙(-) intermediate, which is consistent with a fully ergodic reaction and also with the small efficiency. Ab initio molecular dynamics simulations corroborate this picture and indicate that the CO4˙(-) intermediate has a lifetime significantly above the ps regime.

  13. The effect of temperature and time on the formation of amylose- lysophosphatidylcholine inclusion complexes

    NARCIS (Netherlands)

    Ahmadi-Abhari, S.; Woortman, A.J.J.; Oudhuis, A.A.C.M.; Hamer, R.J.; Loos, K.

    2014-01-01

    The formation of amylose inclusion complexes could help to decrease the susceptibility of starch granules against amylase digestion. We studied the formation of amyloselysophosphatidylcholine (LPC) inclusion complexes at temperatures at and below the gelatinization temperature of starch, using DSC,

  14. Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture Processes

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen

    A novel gas separation technique based on gas hydrate formation (solid precipitation) is investigated by means of thermodynamic modeling and experimental investigations. This process has previously been proposed for application in post-combustion carbon dioxide capture from power station flue gases...... formation may be performed at pressures of approximately 20 MPa and temperatures below 280 K. Thermodynamic promoters are needed, to reduce the pressure requirement of the process, thereby making it competitive to existing capture technologies. A literature study is presented focusing mainly...... on thermodynamic gas hydrate promotion by hydrate formers stabilising the classical gas clathrate hydrate structures (sI, sII and sH) at low to moderate pressures. Much literature is available on this subject. Both experimental and theoretical studies presented in the literature have pointed out cyclopentane...

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

    Science.gov (United States)

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

    2017-12-01

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

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

    Science.gov (United States)

    Sridhara, Prathyusha

    transport properties with change in pressure and temperature due to the presence of the simple CO2-hydrate and mixed hydrates (mainly CH4-CO2 hydrate and CH4 -CO2-N2 hydrate) in the porous geologic media. These simulations on CO2/ CH4-CO2 hydrate reservoirs provided a basic insight to formulate and interpret a novel technological approach. This approach aims at prediction of enhanced gas production profiles from Class 2 hydrate accumulations by utilizing CO2 sequestration. The approach also offers a possibility to permanently store CO 2 in the geologic formation to a greater extent compared to a direct injection of CO2 into gas hydrate sediments. The production technique implies a three-stage approach using one vertical well design. In Stage I, the CO2 is injected into the underlying aquifer. In Stage II, the well is shut in and injected CO2 is allowed to be converted into immobile CO2 hydrate. Finally, during Stage III, decomposition of CH4 hydrate is induced by the depressurization method. The gas production potential is estimated over 15 years. The results reveal that methane production is increased together with simultaneous reduction of concomitant water production rate comparing to a conventional Class 2 reservoir production.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  18. Temperature Effect on Micelle Formation: Molecular Thermodynamic Model Revisited.

    Science.gov (United States)

    Khoshnood, Atefeh; Lukanov, Boris; Firoozabadi, Abbas

    2016-03-08

    Temperature affects the aggregation of macromolecules such as surfactants, polymers, and proteins in aqueous solutions. The effect on the critical micelle concentration (CMC) is often nonmonotonic. In this work, the effect of temperature on the micellization of ionic and nonionic surfactants in aqueous solutions is studied using a molecular thermodynamic model. Previous studies based on this technique have predicted monotonic behavior for ionic surfactants. Our investigation shows that the choice of tail transfer energy to describe the hydrophobic effect between the surfactant tails and the polar solvent molecules plays a key role in the predicted CMC. We modify the tail transfer energy by taking into account the effect of the surfactant head on the neighboring methylene group. The modification improves the description of the CMC and the predicted micellar size for aqueous solutions of sodium n-alkyl sulfate, dodecyl trimethylammonium bromide (DTAB), and n-alkyl polyoxyethylene. The new tail transfer energy describes the nonmonotonic behavior of CMC versus temperature. In the DTAB-water system, we redefine the head size by including the methylene group, next to the nitrogen, in the head. The change in the head size along with our modified tail transfer energy improves the CMC and aggregation size prediction significantly. Tail transfer is a dominant energy contribution in micellar and microemulsion systems. It also promotes the adsorption of surfactants at fluid-fluid interfaces and affects the formation of adsorbed layer at fluid-solid interfaces. Our proposed modifications have direct applications in the thermodynamic modeling of the effect of temperature on molecular aggregation, both in the bulk and at the interfaces.

  19. 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.

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

    Science.gov (United States)

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

    2013-12-01

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

  1. 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

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

    Science.gov (United States)

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

    2006-01-01

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

  3. Methods and compositions for treating low temperature subterranean well formations

    Energy Technology Data Exchange (ETDEWEB)

    Chatterji, J.

    1979-08-21

    An aqueous composition is described for treating subterranean formations having temperatures of up to 120 F. The aqueous composition consists of water, a water-soluble organic gelling agent, an oxidizing agent to supply free radicals, and a reducing agent to accelerate the generation of free radicals. Reducing agents are water-soluble metal salts of the halides, sulfates, nitrates or mixtures thereof. Oxidizing agents are water-soluble peroxides, persulfates or mixtures thereof. Gelling agents may be sodium polyacrylate, polyacrylic acid, polysodium-2-acrylamide-3-propylsulfonate polyacrylamides or polymetharylamides that have been hydrolyzed from 0 to 70% and neturalized with ammonium or alkali metal hydroxides; or gums such as guar, locust bean, taaga tragacanth, hydroxyethyl guar, hydroxy-propyl guar, carboxymethyl guar or mixtures thereof. 22 claims.

  4. Hydrogen bond basicity of ionic liquids and molar entropy of hydration of salts as major descriptors in the formation of aqueous biphasic systems.

    Science.gov (United States)

    Passos, Helena; Dinis, Teresa B V; Cláudio, Ana Filipa M; Freire, Mara G; Coutinho, João A P

    2018-05-23

    Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and conventional salts have been largely investigated and successfully used in separation processes, for which the determination of the corresponding ternary phase diagrams is a prerequisite. However, due the large number of ILs that can be prepared and their high structural versatility, it is impossible to experimentally cover and characterize all possible combinations of ILs and salts that may form ABS. The development of tools for the prediction and design of IL-based ABS is thus a crucial requirement. Based on a large compilation of experimental data, a correlation describing the formation of IL-based ABS is shown here, based on the hydrogen-bonding interaction energies of ILs (EHB) obtained by the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) and the molar entropy of hydration of the salt ions. The ability of the proposed model to predict the formation of novel IL-based ABS is further ascertained.

  5. Hydrate-based technology for CO2 capture from fossil fuel power plants

    International Nuclear Information System (INIS)

    Yang, Mingjun; Song, Yongchen; Jiang, Lanlan; Zhao, Yuechao; Ruan, Xuke; Zhang, Yi; Wang, Shanrong

    2014-01-01

    Graphical abstract: Application of hydrate based technology on carbon dioxide capture and storage (CCS). - Highlights: • Hydrate-based CO 2 –N 2 separation data was obtained for flow in porous media. • Tetrahydrofuran and sodium dodecyl sulphate are used as additives simultaneously. • Solution movement rarely occurs when residual solution saturations are low. • Bothe of pressure and temperature have remarkable impacts on gas compositions. • A suitable operation parameter choice is proposed for hydrate-based CO 2 capture. - Abstract: Hydrate-based CO 2 capture is a promising technology. To obtain fundamental data for a flowing system, we measured the distribution of pore solution to analyse hydrate formation/dissociation and gas separation properties. An orthogonal experiment was carried out to investigate the effects of glass beads, flow rates, pressures and temperatures on it. Magnetic resonance imaging (MRI) images were obtained using a spin echo multi-slice pulse sequence. Hydrate saturations were calculated quantitatively using an MRI mean intensity. The results show that hydrate blockages were frequently present. During the hydrate formation and dissociation process, the movement of the solution occurred in cycles. However, the solution movement rarely occurred for residual solution saturations obtained with a high backpressure. The solution concentrate phenomenon occurred mostly in BZ-04. The highest hydrate saturation was 30.2%, and the lowest was 0.70%. Unlike that in BZ-01, there was no stability present in BZ-02 and BZ-04. The different CO 2 concentrations for the three processes of each cycle verified hydrate formation during the gas flow process. The highest CO 2 concentration was 38.8%, and the lowest one was 11.4%. To obtain high hydrate saturation and good separation effects, the values of 5.00 MPa, 1.0 ml min −1 and 280.00 K were chosen. For the gas flow process, only the pressure had a significant impact on gas composition, and all

  6. Formation of bainite below the MS temperature: Kinetics and crystallography

    International Nuclear Information System (INIS)

    Samanta, Santigopal; Biswas, Pinaki; Giri, Sushil; Singh, Shiv Brat; Kundu, Saurabh

    2016-01-01

    Isothermal transformation below the M S temperature has been reported quite some time ago and has been confirmed in the present work. The nature of the transformation product and the mechanism of the transformation have been debated in literature. It has been inferred using existing models of isothermal martensite transformation that the product forming below M S cannot be martensite. The product has been identified as bainite. It has further been shown that the diffusion-controlled growth rate of bainite at such a low temperature is too slow to explain the observed transformation kinetics. On the other hand, the kinetics of isothermal transformation below M S has been shown to be consistent with the model based on the formation of bainite by displacive mechanism. Detailed analysis of crystallographic features of mixed martensite and bainite microstructure was done using electron backscatter diffraction (EBSD) and mathematical modelling. It has been shown that the crystallographic features of martensite and the bainite formed below M S are exactly the same; these include orientation relationship, habit planes, displacement directions and the shape deformation. It has also been shown that bainite poles can get shifted due to plastic accommodation of austenite caused by martensite laths. The shift was predicted accurately using crystal plasticity and theory of variant selection. All these results lead to the conclusion that bainite forms by a displacive mechanism of transformation.

  7. Mechanisms of detonation formation due to a temperature gradient

    Science.gov (United States)

    Kapila, A. K.; Schwendeman, D. W.; Quirk, J. J.; Hawa, T.

    2002-12-01

    Emergence of a detonation in a homogeneous, exothermically reacting medium can be deemed to occur in two phases. The first phase processes the medium so as to create conditions ripe for the onset of detonation. The actual events leading up to preconditioning may vary from one experiment to the next, but typically, at the end of this stage the medium is hot and in a state of nonuniformity. The second phase consists of the actual formation of the detonation wave via chemico-gasdynamic interactions. This paper considers an idealized medium with simple, rate-sensitive kinetics for which the preconditioned state is modelled as one with an initially prescribed linear gradient of temperature. Accurate and well-resolved numerical computations are carrried out to determine the mode of detonation formation as a function of the size of the initial gradient. For shallow gradients, the result is a decelerating supersonic reaction wave, a weak detonation, whose trajectory is dictated by the initial temperature profile, with only weak intervention from hydrodynamics. If the domain is long enough, or the gradient less shallow, the wave slows down to the Chapman-Jouguet speed and undergoes a swift transition to the ZND structure. For sharp gradients, gasdynamic nonlinearity plays a much stronger role. Now the path to detonation is through an accelerating pulse that runs ahead of the reaction wave and rearranges the induction-time distribution there to one that bears little resemblance to that corresponding to the initial temperature gradient. The pulse amplifies and steepens, transforming itself into a complex consisting of a lead shock, an induction zone, and a following fast deflagration. As the pulse advances, its three constituent entities attain progressively higher levels of mutual coherence, to emerge as a ZND detonation. For initial gradients that are intermediate in size, aspects of both the extreme scenarios appear in the path to detonation. The novel aspect of this study

  8. Experimental preparation of Kr/Xe hydrate at pressures up to 160 bar

    International Nuclear Information System (INIS)

    Simonis, R.

    1985-06-01

    A compound called gas (mixture) hydrate is formed under pressurized atmosphere by reaction of krypton, xenon and a mixture of both with water. The study under review reports on preparing such hydrates experimentally under pressures up to 160 bar. The dissociation function of the hydrates is determined by low and medium-pressure experiments. Observing the formation process it was found that a hydrate layer is formed at the interface of gas and water, its separating effect almost inhibiting continuance of hydrate reactions. Strong stirring will avoid or destroy the separating layer. It is shown that at pressures above 50 bar the dissociation function psub(D) (T) gets non-linear with logarithmic pressure plotting above the absolute, reciprocal temperature. The medium-temperature experiments show that the density of the gas consisting of Xe or Kr and Xe, respectively, reaches higher values than that of the water. In this case, the system collapses and the gas is found at the bottom of the pressure flask, and the water in the top region. The gas samples taken during the mixed hydrate preparation show that Kr is accumulated in the gaseous phase, and Xe in the hydrate phase. (orig./RB) [de

  9. 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

  10. 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.

  11. 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.

  12. Effect of carbonization temperatures on biochar formation of bamboo leaves

    Science.gov (United States)

    Pattnaik, D.; Kumar, S.; Bhuyan, S. K.; Mishra, S. C.

    2018-03-01

    Bamboo is a typical plant native in Asia, been used in many sectors, which also produces a large volume of leaves which goes waste and not find its application for any useful purposes; is often considered as a bio-waste and normally incinerated or dumped; as its applications are not yet fully explored. However, some research work done on bamboo fibers for use as a reinforcement in making polymer matrix composite. In the present piece of research work, the influence of burning/carbonization of bamboo leaves (at different temperatures) have been studied and characterized. Proximate analysis gave the fixed carbon content (of ~nearly21%). X-Ray diffraction results revealed the presence of various phases viz. cristobalite (SiO2), Calcite (Ca2O3) etc. accompanied with changes in crystal structures. Fourier transform infrared spectroscopy results showed various modes of vibrations viz. O-H stretching bending of other bonds; (for aromatic benzene derivatives) etc. Scanning Electron Microscopic observation (of morphology) showed irregular stacking arrangements between the randomly spaced lamellae structure, with variation in carbonizing temperature. Results revealed the advantages of pyrolysis process in biochar production/formation. It appears that, the bamboo biochar can have suitable properties for its use as an alternative energy source and also for agricultural applications. Its high porosity and carbon content suggest its application as activated carbon also; after physical or chemical treatments. The present research focuses on extending the frontiers of use of bamboo leaves from being an unutilized biowaste to its conversion into a value added product, which can be compassed in terms of sustainable applications.

  13. 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

  14. Dynamics of Permafrost Associated Methane Hydrate in Response to Climate Change

    Science.gov (United States)

    You, K.; Flemings, P. B.

    2014-12-01

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

  15. Temperature dependence of the hydrated electron's excited-state relaxation. I. Simulation predictions of resonance Raman and pump-probe transient absorption spectra of cavity and non-cavity models

    Science.gov (United States)

    Zho, Chen-Chen; Farr, Erik P.; Glover, William J.; Schwartz, Benjamin J.

    2017-08-01

    We use one-electron non-adiabatic mixed quantum/classical simulations to explore the temperature dependence of both the ground-state structure and the excited-state relaxation dynamics of the hydrated electron. We compare the results for both the traditional cavity picture and a more recent non-cavity model of the hydrated electron and make definite predictions for distinguishing between the different possible structural models in future experiments. We find that the traditional cavity model shows no temperature-dependent change in structure at constant density, leading to a predicted resonance Raman spectrum that is essentially temperature-independent. In contrast, the non-cavity model predicts a blue-shift in the hydrated electron's resonance Raman O-H stretch with increasing temperature. The lack of a temperature-dependent ground-state structural change of the cavity model also leads to a prediction of little change with temperature of both the excited-state lifetime and hot ground-state cooling time of the hydrated electron following photoexcitation. This is in sharp contrast to the predictions of the non-cavity model, where both the excited-state lifetime and hot ground-state cooling time are expected to decrease significantly with increasing temperature. These simulation-based predictions should be directly testable by the results of future time-resolved photoelectron spectroscopy experiments. Finally, the temperature-dependent differences in predicted excited-state lifetime and hot ground-state cooling time of the two models also lead to different predicted pump-probe transient absorption spectroscopy of the hydrated electron as a function of temperature. We perform such experiments and describe them in Paper II [E. P. Farr et al., J. Chem. Phys. 147, 074504 (2017)], and find changes in the excited-state lifetime and hot ground-state cooling time with temperature that match well with the predictions of the non-cavity model. In particular, the experiments

  16. Integrating Natural Gas Hydrates in the Global Carbon Cycle

    Energy Technology Data Exchange (ETDEWEB)

    David Archer; Bruce Buffett

    2011-12-31

    We produced a two-dimensional geological time- and basin-scale model of the sedimentary margin in passive and active settings, for the simulation of the deep sedimentary methane cycle including hydrate formation. Simulation of geochemical data required development of parameterizations for bubble transport in the sediment column, and for the impact of the heterogeneity in the sediment pore fluid flow field, which represent new directions in modeling methane hydrates. The model is somewhat less sensitive to changes in ocean temperature than our previous 1-D model, due to the different methane transport mechanisms in the two codes (pore fluid flow vs. bubble migration). The model is very sensitive to reasonable changes in organic carbon deposition through geologic time, and to details of how the bubbles migrate, in particular how efficiently they are trapped as they rise through undersaturated or oxidizing chemical conditions and the hydrate stability zone. The active margin configuration reproduces the elevated hydrate saturations observed in accretionary wedges such as the Cascadia Margin, but predicts a decrease in the methane inventory per meter of coastline relative to a comparable passive margin case, and a decrease in the hydrate inventory with an increase in the plate subduction rate.

  17. [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.

  18. Impact of CO{sub 2} hydrates on ocean carbon dioxide deposition options

    Energy Technology Data Exchange (ETDEWEB)

    Lund, P C

    1995-04-01

    The objective of the research project described in this report was to contribute to the research on greenhouse gases and the global environment. The focus is on the concept of storing large amounts of CO{sub 2} in the ocean. The project was divided into three subtasks: (1) a comprehensive study of the thermodynamic, physical and chemical properties of the seawater/CO{sub 2}/hydrate system, (2) establishment of a micro-scale kinetic model for CO{sub 2} hydrate formation and stability, based on (1), and (3) establishment of macro-scale models for various ocean deposition options based on (2). A database of selected thermodynamic functions has been set up. A large database of oceanic data has also been made; for any given coordinates at sea a computer program provides the temperature, salinity and oxygen profiles from the sea surface to the sea floor. The kinetic model predicts the formation and pseudo-stability of a very thin hydrate film which acts as an inhibitor for diffusion of CO{sub 2} into the sea water. The model predicts that the hydrate film reduces the overall flux from a liquid CO{sub 2} source with about 90%. Thermodynamically, pure CO{sub 2} in contact with water might form hydrates at depths below about 400 m, which would indicate that hydrate formation could play a role for all ocean CO{sub 2} deposition options. However, this study shows that other mechanisms significantly reduce the role of hydrate formation. It is finally concluded that although more modelling and experimental work is required within this field of research, the hydrate film may play an important role for all options except from shallow water injection. 86 refs., 32 figs., 16 tabs.

  19. Preparation of americium metal of high purity and determination of the heat of formation of the hydrated trivalent americium ion

    International Nuclear Information System (INIS)

    Spirlet, J.C.

    1975-10-01

    In order to redetermine some physical and chemical properties of americium metal, several grams of Am-241 have been prepared by two independent methods: lanthanum reduction of the oxide and thermal dissociation of the intermetallic compound Pt 5 Am. After its separation from excess lanthanum or alloy constituent by evaporation, americium metal was further purified by sublimation at 1100 deg C and 10 -6 Torr. Irrespective of the method of preparation, the americium samples displayed the same d.h.c.p. crystal structure. As determined by vacuum hot extraction, the oxygen, nitrogen and hydrogen contents are equal to or smaller than 250, 50 and 20 ppm, respectively. The heats of solution of americium metal (d.c.h.p. structure) in aqueous hydrochloric acid solutions have been measured at 298.15+-0.05K. The standard enthalpy of formation of Am 3+ (aq) is obtained as -616.7+-1.2 kJ mol -1 [fr

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-07-01

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

  1. The temperature of intracellular ice formation in mouse oocytes vs. the unfrozen fraction at that temperature.

    Science.gov (United States)

    Mazur, Peter; Pinn, Irina L; Kleinhans, F W

    2007-04-01

    We have previously reported [Cryobiology 51 (2005) 29-53] that intracellular ice formation (IIF) in mouse oocytes suspended in various concentrations of glycerol and ethylene glycol (EG) occurs at temperatures where the percentage of unfrozen water is about 6% and 12%, respectively, even though the IIF temperatures varied from -14 to -41 degrees C. However, because of the way the solutions were prepared, the concentrations of salt and glycerol or EG in that unfrozen fraction at IIF were also rather tightly grouped. The experiments reported in the present paper were designed to separate the effects of the unfrozen fraction at IIF from that of the solute concentration in the unfrozen fraction. This separation makes use of two facts. One is that the concentration of solutes in the residual liquid at a given subzero temperature is fixed regardless of their concentration in the initial unfrozen solution. However, second, the fraction unfrozen at a given temperature is dependent on the initial solute concentration. Experimentally, oocytes were suspended in solutions of glycerol/buffered saline and EG/buffered saline of varying total solute concentration with the restriction that the mass ratios of glycerol and EG to salts are held constant. The oocytes were then cooled rapidly enough (20 degrees C/min) to avoid significant osmotic shrinkage, and the temperature at which IIF occurred was noted. When this is done, we find, as previously that the fraction of water remaining unfrozen at the temperature of IIF remains nearly constant at 5-8% for both glycerol and EG even though the IIF temperatures vary from -14 to -50 degrees C. But unlike the previous results, the salt and CPA concentrations in the unfrozen fraction vary by a factor of three. The present procedure for preparing the solutions produces a potentially complicating factor; namely, the cell volumes vary substantially prior to freezing: substantially greater than isotonic in some solutions; substantially smaller

  2. Free energy of hydration of niobium oxide

    International Nuclear Information System (INIS)

    Plodinec, M.J.

    1996-01-01

    Some of the glasses being formulated by SRTC researchers contain niobium oxide. In this report, the free energy of hydration of the oxide is calculated from the free energies of formation of the oxide, the hydroxide, and water. This value can be used in calculations of the free energy of hydration of glasses containing niobium

  3. A study of liposome formation using a solution (isoperibol) calorimeter.

    Science.gov (United States)

    Barriocanal, L; Taylor, K M G; Buckton, G

    2004-12-09

    A solution (isoperibol) calorimeter has been employed to study the process of formation of phospholipid vesicles from natural and synthetic phospholipid films. Phospholipid films were hydrated in the solution calorimeter at temperatures exceeding the main phospholipid phase transition temperature, with continuous agitation to ensure conversion of the hydrating bilayers into multilamellar liposomes. It was seen that retention of chloroform in phospholipid films altered the apparent enthalpy change of vesicle formation to a far greater extent than would be expected from the contribution of the enthalpy of solution of chloroform; this indicates that chloroform alters the hydration process of the lipid. The overall measured enthalpy change for the formation of egg phosphatidylcholine vesicles was exothermic, whilst that for dimyristoylphosphatidylcholine was endothermic. This difference, it is suggested, results from the influence of the hydrocarbon chains mostly on the hydration process and also on the process of vesicle formation.

  4. Tracking all-vapor instant gas-hydrate formation and guest molecule populations: A possible probe for molecules trapped in water nanodroplets

    Czech Academy of Sciences Publication Activity Database

    Uras-Aytemiz, N.; Cwiklik, Lukasz; Devlin, J. P.

    2012-01-01

    Roč. 137, č. 20 (2012), s. 204501 ISSN 0021-9606 Institutional support: RVO:61388955 Keywords : Fourier transform infrared emission spectra * clathrate hydrate * simulations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.164, year: 2012

  5. CO2 capture by gas hydrate crystallization: Application on the CO2-N2 mixture

    International Nuclear Information System (INIS)

    Bouchemoua, A.

    2012-01-01

    CO 2 capture and sequestration represent a major industrial and scientific challenge of this century. There are different methods of CO 2 separation and capture, such as solid adsorption, amines adsorption and cryogenic fractionation. Although these processes are well developed at industrial level, they are energy intensive. Hydrate formation method is a less energy intensive and has an interesting potential to separate carbon dioxide. Gas hydrates are Document crystalline compounds that consist of hydrogen bonded network of water molecules trapping a gas molecule. Gas hydrate formation is favored by high pressure and low temperature. This study was conducted as a part of the SECOHYA ANR Project. The objective is to study the thermodynamic and kinetic conditions of the process to capture CO 2 by gas hydrate crystallization. Firstly, we developed an experimental apparatus to carry out experiments to determine the thermodynamic and kinetic formation conditions of CO 2 -N 2 gas hydrate mixture in water as liquid phase. We showed that the operative pressure may be very important and the temperature very low. For the feasibility of the project, we used TBAB (Tetrabutylammonium Bromide) as thermodynamic additive in the liquid phase. The use of TBAB may reduce considerably the operative pressure. In the second part of this study, we presented a thermodynamic model, based on the van der Waals and Platteeuw model. This model allows the estimation of thermodynamic equilibrium conditions. Experimental equilibrium data of CO 2 -CH 4 and CO 2 -N 2 mixtures are presented and compared to theoretical results. (author)

  6. 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.

  7. Hydration structure and dynamics of a hydroxide ion in water clusters of varying size and temperature: Quantum chemical and ab initio molecular dynamics studies

    International Nuclear Information System (INIS)

    Bankura, Arindam; Chandra, Amalendu

    2012-01-01

    Highlights: ► A theoretical study of hydroxide ion-water clusters is carried for varying cluster size and temperature. ► The structures of OH − (H 2 O) n are found out through quantum chemical calculations for n = 4, 8, 16 and 20. ► The finite temperature behavior of the clusters is studied through ab initio dynamical simulations. ► The spectral features of OH modes (deuterated) and their dependence on hydrogen bonding states of water are discussed. ► The mechanism and kinetics of proton transfer processes in these anionic clusters are also investigated. - Abstract: We have investigated the hydration structure and dynamics of OH − (H 2 O) n clusters (n = 4, 8, 16 and 20) by means of quantum chemical and ab initio molecular dynamics calculations. Quantum chemical calculations reveal that the solvation structure of the hydroxide ion transforms from three and four-coordinated surface states to five-coordinated interior state with increase in cluster size. Several other isomeric structures with energies not very different from the most stable isomer are also found. Ab initio simulations show that the most probable configurations at higher temperatures need not be the lowest energy isomeric structure. The rates of proton transfer in these clusters are found to be slower than that in bulk water. The vibrational spectral calculations reveal distinct features for free OH (deuterated) stretch modes of water in different hydrogen bonding states. Effects of temperature on the structural and dynamical properties are also investigated for the largest cluster considered here.

  8. 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

  9. Formation and early hydration characteristics of C2.75B1.25A3$ in binary system of C2.75B1.25A3$-C2S

    Directory of Open Access Journals (Sweden)

    Wang, Shoude

    2016-09-01

    Full Text Available C2.75B1.25A3$ (2.75CaO•1.25BaO• 3Al2O3• SO3 is one of the important minerals and it govern-directly the early-strength of belite-barium calcium sulphoaluminate cement. In this paper a binary system C2.75B1.25A3$-C2S is selected to investigate the formation of C2.75B1.25A3$. In the range of 1100 °C–1200 °C, the earlier formed C2S hinders the formation of C2.75B1.25A3$. On the contrary, when the temperature is in the range of 1200 °C–1350 °C, the initially formed C2S could provide a surface for the nucleation of C2.75B1.25A3$ and cut down the potential barrier (?Gk* for the heterogeneous nucleation of C2.75B1.25A3$, which contributes to its formation. Moreover, at 1350 °C, the large amount of previously formed C2S benefits the extent of formation of C2.75B1.25A3$. The possible reason was that it could prevent sulfur evaporation. In early hydration age, AFm and AFt originating from C2.75B1.25A3$ hydration are found within 2 h and 12 h under 95% RH at 1 °C, respectively, whereas C2S is unhydrated at this moment.En el cemento de sulfoaluminato de calcio y bario, el C2.75B1.25A3$ (2.75CaO•1.25BaO• 3Al2 O3• SO3 es una de las principales fases, y regula directamente la resistencia inicial del cemento. En este trabajo, se ha seleccionado el sistema binario C2.75B1.25A3$-C2S para investigar la formación de C2.75B1.25A3$. En el rango de 1100 °C-1200 °C, el C2S formado anteriormente impide la formación de C2.75B1.25A3$, mientras que cuando la temperatura está entre 1200 °C-1350 °C, el C2S proporcionaría una superficie de nucleación de C2.75B1.25A3$ reduciendo la barrera de potencial (?Gk* para la nucleación heterogénea de C2.75B1.25A3$, lo que contribuye a su formación. Además, a 1350 °C, la gran cantidad de C2S formado beneficia la formación de C2.75B1.25A3$, ya que podía prevenir la evaporación del azufre. En las primeras etapas de la hidratación (entre 2 y 12h y 95% HR a 1 ºC se pueden encontrar AFM y AFt

  10. 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.)

  11. 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)

  12. Kinetics of the reaction of hydrated lime with SO{sub 2} at low temperatures: effects of the presence of CO{sub 2}, O{sub 2}, and NOx

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C.F.; Shih, S.M. [National Taiwan University, Taipei (Taiwan). Dept. of Chemical Engineering

    2008-12-15

    The effects of the presence Of CO{sub 2}, O{sub 2}, and NOx in the flue gas on the kinetics of the sulfation of hydrated lime at low temperatures were studied using a differential fixed-bed reactor. When O{sub 2} and NOx were not present together the reaction kinetics was about the same as that under gas mixtures containing SO{sub 2}, H{sub 2}O, and N2 only. When both O{sub 2} and NOx were present, sulfation of hydrated lime was greatly enhanced, forming a large amount of calcium sulfate in addition to calcium sulfite. Sulfation of hydrated lime was well described by the surface coverage model, despite the gas-phase conditions being different. Relative humidity is the major factor affecting the reaction, and its effect was more marked when both O{sub 2} and NOx were present. The kinetic model equations obtained in this work can be used to describe the sulfation of hydrated lime in the low-temperature dry and semidry flue gas desulfurization processes with or without an upstream NOx removal unit.

  13. 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.

  14. 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.

  15. 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)

  16. Stability Zone of Natural Gas Hydrates in a Permafrost-Bearing Region of the Beaufort-Mackenzie Basin: Study of a Feasible Energy Source (Geological Survey of Canada Contribution No.1999275)

    International Nuclear Information System (INIS)

    Majorowicz, J. A.; Hannigan, P. K.

    2000-01-01

    Analysis of geological and geophysical data from 150 wells in the Beaufort-Mackenzie region(study area between 68 deg. 30'-70 deg. 00'N and 131 deg. -39 deg. W) led to reinterpretation of the depth of methane hydrate stability and construction of the first contour maps displaying thickness of hydrate stability zones as well as hydrate stability zone thicknesses below permafrost. Calculations were based on construction of temperature-depth profiles incorporating regional heat-flow values, temperature at the base of ice-bearing permafrost, and models relating thermal conductivity with depth. Data analysis indicates the presence and extent of the methane hydrate stability zone is related mainly to the history of permafrost development and less so by the relatively small regional variations of temperature gradients. Analysis of well logs and other indicators in conjunction with knowledge of the hydrate stability zone allows reevaluation of the location of possible gas hydrate occurrences. Log analysis indicates that in the onshore and shallow sea area of the Beaufort-Mackenzie Basin, methane hydrate occurs in 27 wells. Fifteen of these locations coincides with underlying conventional hydrocarbon occurrences. Previous analyses place some of the hydrate occurrences at greater depths than proposed for the methane hydrate stability zone described in this study. Interpretation of geological cross sections reveals that hydrates are related mainly to sandy deltaic and delta-plain deposits in Iperk, Kugmallit, and Reindeer sequences although additional hydrate picks have been inferred in other sequences, such as Richards. Overlying permafrost may act as seal for hydrate accumulations; however, the thickness of permafrost and its related hydrate stability zone fluctuated during geological time. It is interpreted that only in the last tens of thousand of years (i.e., Sangamonian to Holocene), conditions for hydrates changed from nonstable to stable. During Early and Late

  17. The effect of temperature and time on the formation of amylose- lysophosphatidylcholine inclusion complexes

    NARCIS (Netherlands)

    Ahmadiabhari, Salomeh; Woortman, Albert J. J.; Oudhuis, A. A. C. M. (Lizette); Hamer, Rob J.; Loos, Katja

    The formation of amylose inclusion complexes could help to decrease the susceptibility of starch granules against amylase digestion. We studied the formation of amylose-lysophosphatidylcholine (LPC) inclusion complexes at temperatures at and below the gelatinization temperature of starch, using DSC,

  18. The effect of temperature and time on the formation of amylose–lysophosphatidylcholine inclusion complexes

    NARCIS (Netherlands)

    Ahmadi-Abhari, S.; Woortman, A.J.J.; Oudhuis, A.A.C.M.; Hamer, R.J.; Loos, K.

    2014-01-01

    The formation of amylose inclusion complexes could help to decrease the susceptibility of starch granules against amylase digestion. We studied the formation of amylose–lysophosphatidylcholine (LPC) inclusion complexes at temperatures at and below the gelatinization temperature of starch, using DSC,

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

    Digital Repository Service at National Institute of Oceanography (India)

    Karisiddaiah, S.M.

    formations, while Dr. L. Stern presented ne insights into the phenomena of anomalous or self- preservation of gas hydrates. JOUR.GEOL.SOC.INDIA, VOL.61, JAN. 2001 Posters on hydrate formation and prevention in pipelines and hydrate based...-1 REPORT ON THE 4TH INTERNATIONAL CONFERENCE ON GAS HYDRATES The fourth International Conference on Gas Hydrates was recently held at Yokohama, Japan, between 19-23 May 2002 following the earlier conferences held in USA (1993...

  20. 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

  1. Influence of temperature on the formation and encapsulation of gold nanoparticles using a temperature-sensitive template

    Directory of Open Access Journals (Sweden)

    Noel Peter Bengzon Tan

    2015-12-01

    Full Text Available This data article describes the synthesis of temperature-sensitive and amine-rich microgel particle as a dual reductant and template to generate smart gold/polymer nanocomposite particle. TEM images illustrate the influence of reaction temperature on the formation and in-site encapsulation of gold nanoparticles using the temperature-sensitive microgel template. Thermal stability of the resultant gold/polymer composite particles was also examined.

  2. 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)

  3. Positronium formation at low temperatures: The role of trapped electrons

    DEFF Research Database (Denmark)

    Hirade, T.; Maurer, F.H.J.; Eldrup, Morten Mostgaard

    2000-01-01

    Measurements have been carried out of electron spin densities (by electron spin resonance technique) and positronium (Ps) formation probability as functions of Co-60 gamma-irradiation dose in poly(methyl methacrylate) and linear poly(ethylene) at 77 K. We observe a linear relationship between...

  4. A Computationally Efficient Equation of State for Ternary Gas Hydrate Systems

    Science.gov (United States)

    White, M. D.

    2012-12-01

    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 phase transitions. The phase equilibria for the ternary gas hydrate system within the gas hydrate stability range of composition, temperature and pressure, includes regions where the gas hydrate is in equilibrium with gas, nonaqueous liquid, or mixtures of gas and nonaqeuous liquid near the CO2-CH4-N2 mixture critical point. In these regions, solutions to cubic equations of state can be nonconvergent without accurate initial guesses. A hybrid tabular-cubic equation of state is described which avoids convergence issues, but conserves the characteristics and advantages of the cubic equation of state approaches to phase equilibria calculations. The application of interest will be the production of a natural gas hydrate deposit from a geologic formation, using the guest molecule exchange process; where, a mixture of CO2 and N2 are injected into the formation. During the guest-molecule exchange, CO2 and N2 will predominately replace CH4 in the large and small cages of the sI structure, respectively.

  5. Effects of obesity on body temperature in otherwise-healthy females when controlling hydration and heat production during exercise in the heat.

    Science.gov (United States)

    Adams, J D; Ganio, Matthew S; Burchfield, Jenna M; Matthews, Andy C; Werner, Rachel N; Chokbengboun, Amanda J; Dougherty, Erin K; LaChance, Alex A

    2015-01-01

    Previous studies investigating body temperature responses in obese individuals during exercise in the heat fail to control metabolic heat production or hydration status during exercise. To determine if there are differences in body temperature responses between obese and non-obese females when controlling metabolic heat production during exercise. Twenty healthy females, ten obese (43.5 ± 4.5 % fat, 77.5 ± 14.4 kg) and ten non-obese (26.3 ± 6.2 % fat, 53.7 ± 6.4 kg), cycled for 60 min in a warm environment (40 °C, 30 % humidity) at a work load that elicited either 300 W of metabolic heat production (fixed heat production; FHP) or 175 W/m(2) of skin surface area (body surface area, BSA). Before and during exercise, rectal temperature (T re), mean skin temperature (T sk), oxygen uptake (VO2), and sweat rate were measured. Fluid was provided throughout exercise so that euhydration was maintained throughout. In the FHP trial, when absolute heat production was similar between obese (287 ± 15 W) and non-obese (295 ± 18 W) individuals (P > 0.05), there were no differences at the end of exercise in T re (38.26 ± 0.40 vs. 38.30 ± 0.30 °C, respectively) or T sk (36.94 ± 1.65 vs. 35.85 ± 0.67 °C) (all P > 0.05). In the BSA trials, relative heat production was similar between obese and non-obese individuals (168 ± 8 vs. 176 ± 5 W/m(2), respectively; P > 0.05). Similar to the FHP trials, there were no differences between obese and non-obese T re (38.45 ± 0.33 vs. 38.08 ± 0.29 °C, respectively) or T sk (36.82 ± 1.04 vs. 36.11 ± 0.64 °C) at the end of exercise (all P > 0.05). When obese and non-obese females exercised at a fixed metabolic heat production and euhydration was maintained, there were no differences in body temperature between groups.

  6. Life Origination Hydrate Hypothesis (LOH-Hypothesis

    Directory of Open Access Journals (Sweden)

    Victor Ostrovskii

    2012-01-01

    Full Text Available The paper develops the Life Origination Hydrate Hypothesis (LOH-hypothesis, according to which living-matter simplest elements (LMSEs, which are N-bases, riboses, nucleosides, nucleotides, DNA- and RNA-like molecules, amino-acids, and proto-cells repeatedly originated on the basis of thermodynamically controlled, natural, and inevitable processes governed by universal physical and chemical laws from CH4, niters, and phosphates under the Earth's surface or seabed within the crystal cavities of the honeycomb methane-hydrate structure at low temperatures; the chemical processes passed slowly through all successive chemical steps in the direction that is determined by a gradual decrease in the Gibbs free energy of reacting systems. The hypothesis formulation method is based on the thermodynamic directedness of natural movement and consists ofan attempt to mentally backtrack on the progression of nature and thus reveal principal milestones alongits route. The changes in Gibbs free energy are estimated for different steps of the living-matter origination process; special attention is paid to the processes of proto-cell formation. Just the occurrence of the gas-hydrate periodic honeycomb matrix filled with LMSEs almost completely in its final state accounts for size limitation in the DNA functional groups and the nonrandom location of N-bases in the DNA chains. The slowness of the low-temperature chemical transformations and their “thermodynamic front” guide the gross process of living matter origination and its successive steps. It is shown that the hypothesis is thermodynamically justified and testable and that many observed natural phenomena count in its favor.

  7. 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.

  8. 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

  9. Inter-cage dynamics in structure I, II, and H fluoromethane hydrates as studied by NMR and molecular dynamics simulations

    International Nuclear Information System (INIS)

    Trueba, Alondra Torres; Kroon, Maaike C.; Peters, Cor J.; Moudrakovski, Igor L.; Ratcliffe, Christopher I.; Ripmeester, John A.; Alavi, Saman

    2014-01-01

    Prospective industrial applications of clathrate hydrates as materials for gas separation require further knowledge of cavity distortion, cavity selectivity, and defects induction by guest-host interactions. The results presented in this contribution show that under certain temperature conditions the guest combination of CH 3 F and a large polar molecule induces defects on the clathrate hydrate framework that allow intercage guest dynamics. 13 C NMR chemical shifts of a CH 3 F/CH 4 /TBME sH hydrate and a temperature analysis of the 2 H NMR powder lineshapes of a CD 3 F/THF sII and CD 3 F/TBME sH hydrate, displayed evidence that the populations of CH 4 and CH 3 F in the D and D ′ cages were in a state of rapid exchange. A hydrogen bonding analysis using molecular dynamics simulations on the TBME/CH 3 F and TBME/CH 4 sH hydrates showed that the presence of CH 3 F enhances the hydrogen bonding probability of the TBME molecule with the water molecules of the cavity. Similar results were obtained for THF/CH 3 F and THF/CH 4 sII hydrates. The enhanced hydrogen bond formation leads to the formation of defects in the water hydrogen bonding lattice and this can enhance the migration of CH 3 F molecules between adjacent small cages

  10. 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

  11. 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

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

    DEFF Research Database (Denmark)

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

    2004-01-01

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

  13. 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

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

    Science.gov (United States)

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

    2010-09-09

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

  15. A method to measure the thermal-physical parameter of gas hydrate in porous media

    Energy Technology Data Exchange (ETDEWEB)

    Diao, S.B.; Ye, Y.G.; Yue, Y.J.; Zhang, J.; Chen, Q.; Hu, G.W. [Qingdao Inst. of Marine Geology, Qingdao (China)

    2008-07-01

    It is important to explore and make good use of gas hydrates through the examination of the thermal-physical parameters of sediment. This paper presented a new type of simulation experiment using a device that was designed based on the theories of time domain reflection and transient hot wire method. A series of investigations were performed using this new device. The paper described the experiment, with reference to the experiment device and materials and method. It also presented the results of thermal physical properties; result of the thermal conductivity of water, dry sand and wet sand; and results of wet sand under various pressures. The time domain reflection (TDR) method was utilized to monitor the saturation of the hydrates. Both parallel hot-wire method and cross hot-wire method were utilized to measure the thermal conductivity of the gas hydrate in porous media. A TDR sensor which was equipped with both cross hot-wire probe and parallel hot-wire probe was developed in order to measure the cell temperature with these two methods at one time. It was concluded that the TDR probe could be taken as an online measurement skill in investigating the hydrate thermal physical property in porous media. The TDR sensor could monitor the hydrate formation process and the parallel hot-wire method and cross hot-wire method could effectively measure the thermal physical properties of the hydrates in porous media. 10 refs., 7 figs.

  16. Methane rising from the Deep: Hydrates, Bubbles, Oil Spills, and Global Warming

    Science.gov (United States)

    Leifer, I.; Rehder, G. J.; Solomon, E. A.; Kastner, M.; Asper, V. L.; Joye, S. B.

    2011-12-01

    Elevated methane concentrations in near-surface waters and the atmosphere have been reported for seepage from depths of nearly 1 km at the Gulf of Mexico hydrate observatory (MC118), suggesting that for some methane sources, deepsea methane is not trapped and can contribute to atmospheric greenhouse gas budgets. Ebullition is key with important sensitivity to the formation of hydrate skins and oil coatings, high-pressure solubility, bubble size and bubble plume processes. Bubble ROV tracking studies showed survival to near thermocline depths. Studies with a numerical bubble propagation model demonstrated that consideration of structure I hydrate skins transported most methane only to mid-water column depths. Instead, consideration of structure II hydrates, which are stable to far shallower depths and appropriate for natural gas mixtures, allows bubbles to survive to far shallower depths. Moreover, model predictions of vertical methane and alkane profiles and bubble size evolution were in better agreement with observations after consideration of structure II hydrate properties as well as an improved implementation of plume properties, such as currents. These results demonstrate the importance of correctly incorporating bubble hydrate processes in efforts to predict the impact of deepsea seepage as well as to understand the fate of bubble-transported oil and methane from deepsea pipeline leaks and well blowouts. Application to the DWH spill demonstrated the importance of deepsea processes to the fate of spilled subsurface oil. Because several of these parameters vary temporally (bubble flux, currents, temperature), sensitivity studies indicate the importance of real-time monitoring data.

  17. THCM Coupled Model for Hydrate-Bearing Sediments: Data Analysis and Design of New Field Experiments (Marine and Permafrost Settings)

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez, Marcelo J. [Texas A & M Univ., College Station, TX (United States); Santamarina, J. Carlos [King Abdullah Univ. of Science and Technology (Saudi Arabia)

    2017-02-14

    Gas hydrates are solid compounds made of water molecules clustered around low molecular weight gas molecules such as methane, hydrogen, and carbon dioxide. Methane hydrates form under pressure (P) and temperature (T) conditions that are common in sub-permafrost layers and in deep marine sediments. Stability conditions constrain the occurrence of gas hydrates to submarine sediments and permafrost regions. The amount of technically recoverable methane trapped in gas hydrate may exceed 104tcf. Gas hydrates are a potential energy resource, can contribute to climate change, and can cause large-scale seafloor instabilities. In addition, hydrate formation can be used for CO2 sequestration (also through CO2-CH4 replacement), and efficient geological storage seals. The experimental study of hydrate bearing sediments has been hindered by the very low solubility of methane in water (lab testing), and inherent sampling difficulties associated with depressurization and thermal changes during core extraction. This situation has prompted more decisive developments in numerical modeling in order to advance the current understanding of hydrate bearing sediments, and to investigate/optimize production strategies and implications. The goals of this research has been to addresses the complex thermo-hydro-chemo-mechanical THCM coupled phenomena in hydrate-bearing sediments, using a truly coupled numerical model that incorporates sound and proven constitutive relations, satisfies fundamental conservation principles. Analytical solutions aimed at verifying the proposed code have been proposed as well. These tools will allow to better analyze available data and to further enhance the current understanding of hydrate bearing sediments in view of future field experiments and the development of production technology.

  18. Solid density, low temperature plasma formation in a capillary discharge

    International Nuclear Information System (INIS)

    Kania, D.R.; Jones, L.A.; Maestas, M.D.; Shepherd, R.L.

    1987-01-01

    This work discusses the ability of the authors to produce solid density, low temperature plasmas in polyurethane capillary discharges. The initial capillary diameter is 20 μm. The plasma is produced by discharging a one Ohm parallel plate waterline and Marx generator system through the capillary. A peak current of 340 kA in 300 ns heats the inner wall of the capillary, and the plasma expands into the surrounding material. The authors studied the evolution of the discharge using current and voltage probes, axial and radial streak photography, axial x-ray diode array and schlieren photography, and have estimated the peak temperature of the discharge to be approximately 10 eV and the density to be near 10/sup 23/cm/sup -3/. This indicates that the plasma may approach the strongly coupled regime. They discuss their interpretation of the data and compare their results with theoretical models of the plasma dynamics

  19. 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

  20. Study of the glass formation of high temperature superconductors

    Science.gov (United States)

    Ethridge, Edwin C.; Kaukler, William F.; Rolin, Terry

    1992-01-01

    A number of compositions of ceramic oxide high T(sub c) superconductors were elevated for their glass formation ability by means of rapid thermal analysis during quenching, optical, and electron microscopy of the quenched samples, and with subsequent DSC measurements. Correlations between experimental measurements and the methodical composition changes identified the formulations of superconductors that can easily form glass. The superconducting material was first formed as a glass; then, with subsequent devitrification, it was formed into a bulk crystalline superconductor by a series of processing methods.

  1. Temperature dependence of underdense nanostructure formation in tungsten under helium irradiation

    International Nuclear Information System (INIS)

    Valles, G.; Martin-Bragado, I.; Nordlund, K.; Lasa, A.; Björkas, C.; Safi, E.; Perlado, J.M.; Rivera, A.

    2017-01-01

    Recently, tungsten has been found to form a highly underdense nanostructured morphology (“W fuzz”) when bombarded by an intense flux of He ions, but only in the temperature window 900–2000 K. Using object kinetic Monte Carlo simulations (pseudo-3D simulations) parameterized from first principles, we show that this temperature dependence can be understood based on He and point defect clustering, cluster growth, and detrapping reactions. At low temperatures (<900 K), fuzz does not grow because almost all He is trapped in very small He-vacancy clusters. At high temperatures (>2300 K), all He is detrapped from clusters, preventing the formation of the large clusters that lead to fuzz growth in the intermediate temperature range. - Highlights: •OKMC simulation of temperature window for fuzz formation. •Stable He-V clusters prevent fuzz formation at low temperatures. •Dissociation of He-V clusters prevent fuzz formation at high temperatures. •Fuzz formation rate increases with increasing temperature. •An incubation fluence observed in the simulations, similar to experimental observations.

  2. Temperature dependence of underdense nanostructure formation in tungsten under helium irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Valles, G., E-mail: gonzalovallesalberdi@hotmail.com [Instituto de Fusión Nuclear, Universidad Politécnica de Madrid, C/ José Gutiérrez Abascal 2, 28006, Madrid (Spain); Martin-Bragado, I. [UCAM, Universidad Católica de Murcia, Campus de los Jerónimos, Guadalupe, 30107, Murcia (Spain); Nordlund, K. [Department of Physics, University of Helsinki, P.O. Box 43, Helsinki, FI-00014 (Finland); National Research Nuclear University MEPhI, 115409, Moscow (Russian Federation); Lasa, A. [Department of Physics, University of Helsinki, P.O. Box 43, Helsinki, FI-00014 (Finland); Oak Ridge National Laboratory, Oak Ridge, TN, 37831-6169 (United States); Björkas, C.; Safi, E. [Department of Physics, University of Helsinki, P.O. Box 43, Helsinki, FI-00014 (Finland); Perlado, J.M.; Rivera, A. [Instituto de Fusión Nuclear, Universidad Politécnica de Madrid, C/ José Gutiérrez Abascal 2, 28006, Madrid (Spain)

    2017-07-15

    Recently, tungsten has been found to form a highly underdense nanostructured morphology (“W fuzz”) when bombarded by an intense flux of He ions, but only in the temperature window 900–2000 K. Using object kinetic Monte Carlo simulations (pseudo-3D simulations) parameterized from first principles, we show that this temperature dependence can be understood based on He and point defect clustering, cluster growth, and detrapping reactions. At low temperatures (<900 K), fuzz does not grow because almost all He is trapped in very small He-vacancy clusters. At high temperatures (>2300 K), all He is detrapped from clusters, preventing the formation of the large clusters that lead to fuzz growth in the intermediate temperature range. - Highlights: •OKMC simulation of temperature window for fuzz formation. •Stable He-V clusters prevent fuzz formation at low temperatures. •Dissociation of He-V clusters prevent fuzz formation at high temperatures. •Fuzz formation rate increases with increasing temperature. •An incubation fluence observed in the simulations, similar to experimental observations.

  3. Volatile inventories in clathrate hydrates formed in the primordial nebula.

    Science.gov (United States)

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

    2010-01-01

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

  4. Tritium Formation and Mitigation in High Temperature Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Piyush Sabharwall; Carl Stoots

    2012-08-01

    Tritium is a radiologically active isotope of hydrogen. It is formed in nuclear reactors by neutron absorption and ternary fission events and can subsequently escape into the environment. In order to prevent the tritium contamination of proposed reactor buildings and surrounding sites, this paper examines the root causes and potential solutions for the production of this radionuclide, including materials selection and inert gas sparging. A model is presented that can be used to predict permeation rates of hydrogen through metallic alloys at temperatures from 450–750°C. Results of the diffusion model are presented for one steadystate value of tritium production in the reactor.

  5. 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

  6. 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 ...

  7. Topological modeling of methane hydrate crystallization from low to high water cut emulsion systems

    OpenAIRE

    Melchuna , Aline; Cameirão , Ana; Herri , Jean-Michel; Glénat , Philippe

    2016-01-01

    International audience; Hydrate formation and remediation in oil flowlines facilities represent a major concern for oil industry in respect of capital and operational costs. It is necessary to have a better understanding on the hydrate formation process to be more efficient in hydrate prevention, especially in respect to additive dosage. This work is a contribution to enhance the knowledge of hydrate formation at high water cuts, by introducing new techniques of analysis in the Archimede flow...

  8. Effect of high temperature deposition on CoSi2 phase formation

    International Nuclear Information System (INIS)

    Comrie, C. M.; Ahmed, H.; Smeets, D.; Demeulemeester, J.; Vantomme, A.; Turner, S.; Van Tendeloo, G.; Detavernier, C.

    2013-01-01

    This paper discusses the nucleation behaviour of the CoSi to CoSi 2 transformation from cobalt silicide thin films grown by deposition at elevated substrate temperatures ranging from 375 °C to 600 °C. A combination of channelling, real-time Rutherford backscattering spectrometry, real-time x-ray diffraction, and transmission electron microscopy was used to investigate the effect of the deposition temperature on the subsequent formation temperature of CoSi 2 , its growth behaviour, and the epitaxial quality of the CoSi 2 thus formed. The temperature at which deposition took place was observed to exert a significant and systematic influence on both the formation temperature of CoSi 2 and its growth mechanism. CoSi films grown at the lowest temperatures were found to increase the CoSi 2 nucleation temperature above that of CoSi 2 grown by conventional solid phase reaction, whereas the higher deposition temperatures reduced the nucleation temperature significantly. In addition, a systematic change in growth mechanism of the subsequent CoSi 2 growth occurs as a function of deposition temperature. First, the CoSi 2 growth rate from films grown at the lower reactive deposition temperatures is substantially lower than that grown at higher reactive deposition temperatures, even though the onset of growth occurs at a higher temperature, Second, for deposition temperatures below 450 °C, the growth appears columnar, indicating nucleation controlled growth. Elevated deposition temperatures, on the other hand, render the CoSi 2 formation process layer-by-layer which indicates enhanced nucleation of the CoSi 2 and diffusion controlled growth. Our results further indicate that this observed trend is most likely related to stress and changes in microstructure introduced during reactive deposition of the CoSi film. The deposition temperature therefore provides a handle to tune the CoSi 2 growth mechanism.

  9. 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)

  10. Formation of crystalline telluridomercurates from ionic liquids near room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Donsbach, Carsten; Dehnen, Stefanie [Fachbereich Chemie und Wissenschaftliches Zentrum fuer Materialwissenschaften, Philipps-Universitaet Marburg, Hans-Meerwein-Strasse 4, 35043, Marburg (Germany)

    2017-01-15

    The ternary telluridomercurate Na{sub 2}[HgTe{sub 2}] (1) was formed by fusion of Na{sub 2}Te and HgTe at 600 C and further treated in the ionic liquid (C{sub 4}C{sub 1}Im)[BF{sub 4}] (C{sub 4}C{sub 1}Im = 1-butyl-3-methylimidazolium) at moderately elevated temperatures (60 C), leading to replacement of the Na{sup +} cations with (C{sub 4}C{sub 1}Im){sup +} and re-arrangement of the inorganic substructure. As a result, we obtained the telluridomercurate (C{sub 4}C{sub 1}Im){sub 2}[HgTe{sub 2}] (2) and the tellurido/ditelluridomercurate (C{sub 4}C{sub 1}Im){sub 2}[Hg{sub 2}Te{sub 4}] (3) besides polytellurides and HgTe as by-products. The heavy atom compositions of the compounds were confirmed by micro X-ray fluorescence spectroscopy (μ-XFS), and their structures were determined by single-crystal diffraction. The cation-exchanged salts were further investigated by UV/Vis spectroscopy, indicating narrow band-gap optical transitions at 2.80 eV (2) and 1.63 eV (3), in agreement with their visible yellow or reddish-black color, respectively. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. 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

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

    Science.gov (United States)

    Sabase, Yuichiro; Nagashima, Kazushige

    2009-11-19

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

  13. 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.

  14. Estimate of subsurface formation temperature in the Tarim basin, northwest China

    Science.gov (United States)

    Liu, Shaowen; Lei, Xiao; Feng, Changge; Hao, Chunyan

    2015-04-01

    Subsurface formation temperature in the Tarim basin, the largest sedimentary basin in China, is significant for its hydrocarbon generation, preservation and geothermal energy potential assessment, but till now is not well understood, due to poor data coverage and a lack of highly accurate temperature data. Here, we combined recently acquired steady-state temperature logging data, drill stem test temperature data and measured rock thermal properties, to investigate the geothermal regime, and estimate the formation temperature at specific depths in the range 1000~5000 m in this basin. Results show that the heat flow of the Tarim basin ranges between 26.2 and 66.1 mW/m2, with a mean of 42.5±7.6 mW/m2; geothermal gradient at the depth of 3000 m varies from 14.9 to 30.2 °C/km, with a mean of 20.7±2.9 °C/km. Formation temperature at the depth of 1000 m is estimated to be between 29 °C and 41°C, with a mean of 35°C; whilst the temperature at 2000 m ranges from 46~71°C with an average of 59°C; 63~100°C is for that at the depth of 3000 m, and the mean is 82°C; the temperature at 4000 m varies from 80 to 130°C, with a mean of 105°C; 97~160°C is for the temperature at 5000 m depth. In addition, the general pattern of the subsurface formation temperatures at different depths is basically similar and is characterized by high temperatures in the uplift areas and low temperatures in the sags. Basement structure and lateral variations in thermal properties account for this pattern of the geo-temperature field in the Tarim basin.

  15. Clustering mechanism of oxocarboxylic acids involving hydration reaction: Implications for the atmospheric models

    Science.gov (United States)

    Liu, Ling; Kupiainen-Määttä, Oona; Zhang, Haijie; Li, Hao; Zhong, Jie; Kurtén, Theo; Vehkamäki, Hanna; Zhang, Shaowen; Zhang, Yunhong; Ge, Maofa; Zhang, Xiuhui; Li, Zesheng

    2018-06-01

    The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.

  16. Formation of Medium Carbon TRIP Steel Microstructure During Annealing in the Intercritical Temperature Range

    Directory of Open Access Journals (Sweden)

    Kokosza A.

    2014-10-01

    Full Text Available The paper presents the results of research conducted on austenite formation in the microstructure of 41MnSi6-5 TRIP steel during annealing in the intercritical temperature range. The influence of the annealing temperature on the volume fraction of retained austenite in the microstructure of the investigated steel after water quenching was also determined.

  17. Twin solution calorimeter determines heats of formation of alloys at high temperatures

    Science.gov (United States)

    Darby, J. B., Jr.; Kleb, R.; Kleppa, O. J.

    1968-01-01

    Calvert-type, twin liquid metal solution calorimeter determines the heats of formation of transition metal alloys at high temperatures. The twin differential calorimeter measures the small heat effects generated over extended periods of time, has maximum operating temperature of 1073 degrees K and an automatic data recording system.

  18. Comparison of temperature calculations for an arbitrary high-level waste disposal configuration in salt formations

    International Nuclear Information System (INIS)

    Kevenaar, J.W.A.M.; Janssen, L.G.J.; Ploumen, P.; Winske, P.

    1979-05-01

    The objective of this report is the comparison of the results of temperature analyses for an arbitrary high-level radioactive waste disposal configuration in salt formations. The analyses were carried out at the RWTH and ECN. The computer programs used are based on finite difference and finite element techniques. From the local temperature analyses that were intended to check the solution techniques, it could be concluded that both finite difference and finite elements are capable to analyse this type of problems. From the global temperature analyses it could be concluded that both analysis approaches: temperature dependent and iteratively determined temperature independent material properties, are suited to analyse the global temperature distribution in the salt formation

  19. Sensitivity Analysis of Methane Hydrate Reservoirs: Effects of Reservoir Parameters on Gas Productivity and Economics

    Science.gov (United States)

    Anderson, B. J.; Gaddipati, M.; Nyayapathi, L.

    2008-12-01

    This paper presents a parametric study on production rates of natural gas from gas hydrates by the method of depressurization, using CMG STARS. Seven factors/parameters were considered as perturbations from a base-case hydrate reservoir description based on Problem 7 of the International Methane Hydrate Reservoir Simulator Code Comparison Study led by the Department of Energy and the USGS. This reservoir is modeled after the inferred properties of the hydrate deposit at the Prudhoe Bay L-106 site. The included sensitivity variables were hydrate saturation, pressure (depth), temperature, bottom-hole pressure of the production well, free water saturation, intrinsic rock permeability, and porosity. A two-level (L=2) Plackett-Burman experimental design was used to study the relative effects of these factors. The measured variable was the discounted cumulative gas production. The discount rate chosen was 15%, resulting in the gas contribution to the net present value of a reservoir. Eight different designs were developed for conducting sensitivity analysis and the effects of the parameters on the real and discounted production rates will be discussed. The breakeven price in various cases and the dependence of the breakeven price on the production parameters is given in the paper. As expected, initial reservoir temperature has the strongest positive effect on the productivity of a hydrate deposit and the bottom-hole pressure in the production well has the strongest negative dependence. Also resulting in a positive correlation is the intrinsic permeability and the initial free water of the formation. Negative effects were found for initial hydrate saturation (at saturations greater than 50% of the pore space) and the reservoir porosity. These negative effects are related to the available sensible heat of the reservoir, with decreasing productivity due to decreasing available sensible heat. Finally, we conclude that for the base case reservoir, the break-even price (BEP

  20. Tripolar vortex formation in dense quantum plasma with ion-temperature-gradients

    Science.gov (United States)

    Qamar, Anisa; Ata-ur-Rahman, Mirza, Arshad M.

    2012-05-01

    We have derived system of nonlinear equations governing the dynamics of low-frequency electrostatic toroidal ion-temperature-gradient mode for dense quantum magnetoplasma. For some specific profiles of the equilibrium density, temperature, and ion velocity gradients, the nonlinear equations admit a stationary solution in the form of a tripolar vortex. These results are relevant to understand nonlinear structure formation in dense quantum plasmas in the presence of equilibrium ion-temperature and density gradients.

  1. Tripolar vortex formation in dense quantum plasma with ion-temperature-gradients

    Energy Technology Data Exchange (ETDEWEB)

    Qamar, Anisa; Ata-ur-Rahman [Institute of Physics and Electronics, University of Peshawar, Khyber Pakhtoon Khwa 25000 (Pakistan); National Center for Physics Shahdrah Valley Road, Islamabad 44000 (Pakistan); Mirza, Arshad M. [Theoretical Plasma Physics Group, Physics Department, Quaid-i-Azam University, Islamabad 45320 (Pakistan)

    2012-05-15

    We have derived system of nonlinear equations governing the dynamics of low-frequency electrostatic toroidal ion-temperature-gradient mode for dense quantum magnetoplasma. For some specific profiles of the equilibrium density, temperature, and ion velocity gradients, the nonlinear equations admit a stationary solution in the form of a tripolar vortex. These results are relevant to understand nonlinear structure formation in dense quantum plasmas in the presence of equilibrium ion-temperature and density gradients.

  2. Tripolar vortex formation in dense quantum plasma with ion-temperature-gradients

    International Nuclear Information System (INIS)

    Qamar, Anisa; Ata-ur-Rahman; Mirza, Arshad M.

    2012-01-01

    We have derived system of nonlinear equations governing the dynamics of low-frequency electrostatic toroidal ion-temperature-gradient mode for dense quantum magnetoplasma. For some specific profiles of the equilibrium density, temperature, and ion velocity gradients, the nonlinear equations admit a stationary solution in the form of a tripolar vortex. These results are relevant to understand nonlinear structure formation in dense quantum plasmas in the presence of equilibrium ion-temperature and density gradients.

  3. 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.

  4. 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

  5. Low temperature and Daphnia-associated infochemicals promote colony formation of Scenedesmus obliquus and its harvesting.

    Science.gov (United States)

    Zhu, Xuexia; Yang, Jingwen; Zhang, Xingxing; Zhang, Lu; Wang, Xiaojun; Huang, Yuan; Yang, Zhou

    2017-01-01

    To explore the combined effects of temperature and Daphnia-associated infochemicals on colony formation of Scenedesmus obliquus to faciliate harvesting the algal biomass. A three-parameter modified Gaussian model fitted the changes of the number of cells per particle in S. obliquus induced by Daphnia culture filtrate well under any temperature. Decreases in temperature enhanced the induced-colony formation of Scenedesmus. The maximum colony size at 15-25 °C was significantly larger than those at 30-35 °C. An additional 1 or 2 days at low temperature was needed to reach the maximum colony size, which indicates the best harvest time for algal biomass. Induced-colony formation of Scenedesmus by Daphnia culture filtrate at 15-25 °C is recommended to settle algal cells. This condition facilitates harvesting the biomass.

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

    Science.gov (United States)

    Yamamoto, K.; Nagakubo, S.

    2009-04-01

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

  7. 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.

  8. Simulating the gas hydrate production test at Mallik using the pilot scale pressure reservoir LARS

    Science.gov (United States)

    Heeschen, Katja; Spangenberg, Erik; Schicks, Judith M.; Priegnitz, Mike; Giese, Ronny; Luzi-Helbing, Manja

    2014-05-01

    LARS, the LArge Reservoir Simulator, allows for one of the few pilot scale simulations of gas hydrate formation and dissociation under controlled conditions with a high resolution sensor network to enable the detection of spatial variations. It was designed and built within the German project SUGAR (submarine gas hydrate reservoirs) for sediment samples with a diameter of 0.45 m and a length of 1.3 m. During the project, LARS already served for a number of experiments simulating the production of gas from hydrate-bearing sediments using thermal stimulation and/or depressurization. The latest test simulated the methane production test from gas hydrate-bearing sediments at the Mallik test site, Canada, in 2008 (Uddin et al., 2011). Thus, the starting conditions of 11.5 MPa and 11°C and environmental parameters were set to fit the Mallik test site. The experimental gas hydrate saturation of 90% of the total pore volume (70 l) was slightly higher than volumes found in gas hydrate-bearing formations in the field (70 - 80%). However, the resulting permeability of a few millidarcy was comparable. The depressurization driven gas production at Mallik was conducted in three steps at 7.0 MPa - 5.0 MPa - 4.2 MPa all of which were used in the laboratory experiments. In the lab the pressure was controlled using a back pressure regulator while the confining pressure was stable. All but one of the 12 temperature sensors showed a rapid decrease in temperature throughout the sediment sample, which accompanied the pressure changes as a result of gas hydrate dissociation. During step 1 and 2 they continued up to the point where gas hydrate stability was regained. The pressure decreases and gas hydrate dissociation led to highly variable two phase fluid flow throughout the duration of the simulated production test. The flow rates were measured continuously (gas) and discontinuously (liquid), respectively. Next to being discussed here, both rates were used to verify a model of gas

  9. Effect of mass concentration of composite phase change material CA-DE on HCFC-141b hydrate induction time and system stability

    Science.gov (United States)

    Li, Juan; Sun, Zhigao; Liu, Chenggang; Zhu, Minggui

    2018-03-01

    HCFC-141b hydrate is a new type of environment-friendly cold storage medium which may be adopted to balance energy supply and demand, achieve peak load shifting and energy saving, wherein the hydrate induction time and system stability are key factors to promote and realize its application in industrial practice. Based on step cooling curve measurement, two kinds of aliphatic hydrocarbon organics, n-capric acid (CA) and lauryl alcohol (DE), were selected to form composite phase change material and to promote the generation of HCFC-141b hydrate. Five kinds of CA-DE mass concentration were chosen to compare the induction time and hydration system stability. In order to accelerate temperature reduction rate, the metal Cu with high heat conductivity performance was adopted to conduct out the heat generated during phase change. Instability index was introduced to appraise system stability. Experimental results show that phase change temperature and sub-cooling degree of CA-DE is 11.1°C and 3.0°C respectively, which means it is a preferable medium for HCFC-141b hydrate formation. For the experimental hydration systems, segmented emulsification is achieved by special titration manner to avoid rapid layering under static condition. Induction time can achieve up to 23.3min with the densest HCFC-141b hydrate and the lowest instability index, wherein CA-DE mass concentration is 3%.

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

    Digital Repository Service at National Institute of Oceanography (India)

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

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

  11. Sclerotial formation of Polyporus umbellatus by low temperature treatment under artificial conditions.

    Science.gov (United States)

    Xing, Yong-Mei; Zhang, Li-Chun; Liang, Han-Qiao; Lv, Jing; Song, Chao; Guo, Shun-Xing; Wang, Chun-Lan; Lee, Tae-Soo; Lee, Min-Woong

    2013-01-01

    Polyporus umbellatus sclerotia have been used as a diuretic agent in China for over two thousand years. A shortage of the natural P. umbellatus has prompted researchers to induce sclerotial formation in the laboratory. P. umbellatus cultivation in a sawdust-based substrate was investigated to evaluate the effect of low temperature conditions on sclerotial formation. A phenol-sulfuric acid method was employed to determine the polysaccharide content of wild P. umbellatus sclerotia and mycelia and sclerotia grown in low-temperature treatments. In addition, reactive oxygen species (ROS) content, expressed as the fluorescence intensity of mycelia during sclerotial differentiation was determined. Analysis of ROS generation and sclerotial formation in mycelia after treatment with the antioxidants such as diphenyleneiodonium chloride (DPI), apocynin (Apo), or vitamin C were studied. Furthermore, macroscopic and microscopic characteristics of sclerotial differentiation were observed. Sclerotia were not induced by continuous cultivation at 25°C. The polysaccharide content of the artificial sclerotia is 78% of that of wild sclerotia. In the low-temperature treatment group, the fluorescent intensity of ROS was higher than that of the room temperature (25°C) group which did not induce sclerotial formation all through the cultivation. The antioxidants DPI and Apo reduced ROS levels and did not induce sclerotial formation. Although the concentration-dependent effects of vitamin C (5-15 mg mL(-1)) also reduced ROS generation and inhibited sclerotial formation, using a low concentration of vitamin C (1 mg mL(-1)) successfully induced sclerotial differentiation and increased ROS production. Exposure to low temperatures induced P. umbellatus sclerotial morphogenesis during cultivation. Low temperature treatment enhanced ROS in mycelia, which may be important in triggering sclerotial differentiation in P. umbellatus. Moreover, the application of antioxidants impaired ROS generation

  12. 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)

  13. 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

  14. Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO{sub 2} hydrate equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Sabil, Khalik M., E-mail: khalik_msabil@petronas.com.m [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Universiti Teknologi PETRONAS, Chemical Engineering Programme, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Roman, Vicente R.; Witkamp, Geert-Jan [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Peters, Cor J., E-mail: C.J.Peters@tudelft.n [Delft University of Technology, Laboratory of Process Equipment, Mechanical, Maritime and Materials Engineering, Leeghwaterstraat 44, 2628 CA Delft (Netherlands); Petroleum Institute, Chemical Engineering Program, Bu Hasa Building, Room 2207A, P.O. Box 2533, Abu Dhabi (United Arab Emirates)

    2010-03-15

    In the present work, experimental data on the equilibrium conditions of mixed CO{sub 2} and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl{sub 2}), magnesium chloride (MgCl{sub 2}), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO{sub 2} and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L{sub W}), liquid organic (L{sub V}), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid-liquid phase split of (water + THF) mixture when pressurized with CO{sub 2} and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF < KBr < NaCl < NaBr < CaCl{sub 2} < MgCl{sub 2}. Among the cations studied, the strength of hydrate inhibition increases in the following order: K{sup +} < Na{sup +} < Ca{sup 2+} < Mg{sup 2+}. Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br{sup -} > Cl{sup -} > F{sup -}. Based on the results, it is suggested that the probability of formation and

  15. Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO2 hydrate equilibria

    International Nuclear Information System (INIS)

    Sabil, Khalik M.; Roman, Vicente R.; Witkamp, Geert-Jan; Peters, Cor J.

    2010-01-01

    In the present work, experimental data on the equilibrium conditions of mixed CO 2 and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl 2 ), magnesium chloride (MgCl 2 ), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO 2 and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L W ), liquid organic (L V ), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid-liquid phase split of (water + THF) mixture when pressurized with CO 2 and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF 2 2 . Among the cations studied, the strength of hydrate inhibition increases in the following order: K + + 2+ 2+ . Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br - > Cl - > F - . Based on the results, it is suggested that the probability of formation and the strength of ionic-hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water

  16. 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.

  17. The effect of temperature on primary defect formation in Ni–Fe alloy

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chengbin, E-mail: wangchengbin@sinap.ac.cn [Key Laboratory of Interfacial Physics and Technology, Chinese Academy of Sciences, Shanghai 201800 (China); Zhang, Wei; Ren, Cuilan [Key Laboratory of Interfacial Physics and Technology, Chinese Academy of Sciences, Shanghai 201800 (China); Huai, Ping [Key Laboratory of Nuclear Radiation and Nuclear Energy Technology, Chinese Academy of Sciences, Shanghai 201800 (China); Zhu, Zhiyuan [Key Laboratory of Interfacial Physics and Technology, Chinese Academy of Sciences, Shanghai 201800 (China)

    2014-02-15

    Molecular dynamics (MD) simulations have been used to study the influence of temperature on defect generation and evolution in nickel and Ni–Fe alloy (with 15% and 50% Fe content) with a 10-keV primary knock-on atom (PKA) at six different temperatures from 0 to 1500 K. The recently available Ni–Fe potential is used with its repulsive part modified by Vörtler. The temporal evolution and temperature dependence of stable defect formation and in-cascade clustering processes are analysed. The number of stable defect and the interstitial clustering fraction are found to increase with temperature whereas the vacancy clustering fraction decreases with temperature. The alloy composition dependence of the stable defect number is also found for the PKA energy considered here. Additionally, a study of the temperature influence on the cluster size distribution is performed, revealing a systematic change in the cluster size distributions, with higher temperature cascades producing larger interstitial clusters.

  18. Dimer and String Formation during Low Temperature Silicon Deposition on Si(100)

    DEFF Research Database (Denmark)

    Smith, A. P.; Jonsson, Hannes

    1996-01-01

    We present theoretical results based on density functional theory and kinetic Monte Carlo simulations of silicon deposition and address observations made in recently reported low temperature scanning tunneling microscopy studies. A mechanism is presented which explains dimer formation on top...... of the substrate's dimer rows at 160 K and up to room temperature, while between-row dimers and longer strings of adatoms (''diluted dimer rows'') form at higher temperature. A crossover occurs at around room temperature between two different mechanisms for adatom diffusion in our model....

  19. The structure of hydrate bearing fine grained marine sediments

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  20. A numerical study of natural hydrate formation kinetics in petroleum pipelines by the phase field method: influence of the model parameters; Estudo da cinetica de formacao de hidratos em dutos de petroleo pelo metodo do campo de fase: influencia dos parametros do modelo

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-07-01

    The objective of this work is to study the influence of the parameters of the phase field model field on the formation of natural hydrates. It was investigated parameters such as superficial tension, effect of the super-cooling, homogeneous and heterogeneous nucleation. The influence of these parameters was analyzed according to morphology of the interface and the rate of formation. The mathematical model to describe the evolution of the natural hydrates formation is based on the simultaneous solution of the phase and energy equations. The finite volume numerical method was used to discretize the governing differential equations. Results of the simulation indicated that the reduction of the superficial tension leads to the increase of the surface rugosity, interface thickness and instability of the interface resulting in a decrease of the rate growth. In order to investigate the nucleation effect of the natural hydrates, two conditions had been simulated a) the random distribution of nuclei: where the evolution of formed hydrates suffered coalescence and the kinetic decreased due to impingement of hydrates regions and b) Nucleation in the pipeline wall, where rough interfaces were observed. (author)

  1. 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.

  2. [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.

  3. 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.

  4. The Characteristics of Fluid Potential in Mud Diapirs Associated with Gas Hydrates in the Okinawa Trough

    Directory of Open Access Journals (Sweden)

    Ning Xu

    2006-01-01

    Full Text Available Many mud diapirs have been identified in the southern Okinawa Trough from a seismic survey using R/V KEXUE I in 2001. The movement and accumulation of free gas related to mud diapirs are discussed in detail by an analysis of fluid potential which is based upon velocity data. It can be found that free gas moves from the higher fluid potential strata to the lower ones and the gas hydrate comes into being during free gas movement meeting the proper criteria of temperature and pressure. In fact, gas hydrates have been found in the upper layers above the mud diapirs and in host rocks exhibiting other geophysical characteristics. As the result of the formation of the gas hydrate, the free gas bearing strata are enclosed by the gas hydrate bearing strata. Due to the high pressure anomalies of the free gas bearing strata the fluid potential increases noticeably. It can then be concluded that the high fluid potential anomaly on the low fluid potential background may be caused by the presence of the free gas below the gas hydrate bearing strata.

  5. Densities and temperatures at fragment formation in heavy-ion collision

    Energy Technology Data Exchange (ETDEWEB)

    Ohnishi, Akira [Hokkaido Univ., Sapporo (Japan)

    1998-07-01

    In order to clarify whether the liquid-gas phase transition is relevant to the multi-fragment formation found in intermediate energy heavy-ion collisions, we estimate the densities and temperatures at fragment formation in Au+Au collisions at incident energies of 150 MeV/A and 400 MeV/A within the Quantum Molecular Dynamics (QMD) model with and without quantum fluctuations implemented according to the Quantal Langevin (QL) model. The calculated results show that the IMFs are mainly produced inside the unstable region of nuclear matter, which supports the idea of the fragment formation from supercooled nuclear matter. (author)

  6. Temperature dependence study of positronium formation in high density polyethylene by positron annihilation lifetime spectroscopy

    International Nuclear Information System (INIS)

    Nahid, F.; Beling, C.D.; Fung, S.

    2007-01-01

    Positron annihilation lifetime spectroscopy has been used to study the formation of positronium in high density polyethylene as a function of temperature over the range 30 K-350 K. It is observed that the thermal history of the sample, while having no influence on the positronium lifetime, has a strong effect on the formation of positronium. A hysteresis is seen in the positronium formation probability in cooling and heating cycles. This is explained on a two channel formation model, the first channel being through ''blob'' formation and the second through the pick-up of shallow trapped electrons. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  7. [Impact of low temperature in young ear formation stage on rice seed setting.

    Science.gov (United States)

    Ma, Shu Qing; Liu, Xiao Hang; Deng, Kui Cai; Quan, Hu Jie; Tong, Li Yuan; Xi, Zhu Xiang; Chai, Qing Rong; Yang, Jun

    2018-01-01

    A low temperature treatment in rice booting key period was executed on the north slope of Changbai Mountains to construct the impact model of low temperature on rice shell rate, and to reveal the effects of low temperature at different stages of rice young panicle on seed setting. The results showed that effects of low temperature in the young ear formation stage on rice shell rate generally followed the logarithmic function, the lower the temperature was, the greater the temperature influence coefficient was, and the longer the low temperature duration was, the higher rice shell rate was. The seed setting rate was most sensitive to low temperature in the middle time of booting stage (the period from formation to meiosis of the pollen mother cell), followed by the early and later stages. During the booting stage, with 1 ℃ decrease of daily temperature under 2-, 3- and 5-day low temperature treatments, the shell rate increased by 0.5, 1.7 and 4.3 percentage, respectively, and with 1 ℃ decrease of daily minimum temperature, the shell rate increased by 0.4,1.8 and 4.5 percentage, respectively. The impact of 2-day low temperature was smaller than that of 3 days or more. The impact of accumulative cold-temperature on the shell rate followed exponential function. In the range of harmful low temperature, rice shell rate increased about 8.5 percentage with the accumulative cold-temperature increasing 10 ℃·d. When the 3 days average temperature dropped to 21.6, 18.0 and 15.0 ℃, or the 5 days average temperature dropped to 22.0, 20.4 and 18.5 ℃, or the accumulative cold-temperature was more than 8, 19, 26 ℃·d, the light, moderate and severe booting stage chilling injury would occur, respectively. In Northeast China, low temperature within 2 d in rice booting stage might not cause moderate and severe chilling injury.

  8. Naphthenic acids hydrates of gases: influence of the water/oil interface on the dispersing properties of an acidic crude oil; Acides naphteniques hydrates de gaz de l'interface eau/huile sur les proprietes dispersantes d'un brut acide

    Energy Technology Data Exchange (ETDEWEB)

    Arla, D.

    2006-01-15

    Nowadays, the development of offshore oil production under increasing water depths (high pressures and low temperatures) has led oil companies to focus on gas hydrates risks. Hydrates are crystals containing gas and water molecules which can plug offshore pipelines. It has been shown that some asphaltenic crude oils stabilize water-in-oil emulsions (W/O) during several months and exhibit very good anti-agglomerant properties avoiding hydrate plugs formation. In this work, we have studied the 'anti-hydrate' properties of a West African acidic crude oil called crude AH. This oil contains naphthenic acids, RCOOH hydrocarbons which are sensitive to both the pH and the salinity of the water phase.The emulsifying properties of the crude AH have firstly been explored. It has been shown that heavy resins and asphaltenes are the main compounds of the crude AH responsible for the long term stability of the W/O emulsions whereas the napthenates RCOO{sup -} lead to less stable W/O emulsions. Dealing with hydrates, the crude AH exhibits moderate anti-agglomerant properties due to the presence of heavy resins and asphaltenes. However, the naphthenates RCOO{sup -} drastically increase the formation of hydrate plugs. Moreover, it has been pointed out that hydrate particles agglomeration accelerates the kinetics of hydrate formation and enhances the water/oil separation. In order to explain these behaviours, a mechanism of agglomeration by 'sticking' between a hydrate particle and a water droplet has been proposed. Finally, we have developed a model which describes the physico-chemical equilibria of the naphthenic acids in the binary system water/crude AH, in order to transpose the results obtained in the laboratory to the real oil field conditions. (author)

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

    Science.gov (United States)

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

    2003-04-01

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

  10. Reversibility of temperature driven discrete layer-by-layer formation of dioctyl-benzothieno-benzothiophene films.

    Science.gov (United States)

    Dohr, M; Ehmann, H M A; Jones, A O F; Salzmann, I; Shen, Q; Teichert, C; Ruzié, C; Schweicher, G; Geerts, Y H; Resel, R; Sferrazza, M; Werzer, O

    2017-03-22

    Film forming properties of semiconducting organic molecules comprising alkyl-chains combined with an aromatic unit have a decisive impact on possible applications in organic electronics. In particular, knowledge on the film formation process in terms of wetting or dewetting, and the precise control of these processes, is of high importance. In the present work, the subtle effect of temperature on the morphology and structure of dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) films deposited on silica surfaces by spin coating is investigated in situ via X-ray diffraction techniques and atomic force microscopy. Depending on temperature, bulk C8-BTBT exhibits a crystalline, a smectic A and an isotropic phase. Heating of thin C8-BTBT layers at temperatures below the smectic phase transition temperature leads to a strong dewetting of the films. Upon approaching the smectic phase transition, the molecules start to rewet the surface in the form of discrete monolayers with a defined number of monolayers being present at a given temperature. The wetting process and layer formation is well defined and thermally stable at a given temperature. On cooling the reverse effect is observed and dewetting occurs. This demonstrates the full reversibility of the film formation behavior and reveals that the layering process is defined by an equilibrium thermodynamic state, rather than by kinetic effects.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. Potential Formation in Front of an Electron Emitting Electrode in a Two-Electron Temperature Plasma

    International Nuclear Information System (INIS)

    Gyergyek, T.; Cercek, M.; Erzen, D.

    2003-01-01

    Plasma potential formation in the pre-sheath region of a floating electron emitting electrode (collector) is studied theoretically in a two-electron-temperature plasma using a static kinetic plasma-sheath model. Dependence of the collector floating potential, the plasma potential in the pre-sheath region, and the critical emission coefficient on the hot electron density and temperature is calculated. It is found that for high hot to cool electron temperature ratio a double layer like solutions exist in a certain range of hot to cool electron densities

  16. Formation and termination of High ion temperature mode in Heliotron/torsatron plasmas

    International Nuclear Information System (INIS)

    Ida, K.; Kondo, K.; Nagasaki, K.

    1997-01-01

    Physics of the formation and termination of High ion temperature mode (high T i mode) are studied by controlling density profiles and radial electric field. High ion temperature mode is observed for neutral beam heated plasmas in Heliotron/torsatron plasmas (Heliotron-E). This high T i mode plasma is characterized by a peaked ion temperature profile and is associated with a peaked electron density profile produced by neutral beam fueling with low wall recycling. This high T i mode is terminated by flattening the electron density caused by either gas puffing or second harmonic ECH (core density 'pump-out'). (author)

  17. Alginate overproduction and biofilm formation by psychrotolerant Pseudomonas mandelii depend on temperature in Antarctic marine sediments

    Directory of Open Access Journals (Sweden)

    Felipe Vásquez-Ponce

    2017-07-01

    Conclusion: Because biofilm formation is an efficient bacterial strategy to overcome stressful conditions, alginate overproduction might represent the best solution for the successful adaptation of P. mandelii to the extreme temperatures of the Antarctic. Through additional research, it is possible that this novel P. mandelii strain could become an additional source for biotechnological alginate production.

  18. Proton transfer and complex formation of angiotensin I ions with gaseous molecules at various temperature

    International Nuclear Information System (INIS)

    Nonose, Shinji; Yamashita, Kazuki; Sudo, Ayako; Kawashima, Minami

    2013-01-01

    Highlights: • Proton transfer from angiotensin I ions (z = 2, 3) to gaseous molecules was studied. • Temperature dependence of absolute reaction rate constants was measured. • Remarkable changes were obtained for distribution of product ions and reaction rate constants. • Proton transfer reaction was enhanced and reduced by complex formation. • Conformation changes are induced by complex formation and or by thermal collision with He. - Abstract: Proton transfer reactions of angiotensin I ions for +2 charge state, [M + 2H] 2+ , to primary, secondary and aromatic amines were examined in the gas phase. Absolute reaction rate constants for proton transfer were determined from intensities of parent and product ions in the mass spectra. Temperature dependence of the reaction rate constants was measured. Remarkable change was observed for distribution of product ions and reaction rate constants. Proton transfer reaction was enhanced or reduced by complex formation of [M + 2H] 2+ with gaseous molecules. The results relate to conformation changes of [M + 2H] 2+ with change of temperature, which are induced by complex formation and or by thermal collision with He. Proton transfer reactions of angiotensin I ions for +3 charge state, [M + 3H] 3+ , were also studied. The reaction rates did not depend on temperature so definitely

  19. Formation of temperature fields in doped anisotropic crystals under spatially inhomogeneous light beams passing through them

    Energy Technology Data Exchange (ETDEWEB)

    Zaitseva, E. V.; Markelov, A. S.; Trushin, V. N., E-mail: trushin@phys.unn.ru; Chuprunov, E. V. [Nizhni Novgorod State University (Russian Federation)

    2013-12-15

    The features of formation of thermal fields in potassium dihydrophosphate crystal doped with potassium permanganate under a 532-nm laser beam passing through it have been investigated. Data on the influence of birefringence on the temperature distribution in an anisotropic crystal whose surface is illuminated by a spatially modulated light beam are presented.

  20. Controlling the selective formation of calcium sulfate polymorphs at room temperature.

    Science.gov (United States)

    Tritschler, Ulrich; Van Driessche, Alexander E S; Kempter, Andreas; Kellermeier, Matthias; Cölfen, Helmut

    2015-03-23

    Calcium sulfate is a naturally abundant and technologically important mineral with a broad scope of applications. However, controlling CaSO4 polymorphism and, with it, its final material properties still represents a major challenge, and to date there is no universal method for the selective production of the different hydrated and anhydrous forms under mild conditions. Herein we report the first successful synthesis of pure anhydrite from solution at room temperature. We precipitated calcium sulfate in alcoholic media at low water contents. Moreover, by adjusting the amount of water in the syntheses, we can switch between the distinct polymorphs and fine-tune the outcome of the reaction, yielding either any desired CaSO4 phase in pure state or binary mixtures with predefined compositions. This concept provides full control over phase selection in CaSO4 mineralization and may allow for the targeted fabrication of corresponding materials for use in various areas. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Putting the Deep Biosphere and Gas Hydrates on the Map

    Science.gov (United States)

    Sikorski, Janelle J.; Briggs, Brandon R.

    2016-01-01

    Microbial processes in the deep biosphere affect marine sediments, such as the formation of gas hydrate deposits. Gas hydrate deposits offer a large source of natural gas with the potential to augment energy reserves and affect climate and seafloor stability. Despite the significant interdependence between life and geology in the ocean, coverage…

  2. Culture temperature affects redifferentiation and cartilaginous extracellular matrix formation in dedifferentiated human chondrocytes.

    Science.gov (United States)

    Ito, Akira; Aoyama, Tomoki; Iijima, Hirotaka; Tajino, Junichi; Nagai, Momoko; Yamaguchi, Shoki; Zhang, Xiangkai; Kuroki, Hiroshi

    2015-05-01

    To date, there have been few studies on how temperature affects the phenotype and metabolism of human chondrocytes. Thus, the purpose of this study was to elucidate the effects of culture temperature on chondrocyte redifferentiation and extracellular matrix (ECM) formation using dedifferentiated mature human chondrocytes in vitro. Dedifferentiated chondrocytes were cultured in a pellet culture system for up to 21 days. The pellets were randomly divided into three groups with different culture temperature (32, 37, and 41°C). Chondrocyte redifferentiation and ECM formation were evaluated by wet weight, messenger ribonucleic acid (mRNA), histological, and biochemical analyses. The results showed that the wet weight and the mRNA expressions of collagen type II A1 and cartilage oligomeric matrix protein at 37°C were higher than the corresponding values at 32°C. The histological and biochemical analyses revealed that the syntheses of type II collagen and proteoglycan were promoted at 37°C compared to those at 32°C, whereas they were considerably inhibited at 41°C. In conclusion, the results obtained herein indicated that temperature affects chondrocyte redifferentiation and ECM formation, and modulation of temperature might thus represent an advantageous means to regulate the phenotype and biosynthetic activity of chondrocytes. © 2015 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.

  3. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-01-31

    This study was designed to investigate temporal variations in hydrate system dynamics by measuring changes in volumes of hydrate beneath hydrate-bearing mounds on the continental slope of the northern Gulf of Mexico, the landward extreme of hydrate occurrence in this region. Direct Current Resistivity (DCR) measurements were made contemporaneously with measurements of oceanographic parameters at Woolsey Mound,