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Sample records for simulated supercritical water

  1. Simulations of dissociation constants in low pressure supercritical water

    NASA Astrophysics Data System (ADS)

    Halstead, S. J.; An, P.; Zhang, S.

    2014-09-01

    This article reports molecular dynamics simulations of the dissociation of hydrochloric acid and sodium hydroxide in water from ambient to supercritical temperatures at a fixed pressure of 250 atm. Corrosion of reaction vessels is known to be a serious problem of supercritical water, and acid/base dissociation can be a significant contributing factor to this. The SPC/e model was used in conjunction with solute models determined from density functional calculations and OPLSAA Lennard-Jones parameters. Radial distribution functions were calculated, and these show a significant increase in solute-solvent ordering upon forming the product ions at all temperatures. For both dissociations, rapidly decreasing entropy of reaction was found to be the controlling thermodynamic factor, and this is thought to arise due to the ions produced from dissociation maintaining a relatively high density and ordered solvation shell compared to the reactants. The change in entropy of reaction reaches a minimum at the critical temperature. The values of pKa and pKb were calculated and both increased with temperature, in qualitative agreement with other work, until a maximum value at 748 K, after which there was a slight decrease.

  2. Oxidation behavior of Incoloy 800 under simulated supercritical water conditions

    NASA Astrophysics Data System (ADS)

    Fulger, M.; Ohai, D.; Mihalache, M.; Pantiru, M.; Malinovschi, V.

    2009-03-01

    For a correct design of supercritical water-cooled reactor (SCWR) components, data regarding the behavior of candidate materials in supercritical water are necessary. Corrosion has been identified as a critical problem because the high temperature and the oxidative nature of supercritical water may accelerate the corrosion kinetics. The goal of this paper is to investigate the oxidation behavior of Incoloy 800 exposed in autoclaves under supercritical water conditions for up to 1440 h. The exposure conditions (thermal deaerated water, temperatures of 723, 773, 823 and 873 K and a pressure of 25 MPa) have been selected as relevant for a supercritical power plant concept. To investigate the structural changes of the oxide films, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and electrochemical impedance spectroscopy (EIS) analyses were used. Results show changes in the oxides chemical composition, microstructure and thickness versus testing conditions (pressure, temperature and time). The oxide films are composed of two layers: an outer layer enriched in Fe oxide and an inner layer enriched in Cr and Ni oxides corresponding to small cavities supposedly due to internal oxidation.

  3. Molecular Dynamics Simulations of Aqueous and Confined Systems Relevant to the Supercritical Water Cooled Nuclear Reactor

    NASA Astrophysics Data System (ADS)

    Kallikragas, Dimitrios Theofanis

    Supercritical water (SCW) is the intended heat transfer fluid and potential neutron moderator in the proposed GEN-IV Supercritical Water Cooled Reactor (SCWR). The oxidative environment poses challenges in choosing appropriate design materials, and the behaviour of SCW within crevices of the passivation layer is needed for developing a corrosion control strategy to minimize corrosion. Molecular Dynamics simulations have been employed to obtain diffusion coefficients, coordination number and surface density characteristics, of water and chloride in nanometer-spaced iron hydroxide surfaces. Diffusion models for hydrazine are evaluated along with hydration data. Results demonstrate that water is more likely to accumulate on the surface at low density conditions. The effect of confinement on the water structure diminishes as the gap size increases. The diffusion coefficient of chloride decreases with larger surface spacing. Clustering of water at the surface implies that the SCWR will be most susceptible to pitting corrosion and stress corrosion cracking.

  4. Molecular dynamic simulations of iron (II) hydroxide in high temperature and supercritical water

    NASA Astrophysics Data System (ADS)

    Meng, Yuanliang

    In this study, the iron (II) hydroxide -- water system has been investigated at high temperatures by using molecular dynamics (MD) simulations. The simulation results reveal that at infinite dilution both Fe2+ cation and OH- anion have 6 water molecules within their first hydration shell and both types of ionic species experience a dramatic increase in their diffusion coefficients at near and supercritical conditions. The process of iron (II) hydroxide cluster formation has been simulated. The nano-clusters of larger sizes formed in supercritical water tend to be in an amorphous state. After having been quenched by an inert gas bath, iron (II) hydroxide nano-clusters with various structures have been produced. The geometries and associated binding energies of these species are given in detail. The vibrational spectra of iron (II) hydroxide clusters are also derived and compared with the spectrum of a bulk solid. The obtained results have a practical value for the analysis of potential corrosion products in supercritical water-cooled reactor (SCWR) which is employed in the new generation nuclear power plant design (GEN IV). This work also illustrates the process of hydrothermal synthesis of oxide nano-particles.

  5. Microstructure of ambient and supercritical water. Direct comparison between simulation and neutron scattering experiments

    SciTech Connect

    Chialvo, A.A.; Cummings, P.T. |

    1996-01-25

    Molecular dynamics simulations of SPC, SPC/E, TIP4P, and ST2 water models are performed at ambient and two supercritical conditions make a direct comparison with recent microstructural data obtained by neutron diffraction with isotopic substitution (NDIS) experiments. The models generally fail to accurately predict details of the NDIS results at supercritical conditions, even though they are somewhat successful at ambient conditions. The failure is not as pronounced as that expected by Postorino et al. because of an unusual density dependence in the structure predicted by two of the models. We also evaluate a model for supercritical water denoted SPCG, a modification of the SPC and SPC/E models, in which the dipole moment is reduced to the bare dipole moment of water. For this model, the predicted structure at supercritical conditions is in much better agreement with experiment. A geometric definition of hydrogen bonding is used to gain insight into the angular dependence of the H...O pair distribution function g{sub OH}(r,{omega}). The simulation results for the five models indicate a strong orientational dependence for the g{sub OH}(r,{omega}) along the H-bonding orientations, with an approximately constant relative strength from ambient to supercritical conditions, suggesting that the angle-averaged radial distribution function, g{sub OH}(r), and its volume integral over the first solvation shell, n{sub OH}(r), may not in themselves be good measures of the strength of the H-bonding. 46 refs., 15 figs., 2 tabs.

  6. Study of the Hydrogen Bond Network in sub-and supercritical Water by Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Krishtal, S.; Kiselev, M.; Puhovski, Y.; Kerdcharoen, T.; Hannongbua, S.; Heinzinger, K.

    2001-08-01

    For 12 points along the tangent to the saturation curve at the critical point the temperature dependen­cies of the heights of the first maximum in the 0 -0 RDF, the average number of hydrogen bonds, and the self-diffusion coefficients have been calculated from MD simulations. The curves of these three properties show an inflection near the critical point. To improve the understanding of these changes in going from subcritical to supercritical water the librational spectra and the change in the fractions of wa­ter molecules with a given number of hydrogen bonds as a function of temperature have been derived from the simulations, additionally.

  7. Survey: Destruction of chemical agent simulants in supercritical water oxidation. Master's thesis

    SciTech Connect

    Blank, M.R.

    1992-07-01

    The supercritical water oxidation (SCWO) process exhibits distinct advantages for destruction of toxic wastes. Examples of these wastes are two chemical agent simulants, dimethyl methylphosphonate (DMMP) and thiodiglycol (2,2'-thiodiethanol). DMMP is similar to the nerve agent GB Sarin in structure, and thiodiglycol is a hydrolysis product of the blister agent HD Sulfur Mustard. Both simulants are miscible in water and relatively non-toxic in comparison to the actual chemical agents. Using a Laboratory-scale, batch three temperatures were investigated: 425 deg C, 450 deg C, and 500 deg C with an initial concentration of one percent by volume, 11,450 mg/L for DMMP and 12,220 mg/L for thiodiglycol. Residence times investigated were: 1, 2, 3, 6, and 8 minutes. Reactor beat-up (H.U.) was determined to be one minute. Both pyrolysis and oxidation tests were conducted. Oxygen levels were uniformly set at 200% of stoichiometric requirements for the parent compounds.

  8. Simulations of acid dissociation constants of polyprotic acids in near-critical and supercritical water.

    PubMed

    Halstead, Simon J; An, Pengna

    2013-12-01

    This paper reports a molecular dynamics study on the dissociation of sulfuric acid and phosphoric acid in near-critical and supercritical water. pK(a) is known to vary as the temperature and pressure vary, and this variation has important implications for corrosion in supercritical water reaction vessels. This work uses the SPC/E water model and solutes based upon DFT calculations to examine both structural and thermodynamic properties of the dissociation processes. An increase in solute-solvent ordering is observed for larger charges, and this also corresponds to a lower rate of diffusion. All dissociation reactions become less favored with increasing temperature except pK(a1) for sulfuric acid which becomes significantly more favored until 748 K.

  9. Destruction of chemical agent simulants in a supercritical water oxidation bench-scale reactor.

    PubMed

    Veriansyah, Bambang; Kim, Jae-Duck; Lee, Jong-Chol

    2007-08-17

    A new design of supercritical water oxidation (SCWO) bench-scale reactor has been developed to handle high-risk wastes resulting from munitions demilitarization. The reactor consists of a concentric vertical double wall in which SCWO reaction takes place inside an inner tube (titanium grade 2, non-porous) whereas pressure resistance is ensured by a Hastelloy C-276 external vessel. The performances of this reactor were investigated with two different kinds of chemical warfare agent simulants: OPA (a mixture of isopropyl amine and isopropyl alcohol) as the binary precursor for nerve agent of sarin and thiodiglycol [TDG, (HOC(2)H(4))2S] as the model organic sulfur heteroatom. High destruction rates based on total organic carbon (TOC) were achieved (>99.99%) without production of chars or undesired gases such as carbon monoxide and methane. The carbon-containing product was carbon dioxide whereas the nitrogen-containing products were nitrogen and nitrous oxide. Sulfur was totally recovered in the aqueous effluent as sulfuric acid. No corrosion was noticed in the reactor after a cumulative operation time of more than 250 h. The titanium tube shielded successfully the pressure vessel from corrosion.

  10. Correlated Particle Motion and THz Spectral Response of Supercritical Water

    NASA Astrophysics Data System (ADS)

    Śmiechowski, Maciej; Schran, Christoph; Forbert, Harald; Marx, Dominik

    2016-01-01

    Molecular dynamics simulations of supercritical water reveal distinctly different distance-dependent modulations of dipolar response and correlations in particle motion compared to ambient conditions. The strongly perturbed H-bond network of water at supercritical conditions allows for considerable translational and rotational freedom of individual molecules. These changes give rise to substantially different infrared spectra and vibrational density of states at THz frequencies for densities above and below the Widom line that separates percolating liquidlike and clustered gaslike supercritical water.

  11. Removing Solids From Supercritical Water

    NASA Technical Reports Server (NTRS)

    Hong, Glenn T.

    1992-01-01

    Apparatus removes precipitated inorganic salts and other solids in water-recycling process. Designed for use with oxidation in supercritical water which treats wastes and yields nearly pure water. Heating coils and insulation around vessel keep it hot. Locking bracket seals vessel but allows it to be easily opened for replacement of filled canisters.

  12. iTOUGH2-EOS1SC. Multiphase Reservoir Simulator for Water under Sub- and Supercritical Conditions. User's Guide

    SciTech Connect

    Magnusdottir, Lilja; Finsterle, Stefan

    2015-03-01

    Supercritical fluids exist near magmatic heat sources in geothermal reservoirs, and the high enthalpy fluid is becoming more desirable for energy production with advancing technology. In geothermal modeling, the roots of the geothermal systems are normally avoided but in order to accurately predict the thermal behavior when wells are drilled close to magmatic intrusions, it is necessary to incorporate the heat sources into the modeling scheme. Modeling supercritical conditions poses a variety of challenges due to the large gradients in fluid properties near the critical zone. This work focused on using the iTOUGH2 simulator to model the extreme temperature and pressure conditions in magmatic geothermal systems.

  13. Independent pairs and Monte-Carlo simulations of the geminate recombination of solvated electrons in liquid-to-supercritical water.

    PubMed

    Torres-Alacan, Joel; Kratz, Stephan; Vöhringer, Peter

    2011-12-14

    Independent pairs (IP) and Monte Carlo (MC) simulations are employed to model experimental femtosecond time-resolved pump-probe spectroscopic data on the geminate recombination dynamics of solvated electrons in liquid-to-supercritical water. The hydrated electron was created by two-photon ionization of the neat fluid with a total ionization energy of 9.3 eV. In both numerical approaches, the ejection length, , (i.e. the distance from the ionization core, at which the electron is thermally and spatially localized) is used as the primary adjustable fitting parameter that can bring both model simulations into quantitative agreement with the ultrafast kinetic experiment. The influence of the thermodynamic conditions on the ejection length and on the recombination mechanism is discussed. Whereas in the compressed liquid associated with a high dielectric constant (ε ≥ 20), the electron recombines predominantly with the OH radical, the dissociative recombination via charge neutralization with the hydronium cation takes over at small dielectric constants (ε < 20). The importance of charge-dipole interactions for Monte-Carlo simulations of the recombination reactions of the hydrated electrons in the low-permittivity region is stressed. PMID:21996942

  14. Supercritical Water Mixture (SCWM) Experiment

    NASA Technical Reports Server (NTRS)

    Hicks, Michael C.; Hegde, Uday G.

    2012-01-01

    The subject presentation, entitled, Supercritical Water Mixture (SCWM) Experiment, was presented at the International Space Station (ISS) Increment 33/34 Science Symposium. This presentation provides an overview of an international collaboration between NASA and CNES to study the behavior of a dilute aqueous solution of Na2SO4 (5% w) at near-critical conditions. The Supercritical Water Mixture (SCWM) investigation, serves as important precursor work for subsequent Supercritical Water Oxidation (SCWO) experiments. The SCWM investigation will be performed in DECLICs High Temperature Insert (HTI) for the purpose of studying critical fluid phenomena at high temperatures and pressures. The HTI includes a completely sealed and integrated test cell (i.e., Sample Cell Unit SCU) that will contain approximately 0.3 ml of the aqueous test solution. During the sequence of tests, scheduled to be performed in FY13, temperatures and pressures will be elevated to critical conditions (i.e., Tc = 374C and Pc = 22 MPa) in order to observe salt precipitation, precipitate agglomeration and precipitate transport in the presence of a temperature gradient without the influences of gravitational forces. This presentation provides an overview of the motivation for this work, a description of the DECLIC HTI hardware, the proposed test sequences, and a brief discussion of the scientific research objectives.

  15. Lattice Boltzmann simulations of supercritical CO2-water drainage displacement in porous media: CO2 saturation and displacement mechanism.

    PubMed

    Yamabe, Hirotatsu; Tsuji, Takeshi; Liang, Yunfeng; Matsuoka, Toshifumi

    2015-01-01

    CO2 geosequestration in deep aquifers requires the displacement of water (wetting phase) from the porous media by supercritical CO2 (nonwetting phase). However, the interfacial instabilities, such as viscous and capillary fingerings, develop during the drainage displacement. Moreover, the burstlike Haines jump often occurs under conditions of low capillary number. To study these interfacial instabilities, we performed lattice Boltzmann simulations of CO2-water drainage displacement in a 3D synthetic granular rock model at a fixed viscosity ratio and at various capillary numbers. The capillary numbers are varied by changing injection pressure, which induces changes in flow velocity. It was observed that the viscous fingering was dominant at high injection pressures, whereas the crossover of viscous and capillary fingerings was observed, accompanied by Haines jumps, at low injection pressures. The Haines jumps flowing forward caused a significant drop of CO2 saturation, whereas Haines jumps flowing backward caused an increase of CO2 saturation (per injection depth). We demonstrated that the pore-scale Haines jumps remarkably influenced the flow path and therefore equilibrium CO2 saturation in crossover domain, which is in turn related to the storage efficiency in the field-scale geosequestration. The results can improve our understandings of the storage efficiency by the effects of pore-scale displacement phenomena.

  16. Supercritical Water Oxidation Data Acquisition Testing

    SciTech Connect

    K. M. Garcia

    1996-08-01

    Supercritical Water Oxidation (SCWO) is a high pressure oxidation process that blends air, water, and organic waste material in an oxidizer in which where the temperature and pressure in the oxidizer are maintained above the critical point of water. Supercritical water mixed with hydrocarbons, which would be insoluble at subcritical conditions, forms a homogeneous phase which possesses properties associated with both a gas and a liquid. Hydrocarbons in contact with oxygen and SCW are readily oxidized. These properties of SCW make it an attractive means for the destruction of waste streams containing organic materials. SCWO technology holds great promise for treating mixed wastes in an environmentally safe and efficient manner. In the spring of 1994 the U.S. Department of Energy (DOE) initiated a Supercritical Water Oxidation Data Acquisition Testing (SCWODAT) program. The SCWODAT program provided further information and operational data on the effectiveness of treating both simulated mixed waste and typical Navy hazardous waste using the SCWO technology. The program concentrated on the acquisition of data through pilot plant testing. The Phase I DOE testing used a simulated waste stream that contained a complex machine cutting oil and metals, that acted as surrogates for radionuclides. The Phase II Navy testing included pilot testing using hazardous waste materials to demonstrate the effectiveness of the SCWO technology. The SCWODAT program demonstrated that the SCWO process oxidized the simulated waste stream containing complex machine cutting oil, selected by DOE as representative of one of the most difficult of the organic waste streams for which SCWO had been applied. The simulated waste stream with surrogate metals in solution was oxidized, with a high destruction efficiency, on the order of 99.97%, in both the neutralized and unneutralized modes of operation.

  17. The solvated electron in supercritical water

    SciTech Connect

    Bartels, D. M.; Takahashi, K.; Cline, J.; Jonah, C. D.

    2000-03-09

    In order to investigate the feasibility for high-efficiency supercritical-water-cooled nuclear reactors, a study of radiation chemistry in supercritical water has been undertaken. Preliminary results in measurement of the optical absorption of the hydrated electron are reported, and compared with recent anion cluster data.

  18. Supercritical water oxidation - Microgravity solids separation

    NASA Technical Reports Server (NTRS)

    Killilea, William R.; Hong, Glenn T.; Swallow, Kathleen C.; Thomason, Terry B.

    1988-01-01

    This paper discusses the application of supercritical water oxidation (SCWO) waste treatment and water recycling technology to the problem of waste disposal in-long term manned space missions. As inorganic constituents present in the waste are not soluble in supercritical water, they must be removed from the organic-free supercritical fluid reactor effluent. Supercritical water reactor/solids separator designs capable of removing precipitated solids from the process' supercritical fluid in zero- and low- gravity environments are developed and evaluated. Preliminary experiments are then conducted to test the concepts. Feed materials for the experiments are urine, feces, and wipes with the addition of reverse osmosis brine, the rejected portion of processed hygiene water. The solid properties and their influence on the design of several oxidation-reactor/solids-separator configurations under study are presented.

  19. Fundamental kinetics and mechanistic pathways for oxidation reactions in supercritical water

    NASA Technical Reports Server (NTRS)

    Webley, Paul A.; Tester, Jefferson W.

    1988-01-01

    Oxidation of the products of human metabolism in supercritical water has been shown to be an efficient way to accomplish the on-board water/waste recycling in future long-term space flights. Studies of the oxidation kinetics of methane to carbon dioxide in supercritical water are presented in this paper in order to enhance the fundamental understanding of the oxidation of human waste compounds in supercritical water. It is concluded that, although the elementary reaction models remain the best hope for simulating oxidation in supercritical water, several modifications to existing mechanisms need to be made to account for the role of water in the reaction mechanism.

  20. Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

    NASA Astrophysics Data System (ADS)

    Olanrewaju, Kazeem Bode

    The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

  1. Supercritical water oxidation of landfill leachate

    SciTech Connect

    Wang Shuzhong; Guo Yang; Chen Chongming; Zhang Jie; Gong Yanmeng; Wang Yuzhen

    2011-09-15

    Highlights: > Thermal analysis of NH{sub 3} in supercritical water oxidation reaction. > Research on the catalytic reaction of landfill leachate by using response surface method. > Kinetic research of supercritical water oxidation of NH{sub 3} with and without MnO{sub 2} catalyst. - Abstract: In this paper, ammonia as an important ingredient in landfill leachate was mainly studied. Based on Peng-Robinson formulations and Gibbs free energy minimization method, the estimation of equilibrium composition and thermodynamic analysis for supercritical water oxidation of ammonia (SCWO) was made. As equilibrium is reached, ammonia could be totally oxidized in SCW. N{sub 2} is the main product, and the formation of NO{sub 2} and NO could be neglected. The investigation on SCWO of landfill leachate was conducted in a batch reactor at temperature of 380-500 deg. C, reaction time of 50-300 s and pressure of 25 MPa. The effect of reaction parameters such as oxidant equivalent ratio, reaction time and temperature were investigated. The results showed that COD and NH{sub 3} conversion improved as temperature, reaction time and oxygen excess increased. Compared to organics, NH{sub 3} is a refractory compound in supercritical water. The conversion of COD and NH{sub 3} were higher in the presence of MnO{sub 2} than that without catalyst. The interaction between reaction temperature and time was analyzed by using response surface method (RSM) and the results showed that its influence on the NH{sub 3} conversion was relatively insignificant in the case without catalyst. A global power-law rate expression was regressed from experimental data to estimate the reaction rate of NH{sub 3}. The activation energy with and without catalyst for NH{sub 3} oxidation were 107.07 {+-} 8.57 kJ/mol and 83.22 {+-} 15.62 kJ/mol, respectively.

  2. Supercritical water oxidation data acquisition testing. Final report, Volume II

    SciTech Connect

    1996-11-01

    Supercritical Water Oxidation (SCWO) technology holds great promise for treating mixed wastes, in an environmentally safe and efficient manner. In the spring of 1994 the US Department of Energy (DOE), Idaho Operations Office awarded Stone & Webster Engineering Corporation, of Boston Massachusetts and its sub-contractor MODAR, Inc. of Natick Massachusetts a Supercritical Water Oxidation Data Acquisition Testing (SCWODAT) program. The SCWODAT program was contracted through a Cooperative Agreement that was co-funded by the US Department of Energy and the Strategic Environmental Research and Development Program. The SCWODAT testing scope outlined by the DOE in the original Cooperative Agreement and amendments thereto was initiated in June 1994 and successfully completed in December 1995. The SCWODAT program provided further information and operational data on the effectiveness of treating both simulated mixed waste and typical Navy hazardous waste using the MODAR SCWO technology.

  3. Supercritical methanol for polyethylene terephthalate depolymerization: Observation using simulator

    SciTech Connect

    Genta, Minoru; Iwaya, Tomoko; Sasaki, Mitsuru; Goto, Motonobu

    2007-07-01

    To apply PET depolymerization in supercritical methanol to commercial recycling, the benefits of supercritical methanol usage in PET depolymerization was investigated from the viewpoint of the reaction rate and energy demands. PET was depolymerized in a batch reactor at 573 K in supercritical methanol under 14.7 MPa and in vapor methanol under 0.98 MPa in our previous work. The main products of both reactions were the PET monomers of dimethyl terephthalate (DMT) and ethylene glycol (EG). The rate of PET depolymerization in supercritical methanol was faster than that of PET depolymerization in vapor methanol. This indicates supercritical fluid is beneficial in reducing reaction time without the use of a catalyst. We depicted the simple process flow of PET depolymerization in supercritical methanol and in vapor methanol, and by simulation evaluated the total heat demand of each process. In this simulation, bis-hydroxyethyl terephthalate (BHET) was used as a model component of PET. The total heat demand of PET depolymerization in supercritical methanol was 2.35 x 10{sup 6} kJ/kmol Produced-DMT. That of PET depolymerization in vapor methanol was 2.84 x 10{sup 6} kJ/kmol Produced-DMT. The smaller total heat demand of PET depolymerization in supercritical methanol clearly reveals the advantage of using supercritical fluid in terms of energy savings.

  4. Supercritical water oxidation of products of human metabolism

    NASA Technical Reports Server (NTRS)

    Tester, Jefferson W.; Orge A. achelling, Richard K. ADTHOMASSON; Orge A. achelling, Richard K. ADTHOMASSON

    1986-01-01

    Although the efficient destruction of organic material was demonstrated in the supercritical water oxidation process, the reaction kinetics and mechanisms are unknown. The kinetics and mechanisms of carbon monoxide and ammonia oxidation in and reaction with supercritical water were studied experimentally. Experimental oxidation of urine and feces in a microprocessor controlled system was performed. A minaturized supercritical water oxidation process for space applications was design, including preliminary mass and energy balances, power, space and weight requirements.

  5. Etching of glass microchips with supercritical water.

    PubMed

    Karásek, Pavel; Grym, Jakub; Roth, Michal; Planeta, Josef; Foret, František

    2015-01-01

    A novel method of etching channels in glass microchips with the most tunable solvent, water, was tested as an alternative to common hydrogen fluoride-containing etchants. The etching properties of water strongly depend on temperature and pressure, especially in the vicinity of the water critical point. The chips were etched at the subcritical, supercritical and critical temperature of water, and the resulting channel shape, width, depth and surface morphology were studied by scanning electron microscopy and 3D laser profilometry. Channels etched with the hot water were compared with the chips etched with standard hydrogen fluoride-containing solution. Depending on the water pressure and temperature, the silicate dissolved from the glass could be re-deposited on the channel surface. This interesting phenomenon is described together with the conditions necessary for its utilization. The results illustrate the versatility of pure water as a glass etching and surface morphing agent.

  6. Supercritical water oxidation of ammonium picrate

    SciTech Connect

    LaJeunesse, C.A.; Mills, B.E.; Brown, B.G.

    1994-11-01

    This study demonstrates the feasibility of using supercritical water oxidation to destroy ammonium picrate. Analyses of reactor effluent composition at various temperatures, residence times, and oxidant concentrations were used to design an improved reactor configuration for achieving destruction with minimum corrosion. The engineering evaluation reactor, a room-sized laboratory scale reactor, was reconfigured to incorporate this design change. Destruction of ammonium picrate with minimized corrosion was demonstrated on this reconfigured reactor. Factors that must be considered in scaling up to pilot plant size are discussed.

  7. Supercritical water oxidation technology for DWPF

    SciTech Connect

    Carter, J.T.; Gentilucci, J.A.

    1992-02-07

    At the request of Mr. H.L. Brandt and others in the Savannah River Field Office High Level Waste Division office, DWPF, and SRL personnel have reviewed two potential applications for supercritical water oxidation technology in DWPF. The first application would replace the current hydrolysis process by destroying the organic fractions of the precipitated cesium / potassium tetraphenylborate slurry. The second application pertains to liquid benzene destruction. After a thorough evaluation the first application is not recommended. The second is ready to be tested if needed.

  8. Supercritical Water Process for the Chemical Recycling of Waste Plastics

    NASA Astrophysics Data System (ADS)

    Goto, Motonobu

    2010-11-01

    The development of chemical recycling of waste plastics by decomposition reactions in sub- and supercritical water is reviewed. Decomposition reactions proceed rapidly and selectively using supercritical fluids compared to conventional processes. Condensation polymerization plastics such as PET, nylon, and polyurethane, are relatively easily depolymerized to their monomers in supercritical water. The monomer components are recovered in high yield. Addition polymerization plastics such as phenol resin, epoxy resin, and polyethylene, are also decomposed to monomer components with or without catalysts. Recycling process of fiber reinforced plastics has been studied. Pilot scale or commercial scale plants have been developed and are operating with sub- and supercritical fluids.

  9. Computational Fluid Dynamics Analysis of Canadian Supercritical Water Reactor (SCWR)

    NASA Astrophysics Data System (ADS)

    Movassat, Mohammad; Bailey, Joanne; Yetisir, Metin

    2015-11-01

    A Computational Fluid Dynamics (CFD) simulation was performed on the proposed design for the Canadian SuperCritical Water Reactor (SCWR). The proposed Canadian SCWR is a 1200 MW(e) supercritical light-water cooled nuclear reactor with pressurized fuel channels. The reactor concept uses an inlet plenum that all fuel channels are attached to and an outlet header nested inside the inlet plenum. The coolant enters the inlet plenum at 350 C and exits the outlet header at 625 C. The operating pressure is approximately 26 MPa. The high pressure and high temperature outlet conditions result in a higher electric conversion efficiency as compared to existing light water reactors. In this work, CFD simulations were performed to model fluid flow and heat transfer in the inlet plenum, outlet header, and various parts of the fuel assembly. The ANSYS Fluent solver was used for simulations. Results showed that mass flow rate distribution in fuel channels varies radially and the inner channels achieve higher outlet temperatures. At the outlet header, zones with rotational flow were formed as the fluid from 336 fuel channels merged. Results also suggested that insulation of the outlet header should be considered to reduce the thermal stresses caused by the large temperature gradients.

  10. Containment system for supercritical water oxidation reactor

    DOEpatents

    Chastagner, Philippe

    1994-01-01

    A system for containment of a supercritical water oxidation reactor in the event of a rupture of the reactor. The system includes a containment for housing the reaction vessel and a communicating chamber for holding a volume of coolant, such as water. The coolant is recirculated and sprayed to entrain and cool any reactants that might have escaped from the reaction vessel. Baffles at the entrance to the chamber prevent the sprayed coolant from contacting the reaction vessel. An impact-absorbing layer is positioned between the vessel and the containment to at least partially absorb momentum of any fragments propelled by the rupturing vessel. Remote, quick-disconnecting fittings exterior to the containment, in cooperation with shut-off valves, enable the vessel to be isolated and the system safely taken off-line. Normally-closed orifices throughout the containment and chamber enable decontamination of interior surfaces when necessary.

  11. Containment system for supercritical water oxidation reactor

    DOEpatents

    Chastagner, P.

    1994-07-05

    A system is described for containment of a supercritical water oxidation reactor in the event of a rupture of the reactor. The system includes a containment for housing the reaction vessel and a communicating chamber for holding a volume of coolant, such as water. The coolant is recirculated and sprayed to entrain and cool any reactants that might have escaped from the reaction vessel. Baffles at the entrance to the chamber prevent the sprayed coolant from contacting the reaction vessel. An impact-absorbing layer is positioned between the vessel and the containment to at least partially absorb momentum of any fragments propelled by the rupturing vessel. Remote, quick-disconnecting fittings exterior to the containment, in cooperation with shut-off valves, enable the vessel to be isolated and the system safely taken off-line. Normally-closed orifices throughout the containment and chamber enable decontamination of interior surfaces when necessary. 2 figures.

  12. Pyrite in contact with supercritical water: the desolation of steam.

    PubMed

    Stirling, András; Rozgonyi, Tamás; Krack, Matthias; Bernasconi, Marco

    2015-07-14

    The supercritical water-pyrite interface has been studied by ab initio molecular dynamics simulation. Extreme conditions are relevant in the iron-sulfur world (ISW) theory where prebiotic chemical reactions are postulated to occur at the mineral-water interface. We have investigated the properties of this interface under such conditions. We have come to the conclusion that hot-pressurized water on pyrite leads to an interface where a dry pyrite surface is in contact with the nearby SC water without significant chemical interactions. This picture is markedly different from that under ambient conditions where the surface is fully covered with adsorbed water molecules which is of relevance for the surface reactions of the ISW hypothesis.

  13. Pyrite in contact with supercritical water: the desolation of steam.

    PubMed

    Stirling, András; Rozgonyi, Tamás; Krack, Matthias; Bernasconi, Marco

    2015-07-14

    The supercritical water-pyrite interface has been studied by ab initio molecular dynamics simulation. Extreme conditions are relevant in the iron-sulfur world (ISW) theory where prebiotic chemical reactions are postulated to occur at the mineral-water interface. We have investigated the properties of this interface under such conditions. We have come to the conclusion that hot-pressurized water on pyrite leads to an interface where a dry pyrite surface is in contact with the nearby SC water without significant chemical interactions. This picture is markedly different from that under ambient conditions where the surface is fully covered with adsorbed water molecules which is of relevance for the surface reactions of the ISW hypothesis. PMID:26077541

  14. Code System for Supercritical Water Cooled Reactor LOCA Analysis.

    1999-10-13

    Version 00 The new SCRELA code was developed to analyze the LOCA of the supercritical water cooled reactor. Since the currently available LWR codes for LOCA analysis could not analyze the significant differences in reactor characteristics between the supercritical-water cooled reactor and the current LWR, the first objective of this code development was to analyze the uniqueness of this reactor. The behavior of the supercritical water in the blowdown phase and the reflood phase ismore » modeled.« less

  15. Stability Analysis of a Uniformly Heated Channel with Supercritical Water

    SciTech Connect

    Ortega Gomez, T.; Class, A.; Schulenberg, T.; Lahey, R.T. Jr.

    2006-07-01

    The thermal-hydraulic stability of a uniformly heated channel at supercritical water pressure has been investigated to help understand the system instability phenomena which may occur in Supercritical Water Nuclear Reactors (SCWR). We have extended the modeling approach often used for Boiling Water Nuclear Reactor (BWR) stability analysis to supercritical pressure operation conditions. We have shown that Ledinegg excursive instabilities and pressure-drop oscillations (PDO) will not occur in supercritical water systems. The linear stability characteristics of a typical uniformly heated channel were computed by evaluating the eigenvalues of the model. An analysis of non-linear instability phenomena was also performed in the time domain and the dynamic bifurcations were evaluated. (authors)

  16. Corrosion Behavior of Candidate Alloys for Supercritical Water Reactors

    SciTech Connect

    Sridharan, K.; Zillmer, A.; Licht, J.R.; Allen, T.R.; Anderson, M.H.; Tan, L.

    2004-07-01

    The corrosion and stress corrosion cracking behavior of metallic cladding and other core internal structures is critical to the success of the Generation IV Supercritical Water-cooled Reactors (SCWR). The eventual materials selected will be chosen based on the combined corrosion, stress-corrosion, mechanical performance, and radiation stability properties. Among the materials being considered are austenitic stainless steels, ferritic/martensitic steels, and nickel-base alloys. This paper reports initial studies on the corrosion performance of the candidate alloys 316 austenitic stainless steel, Inconel 718, and Zircaloy-2, all exposed to supercritical water at 300-500 deg. C in a corrosion loop at the University of Wisconsin. Long-term corrosion performance of AISI 347, also a candidate austenitic steel, has also been examined by sectioning samples from a component that was exposed for a period of about 30 years in supercritical water at the Genoa 3 Supercritical Water fossil power plant located in Genoa, Wisconsin. (authors)

  17. Near Term Application of Supercritical Water Technologies

    SciTech Connect

    Vogt, Bastian; Starflinger, Joerg; Schulenberg, Thomas

    2006-07-01

    A pressurized water reactor with a supercritical water primary loop is analyzed (PWR-SC) within this paper. It will be shown that the PWR-SC offers considerable advantages in the fields of safety, economy and efficiency compared with a conventional PWR design. A cycle analysis shows that the net plant efficiency increases by 2% compared to currently operated or built systems. In addition, the mass flow rate of the primary side is strongly decreased, which enables a reduction of the primary pump power by a factor of 4. In the secondary loop, the mass flow rate can be decreased by about 15%, which allows down-scaling of all secondary side components such as turbines, condensers and feed-water preheat systems as a consequence of the high core exit temperature. A coupled core analysis and a hot channel factor analysis are performed to demonstrate the promising safety features of the PWR-SC and to show the technical feasibility of such a system. (authors)

  18. Process for treating effluent from a supercritical water oxidation reactor

    DOEpatents

    Barnes, C.M.; Shapiro, C.

    1997-11-25

    A method for treating a gaseous effluent from a supercritical water oxidation reactor containing entrained solids is provided comprising the steps of expanding the gas/solids effluent from a first to a second lower pressure at a temperature at which no liquid condenses; separating the solids from the gas effluent; neutralizing the effluent to remove any acid gases; condensing the effluent; and retaining the purified effluent to the supercritical water oxidation reactor. 6 figs.

  19. Process for treating effluent from a supercritical water oxidation reactor

    DOEpatents

    Barnes, Charles M.; Shapiro, Carolyn

    1997-01-01

    A method for treating a gaseous effluent from a supercritical water oxidation reactor containing entrained solids is provided comprising the steps of expanding the gas/solids effluent from a first to a second lower pressure at a temperature at which no liquid condenses; separating the solids from the gas effluent; neutralizing the effluent to remove any acid gases; condensing the effluent; and retaining the purified effluent to the supercritical water oxidation reactor.

  20. The Widom line and dynamical crossover in supercritical water: Popular water models versus experiments

    NASA Astrophysics Data System (ADS)

    Corradini, D.; Rovere, M.; Gallo, P.

    2015-09-01

    In a previous study [Gallo et al., Nat. Commun. 5, 5806 (2014)], we have shown an important connection between thermodynamic and dynamical properties of water in the supercritical region. In particular, by analyzing the experimental viscosity and the diffusion coefficient obtained in simulations performed using the TIP4P/2005 model, we have found that the line of response function maxima in the one phase region, the Widom line, is connected to a crossover from a liquid-like to a gas-like behavior of the transport coefficients. This is in agreement with recent experiments concerning the dynamics of supercritical simple fluids. We here show how different popular water models (TIP4P/2005, TIP4P, SPC/E, TIP5P, and TIP3P) perform in reproducing thermodynamic and dynamic experimental properties in the supercritical region. In particular, the comparison with experiments shows that all the analyzed models are able to qualitatively predict the dynamical crossover from a liquid-like to a gas-like behavior upon crossing the Widom line. Some of the models perform better in reproducing the pressure-temperature slope of the Widom line of supercritical water once a rigid shift of the phase diagram is applied to bring the critical points to coincide with the experimental ones.

  1. The Widom line and dynamical crossover in supercritical water: Popular water models versus experiments

    SciTech Connect

    Corradini, D.; Rovere, M.; Gallo, P.

    2015-09-21

    In a previous study [Gallo et al., Nat. Commun. 5, 5806 (2014)], we have shown an important connection between thermodynamic and dynamical properties of water in the supercritical region. In particular, by analyzing the experimental viscosity and the diffusion coefficient obtained in simulations performed using the TIP4P/2005 model, we have found that the line of response function maxima in the one phase region, the Widom line, is connected to a crossover from a liquid-like to a gas-like behavior of the transport coefficients. This is in agreement with recent experiments concerning the dynamics of supercritical simple fluids. We here show how different popular water models (TIP4P/2005, TIP4P, SPC/E, TIP5P, and TIP3P) perform in reproducing thermodynamic and dynamic experimental properties in the supercritical region. In particular, the comparison with experiments shows that all the analyzed models are able to qualitatively predict the dynamical crossover from a liquid-like to a gas-like behavior upon crossing the Widom line. Some of the models perform better in reproducing the pressure-temperature slope of the Widom line of supercritical water once a rigid shift of the phase diagram is applied to bring the critical points to coincide with the experimental ones.

  2. Application of Neutron Radiography to Flow Visualization in Supercritical Water

    NASA Astrophysics Data System (ADS)

    Takenaka, N.; Sugimoto, K.; Takami, S.; Sugioka, K.; Tsukada, T.; Adschiri, T.; Saito, Y.

    Supercritical water is used in various chemical reaction processes including hydrothermal synthesis of metal oxide nano-particles, oxidation, chemical conversion of biomass and plastics. Density of the super critical water is much less than that of the sub-critical water. By using neutron radiography, Peterson et al. have studied salt precipitation processes in supercritical water and the flow pattern in a reverse-flow vessel for salt precipitation, and Balasko et al. have revealed the behaviour of supercritical water in a container. The nano-particles were made by mixing the super critical flow and the sub critical water solution. In the present study, neutron radiography was applied to the flow visualization of the super and sub critical water mixture in a T-junction made of stainless steel pipes for high pressure and temperature conditions to investigate their mixing process. Still images by a CCD camera were obtained by using the neutron radiography system at B4 port in KUR.

  3. Effects of Gravity on Supercritical Water Oxidation (SCWO) Processes

    NASA Technical Reports Server (NTRS)

    Hegde, Uday; Hicks, Michael

    2013-01-01

    The effects of gravity on the fluid mechanics of supercritical water jets are being studied at NASA to develop a better understanding of flow behaviors for purposes of advancing supercritical water oxidation (SCWO) technologies for applications in reduced gravity environments. These studies provide guidance for the development of future SCWO experiments in new experimental platforms that will extend the current operational range of the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on board the International Space Station (ISS). The hydrodynamics of supercritical fluid jets is one of the basic unit processes of a SCWO reactor. These hydrodynamics are often complicated by significant changes in the thermo-physical properties that govern flow behavior (e.g., viscosity, thermal conductivity, specific heat, compressibility, etc), particularly when fluids transition from sub-critical to supercritical conditions. Experiments were conducted in a 150 ml reactor cell under constant pressure with water injections at various flow rates. Flow configurations included supercritical jets injected into either sub-critical or supercritical water. Profound gravitational influences were observed, particularly in the transition to turbulence, for the flow conditions under study. These results will be presented and the parameters of the flow that control jet behavior will be examined and discussed.

  4. Coal gasification with water under supercritical conditions

    SciTech Connect

    A.A. Vostrikov; S.A. Psarov; D.Yu. Dubov; O.N. Fedyaeva; M.Ya. Sokol

    2007-08-15

    The conversion of an array of coal particles in supercritical water (SCW) was studied in a semibatch reactor at a pressure of 30 MPa, 500-750{sup o}C, and a reaction time of 1-12 min. The bulk conversion, surface conversion, and random pore models were used to describe the conversion. The quantitative composition of reaction products was determined, and the dependence of the rate of reaction on the degree of coal conversion, reaction time, and reaction temperature was obtained on the assumption of a first-order reaction and the Arrhenius function. It was found that the gasification of coal under SCW conditions without the addition of oxidizing agents is a weakly endothermic process. The addition of CO{sub 2} to SCW decreased the rate of conversion and increased the yield of CO. It was found that, at a 90% conversion of the organic matter of coal (OMC) in a flow of SCW in a time of 2 min, the process power was 26 W/g per gram of OMC.

  5. Kinetics of coal conversion in supercritical water

    SciTech Connect

    Anatoli A. Vostrikov; Sergey A. Psarov; Dmitri Yu. Dubov; Oxana N. Fedyaeva; Mikhail Ya. Sokol

    2007-09-15

    Conversion of the coal particle pack in supercritical water (SCW) was studied in the semibatch reactor under the pressure of P = 30 MPa, in the temperature range of T = 500-750{sup o}C, and in the reaction time of t = 60-720 s. The experimental results were analyzed within the framework of homogeneous, nonreacted core, and random pore models. The quantitative composition of conversion products was determined. Dependences of the conversion rate on the degree of coal conversion, reaction time, and temperature were described in an assumption of the first-order reaction and Arrhenius dependence. It was found that activation energy of conversion is E = 103 kJ/mol and the pre-exponential factor is A{sub 0} = 1.3 x 10{sup 3.1} s{sup -1}. It was revealed that coal gasification in SCW without oxidants is the weakly endothermic process. The addition of CO{sub 2} into SCW decreases the conversion rate and increases the CO yield. 20 refs., 8 figs.

  6. Digested sewage sludge gasification in supercritical water.

    PubMed

    Zhai, Yunbo; Wang, Chang; Chen, Hongmei; Li, Caiting; Zeng, Guangming; Pang, Daoxiong; Lu, Pei

    2013-04-01

    Digested sewage sludge gasification in supercritical water was studied. Influences of main reaction parameters, including temperature (623-698 K), pressure (25-35 Mpa), residence time (10-15 min) and dry matter content (5-25 wt%), were investigated to optimize the gasification process. The main gas products were methane, carbon monoxide, carbon dioxide and traces of ethene, etc. Results showed that 10 wt% dry matter content digested sewage sludge at a temperature of 698 K and residence time of 50 min, with a pressure of 25 MPa, were the most favorable conditions for the sewage sludge gasification and carbon gasification efficiencies. In addition, potassium carbonate (K2CO3) was also employed as the catalyst to make a comparison between gasification with and without catalyst. When 2.6 g K2CO3 was added, a gasification efficiency of 25.26% and a carbon gasification efficiency of 20.02% were achieved, which were almost four times as much as the efficiencies without catalyst. K2CO3 has been proved to be effective in sewage sludge gasification.

  7. Multidimensional Model of Fluid Flow and Heat Transfer in Generation-IV Supercritical Water Reactors

    SciTech Connect

    Gallaway, Tara; Antal, Steven P.; Podowski, Michael Z.

    2006-07-01

    This paper is concerned with the mechanistic modeling and theoretical/computational analysis of flow and heat transfer in future Generation-IV Supercritical Water Cooled Reactors (SCWR). The issues discussed in the paper include: the development of analytical models of the properties of supercritical water, and the application of full three-dimensional computational modeling framework to simulate fluid flow and heat transfer in SCWRs. Several results of calculations are shown, including the evaluation of water properties (density, specific heat, thermal conductivity, viscosity, and Prandtl number) near the pseudo-critical temperature for various supercritical pressures, and the CFD predictions using the NPHASE computer code. It is demonstrated that the proposed approach is very promising for future mechanistic analyses of SCWR thermal-hydraulics and safety. (authors)

  8. Diffusion Limited Supercritical Water Oxidation (SCWO) in Microgravity Environments

    NASA Technical Reports Server (NTRS)

    Hicks, M. C.; Lauver, R. W.; Hegde, U. G.; Sikora, T. J.

    2006-01-01

    Tests designed to quantify the gravitational effects on thermal mixing and reactant injection in a Supercritical Water Oxidation (SCWO) reactor have recently been performed in the Zero Gravity Facility (ZGF) at NASA s Glenn Research Center. An artificial waste stream, comprising aqueous mixtures of methanol, was pressurized to approximately 250 atm and then heated to 450 C. After uniform temperatures in the reactor were verified, a controlled injection of air was initiated through a specially designed injector to simulate diffusion limited reactions typical in most continuous flow reactors. Results from a thermal mapping of the reaction zone in both 1-g and 0-g environments are compared. Additionally, results of a numerical model of the test configuration are presented to illustrate first order effects on reactant mixing and thermal transport in the absence of gravity.

  9. In-situ Neutron Tomography on Mixing Behavior of Supercritical Water and Room Temperature Water in a Tubular Flow Reactor

    NASA Astrophysics Data System (ADS)

    Takami, Seiichi; Sugioka, Ken-ichi; Ozawa, Kyohei; Tsukada, Takao; Adschiri, Tadafumi; Sugimoto, Katsumi; Takenaka, Nobuyuki; Saito, Yasushi

    We have synthesized metal oxide nanoparticles through hydrothermal reaction at around 400 °C and 25 MPa by mixing the stream of metal ion solution at room temperature with another stream of supercritical water in a continuous flow-type reactor. In order to visualize the mixing behavior of the two streams, we performed neutron tomography measurements. By performing tomography measurements while rotating the mixing piece with supplying supercritical water and room temperature water, we succeeded in obtaining the three dimensional distribution of neutron attenuation. The results clearly showed how the two streams mix, which serves as a reference for numerical simulation.

  10. Research and Development of High Temperature Light Water Cooled Reactor Operating at Supercritical-Pressure in Japan

    SciTech Connect

    Yoshiaki Oka; Katsumi Yamada

    2004-07-01

    This paper summarizes the status and future plans of research and development of the high temperature light water cooled reactor operating at supercritical-pressure in Japan. It includes; the concept development; material for the fuel cladding; water chemistry under supercritical pressure; thermal hydraulics of supercritical fluid; and the conceptual design of core and plant system. Elements of concept development of the once-through coolant cycle reactor are described, which consists of fuel, core, reactor and plant system, stability and safety. Material studies include corrosion tests with supercritical water loops and simulated irradiation tests using a high-energy transmission electron microscope. Possibilities of oxide dispersion strengthening steels for the cladding material are studied. The water chemistry research includes radiolysis and kinetics of supercritical pressure water, influence of radiolysis and radiation damage on corrosion and behavior on the interface between water and material. The thermal hydraulic research includes heat transfer tests of single tube, single rod and three-rod bundles with a supercritical Freon loop and numerical simulations. The conceptual designs include core design with a three-dimensional core simulator and sub-channel analysis, and balance of plant. (authors)

  11. Heat transfer research on supercritical water flow upward in tube

    SciTech Connect

    Li, H. B.; Yang, J.; Gu, H. Y.; Zhao, M.; Lu, D. H.; Zhang, J. M.; Wang, F.; Zhang, Y.

    2012-07-01

    The experimental research of heat transfer on supercritical water has been carried out on the supercritical water multipurpose test loop with a 7.6 mm upright tube. The experimental data of heat transfer is obtained. The experimental results of thermal-hydraulic parameters on flow and heat transfer of supercritical water show that: Heat transfer enhancement occurs when the fluid temperature reaches pseudo-critical point with low mass flow velocity, and peters out when the mass flow velocity increases. The heat transfer coefficient and Nusselt number decrease with the heat flux or system pressure increases, and increase with the increasing of mass flow velocity. The wall temperature increases when the mass flow velocity decreases or the system pressure increases. (authors)

  12. Spatial and Orientational Structure of the Hydration Shell of Benzene in Sub- and Supercritical Water.

    PubMed

    Choudhary, Ashu; Chandra, Amalendu

    2015-07-01

    The spatial and orientational structure of the solvation shell of benzene in sub- and supercritical water are investigated by means of molecular dynamics simulations. The present study reveals different local organization of water molecules at different parts of the solute. The π-hydrogen-bonding between benzene and water along the axial direction is found to exist even at supercritical conditions although to a reduced extent. The coordination number of benzene decreases substantially on increase of temperature and decrease of density. While the π-hydrogen-bonded part in the axial region shows a slight expansion, the hydrophobically solvated part in the equatorial plane shows an opposite behavior as the temperature is increased from normal to the supercritical temperature. Two other distribution functions, namely the radial/angular and spatial orientational functions (SOFs) are calculated to explore the spatially resolved angular preferences of water molecules around the benzene solute. Water molecules located axial to the benzene are found to have strong inward orientation toward the solute, however an opposite behavior is found in the equatorial region. Although at supercritical conditions, the orientational distributions of water molecules are broadened, the preferential orientations in the axial and equatorial regions remain similar to that under ambient condition on average.

  13. Supercritical water oxidation data acquisition testing. Final report, Volume I

    SciTech Connect

    1996-11-01

    This report discusses the phase one testing of a data acquisition system for a supercritical water waste oxidation system. The system is designed to destroy a wide range of organic materials in mixed wastes. The design and testing of the MODAR Oxidizer is discussed. An analysis of the optimized runs is included.

  14. SUPERCRITICAL WATER OXIDATION MODEL DEVELOPMENT FOR SELECTED EPA PRIORITY POLLUTANTS

    EPA Science Inventory

    Supercritical Water Oxidation (SCWO) evaluated for five compounds: acetic acid, 2,4-dichlorophenol, pentachlorophenol, pyridine, 2,4-dichlorophenoxyacetic acid (methyl ester). inetic models were developed for acetic acid, 2,4-dichlorophenol, and pyridine. he test compounds were e...

  15. Large-eddy simulation of trans- and supercritical injection

    NASA Astrophysics Data System (ADS)

    Müller, H.; Niedermeier, C. A.; Jarczyk, M.; Pfitzner, M.; Hickel, S.; Adams, N. A.

    2016-07-01

    In a joint effort to develop a robust numerical tool for the simulation of injection, mixing, and combustion in liquid rocket engines at high pressure, a real-gas thermodynamics model has been implemented into two computational fluid dynamics (CFD) codes, the density-based INCA and a pressure-based version of OpenFOAM. As a part of the validation process, both codes have been used to perform large-eddy simulations (LES) of trans- and supercritical nitrogen injection. Despite the different code architecture and the different subgrid scale turbulence modeling strategy, both codes yield similar results. The agreement with the available experimental data is good.

  16. Heat Transfer Phenomena in Supercritical Water Nuclear Reactors

    SciTech Connect

    Mark H. Anderson; MichaelL. Corradini; Riccardo Bonazza; Jeremy R. Licht

    2007-10-03

    A supercritical water heat transfer facility has been built at the University of Wisconsin to study heat transfer in ancircular and square annular flow channel. A series of integral heat transfer measurements has been carried out over a wide range of heat flux, mas velocity and bulk water temperatures at a pressure of 25 MPa. The circular annular test section geometry is a 1.07 cm diameter heater rod within a 4.29 diameter flow channel.

  17. Valorization of horse manure through catalytic supercritical water gasification.

    PubMed

    Nanda, Sonil; Dalai, Ajay K; Gökalp, Iskender; Kozinski, Janusz A

    2016-06-01

    The organic wastes such as lignocellulosic biomass, municipal solid waste, sewage sludge and livestock manure have attracted attention as alternative sources of energy. Cattle manure, a waste generated in surplus amounts from the feedlot, has always been a chief environmental concern. This study is focused on identifying the candidacy of horse manure as a next generation feedstock for biofuel production through supercritical water gasification. The horse manure was gasified in supercritical water to examine the effects of temperature (400-600°C), biomass-to-water ratio (1:5 and 1:10) and reaction time (15-45min) at a pressure range of 23-25MPa. The horse manure and resulting biochar were characterized through carbon-hydrogen-nitrogen-sulfur (CHNS), inductively coupled plasma-mass spectrometry (ICP-MS), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy and scanning electron microscopy (SEM). The effects of alkali catalysts such as NaOH, Na2CO3 and K2CO3 at variable concentrations (1-2wt%) were investigated to maximize the hydrogen yields. Supercritical water gasification of horse manure with 2wt% Na2CO3 at 600°C and 1:10 biomass-to-water ratio for 45min revealed maximum hydrogen yields (5.31mmol/g), total gas yields (20.8mmol/g) with greater carbon conversion efficiency (43.1%) and enhanced lower heating value of gas products (2920kJ/Nm(3)). The manure-derived biochars generated at temperatures higher than 500°C also demonstrated higher thermal stability (weight loss <34%) and larger carbon content (>70wt%) suggesting their application in enhancing soil fertility and carbon sequestration. The results propose that supercritical water gasification could be a proficient remediation technology for horse manure to generate hydrogen-rich gas products.

  18. Valorization of horse manure through catalytic supercritical water gasification.

    PubMed

    Nanda, Sonil; Dalai, Ajay K; Gökalp, Iskender; Kozinski, Janusz A

    2016-06-01

    The organic wastes such as lignocellulosic biomass, municipal solid waste, sewage sludge and livestock manure have attracted attention as alternative sources of energy. Cattle manure, a waste generated in surplus amounts from the feedlot, has always been a chief environmental concern. This study is focused on identifying the candidacy of horse manure as a next generation feedstock for biofuel production through supercritical water gasification. The horse manure was gasified in supercritical water to examine the effects of temperature (400-600°C), biomass-to-water ratio (1:5 and 1:10) and reaction time (15-45min) at a pressure range of 23-25MPa. The horse manure and resulting biochar were characterized through carbon-hydrogen-nitrogen-sulfur (CHNS), inductively coupled plasma-mass spectrometry (ICP-MS), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy and scanning electron microscopy (SEM). The effects of alkali catalysts such as NaOH, Na2CO3 and K2CO3 at variable concentrations (1-2wt%) were investigated to maximize the hydrogen yields. Supercritical water gasification of horse manure with 2wt% Na2CO3 at 600°C and 1:10 biomass-to-water ratio for 45min revealed maximum hydrogen yields (5.31mmol/g), total gas yields (20.8mmol/g) with greater carbon conversion efficiency (43.1%) and enhanced lower heating value of gas products (2920kJ/Nm(3)). The manure-derived biochars generated at temperatures higher than 500°C also demonstrated higher thermal stability (weight loss <34%) and larger carbon content (>70wt%) suggesting their application in enhancing soil fertility and carbon sequestration. The results propose that supercritical water gasification could be a proficient remediation technology for horse manure to generate hydrogen-rich gas products. PMID:27067100

  19. Transpiring wall supercritical water oxidation test reactor design report

    SciTech Connect

    Haroldsen, B.L.; Ariizumi, D.Y.; Mills, B.E.; Brown, B.G.; Rousar, D.C.

    1996-02-01

    Sandia National Laboratories is working with GenCorp, Aerojet and Foster Wheeler Development Corporation to develop a transpiring wall supercritical water oxidation reactor. The transpiring wall reactor promises to mitigate problems of salt deposition and corrosion by forming a protective boundary layer of pure supercritical water. A laboratory scale test reactor has been assembled to demonstrate the concept. A 1/4 scale transpiring wall reactor was designed and fabricated by Aerojet using their platelet technology. Sandia`s Engineering Evaluation Reactor serves as a test bed to supply, pressurize and heat the waste; collect, measure and analyze the effluent; and control operation of the system. This report describes the design, test capabilities, and operation of this versatile and unique test system with the transpiring wall reactor.

  20. Experimental study of choking flow of water at supercritical conditions

    NASA Astrophysics Data System (ADS)

    Muftuoglu, Altan

    Future nuclear reactors will operate at a coolant pressure close to 25 MPa and at outlet temperatures ranging from 500°C to 625°C. As a result, the outlet flow enthalpy in future Supercritical Water-Cooled Reactors (SCWR) will be much higher than those of actual ones which can increase overall nuclear plant efficiencies up to 48%. However, under such flow conditions, the thermal-hydraulic behavior of supercritical water is not fully known, e.g., pressure drop, forced convection and heat transfer deterioration, critical and blowdown flow rate, etc. Up to now, only a very limited number of studies have been performed under supercritical conditions. Moreover, these studies are conducted at conditions that are not representative of future SCWRs. In addition, existing choked flow data have been collected from experiments at atmospheric discharge pressure conditions and in most cases by using working fluids different than water which constrain researchers to analyze the data correctly. In particular, the knowledge of critical (choked) discharge of supercritical fluids is mandatory to perform nuclear reactor safety analyses and to design key mechanical components (e.g., control and safety relief valves, etc.). Hence, an experimental supercritical water facility has been built at Ecole Polytechnique de Montreal which allows researchers to perform choking flow experiments under supercritical conditions. The facility can also be used to carry out heat transfer and pressure drop experiments under supercritical conditions. In this thesis, we present the results obtained at this facility using a test section that contains a 1 mm inside diameter, 3.17 mm long orifice plate with sharp edges. Thus, 545 choking flow of water data points are obtained under supercritical conditions for flow pressures ranging from 22.1 MPa to 32.1 MPa, flow temperatures ranging from 50°C to 502°C and for discharge pressures from 0.1 MPa to 3.6 MPa. Obtained data are compared with the data given in

  1. Expansion dynamics of supercritical water probed by picosecond time-resolved photoelectron spectroscopy.

    PubMed

    Gladytz, Thomas; Abel, Bernd; Siefermann, Katrin R

    2015-02-21

    Vibrational excitation of liquid water with femtosecond laser pulses can create extreme states of water. Yet, the dynamics directly after initial sub-picosecond delocalization of molecular vibrations remain largely unclear. We study the ultrafast expansion dynamics of an accordingly prepared supercritical water phase with a picosecond time resolution. Our experimental setup combines vacuum-compatible liquid micro-jet technology and a table top High Harmonic light source driven by a femtosecond laser system. An ultrashort laser pulse centered at a wavelength of 2900 nm excites the OH-stretch vibration of water molecules in the liquid. The deposited energy corresponds to a supercritical phase with a temperature of about 1000 K and a pressure of more than 1 GPa. We use a time-delayed extreme ultraviolet pulse centered at 38.6 eV, and obtained via High Harmonic generation (HHG), to record valence band photoelectron spectra of the expanding water sample. The series of photoelectron spectra is analyzed with noise-corrected target transform fitting (cTTF), a specifically developed multivariate method. Together with a simple fluid dynamics simulation, the following picture emerges: when a supercritical phase of water expands into vacuum, temperature and density of the first few nanometers of the expanding phase drop below the critical values within a few picoseconds. This results in a supersaturated phase, in which condensation seeds form and grow from small clusters to large clusters on a 100 picosecond timescale.

  2. Conversion of hazardous materials using supercritical water oxidation

    DOEpatents

    Rofer, Cheryl K.; Buelow, Steven J.; Dyer, Richard B.; Wander, Joseph D.

    1992-01-01

    A process for destruction of hazardous materials in a medium of supercritical water without the addition of an oxidant material. The harzardous material is converted to simple compounds which are relatively benign or easily treatable to yield materials which can be discharged into the environment. Treatment agents may be added to the reactants in order to bind certain materials, such as chlorine, in the form of salts or to otherwise facilitate the destruction reactions.

  3. Solvation structures and dynamics of alkaline earth metal halides in supercritical water: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Keshri, Sonanki; Mandal, Ratnamala; Tembe, B. L.

    2016-09-01

    Constrained molecular dynamics simulations of alkaline earth metal halides have been carried out to investigate their structural and dynamical properties in supercritical water. Potentials of mean force (PMFs) for all the alkaline earth metal halides in supercritical water have been computed. Contact ion pairs (CIPs) are found to be more stable than all other configurations of the ion pairs except for MgI2 where solvent shared ion pair (SShIP) is more stable than the CIP. There is hardly any difference in the PMFs between the M2+ (M = Mg, Ca, Sr, Ba) and the X- (X = F, Cl, Br, I) ions whether the second X- ion is present in the first coordination shell of the M2+ ion or not. The solvent molecules in the solvation shells diffuse at a much slower rate compared to the bulk. Orientational distribution functions of solvent molecules are sharper for smaller ions.

  4. Large Eddy Simulation of Cryogenic Injection Processes at Supercritical Pressure

    NASA Technical Reports Server (NTRS)

    Oefelein, Joseph C.; Garcia, Roberto (Technical Monitor)

    2002-01-01

    This paper highlights results from the first of a series of hierarchical simulations aimed at assessing the modeling requirements for application of the large eddy simulation technique to cryogenic injection and combustion processes in liquid rocket engines. The focus is on liquid-oxygen-hydrogen coaxial injectors at a condition where the liquid-oxygen is injected at a subcritical temperature into a supercritical environment. For this situation a diffusion dominated mode of combustion occurs in the presence of exceedingly large thermophysical property gradients. Though continuous, these gradients approach the behavior of a contact discontinuity. Significant real gas effects and transport anomalies coexist locally in colder regions of the flow, with ideal gas and transport characteristics occurring within the flame zone. The current focal point is on the interfacial region between the liquid-oxygen core and the coaxial hydrogen jet where the flame anchors itself.

  5. Method and apparatus for waste destruction using supercritical water oxidation

    DOEpatents

    Haroldsen, Brent Lowell; Wu, Benjamin Chiau-pin

    2000-01-01

    The invention relates to an improved apparatus and method for initiating and sustaining an oxidation reaction. A hazardous waste, is introduced into a reaction zone within a pressurized containment vessel. An oxidizer, preferably hydrogen peroxide, is mixed with a carrier fluid, preferably water, and the mixture is heated until the fluid achieves supercritical conditions of temperature and pressure. The heating means comprise cartridge heaters placed in closed-end tubes extending into the center region of the pressure vessel along the reactor longitudinal axis. A cooling jacket surrounds the pressure vessel to remove excess heat at the walls. Heating and cooling the fluid mixture in this manner creates a limited reaction zone near the center of the pressure vessel by establishing a steady state density gradient in the fluid mixture which gradually forces the fluid to circulate internally. This circulation allows the fluid mixture to oscillate between supercritical and subcritical states as it is heated and cooled.

  6. Supercritical Water Reactor Cycle for Medium Power Applications

    SciTech Connect

    BD Middleton; J Buongiorno

    2007-04-25

    Scoping studies for a power conversion system based on a direct-cycle supercritical water reactor have been conducted. The electric power range of interest is 5-30 MWe with a design point of 20 MWe. The overall design objective is to develop a system that has minimized physical size and performs satisfactorily over a broad range of operating conditions. The design constraints are as follows: Net cycle thermal efficiency {ge}20%; Steam turbine outlet quality {ge}90%; and Pumping power {le}2500 kW (at nominal conditions). Three basic cycle configurations were analyzed. Listed in order of increased plant complexity, they are: (1) Simple supercritical Rankine cycle; (2) All-supercritical Brayton cycle; and (3) Supercritical Rankine cycle with feedwater preheating. The sensitivity of these three configurations to various parameters, such as reactor exit temperature, reactor pressure, condenser pressure, etc., was assessed. The Thermoflex software package was used for this task. The results are as follows: (a) The simple supercritical Rankine cycle offers the greatest hardware simplification, but its high reactor temperature rise and reactor outlet temperature may pose serious problems from the viewpoint of thermal stresses, stability and materials in the core. (b) The all-supercritical Brayton cycle is not a contender, due to its poor thermal efficiency. (c) The supercritical Rankine cycle with feedwater preheating affords acceptable thermal efficiency with lower reactor temperature rise and outlet temperature. (d) The use of a moisture separator improves the performance of the supercritical Rankine cycle with feedwater preheating and allows for a further reduction of the reactor outlet temperature, thus it was selected for the next step. Preliminary engineering design of the supercritical Rankine cycle with feedwater preheating and moisture separation was performed. All major components including the turbine, feedwater heater, feedwater pump, condenser, condenser pump

  7. Modeling of biomass to hydrogen via the supercritical water pyrolysis process

    SciTech Connect

    Divilio, R.J.

    1998-08-01

    A heat transfer model has been developed to predict the temperature profile inside the University of Hawaii`s Supercritical Water Reactor. A series of heat transfer tests were conducted on the University of Hawaii`s apparatus to calibrate the model. Results of the model simulations are shown for several of the heat transfer tests. Tests with corn starch and wood pastes indicated that there are substantial differences between the thermal properties of the paste compared to pure water, particularly near the pseudo critical temperature. The assumption of constant thermal diffusivity in the temperature range of 250 to 450 C gave a reasonable prediction of the reactor temperatures when paste is being fed. A literature review is presented for pyrolysis of biomass in water at elevated temperatures up to the supercritical range. Based on this review, a global reaction mechanism is proposed. Equilibrium calculations were performed on the test results from the University of Hawaii`s Supercritical Water Reactor when corn starch and corn starch and wood pastes were being fed. The calculations indicate that the data from the reactor falls both below and above the equilibrium hydrogen concentrations depending on test conditions. The data also indicates that faster heating rates may be beneficial to the hydrogen yield. Equilibrium calculations were also performed to examine the impact of wood concentration on the gas mixtures produced. This calculation showed that increasing wood concentrations favors the formation of methane at the expense of hydrogen.

  8. Molecular simulations of supercritical fluid permeation through disordered microporous carbons.

    PubMed

    Boţan, Alexandru; Vermorel, Romain; Ulm, Franz-Josef; Pellenq, Roland J-M

    2013-08-13

    Fluid transport through microporous carbon-based materials is inherent in numerous applications, ranging from gas separation by carbon molecular sieves to natural gas production from coal seams and gas shales. The present study investigates the steady-state permeation of supercritical methane in response to a constant cross-membrane pressure drop. We performed dual control volume grand canonical molecular dynamics (DCV-GCMD) simulations to mimic the conditions of actual permeation experiments. To overcome arbitrary assumptions regarding the investigated porous structures, the membranes were modeled after the CS1000a and CS1000 molecular models, which are representative of real microporous carbon materials. When adsorption-induced molecular trapping (AIMT) mechanisms are negligible, we show that the permeability of the microporous material, although not significantly sensitive to the pressure gradient, monotonically decreases with temperature and reservoir pressures, consistent with diffusion theory. However, when AIMT occurs, the permeability increases with temperature in agreement with experimental data found in the literature. PMID:23886335

  9. Formation of acrylic acid from lactic acid in supercritical water

    SciTech Connect

    Mok, W.S.L.; Antal, M.J. Jr. ); Jones, M. Jr. )

    1989-09-15

    Supercritical (SC) water is an unusual medium in which fast and specific heterolytic reactions can be conducted at temperatures as high as 400{degree}C. In supercritical water, lactic acid decomposes into gaseous and liquid products via three primary reaction pathways. Products of the acid-catalyzed heterolytic decarbonylation pathway are carbon monoxide, water, and acetaldehyde. Products of the homolytic, decarboxylation pathway are carbon dioxide, hydrogen, and acetaldehyde. Products of the heterolytic, dehydration pathway are acrylic acid and water. The intramolecular nucleophilic displacement of the {alpha}-hydroxyl by the carbonyl group of lactic acid, producing {alpha}-propiolactone as an unstable intermediate which subsequently rearranges to become the unsaturated acid, is a likely mechanism for acrylic acid formation, although an intramolecular E2 elimination initiated by attack of the carbonyl oxygen on a methyl hydrogen cannot be ruled out. Support for the former mechanism comes in part from the observed 100% relative yield of acrylic acid from {beta}-propiolactone in SC water.

  10. Hydrogen production from high moisture content biomass in supercritical water

    SciTech Connect

    Antal, M.J. Jr.; Xu, X.

    1998-08-01

    By mixing wood sawdust with a corn starch gel, a viscous paste can be produced that is easily delivered to a supercritical flow reactor by means of a cement pump. Mixtures of about 10 wt% wood sawdust with 3.65 wt% starch are employed in this work, which the authors estimate to cost about $0.043 per lb. Significant reductions in feed cost can be achieved by increasing the wood sawdust loading, but such an increase may require a more complex pump. When this feed is rapidly heated in a tubular flow reactor at pressures above the critical pressure of water (22 MPa), the sawdust paste vaporizes without the formation of char. A packed bed of carbon catalyst in the reactor operating at about 650 C causes the tarry vapors to react with water, producing hydrogen, carbon dioxide, and some methane with a trace of carbon monoxide. The temperature and history of the reactor`s wall influence the hydrogen-methane product equilibrium by catalyzing the methane steam reforming reaction. The water effluent from the reactor is clean. Other biomass feedstocks, such as the waste product of biodiesel production, behave similarly. Unfortunately, sewage sludge does not evidence favorable gasification characteristics and is not a promising feedstock for supercritical water gasification.

  11. Reactions of inorganic nitrogen species in supercritical water

    SciTech Connect

    Dell`Orco, P.C.

    1994-12-31

    Redox reactions of nitrate salts with NH3 and methanol were studied in near-critical and supercritical water at 350 to 530 C and constant pressure of 302 bar. Sodium nitrate decomposition reactions were investigated at similar conditions. Reactions were conducted in isothermal tubular reactor under plug flow. For kinetic modeling, nitrate and nitrite reactants were lumped into an NO{sub x}{sup -} reactant; kinetic expressions were developed for MNO{sub 3}/NH{sub 4}X and sodium nitrate decomposition reactions. The proposed elementary reaction mechanism for MNO{sub 3}/NH{sub 4}X reaction indicated that NO{sub 2} was the primary oxidizing species and that N{sub 2}/N{sub 2}O selectivities could be determined by the form of MNO{sub 3} used. This suggest a nitrogen control strategy for use in SCWO (supercritical water oxidation) processes; nitrate or NH3 could be used to remove the other, at reaction conditions far less severe than required by other methods. Reactions of nitrate with methanol indicated that nitrate was a better oxidant than oxygen in supercritical water. Nitrogen reaction products included NH3 and nitrite, while inorganic carbon was the major carbon reaction product. Analysis of excess experiments indicated that the reaction at 475 C was first order in methanol concentration and second order in NO{sub x}{sup -} concentration. In order to determine phase regimes for these reactions, solubility of sodium nitrate was determined for some 1:1 nitrate electrolytes. Solubilities were measured at 450 to 525 C, from 248 to 302 bar. A semi-empirical solvation model was shown to adequately describe the experimental sodium nitrate solubilities. Solubilities of Li, Na, and K nitrates revealed with cations with smaller ionic radii had greater solubilities with nitrate.

  12. Morphological variation of multiwall carbon nanotubes in supercritical water oxidation

    NASA Astrophysics Data System (ADS)

    Chang, Jia-Yaw; Lo, Bertrand; Jeng, Meili; Tzing, Shin-Hwa; Ling, Yong-Chien

    2004-09-01

    Multiwall carbon nanotubes (MWNTs) with different morphology were prepared using supercritical water (SCW) oxidation and investigated by transmission electron microscope (TEM) and electron energy-loss spectroscopy (EELS). TEM results indicate that the peeling and sharpening of MWNTs are influenced by the etching process in SCW oxidation, of which oxidation time and amount of oxygen used is crucial. A simplified etching model is proposed, which indicates that the difference of mean etching rate between two adjoining blocks causes the morphological variation of MWNTs. The EELS results show change in characteristic energy-loss peaks as a function of total shell numbers along longitudinal axis of individual peeled tube.

  13. Carbon-catalyzed gasification of organic feedstocks in supercritical water

    SciTech Connect

    Xu, X.; Matsumura, Y.; Stenberg, J.; Antal, M.J. Jr.

    1996-08-01

    Spruce wood charcoal, macadamia shell charcoal, coal activated carbon, and coconut shell activated carbon catalyze the gasification of organic compounds in supercritical water. Feedstocks studied in this paper include glycerol, glucose, cellobiose, whole biomass feedstocks (depithed bagasse liquid extract and sewage sludge), and representative Department of Defense (DoD) wastes (methanol, methyl ethyl ketone, ethylene glycol, acetic acid, and phenol). The effects of temperature, pressure, reactant concentration, weight hourly space velocity, and the type of catalyst on the gasification of glucose are reported. Complete conversion of glucose (22% by weight in water) to a hydrogen-rich synthesis gas was realized at a weight hourly space velocity (WHSV) of 22.2 h{sup {minus}1} in supercritical water at 600 C, 34.5 MPa. Complete conversions of the whole biomass feeds were also achieved at the same temperature and pressure. The destruction efficiencies for the representative DoD wastes were also high. Deactivation of the carbon catalyst was observed after 4 h of operation without swirl in the entrance region of the reactor, but the carbon gasification efficiency remained near 100% for more than 6 h when a swirl generator was employed in the entrance of the reactor.

  14. Optical monitoring of the oxidation of methane in supercritical water

    SciTech Connect

    Steeper, R.R.; Rice, S.F.

    1994-08-01

    Supercritical water oxidation is an emerging technology being developed by many laboratories and industries for the treatment of hazardous wastes. It is appropriate for the destruction of a wide variety of waste streams composed of up to 20% organics in water. Experiments were conducted in a static, high-pressure reactor to investigate the oxidation of methane in supercritical water. Pressures ranged from 138 to 275 bar, temperatures from 380 to 440{degrees}C, and equivalence ratios from 0.2 to 2.0 for initial methane concentrations around 0.1 mole/l. In these experiments, Raman spectroscopy was used as an in-situ diagnostic to monitor the concentrations of methane, oxygen, and carbon dioxide. Over this pressure range the reaction rate of methane with oxygen is unexpectedly observed to decrease with increasing pressure. A non-linear least squares fit was performed to determine four global reaction rate parameters. In contrast to results from experiments at lower initial methane concentrations, the reaction order dependency on methane is found here to be greater than unity. This finding implies that the former results cannot safely extrapolate to concentrations around 0.1 mole/l.

  15. General corrosion properties of modified PNC1520 austenitic stainless steel in supercritical water as a fuel cladding candidate material for supercritical water reactor

    NASA Astrophysics Data System (ADS)

    Nakazono, Y.; Iwai, T.; Abe, H.

    2010-03-01

    The Super-Critical Water-cooled Reactor (SCWR) has been designed and investigated because of its high thermal efficiency and plant simplification. There are some advantages including the use of a single phase coolant with high enthalpy but there are numerous potential problems, particularly with materials. As the operating temperature of supercritical water reactor will be between 280°C and 620°C with a pressure of 25MPa, the selection of materials is difficult and important. Austenitic stainless steels were selected for possible use in supercritical water systems because of their corrosion resistance and radiation resistance. The PNC1520 austenitic stainless steel developed by Japan Atomic Energy Agency (JAEA) as a nuclear fuel cladding material for a Na-cooled fast breeder reactor. The corrosion data of PNC1520 in supercritical water (SCW) is required but does not exist. The purpose of the present study is to research the corrosion properties for PNC1520 austenitic stainless steel in supercritical water. The supercritical water corrosion test was performed for the standard PNC1520 (1520S) and the Ti-additional type of PNC1520 (1520Ti) by using a supercritical water autoclave. Corrosion tests on the austenitic 1520S and 1520Ti steels in supercritical water were performed at 400, 500 and 600°C with exposures up to 1000h. The amount of weight gain, weight loss and weight of scale were evaluated after the corrosion test in supercritical water for both austenitic steels. After 1000h corrosion test performed, the weight gains of both austenitic stainless steels were less than 2 g/m2 at 400°C and 500°C . But both weight gain and weight loss of 1520Ti were larger than those of 1520S at 600°C . By increasing the temperature to 600°C, the surface of 1520Ti was covered with magnetite formed in supercritical water and dissolution of the steel alloying elements has been observed. In view of corrosion, 1520S may have larger possibility than 1520Ti to adopt a

  16. Supercritical Water as Nanomedium for Gasification of Lignite-Water Suspension

    NASA Astrophysics Data System (ADS)

    Korzh, Raisa; Bortyshevskyi, Valerii

    2016-05-01

    The gasification of an aqueous suspension of lignite from Alexandria coalfield (Ukraine) under the supercritical pressure was studied. The initial rates of the formation of hydrogen, carbon dioxide and methane were evaluated. The mutually stimulating interaction of the components of "brown coal-water-mineral matter" system was shown due to the influence of nanoscaled water medium on the formation of dipole-inductive, dispersive and ionic associates. In the temperature range of 300-450 °C, the oxygen source for gaseous products of the lignite supercritical gasification is mainly ion-associative nanoclustered water. The source of hydrogen at the subcritical temperature is the organic part of brown coal. For the supercritical water, the source of H is the nanoscale medium with ion associates. The last ones were responsible for the further transformation of coal.

  17. Supercritical Water as Nanomedium for Gasification of Lignite-Water Suspension.

    PubMed

    Korzh, Raisa; Bortyshevskyi, Valerii

    2016-12-01

    The gasification of an aqueous suspension of lignite from Alexandria coalfield (Ukraine) under the supercritical pressure was studied. The initial rates of the formation of hydrogen, carbon dioxide and methane were evaluated. The mutually stimulating interaction of the components of "brown coal-water-mineral matter" system was shown due to the influence of nanoscaled water medium on the formation of dipole-inductive, dispersive and ionic associates. In the temperature range of 300-450 °C, the oxygen source for gaseous products of the lignite supercritical gasification is mainly ion-associative nanoclustered water. The source of hydrogen at the subcritical temperature is the organic part of brown coal. For the supercritical water, the source of H is the nanoscale medium with ion associates. The last ones were responsible for the further transformation of coal.

  18. Synthesis of niobium pentoxide nanoparticles in single-flow supercritical water

    NASA Astrophysics Data System (ADS)

    Fuchigami, Teruaki; Kakimoto, Ken-ichi

    2016-10-01

    The development of a new synthesis method is still required for very fine oxide nanoparticles. In this study, a single-flow supercritical fluid system has been developed for the synthesis of highly crystalline nanosized oxide particles. Niobium oxide particles were synthesized by single-flow supercritical water treatment, batch-type supercritical water treatment and subcritical water treatment. Niobium pentoxide nanoparticles synthesized by single-flow supercritical water treatment at 673 K, 24.5 MPa, and 15 ml min-1 flow rate had a pseudohexagonal structure. The morphology of the nanoparticle was a rod, and it has a smaller particle size and larger crystallite size than those of the oxide particles synthesized by the other methods, because the particle growth and the decomposition of surfactant were rapidly suppressed in the single-flow supercritical water treatment. The nanosized niobium pentoxide is useful as a catalyst in harsh environments and as a precursor powder of lead-free piezoelectric materials.

  19. COAL CONVERSION WASTEWATER TREATMENT BY CATALYTIC OXIDATION IN SUPERCRITICAL WATER

    SciTech Connect

    Phillip E. Savage

    1999-10-18

    Wastewaters from coal-conversion processes contain phenolic compounds in appreciable concentrations. These compounds need to be removed so that the water can be discharged or re-used. Catalytic oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of phenol over different heterogeneous oxidation catalysts in supercritical water. More specifically, we examined the oxidation of phenol over a commercial catalyst and over bulk MnO{sub 2}, bulk TiO{sub 2}, and CuO supported on Al{sub 2} O{sub 3}. We used phenol as the model pollutant because it is ubiquitous in coal-conversion wastewaters and there is a large database for non-catalytic supercritical water oxidation (SCWO) with which we can contrast results from catalytic SCWO. The overall objective of this research project is to obtain the reaction engineering information required to evaluate the utility of catalytic supercritical water oxidation for treating wastes arising from coal conversion processes. All four materials were active for catalytic supercritical water oxidation. Indeed, all four materials produced phenol conversions and CO{sub 2} yields in excess of those obtained from purely homogeneous, uncatalyzed oxidation reactions. The commercial catalyst was so active that we could not reliably measure reaction rates that were not limited by pore diffusion. Therefore, we performed experiments with bulk transition metal oxides. The bulk MnO{sub 2} and TiO{sub 2} catalysts enhance both the phenol disappearance and CO{sub 2} formation rates during SCWO. MnO{sub 2} does not affect the selectivity to CO{sub 2}, or to the phenol dimers at a given phenol conversion. However, the selectivities to CO{sub 2} are increased and the selectivities to phenol dimers are decreased in the presence of TiO{sub 2} , which are desirable trends for a catalytic SCWO process. The role of the catalyst appears to be accelerating the rate of formation of

  20. Coal conversion wastewater treatment by catalytic oxidation in supercritical water

    SciTech Connect

    Phillip E. Savage

    1999-10-20

    Wastewaters from coal-conversion processes contain phenolic compounds in appreciable concentrations. These compounds need to be removed so that the water can be discharged or re-used. Catalytic oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of phenol over different heterogeneous oxidation catalysts in supercritical water. More specifically, the authors examined the oxidation of phenol over a commercial catalyst and over bulk MnO{sub 2}, bulk TiO{sub 2}, and CuO supported on Al{sub 2}O{sub 3}. They used phenol as the model pollutant because it is ubiquitous in coal-conversion wastewaters and there is a large database for non-catalytic supercritical water oxidation (SCWO) with which they can contrast results from catalytic SCWO. The overall objective of this research project is to obtain the reaction engineering information required to evaluate the utility of catalytic supercritical water oxidation for treating wastes arising from coal conversion processes. All four materials were active for catalytic supercritical water oxidation. Indeed, all four materials produced phenol conversions and CO{sub 2} yields in excess of those obtained from purely homogeneous, uncatalyzed oxidation reactions. The commercial catalyst was so active that the authors could not reliably measure reaction rates that were not limited by pore diffusion. Therefore, they performed experiments with bulk transition metal oxides. The bulk MnO{sub 2} and TiO{sub 2} catalysts enhance both the phenol disappearance and CO{sub 2} formation rates during SCWO. MnO{sub 2} does not affect the selectivity to CO{sub 2}, or to the phenol dimers at a given phenol conversion. However, the selectivities to CO{sub 2} are increased and the selectivities to phenol dimers are decreased in the presence of TiO{sub 2}, which are desirable trends for a catalytic SCWO process. The role of the catalyst appears to be accelerating the

  1. Large-eddy simulation of supercritical fluid flow and combustion

    NASA Astrophysics Data System (ADS)

    Huo, Hongfa

    The present study focuses on the modeling and simulation of injection, mixing, and combustion of real fluids at supercritical conditions. The objectives of the study are: (1) to establish a unified theoretical framework that can be used to study the turbulent combustion of real fluids; (2) to implement the theoretical framework and conduct numerical studies with the aim of improving the understanding of the flow and combustion dynamics at conditions representative of contemporary liquid-propellant rocket engine operation; (3) to identify the key design parameters and the flow variables which dictate the dynamics characteristics of swirl- and shear- coaxial injectors. The theoretical and numerical framework is validated by simulating the Sandia Flame D. The calculated axial and radial profiles of velocity, temperature, and mass fractions of major species are in reasonably good agreement with the experimental measurements. The conditionally averaged mass fraction profiles agree very well with the experimental results at different axial locations. The validated model is first employed to examine the flow dynamics of liquid oxygen in a pressure swirl injector at supercritical conditions. Emphasis is placed on analyzing the effects of external excitations on the dynamic response of the injector. The high-frequency fluctuations do not significantly affect the flow field as they are dissipated shortly after being introduced into the flow. However, the lower-frequency fluctuations are amplified by the flow. As a result, the film thickness and the spreading angle at the nozzle exit fluctuate strongly for low-frequency external excitations. The combustion of gaseous oxygen/gaseous hydrogen in a high-pressure combustion chamber for a shear coaxial injector is simulated to assess the accuracy and the credibility of the computer program when applied to a sub-scale model of a combustor. The predicted heat flux profile is compared with the experimental and numerical studies. The

  2. Transpiring wall supercritical water oxidation reactor salt deposition studies

    SciTech Connect

    Haroldsen, B.L.; Mills, B.E.; Ariizumi, D.Y.; Brown, B.G.

    1996-09-01

    Sandia National Laboratories has teamed with Foster Wheeler Development Corp. and GenCorp, Aerojet to develop and evaluate a new supercritical water oxidation reactor design using a transpiring wall liner. In the design, pure water is injected through small pores in the liner wall to form a protective boundary layer that inhibits salt deposition and corrosion, effects that interfere with system performance. The concept was tested at Sandia on a laboratory-scale transpiring wall reactor that is a 1/4 scale model of a prototype plant being designed for the Army to destroy colored smoke and dye at Pine Bluff Arsenal in Arkansas. During the tests, a single-phase pressurized solution of sodium sulfate (Na{sub 2}SO{sub 4}) was heated to supercritical conditions, causing the salt to precipitate out as a fine solid. On-line diagnostics and post-test observation allowed us to characterize reactor performance at different flow and temperature conditions. Tests with and without the protective boundary layer demonstrated that wall transpiration provides significant protection against salt deposition. Confirmation tests were run with one of the dyes that will be processed in the Pine Bluff facility. The experimental techniques, results, and conclusions are discussed.

  3. Computer simulation of water reclamation processors

    NASA Technical Reports Server (NTRS)

    Fisher, John W.; Hightower, T. M.; Flynn, Michael T.

    1991-01-01

    The development of detailed simulation models of water reclamation processors based on the ASPEN PLUS simulation program is discussed. Individual models have been developed for vapor compression distillation, vapor phase catalytic ammonia removal, and supercritical water oxidation. These models are used for predicting the process behavior. Particular attention is given to methodology which is used to complete this work, and the insights which are gained by this type of model development.

  4. Energetic approach of biomass hydrolysis in supercritical water.

    PubMed

    Cantero, Danilo A; Vaquerizo, Luis; Mato, Fidel; Bermejo, M Dolores; Cocero, M José

    2015-03-01

    Cellulose hydrolysis can be performed in supercritical water with a high selectivity of soluble sugars. The process produces high-pressure steam that can be integrated, from an energy point of view, with the whole biomass treating process. This work investigates the integration of biomass hydrolysis reactors with commercial combined heat and power (CHP) schemes, with special attention to reactor outlet streams. The innovation developed in this work allows adequate energy integration possibilities for heating and compression by using high temperature of the flue gases and direct shaft work from the turbine. The integration of biomass hydrolysis with a CHP process allows the selective conversion of biomass into sugars with low heat requirements. Integrating these two processes, the CHP scheme yield is enhanced around 10% by injecting water in the gas turbine. Furthermore, the hydrolysis reactor can be held at 400°C and 23 MPa using only the gas turbine outlet streams.

  5. Energetic approach of biomass hydrolysis in supercritical water.

    PubMed

    Cantero, Danilo A; Vaquerizo, Luis; Mato, Fidel; Bermejo, M Dolores; Cocero, M José

    2015-03-01

    Cellulose hydrolysis can be performed in supercritical water with a high selectivity of soluble sugars. The process produces high-pressure steam that can be integrated, from an energy point of view, with the whole biomass treating process. This work investigates the integration of biomass hydrolysis reactors with commercial combined heat and power (CHP) schemes, with special attention to reactor outlet streams. The innovation developed in this work allows adequate energy integration possibilities for heating and compression by using high temperature of the flue gases and direct shaft work from the turbine. The integration of biomass hydrolysis with a CHP process allows the selective conversion of biomass into sugars with low heat requirements. Integrating these two processes, the CHP scheme yield is enhanced around 10% by injecting water in the gas turbine. Furthermore, the hydrolysis reactor can be held at 400°C and 23 MPa using only the gas turbine outlet streams. PMID:25536511

  6. High-frequency dynamics of liquid and supercritical water

    SciTech Connect

    Bencivenga, F.; Cunsolo, A.; Ruocco, G.

    2007-05-15

    The dynamic structure factor S(Q,{omega}) of water has been determined by high-resolution inelastic x-ray scattering (IXS) in a momentum (Q) and energy (E) transfer range extending from 2 to 4 nm{sup -1} and from {+-}40 meV. IXS spectra have been recorded along an isobaric path (400 bar) in a temperature (T) interval ranging from ambient up to supercritical (T>647 K) conditions. The experimental data have been described in the frame of the generalized hydrodynamic theory, utilizing a model based on the memory function approach. This model allows identifying the active relaxation processes which affect the time decay of density fluctuations, as well as a direct determination of the Q, T, and density ({rho}) dependencies of the involved transport parameters. The experimental spectra are well described by considering three different relaxation processes: the thermal, the structural, and the instantaneous one. On approaching supercritical conditions, we observe that the microscopic mechanism responsible for the structural relaxation is no longer related to the making and breaking of intermolecular bonds, but to binary intermolecular collisions.

  7. Investigation of Supercritical Water Phenomena for Space and Extraterrestrial Application

    NASA Technical Reports Server (NTRS)

    Hicks, Michael C.; Hegde, Uday G.; Fisher, John W.

    2012-01-01

    The cost of carrying or resupplying life support resources for long duration manned space exploration missions such as a mission to Mars is prohibitive and requires the development of suitable recycling technologies. Supercritical Water Oxidation (SCWO) has been identified as an attractive candidate for these extended missions because (i) pre-drying of wet waste streams is not required, (ii) product streams are relatively benign, microbially inert, and easily reclaimed, (iii) waste conversion is complete and relatively fast, and (iv) with proper design and operation, reactions can be self-sustaining. Initial work in this area at NASA was carried out at the Ames Research Center in the 1990 s with a focus on understanding the linkages between feed stock preparation (i.e., particle size and distribution) of cellulosic based waste streams and destruction rates under a range of operating temperatures and pressures. More recently, work in SCWO research for space and extra-terrestrial application has been performed at NASA s Glenn Research Center where various investigations, with a particular focus in the gravitational effects on the thermo-physical processes occurring in the bulk medium, have been pursued. In 2010 a collaborative NASA/CNES (the French Space Agency) experiment on the critical transition of pure water was conducted in the long duration microgravity environment on the International Space Station (ISS). A follow-on experiment, to study the precipitation of salt in sub-critical, trans-critical and supercritical water is scheduled to be conducted on the ISS in 2013. This paper provides a brief history of NASA s earlier work in SCWO, discusses the potential for application of SCWO technology in extended space and extraterrestrial missions, describes related research conducted on the ISS, and provides a list of future research activities to advance this technology in both terrestrial and extra-terrestrial applications.

  8. Amino Acid Synthesis in a Supercritical Carbon Dioxide - Water System

    PubMed Central

    Fujioka, Kouki; Futamura, Yasuhiro; Shiohara, Tomoo; Hoshino, Akiyoshi; Kanaya, Fumihide; Manome, Yoshinobu; Yamamoto, Kenji

    2009-01-01

    Mars is a CO2-abundant planet, whereas early Earth is thought to be also CO2-abundant. In addition, water was also discovered on Mars in 2008. From the facts and theory, we assumed that soda fountains were present on both planets, and this affected amino acid synthesis. Here, using a supercritical CO2/liquid H2O (10:1) system which mimicked crust soda fountains, we demonstrate production of amino acids from hydroxylamine (nitrogen source) and keto acids (oxylic acid sources). In this research, several amino acids were detected with an amino acid analyzer. Moreover, alanine polymers were detected with LC-MS. Our research lights up a new pathway in the study of life’s origin. PMID:19582225

  9. Corrosion behavior of porous chromium carbide in supercritical water

    NASA Astrophysics Data System (ADS)

    Dong, Ziqiang; Chen, Weixing; Zheng, Wenyue; Guzonas, Dave

    2012-01-01

    The corrosion behavior of highly porous chromium carbide (Cr 3C 2) prepared by a reactive sintering process was characterized at temperatures ranging from 375 °C to 625 °C in a supercritical water environment with a pressure of 25-30 MPa. The test results show that porous chromium carbide is stable in SCW environments at temperatures under 425 °C, above which disintegration occurred. The porous carbide was also tested under hydrothermal conditions of pressures between 12 MPa and 50 MPa at constant temperatures of 400 °C and 415 °C, respectively. The pressure showed little effect on the stability of chromium carbide in the tests at those temperatures. The mechanism of disintegration of chromium carbide in SCW environments is discussed.

  10. Destruction of representative submarine food waste using supercritical water oxidation.

    PubMed

    Chen, Shiying; Qu, Xuan; Zhang, Rong; Bi, Jicheng

    2015-03-01

    In this study, 13 types of organic materials were oxidized using H2O2 in a continuous flow reactor under the condition of supercritical water. The effect of the operational parameters on the conversion of total organic carbon (TOC) and total nitrogen (TN) was investigated, and the resulting quality of treated water was analyzed. It was found that these materials were easily oxidized with a TOC conversion achieving 99% at temperature of 460 °C and TN conversion reaching 94% at temperature of 500 °C. Rice decomposition was rapid, with TOC and TN decomposition rates of 99% obtained within residence of 100 s at temperature of 460 °C. At temperature of 460 °C, pressure of 24 MPa, residence time of 100 s, and excess oxygen of 100%, the quality of treated water attained levels commensurate with China's Standards for Drinking Water Quality. Reaction rate equation parameters were obtained by fitting the experimental data to the differential equation obtained using the Runge-Kutta algorithm. The decrease of the TOC in water samples exhibited reaction orders of 0.95 for the TOC concentration and 0.628 for the oxygen concentration. The activation energy was 83.018 kJ/mol.

  11. Destruction of representative submarine food waste using supercritical water oxidation.

    PubMed

    Chen, Shiying; Qu, Xuan; Zhang, Rong; Bi, Jicheng

    2015-03-01

    In this study, 13 types of organic materials were oxidized using H2O2 in a continuous flow reactor under the condition of supercritical water. The effect of the operational parameters on the conversion of total organic carbon (TOC) and total nitrogen (TN) was investigated, and the resulting quality of treated water was analyzed. It was found that these materials were easily oxidized with a TOC conversion achieving 99% at temperature of 460 °C and TN conversion reaching 94% at temperature of 500 °C. Rice decomposition was rapid, with TOC and TN decomposition rates of 99% obtained within residence of 100 s at temperature of 460 °C. At temperature of 460 °C, pressure of 24 MPa, residence time of 100 s, and excess oxygen of 100%, the quality of treated water attained levels commensurate with China's Standards for Drinking Water Quality. Reaction rate equation parameters were obtained by fitting the experimental data to the differential equation obtained using the Runge-Kutta algorithm. The decrease of the TOC in water samples exhibited reaction orders of 0.95 for the TOC concentration and 0.628 for the oxygen concentration. The activation energy was 83.018 kJ/mol. PMID:25315932

  12. Structure and Dynamics of Confined Water and CO2 in Clays under Supercritical Conditions

    NASA Astrophysics Data System (ADS)

    Glezakou, V.; Lee, M.; Schaef, T.; Loring, J.; Davidson, C.; McGrail, P.

    2013-12-01

    Carbon dioxide (CO2) driven enhanced gas recovery (EGR) from depleted fractured shale gas reservoirs has the potential for producing economic benefits and providing long term storage options for anthropogenic derived CO2 emissions. However key scientific processes related to CO2:CH4 exchange rates, mineral volume changes, organic mobility, and mineral stability in the presence of acid gas injections are not well understood. In this paper, we conduct atomistic simulations to examine interactions occurring between model clay minerals and supercritical CO2 equilibrated with water or brines to identify parameters controlling adsorption and desorption of gases. Integrated within these simulations are results derived from a set of newly developed experimental techniques designed to characterize physico-chemical reactions at reservoir conditions. In a series of cell optimizations under pressures relevant to sequestration scenarios, molecular simulations within the NVT and NPT ensembles with varying water/CO2 ratios showed a range of interlayer expansion for specific cation-saturated smectites. In conjunction with experimental in situ high pressure x-ray diffraction (HXRD), semi-quantitative concentrations of interlayer H2O and CO2 were established. For example, Ca saturated smectites maintaining sub-single to single hydration states (<1W to 1W), expand approximately 1.7-2.0 Å when exposed to anhydrous supercritical CO2. In contrast, for single to double hydration states (1W-2W), the simulations indicate formation of a quasi-single, metastable state, leading to a reduced interlayer spacing. Partial dehydration of the interlayer spacing while in contact with CO2 is due to a reduction of the interlayer cation coordination number. Structural analysis of the intercalated species shows an increase in the hydrogen bonding between waters during CO2 intercalation coincident with a decrease in the coordination population around the cations. Power spectra reveal rotationally

  13. The influence of water and supercritical CO2 on the failure behavior of chalk

    NASA Astrophysics Data System (ADS)

    Liteanu, E.; Spiers, C. J.; de Bresser, J. H. P.

    2013-06-01

    Reduction of compressive strength by injection of water into chalk is a well-known mechanism responsible for increased compaction in chalk reservoirs. This raises the question of whether such effects might be enhanced in the context of long-term storage of CO2 or of CO2 injection for enhanced oil and gas recovery (EOR/EGR) purposes. Therefore, data regarding the effect of supercritical CO2 on the mechanical behavior of chalk are needed. The effect of supercritical CO2 on the short-term failure behavior of wet chalk was accordingly investigated by means of conventional triaxial deformation experiments, performed on Maastrichtian chalk cores under dry conditions, in the presence of saturated chalk solution and using CO2-saturated solution at temperatures simulating reservoir conditions (20-80 °C) and effective confining pressures up to 7 MPa. Increasing temperature from 20 to 80 °C did not show any significant effects on the strength of the dry samples. Addition of aqueous solution to the samples led to drastic weakening of the chalk, the effect being more pronounced at high effective confining pressures (Peff > 3 MPa). Addition of 10 MPa supercritical CO2 to wet samples did not produce any significant additional effect in comparison with the wet samples. All samples showed a yield strength envelope characterized by shear failure at low effective mean stresses giving way to a compaction cap at high mean stresses. The weakening effect of aqueous solution was explained in terms of a reduction in frictional resistance of the material, due to water-enhanced grain-contact cracking, and perhaps pressure solution, with a possible contribution by disjoining pressure effects caused by water adsorption. While CO2 does not seem to reduce short-term failure strength of wet chalk, processes such as intergranular pressure solution have to be considered for assessing mechanical stability of chalk in the context of long-term CO2 storage or EOR/EGR operations.

  14. Experiments and numerical simulation of mixing under supercritical conditions

    NASA Astrophysics Data System (ADS)

    Schmitt, T.; Rodriguez, J.; Leyva, I. A.; Candel, S.

    2012-05-01

    Supercritical pressure conditions designate a situation where the working fluid pressure is above the critical point. Among these conditions, it is interesting to identify a transcritical range which corresponds to cases where the pressure is above the critical point, but the injection temperature is below the critical value. This situation is of special interest because it raises fundamental issues which have technological relevance in the analysis of flows in liquid rocket engines. This situation is here envisaged by analyzing the behavior of a nitrogen shear coaxial jet comprising an inner stream injected at temperatures close to the critical temperature and a coaxial flow at a higher temperature. Experiments are carried out both in the absence of external modulation and by imposing a large amplitude transverse acoustic field. Real gas large eddy simulations are performed for selected experiments. The combination of experiments and calculations is used to evaluate effects of injector geometry and operating parameters. Calculations retrieve what is observed experimentally when the momentum flux ratio of the outer to the inner stream J= (ρ _eu_e^2)/(ρ _iu_i^2) is varied. Results exhibit the change in flow structure and the development of a recirculation region when this parameter exceeds a critical value. The instantaneous flow patterns for different momentum flux ratios are used in a second stage to characterize the dynamical behavior of the flow in terms of power spectral density of velocity and density fluctuations. Results obtained under acoustic modulation provide insight into mixing enhancement of coaxial streams with a view of its possible consequences in high frequency combustion instabilities. It is shown in particular that the presence of strong acoustic modulations notably reduces the high density jet core length, indicating an increased mixing efficiency. This behavior is more pronounced when the jet is placed at the location of maximum transverse

  15. Subcritical and supercritical water oxidation of CELSS model wastes.

    PubMed

    Takahashi, Y; Wydeven, T; Koo, C

    1989-01-01

    Controlled-Ecological-Life-Support-System (CELSS) model wastes were wet-oxidized at temperatures from 250 to 500 degrees C, i.e., below and above the critical point of water (374 degrees C and 218 kg/cm2 or 21.4 MPa). A solution of ammonium hydroxide and acetic acid and a slurry of human urine, feces, and wipes were used as model wastes. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 degrees C, i.e., above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. Although the extent of nitrogen oxidation to nitrous oxide (N2O) and/or nitrogen gas (N2) increased with reaction temperature, most of the nitrogen was retained in solution as ammonia near 400 degrees C. This important finding suggests that most of the nitrogen in the waste feed can be retained in solution as ammonia during oxidation at low supercritical temperatures and be subsequently used as a nitrogen source for plants in a CELSS while at the same time organic matter is almost completely oxidized to carbon dioxide and water. It was also found in this study the Hastelloy C-276 alloy reactor corroded during waste oxidation. The rate of corrosion was lower above than below the critical temperature for water.

  16. Subcritical and supercritical water oxidation of CELSS model wastes

    NASA Technical Reports Server (NTRS)

    Takahashi, Y.; Wydeven, T.; Koo, C.

    1989-01-01

    A mixture of ammonium hydroxide with acetic acid and a slurry of human feces, urine, and wipes were used as CELSS model wastes to be wet-oxidized at temperatures from 250 to 500 C, i.e. below and above the critical point of water (374 C and 218 kg/sq cm or 21.4 MPa). The effects of oxidation temperature ( 250-500 C) and residence time (0-120 mn) on carbon and nitrogen and on metal corrosion from the reactor material were studied. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 C, above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. A substantial amount of nitrogen remained in solution in the form of ammonia at temperatures ranging from 350 to 450 C suggesting that, around 400 C, organic carbon is completely oxidized and most of the nitrogen is retained in solution. The Hastelloy C-276 alloy reactor corroded during subcritical and supercritical water oxidation.

  17. Physical properties of rocks and aqueous fluids at conditions simulating near- and supercritical reservoirs

    NASA Astrophysics Data System (ADS)

    Kummerow, Juliane; Raab, Siegfried

    2016-04-01

    The growing interest in exploiting supercritical geothermal reservoirs calls for a thorough identification and understanding of physico-chemical processes occuring in geological settings with a high heat flow. In reservoir engineering, electrical sounding methods are common geophysical exploration and monitoring tools. However, a realistic interpretation of field measurements is based on the knowledge of both, the physical properties of the rock and those of the interacting fluid at defined temperature and pressure conditions. Thus, laboratory studies at simulated in-situ conditions provide a link between the field data and the material properties in the depth. The physico-chemical properties of fluids change dramatically above the critical point, which is for pure water 374.21 °C and 221.2 bar. In supercritical fluids mass transfer and diffusion-controlled chemical reactions are enhanced and cause mineral alterations. Also, ion mobility and ion concentration are affected by the change of physical state. All this cause changes in the electrical resistivity of supercritical fluids and may have considerable effects on the porosity and hydraulic properties of the rocks they are in contact with. While there are some datasets available for physical and chemical properties of water and single component salt solutions above their critical points, there exist nearly no data for electrical properties of mixed brines, representing the composition of natural geothermal fluids. Also, the impact of fluid-rock interactions on the electrical properties of multicomponent fluids in a supercritical region is scarcely investigated. For a better understanding of fluid-driven processes in a near- and supercritical geological environment, in the framework of the EU-funded FP7 program IMAGE we have measured (1) the electrical resistivity of geothermal fluids and (2) physical properties of fluid saturated rock samples at simulated in-situ conditions. The permeability and electrical

  18. EGS rock reactions with Supercritical CO2 saturated with water and water saturated with Supercritical CO2

    SciTech Connect

    Earl D. Mattson; Travis L. McLing; William Smith; Carl Palmer

    2013-02-01

    EGS using CO2 as a working fluid will likely involve hydro-shearing low-permeability hot rock reservoirs with a water solution. After that process, the fractures will be flushed with CO2 that is maintained under supercritical conditions (> 70 bars). Much of the injected water in the main fracture will be flushed out with the initial CO2 injection; however side fractures, micro fractures, and the lower portion of the fracture will contain connate water that will interact with the rock and the injected CO2. Dissolution/precipitation reactions in the resulting scCO2/brine/rock systems have the potential to significantly alter reservoir permeability, so it is important to understand where these precipitates form and how are they related to the evolving ‘free’ connate water in the system. To examine dissolution / precipitation behavior in such systems over time, we have conducted non-stirred batch experiments in the laboratory with pure minerals, sandstone, and basalt coupons with brine solution spiked with MnCl2 and scCO2. The coupons are exposed to liquid water saturated with scCO2 and extend above the water surface allowing the upper portion of the coupons to be exposed to scCO2 saturated with water. The coupons were subsequently analyzed using SEM to determine the location of reactions in both in and out of the liquid water. Results of these will be summarized with regard to significance for EGS with CO2 as a working fluid.

  19. Hazard classification for the supercritical water oxidation test bed. Revision 1

    SciTech Connect

    Ramos, A.G.

    1994-10-01

    A hazard classification of ``routinely accepted by the public`` has been determined for the operation of the supercritical water oxidation test bed at the Idaho National Engineering Laboratory. This determination is based on the fact that the design and proposed operation meet or exceed appropriate national standards so that the risks are equivalent to those present in similar activities conducted in private industry. Each of the 17 criteria for hazards ``routinely accepted by the public,`` identified in the EG and G Idaho, Inc., Safety Manual, were analyzed. The supercritical water oxidation (SCWO) test bed will treat simulated mixed waste without the radioactive component. It will be designed to operate with eight test wastes. These test wastes have been chosen to represent a broad cross-section of candidate mixed wastes anticipated for storage or generation by DOE. In particular, the test bed will generate data to evaluate the ability of the technology to treat chlorinated waste and other wastes that have in the past caused severe corrosion and deposition in SCWO reactors.

  20. Supercritical Water Nuclear Steam Supply System: Innovations In Materials, Neutronics & Thermal-Hydraulics

    SciTech Connect

    Mark Anderson; M.L. Corradini; K. Sridharan; P. WIlson; D. Cho; T.K. Kim; S. Lomperski

    2004-09-02

    In the 1990's supercritical light-water reactors were considered in conceptual designs. A nuclear reactor cooled by supercritical waster would have a much higher thermal efficiency with a once-through direct power cycle, and could be based on standardized water reactor components (light water or heavy water). The theoretical efficiency could be improved by more than 33% over that of other water reactors and could be simplified with higher reliability; e.g., a boiling water reactor without steam separators or dryers.

  1. Hot and cold water as a supercritical solvent

    NASA Astrophysics Data System (ADS)

    Fuentevilla, Daphne Anne

    This dissertation addresses the anomalous properties of water at high temperatures near the vapor-liquid critical point and at low temperatures in the supercooled liquid region. The first part of the dissertation is concerned with the concentration dependence of the critical temperature, density, and pressure of an aqueous sodium chloride solution. Because of the practical importance of an accurate knowledge of critical parameters for industrial, geochemical, and biological applications, an empirical equation for the critical locus of aqueous sodium chloride solutions was adopted in 1999 by the International Association for the Properties of Water and Steam (IAPWS) as a guideline. However, since this original Guideline on the Critical Locus of Aqueous Solutions of Sodium Chloride was developed, two new theoretical developments occurred, motivating the first part of this dissertation. Here, I present a theory-based formulation for the critical parameters of aqueous sodium chloride solutions as a proposed replacement for the empirical formulation currently in use. This formulation has been published in the International Journal of Thermophysics and recommended by the Executive Committee of IAPWS for adoption as a Revised Guideline on the Critical Locus of Aqueous Solutions of Sodium Chloride. The second part of the dissertation addresses a new concept, considering cold water as a supercritical solvent. Based on the idea of a second, liquid-liquid, critical point in supercooled water, we explore the possibility of supercooled water as a novel supercooled solvent through the thermodynamics of critical phenomena. In 2006, I published a Physical Review letter presenting a parametric scaled equation of state for supercooled-water. Further developments based on this work led to a phenomenological mean-field "two-state" model, clarifying the nature of the phase separation in a polyamorphic single-component liquid. In this dissertation, I modify this two-state model to

  2. Effect of supercritical water shell on cavitation bubble dynamics

    NASA Astrophysics Data System (ADS)

    Shao, Wei-Hang; Chen, Wei-Zhong

    2015-05-01

    Based on reported experimental data, a new model for single cavitation bubble dynamics is proposed considering a supercritical water (SCW) shell surrounding the bubble. Theoretical investigations show that the SCW shell apparently slows down the oscillation of the bubble and cools the gas temperature inside the collapsing bubble. Furthermore, the model is simplified to a Rayleigh-Plesset-like equation for a thin SCW shell. The dependence of the bubble dynamics on the thickness and density of the SCW shell is studied. The results show the bubble dynamics depends on the thickness but is insensitive to the density of the SCW shell. The thicker the SCW shell is, the smaller are the wall velocity and the gas temperature in the bubble. In the authors’ opinion, the SCW shell works as a buffering agent. In collapsing, it is compressed to absorb a good deal of the work transformed into the bubble internal energy during bubble collapse so that it weakens the bubble oscillations. Project supported by the National Natural Science Foundation of China (Grant Nos. 11174145 and 11334005).

  3. Thermal decomposition of ammonium nitrate in supercritical water

    SciTech Connect

    Luan, Li; Proesmans, P.I.; Buelow, S.J.

    1996-10-01

    Thermal decomposition of neat NH{sub 4}NO{sub 3} has been the subject of many investigations over the past years. The reaction process is surprisingly complicated and depends largely on the reaction environment. For example, trace amounts of NH{sub 3}, HNO{sub 3} and H{sub 2}O are shown to affect the reaction significantly. In this research, NH{sub 4}NO{sub 3} decompostion was investigated in supercritical water. Reactions were evaluated in the presence of additional components such as organic compounds (CH{sub 3}OH, CH{sub 3}COOH, phenol), KN(NO{sub 2}){sub 2}, H{sub 2}O{sub 2}. Experiments were performed at varying temperatures, reaction times, NH{sub 4}NO{sub 3}, H{sub 2}O{sub 2} and organic compound concentrations. Gaseous, liquid and solid products were collected and analysed. The experimental results provided insight of the reaction chemistry which will be discussed in detail.

  4. Design requirements for the supercritical water oxidation test bed

    SciTech Connect

    Svoboda, J.M.; Valentich, D.J.

    1994-05-01

    This report describes the design requirements for the supercritical water oxidation (SCWO) test bed that will be located at the Idaho National Engineering Laboratory (INEL). The test bed will process a maximum of 50 gph of waste plus the required volume of cooling water. The test bed will evaluate the performance of a number of SCWO reactor designs. The goal of the project is to select a reactor that can be scaled up for use in a full-size waste treatment facility to process US Department of Energy mixed wastes. EG&G Idaho, Inc. will design and construct the SCWO test bed at the Water Reactor Research Test Facility (WRRTF), located in the northern region of the INEL. Private industry partners will develop and provide SCWO reactors to interface with the test bed. A number of reactor designs will be tested, including a transpiring wall, tube, and vessel-type reactor. The initial SCWO reactor evaluated will be a transpiring wall design. This design requirements report identifies parameters needed to proceed with preliminary and final design work for the SCWO test bed. A flow sheet and Process and Instrumentation Diagrams define the overall process and conditions of service and delineate equipment, piping, and instrumentation sizes and configuration Codes and standards that govern the safe engineering and design of systems and guidance that locates and interfaces test bed hardware are provided. Detailed technical requirements are addressed for design of piping, valves, instrumentation and control, vessels, tanks, pumps, electrical systems, and structural steel. The approach for conducting the preliminary and final designs and environmental and quality issues influencing the design are provided.

  5. Insights into Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids

    SciTech Connect

    Miller, Quin RS; Thompson, Christopher J.; Loring, John S.; Windisch, Charles F.; Bowden, Mark E.; Hoyt, David W.; Hu, Jian Z.; Arey, Bruce W.; Rosso, Kevin M.; Schaef, Herbert T.

    2013-07-01

    Long-term geologic storage of carbon dioxide (CO2) is considered an integral part to moderating CO2 concentrations in the atmosphere and subsequently minimizing effects of global climate change. Although subsurface injection of CO2 is common place in certain industries, deployment at the scale required for emission reduction is unprecedented and therefore requires a high degree of predictability. Accurately modeling geochemical processes in the subsurface requires experimental derived data for mineral reactions occurring between the CO2, water, and rocks. Most work in this area has focused on aqueous-dominated systems in which dissolved CO2 reacts to form crystalline carbonate minerals. Comparatively little laboratory research has been conducted on reactions occurring between minerals in the host rock and the wet supercritical fluid phase. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably hydrated supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) that simulate conditions in geologic repositories. Mineral transformation reactions were followed by three novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the supercritical CO2 resulted in increased silicate carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared spectroscopy and determined to be critical for facilitating carbonation processes. Even in extreme low water conditions, magic angle spinning nuclear magnetic resonance detected formation of Q3 [Si(OSi)3OH] and Q4 [Si(OSi)4] amorphous silica species. Unlike the thick (<10 μm) passivating silica layers observed in the fully water saturated scCO2 experiments, images obtained from a focused ion beam sectioned sample indicted these coatings were chemically wollastonite

  6. Steam-Reheat Option for Supercritical-Water-Cooled Reactors

    NASA Astrophysics Data System (ADS)

    Saltanov, Eugene

    SuperCritical-Water-cooled Reactors (SCWRs) are being developed as one of the Generation-IV nuclear-reactor concepts. Main objectives of the development are to increase thermal efficiency of a Nuclear Power Plant (NPP) and to decrease capital and operational costs. The first objective can be achieved by introducing nuclear steam reheat inside a reactor and utilizing regenerative feedwater heaters. The second objective can be achieved by designing a steam cycle that closely matches that of the mature supercritical fossil-fuelled power plants. The feasibility of these objectives is discussed. As a part of this discussion, heat-transfer calculations have been performed and analyzed for SuperCritical-Water (SCW) and SuperHeated-Steam (SHS) channels of the proposed reactor concept. In the calculations a uniform and three non-uniform Axial Heat Flux Profiles (AHFPs) were considered for six different fuels (UO2, ThO 2, MOX, UC2, UC, and UN) and at average and maximum channel power. Bulk-fluid, sheath, and fuel centerline temperatures as well as the Heat Transfer Coefficient (HTC) profiles were obtained along the fuel-channel length. The HTC values are within a range of 4.7--20 kW/m2·K and 9.7--10 kW/m2·K for the SCW and SHS channels respectively. The main conclusion is that while all the mentioned fuels may be used for the SHS channel, only UC2, UC, or UN are suitable for a SCW channel, because their fuel centerline temperatures are at least 1000°C below melting point, while that of UO2, ThO2 , and MOX may reach melting point.

  7. Supercritical water oxidation for wastewater treatment Preliminary study of urea destruction

    NASA Technical Reports Server (NTRS)

    Timberlake, S. H.; Hong, G. T.; Simson, M.; Modell, M.

    1982-01-01

    Supercritical water oxidation is being investigated as a method of treating spacecraft wastewater for recycle. In this process, oxidation is conducted in an aqueous phase maintained above the critical temperature (374 C) and pressure (215 bar) of water. Organic materials are oxidized with efficiencies greater than 99.99 percent in residence times of less than 1 minute. This paper presents preliminary results for urea destruction. Above 650 C, urea can be completely broken down to nitrogen gas, carbon dioxide and water by supercritical water oxidation, without the use of a specific catalyst.

  8. Current and foreseeable applications of supercritical water for energy and the environment.

    PubMed

    Loppinet-Serani, Anne; Aymonier, Cyril; Cansell, François

    2008-01-01

    It is crucial to develop economical and energy-efficient processes for the sustainable transformation of biomass into fuels and chemicals. In this context, supercritical water biomass valorization (SCBV) processes are an alternative way to produce biogas, biofuels, and valuable chemicals. Supercritical water technology has seen much progress over the last fifteen years and an industrial application has merged: the supercritical water oxidation of wastes. The evolution from lab-scale to pilot-scale facilities has provided data on reaction mechanisms, kinetics, modeling, and reactor technology as well as an important know-how, which can now be exploited to use the reactivity in supercritical water to transform biomass into gases (CO, H(2), CO(2), CH(4), and N(2)) or into liquids (liquid fuel and valuable chemicals) with the supercritical water biomass gasification and liquefaction processes, respectively. This Review highlights the potential of SCBV processes to transform biomass into gas and liquid energy sources and highlights the developments that are still necessary to push this technology onto the market. PMID:18702145

  9. Structure and Performance of a 600MWe Supercritical CFB Boiler with Water Cooled Panels

    NASA Astrophysics Data System (ADS)

    Li, Y.; Nie, L.; Hu, X. K.; Yue, G. X.; Li, W. K.; We, Y. X.; Lu, J. F.; Che, D. F.

    The circulating fluidized bed (CFB) combustion technology is one of the approved clean combustion technologies, and the power supply efficiency can be improved combining with the supercritical technology. A 600MWe supercritical CFB boiler is introduced in this paper. This boiler is designed based on the success of 300 MWe CFB boilers, which has a single furnace with three cyclones without external heat exchangers. There are twin furnaces and twin air distributors in the boiler. The water walls of the twin furnace above dense bed combines to a common fence wall with some channels to balance the pressure of the two furnaces. The smooth tubes are adopted in membrane water wall with mixing header. Six cyclones are located beside the furnace as well as six loopseals and six external heat exchangers. The hydrodynamic characteristic of water wall is available with the modeling prediction. And the performance of the 600MWe supercritical CFB boiler is also investigated.

  10. Numerical analysis of flow instability in the water wall of a supercritical CFB boiler with annular furnace

    NASA Astrophysics Data System (ADS)

    Xie, Beibei; Yang, Dong; Xie, Haiyan; Nie, Xin; Liu, Wanyu

    2016-08-01

    In order to expand the study on flow instability of supercritical circulating fluidized bed (CFB) boiler, a new numerical computational model considering the heat storage of the tube wall metal was presented in this paper. The lumped parameter method was proposed for wall temperature calculation and the single channel model was adopted for the analysis of flow instability. Based on the time-domain method, a new numerical computational program suitable for the analysis of flow instability in the water wall of supercritical CFB boiler with annular furnace was established. To verify the code, calculation results were respectively compared with data of commercial software. According to the comparisons, the new code was proved to be reasonable and accurate for practical engineering application in analysis of flow instability. Based on the new program, the flow instability of supercritical CFB boiler with annular furnace was simulated by time-domain method. When 1.2 times heat load disturbance was applied on the loop, results showed that the inlet flow rate, outlet flow rate and wall temperature fluctuated with time eventually remained at constant values, suggesting that the hydrodynamic flow was stable. The results also showed that in the case of considering the heat storage, the flow in the water wall is easier to return to stable state than without considering heat storage.

  11. Implementing supercritical water oxidation technology in a lunar base environmental control/life support system

    NASA Technical Reports Server (NTRS)

    Meyer Sedej, M.

    1985-01-01

    A supercritical water oxidation system (SCWOS) offers several advantages for a lunar base environmental control/life support system (ECLSS) compared to an ECLSS based on Space Station technology. In supercritically heated water (630 K, 250 atm) organic materials mix freely with oxygen and undergo complete combustion. Inorganic salts lose solubility and precipitate out. Implementation of SCWOS can make an ECLSS more efficient and reliable by elimination of several subsystems and by reduction in potential losses of life support consumables. More complete closure of the total system reduces resupply requirements from the earth, a crucial cost item in maintaining a lunar base.

  12. Optimization of power-cycle arrangements for Supercritical Water cooled Reactors (SCWRs)

    NASA Astrophysics Data System (ADS)

    Lizon-A-Lugrin, Laure

    The world energy demand is continuously rising due to the increase of both the world population and the standard of life quality. Further, to assure both a healthy world economy as well as adequate social standards, in a relatively short term, new energy-conversion technologies are mandatory. Within this framework, a Generation IV International Forum (GIF) was established by the participation of 10 countries to collaborate for developing nuclear power reactors that will replace the present technology by 2030. The main goals of these nuclear-power reactors are: economic competitiveness, sustainability, safety, reliability and resistance to proliferation. As a member of the GIF, Canada has decided to orient its efforts towards the design of a CANDU-type Super Critical Water-cooled Reactor (SCWR). Such a system must run at a coolant outlet temperature of about 625°C and at a pressure of 25 MPa. It is obvious that at such conditions the overall efficiency of this kind of Nuclear Power Plant (NPP) will compete with actual supercritical water-power boilers. In addition, from a heat-transfer viewpoint, the use of a supercritical fluid allows the limitation imposed by Critical Heat Flux (CHF) conditions, which characterize actual technologies, to be removed. Furthermore, it will be also possible to use direct thermodynamic cycles where the supercritical fluid expands right away in a turbine without the necessity of using intermediate steam generators and/or separators. This work presents several thermodynamic cycles that could be appropriate to run SCWR power plants. Improving both thermal efficiency and mechanical power constitutes a multi-objective optimization problem and requires specific tools. To this aim, an efficient and robust evolutionary algorithm, based on genetic algorithm, is used and coupled to an appropriate power plant thermodynamic simulation model. The results provide numerous combinations to achieve a thermal efficiency higher than 50% with a

  13. Partitioning of Organic Compounds between Crude Oil and Water under Supercritical CO2 Condition

    NASA Astrophysics Data System (ADS)

    Rod, K. A.; Wang, G.

    2015-12-01

    In recent years depleted oil reservoirs have received special interest as carbon storage reservoirs because of their potential to offset costs through collaboration with enhanced oil recovery projects. Leakage of the injected CO2 may occur either as supercritical CO2 or CO2-saturated (brine) water. The injected supercritical CO2 is a nonpolar solvent that can potentially mobilize the residual oil compounds into supercritical CO2 and brine water through phase partitioning. For detailed risk assessment of CO2 leakage, various models can be used to quantify the mass of organic contaminants transported from carbon storage sites to potential receptors such as potable aquifers, in which the partition coefficients of crude oil hydrocarbons between CO2/crude oil/brines for subsurface CO2 sequestration scenarios are the key parameters controlling the fate and transport of organic contaminants along the CO2 leakage pathways. However, the solubilities of many of the oil organic compounds in brines under supercritical CO2 condition have not been yet fully determined. In this study, we developed a novel method to accurately measure the partitioning of crude oil organic compounds (BTEX, PAHs, etc.) between supercritical CO2 and brines and to study the effects of temperature, pressure, salinity, and compound's cosolvency (solubility enhancement) on the partitioning behavior of oil organic compounds along the various CO2 leakage paths in the subsurface.

  14. Ionic Effects on Supercritical CO2-Brine Interfacial Tensions: Molecular Dynamics Simulations and a Universal Correlation with Ionic Strength, Temperature, and Pressure.

    PubMed

    Zhao, Lingling; Ji, Jiayuan; Tao, Lu; Lin, Shangchao

    2016-09-13

    For geological CO2 storage in deep saline aquifers, the interfacial tension (IFT) between supercritical CO2 and brine is critical for the storage security and design of the storage capacitance. However, currently, no predictive model exists to determine the IFT of supercritical CO2 against complex electrolyte solutions involving various mixed salt species at different concentrations and compositions. In this paper, we use molecular dynamics (MD) simulations to investigate the effect of salt ions on the incremental IFT at the supercritical CO2-brine interface with respect to that at the reference supercritical CO2-water interface. Supercritical CO2-NaCl solution, CO2-CaCl2 solution and CO2-(NaCl+CaCl2) mixed solution systems are simulated at 343 K and 20 MPa under different salinities and salt compositions. We find that the valence of the cations is the primary contributor to the variation in IFT, while the Lennard-Jones potentials for the cations pose a smaller impact on the IFT. Interestingly, the incremental IFT exhibits a general linear correlation with the ionic strength in the above three electrolyte systems, and the slopes are almost identical and independent of the solution types. Based on this finding, a universal predictive formula for IFTs of CO2-complex electrolyte solution systems is established, as a function of ionic strength, temperature, and pressure. The predicted IFTs using the established formula agree perfectly (with a high statistical confidence level of ∼96%) with a wide range of experimental data for CO2 interfacing with different electrolyte solutions, such as those involving MgCl2 and Na2SO4. This work provides an efficient and accurate route to directly predict IFTs in supercritical CO2-complex electrolyte solution systems for practical engineering applications, such as geological CO2 sequestration in deep saline aquifers and other interfacial systems involving complex electrolyte solutions.

  15. Ionic Effects on Supercritical CO2-Brine Interfacial Tensions: Molecular Dynamics Simulations and a Universal Correlation with Ionic Strength, Temperature, and Pressure.

    PubMed

    Zhao, Lingling; Ji, Jiayuan; Tao, Lu; Lin, Shangchao

    2016-09-13

    For geological CO2 storage in deep saline aquifers, the interfacial tension (IFT) between supercritical CO2 and brine is critical for the storage security and design of the storage capacitance. However, currently, no predictive model exists to determine the IFT of supercritical CO2 against complex electrolyte solutions involving various mixed salt species at different concentrations and compositions. In this paper, we use molecular dynamics (MD) simulations to investigate the effect of salt ions on the incremental IFT at the supercritical CO2-brine interface with respect to that at the reference supercritical CO2-water interface. Supercritical CO2-NaCl solution, CO2-CaCl2 solution and CO2-(NaCl+CaCl2) mixed solution systems are simulated at 343 K and 20 MPa under different salinities and salt compositions. We find that the valence of the cations is the primary contributor to the variation in IFT, while the Lennard-Jones potentials for the cations pose a smaller impact on the IFT. Interestingly, the incremental IFT exhibits a general linear correlation with the ionic strength in the above three electrolyte systems, and the slopes are almost identical and independent of the solution types. Based on this finding, a universal predictive formula for IFTs of CO2-complex electrolyte solution systems is established, as a function of ionic strength, temperature, and pressure. The predicted IFTs using the established formula agree perfectly (with a high statistical confidence level of ∼96%) with a wide range of experimental data for CO2 interfacing with different electrolyte solutions, such as those involving MgCl2 and Na2SO4. This work provides an efficient and accurate route to directly predict IFTs in supercritical CO2-complex electrolyte solution systems for practical engineering applications, such as geological CO2 sequestration in deep saline aquifers and other interfacial systems involving complex electrolyte solutions. PMID:27564433

  16. Simulation of supercritical flows in rocket-motor engines: application to cooling channel and injection system

    NASA Astrophysics Data System (ADS)

    Ribert, G.; Taieb, D.; Petit, X.; Lartigue, G.; Domingo, P.

    2013-03-01

    To address physical modeling of supercritical multicomponent fluid flows, ideal-gas law must be changed to real-gas equation of state (EoS), thermodynamic and transport properties have to incorporate dense fluid corrections, and turbulence modeling has to be reconsidered compared to classical approaches. Real-gas thermodynamic is presently investigated with validation by NIST (National Institute of Standards and Technology) data. Two major issues of Liquid Rocket Engines (LRE) are also presented. The first one is the supercritical fluid flow inside small cooling channels. In a context of LRE, a strong heat flux coming from the combustion chamber (locally Φ ≈ 80 MW/m2) may lead to very steep density gradients close to the wall. These gradients have to be thermodynamically and numerically captured to properly reproduce in the simulation the mechanism of heat transfer from the wall to the fluid. This is done with a shock-capturing weighted essentially nonoscillatory (WENO) numerical discretization scheme. The second issue is a supercritical fluid injection following experimental conditions [1] in which a trans- or supercritical nitrogen is injected into warm nitrogen. The two-dimensional results show vortex structures with high fluid density detaching from the main jet and persisting in the low-speed region with low fluid density.

  17. Raman spectroscopic study on the solvation of p-aminobenzonitrile in supercritical water and methanol.

    PubMed

    Osawa, K; Hamamoto, T; Fujisawa, T; Terazima, M; Sato, H; Kimura, Y

    2009-04-01

    Raman spectra of the C[triple bond]N stretching vibration of p-aminobenzonitrile (ABN) have been investigated in water, methanol, and cyclohexane under sub- and supercritical conditions, and in acetonitrile under subcritical condition. In all solvent fluids covering the supercritical region, the vibrational frequency of the C[triple bond]N stretching mode decreased with increasing solvent density from the gaseous region to the medium density region rho(r) approximately = 2, where rho(r) is the reduced density by the critical density of the solvent. However, from the medium density region to the higher density region, the vibrational frequency turned to increase with the solvent density. The temperature-induced low frequency shift of the C[triple bond]N stretching Raman band was also ascertained by the measurement of the temperature dependence of Raman spectrum of ABN vapor above 543 K. The electronic absorption spectra in the UV region of ABN were also measured under the same experimental conditions. The absorption peak energies decreased with an increase of the solvent density, except in water above rho(r) = 2.8. The vibrational frequency shift in cyclohexane was explained by a sum of contributions of the repulsive interaction, the mean field attractive interaction, and the pure temperature effect probably due to the hot-band contribution. The residual frequency shift after the subtraction of the repulsive and temperature effects in water and methanol showed the low frequency shift with increasing solvent density from rho(r) congruent with 0 to 2.8. However, above rho(r) congruent with 2.8 in water, the residual shift showed a high frequency shift with increasing solvent density. The electronic state calculations based on the PCM model using the density functional theory (DFT) indicated that the solvent polarity change caused the low frequency shift of the C[triple bond]N stretching mode, which was also correlated with the shift of the electronic absorption

  18. Gasification characteristics of an activated carbon catalyst during the decomposition of hazardous waste materials in supercritical water

    SciTech Connect

    Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

    1996-10-01

    Recently, carbonaceous materials were proved to be effective catalysts for hazardous waste decomposition in supercritical water. Gasification of the carbonaceous catalyst itself is also expected, however, under supercritical conditions. Thus, it is essential to determine the gasification rate of the carbonaceous materials during this process to determine the active lifetime of the catalysts. For this purpose, the gasification characteristics of granular coconut shell activated carbon in supercritical water alone (600-650{degrees}C, 25.5-34.5 MPa) were investigated. The gasification rate at subatmospheric pressure agreed well with the gasification rate at supercritical conditions, indicating the same reaction mechanism. Methane generation under these conditions is via pyrolysis, and thus is not affected by the water pressure. An iodine number increase of 25% was observed as a result of the supercritical water gasification.

  19. Numerical Analysis of Heat Transfer Test of Supercritical Water in a Tube Using the Three-Dimensional Two-Fluid Model Code

    NASA Astrophysics Data System (ADS)

    Misawa, Takeharu; Yoshida, Hiroyuki; Tamai, Hidesada; Takase, Kazuyuki

    The three-dimensional two-fluid model analysis code ACE-3D is developed in Japan Atomic Energy Agency for the thermal design procedure on two-phase flow thermal-hydraulics of light water-cooled reactors. In order to perform thermal hydraulic analysis of SCWR, ACE-3D is enhanced to supercritical pressure region. As a result, it is confirmed that transient change in subcritical and supercritical pressure region can be simulated smoothly using ACE-3D, that ACE-3D can predict the results of the past heat transfer experiment in the supercritical pressure condition, and that introduction of thermal conductivity effect of the wall restrains fluctuation of wall temperature.

  20. Comparative Study of Materials' Behaviour in Supercritical Water and Superheated Steam

    NASA Astrophysics Data System (ADS)

    McClure, Peter

    Advanced supercritical water cooled nuclear reactors require materials to survive a corrosive, high temperature fluid environment, in addition to radiation effects. This thesis details corrosion testing of A286 (iron-nickel based), AISI 310 stainless steel, and IN625 (nickel based) in supercritical water (29 MPa) and superheated steam (ambient pressure) at 650°C to understand effects of materials' composition and fluid pressure. A superheated steam testing rig was designed and an autoclave was assembled. Samples were tested for 100, 200, and 300 hours, then analysed for weight gain and surface appearance; surface morphology and composition were determined through scanning electron microscope imaging and energy-dispersive X-ray spectroscopy. A286 demonstrated poor corrosion resistance due to low chromium content. AISI 310 and IN625 demonstrated similarly strong corrosion resistance in supercritical water through formation of adherent scales, but poor corrosion resistance in superheated steam due to scale spallation. Supercritical water and superheated steam corrosion behaviour were non-analogous.

  1. Case study on the destruction of organic dyes in supercritical water

    SciTech Connect

    LaJeunesse, C.A.; Rice, S.F.

    1994-11-01

    Organic dyes, which were used in Navy shells to mark ships and structures, need to be disposed of without burning. A study was undertaken to assess the feasibility of using supercritical water oxidation to destroy organic dyes. Experimental destruction efficiencies, product analyses, and process configuration are reported.

  2. Separation of saturated hydrocarbons from coal by treatment with water at supercritical parameters

    SciTech Connect

    M.R. Predtechenskiy; M.V. Pukhovoy

    2008-10-15

    The treatment of coals of various degrees of metamorphism in supercritical water (SCW) over the temperature region 380-800{sup o}C was studied. The yields and compositions of liquid products obtained by treatment in SCW were determined. These data were compared with the results of the semicoking of the above coals.

  3. Treatment of coal and formic acid mixtures with water at supercritical parameters

    SciTech Connect

    M.R. Predtechenskii; M.V. Pukhovoi; A.N. Smal; A.O. Uuemaa

    2007-08-15

    The treatment of coals of various degrees of metamorphism in supercritical water (SCW) over the temperature region 380-800{sup o}C was studied. The possibility of obtaining strong agglomerates from the powders of long-flame and oxidized fat noncoking coals by treatment in SCW was demonstrated. The strength of agglomerates was commensurable with the strength of lump coal.

  4. Comparison of Nitronic 50 and Stainless Steel 316 for use in Supercritical Water Environments

    NASA Astrophysics Data System (ADS)

    Karmiol, Zachary

    Increased efficiency can greatly benefit any mode of power production. Many proposed coal, natural gas, and nuclear reactors attempt to realize this goal through the use of increased operating temperatures and pressures, and as such require materials capable of withstanding extreme conditions. One such design employs supercritical water, which in addition to high temperatures and pressures is also highly oxidizing. A critical understanding of both mechanical and oxidation characteristics of candidate materials are required to determine the viability of materials for these reactors. This work investigates two potential materials, austenitic stainless steels, namely, Nitronic-50 and stainless steel 316, for use in these conditions. The supercritical water loop at the University of Nevada, Reno allowed for the study of materials at both subcritical and supercritical conditions. The materials were investigated mechanically using slow strain rate tests under conditions ranging from an inert nitrogen atmosphere, to both subcritical and supercritical water, with the failed samples surface characterized by optical microscopy, scanning electron microscopy, and Raman spectroscopy. Electrochemical studies were performed via potentiodynamic polarization in subcritical water only, and characterized using Raman spectroscopy. The samples were also exposed to supercritical water, and characterized using Raman spectroscopy. Nitronic-50 was found to have superior mechanical characteristics to stainless steel 316. SS-316 was found to have a surface film consisting of iron oxides, while the surface film of N-50 consisted predominantly of nickel-iron spinel. The crack interior of the sample was different from the exterior, indicating that the time and temperature of the exposure might play a defining role in determining the chemistry of the film.

  5. The isotropic nuclear magnetic shielding constants of acetone in supercritical water: a sequential Monte Carlo/quantum mechanics study including solute polarization.

    PubMed

    Fonseca, Tertius L; Coutinho, Kaline; Canuto, Sylvio

    2008-07-21

    The nuclear isotropic shielding constants sigma((17)O) and sigma((13)C) of the carbonyl bond of acetone in water at supercritical (P=340.2 atm and T=673 K) and normal water conditions have been studied theoretically using Monte Carlo simulation and quantum mechanics calculations based on the B3LYP6-311++G(2d,2p) method. Statistically uncorrelated configurations have been obtained from Monte Carlo simulations with unpolarized and in-solution polarized solute. The results show that solvent effects on the shielding constants have a significant contribution of the electrostatic interactions and that quantitative estimates for solvent shifts of shielding constants can be obtained modeling the water molecules by point charges (electrostatic embedding). In supercritical water, there is a decrease in the magnitude of sigma((13)C) but a sizable increase in the magnitude of sigma((17)O) when compared with the results obtained in normal water. It is found that the influence of the solute polarization is mild in the supercritical regime but it is particularly important for sigma((17)O) in normal water and its shielding effect reflects the increase in the average number of hydrogen bonds between acetone and water. Changing the solvent environment from normal to supercritical water condition, the B3LYP6-311++G(2d,2p) calculations on the statistically uncorrelated configurations sampled from the Monte Carlo simulation give a (13)C chemical shift of 11.7+/-0.6 ppm for polarized acetone in good agreement with the experimentally inferred result of 9-11 ppm.

  6. First Principles Simulations fo the Supercritical Behavior of Ore Forming Fluids

    SciTech Connect

    Weare, John H

    2013-04-19

    measured directly. However, the number of 2nd shell water molecules predicted by the simulation is consistent with experimental estimates. Tetrahedral bulk water coordination reappears just after the 2nd shell. Simulations with 128 waters are close to the maximum size that can effectively be performed with present day methods. While the time scale of our simulation are not long enough to observe transfers of waters from the 1st to the 2nd shell, we do see transfers occurring on a picosecond time scale between the 2nd shell and 3rd shell via an associative mechanism. This is faster than, but consistent with, the results of measurements on the more tightly bound Cr3+ system. For high temperature simulations, proton transfers occur in the solvation shells leading to transient hydrolysis species. The reaction coordinate for proton transfer involves the coordinates of neighboring solvent waters as in the Grotis mechanism for proton transfer in bulk water. Directly removing a proton from the hexaqua Al3+ ion leads to a much more labile solvation shell and to a five coordinated Al3+ ion. This is consistent with very recent rate measurements of ligand exchange and the conjugate base labilization effect. For the Al3+-H2O system results for high but subcritical temperatures are qualitatively similar to room temperature simulations. However, preliminary simulations for supercritical temperatures (750K) suggest that there may be a dramatic change in behavior in the hydration structure of ions for these temperatures. For transition metal ions the presence of d valence electrons plays a significant role in the behavior of the system. Our preliminary results for the Fe3+ ion suggest that this ion which is larger radius than the Al3+ ion has somewhat less rigid 1st and 2nd solvation shell. II. Gibbs Ensemble Monte Carlo Simulation of Vapor/Liquid and Metastable Liquid/Liquid Phase Equilibria in the CO2-CH4-N2 System Many fluid inclusions have compositions in the system CO2-CH4-N2

  7. Feasibility Study of Supercritical Light Water Cooled Reactors for Electric Power Production

    SciTech Connect

    Philip MacDonald; Jacopo Buongiorno; James Sterbentz; Cliff Davis; Robert Witt; Gary Was; J. McKinley; S. Teysseyre; Luca Oriani; Vefa Kucukboyaci; Lawrence Conway; N. Jonsson: Bin Liu

    2005-02-13

    The supercritical water reactor (SCWR) has been the object of interest throughout the nuclear Generation IV community because of its high potential: a simple, direct cycle, compact configuration; elimination of many traditional LWR components, operation at coolant temperatures much higher than traditional LWRs and thus high thermal efficiency. It could be said that the SWR was viewed as the water counterpart to the high temperature gas reactor.

  8. Water solubility measurements in supercritical fluids and high-pressure liquids using near-infrared spectroscopy

    SciTech Connect

    Jackson, K.; Bowman, L.E.; Fulton, J.L.

    1995-07-15

    A small amount of water added to a supercritical fluid can greatly increase the solubility of polar species in nonpolar fluids. These modified supercritical solutions significantly expand the use of the fluids in separations and reactions. In order to successfully utilize these systems, information on the miscibility or solubility of water in the fluid is required. Often solubility data are not available for water in a supercritical fluid under a given set of temperature and pressure conditions, and a costly set of equipment must be assembled in order to make these measurements. A relatively fast and inexpensive technique to measure water solubilities using a simple long path length optical cell in an FT-IR spectrometer is described. This technique is also applicable to common and newly developed refrigerants where water solubilities are often unknown at temperatures much above ambient. In this paper, water solubility data in carbon dioxide and two types of refrigerants (chlorodifluoromethane, R22; 1,1,1,2-tetrafluoroethane, R134a) are presented for temperatures from approximately 40 to 110{degree}C and pressures from approximately 10 to 344.8 bar. 26 refs., 6 figs., 4 tabs.

  9. RPCSIM-SCO2 (Reactor Power and Control SIMulator for Supercritical CO2)

    SciTech Connect

    Wright, Steven A.

    2012-09-12

    The RPCSIM-SCO2 code performs a dynamic simulation of a supercritical CO2 (carbon dioxide) Brayton cycle loop. The code is based on the MathLabTM program SimulinkTM from Mathworks. The Supercritical CO2 (S-CO2) model uses direct calls to the National Institute of Standards Refprop 9.0 Fortran library for the Equation-of-State (EOS) model for the CO2 working fluid (Lemmon, 2010). The calls to Refprop are made in the form of Simulink s-Functions that use a C interface to directly call the compiled Refprop fortran program library functions. Minor changes to the code can be made to use other working fluids. The code is intended to be used to perform many different types of dynamic cycle analysis for supercritical CO2 power producing systems. The code will calculate the transient temperature and pressure and all other thermodynamic properties at the inlet and outlet of each component given user supplied inputs such as rotor shaft speed, and heater power.

  10. RPCSIM-SCO2 (Reactor Power and Control SIMulator for Supercritical CO2)

    2012-09-12

    The RPCSIM-SCO2 code performs a dynamic simulation of a supercritical CO2 (carbon dioxide) Brayton cycle loop. The code is based on the MathLabTM program SimulinkTM from Mathworks. The Supercritical CO2 (S-CO2) model uses direct calls to the National Institute of Standards Refprop 9.0 Fortran library for the Equation-of-State (EOS) model for the CO2 working fluid (Lemmon, 2010). The calls to Refprop are made in the form of Simulink s-Functions that use a C interface tomore » directly call the compiled Refprop fortran program library functions. Minor changes to the code can be made to use other working fluids. The code is intended to be used to perform many different types of dynamic cycle analysis for supercritical CO2 power producing systems. The code will calculate the transient temperature and pressure and all other thermodynamic properties at the inlet and outlet of each component given user supplied inputs such as rotor shaft speed, and heater power.« less

  11. Sorption Phase of Supercritical CO2 in Silica Aerogel: Experiments and Mesoscale Computer Simulations

    SciTech Connect

    Rother, Gernot; Vlcek, Lukas; Gruszkiewicz, Miroslaw {Mirek} S; Chialvo, Ariel A; Anovitz, Lawrence {Larry} M; Banuelos, Jose Leo; Wallacher, Dirk; Grimm, Nico; Cole, David

    2014-01-01

    Adsorption of supercritical CO2 in nanoporous silica aerogel was investigated by a combination of experiments and molecular-level computer modeling. High-pressure gravimetric and vibrating tube densimetry techniques were used to measure the mean pore fluid density and excess sorption at 35 C and 50 C and pressures of 0-200 bar. Densification of the pore fluid was observed at bulk fluid densities below 0.7 g/cm3. Far above the bulk fluid density, near-zero sorption or weak depletion effects were measured, while broad excess sorption maxima form in the vicinity of the bulk critical density region. The CO2 sorption properties are very similar for two aerogels with different bulk densities of 0.1 g/cm3 and 0.2 g/cm3, respectively. The spatial distribution of the confined supercritical fluid was analyzed in terms of sorption- and bulk-phase densities by means of the Adsorbed Phase Model (APM), which used data from gravimetric sorption and small-angle neutron scattering experiments. To gain more detailed insight into supercritical fluid sorption, large-scale lattice gas GCMC simulations were utilized and tuned to resemble the experimental excess sorption data. The computed three-dimensional pore fluid density distributions show that the observed maximum of the excess sorption near the critical density originates from large density fluctuations pinned to the pore walls. At this maximum, the size of these fluctuations is comparable to the prevailing pore sizes.

  12. Evolution of the core physics concept for the Canadian supercritical water reactor

    SciTech Connect

    Pencer, J.; Colton, A.; Wang, X.; Gaudet, M.; Hamilton, H.; Yetisir, M.

    2013-07-01

    The supercritical water cooled reactor (SCWR) is one of the advanced reactor concepts chosen by the GEN-IV International Forum (GIF) for research and development efforts. Canada's contribution is the Canadian SCWR, a heavy water moderated, pressure tube supercritical light water cooled reactor. Recent developments in the SCWR lattice and core concepts, primarily the introduction of a large central flow tube filled with coolant combined with a two-ring fuel assembly, have enabled significant improvements compared to earlier concepts. These improvements include a reduction in coolant void reactivity (CVR) by more than 10 mk, and an almost 40% increase in fuel exit burnup, which is achieved via balanced power distribution between the fuel pins in the fuel assembly. In this paper the evolution of the physics concept is reviewed, and the present lattice and core physics concepts are presented.

  13. Code Development in Coupled PARCS/RELAP5 for Supercritical Water Reactor

    DOE PAGES

    Hu, Po; Wilson, Paul

    2014-01-01

    The new capability is added to the existing coupled code package PARCS/RELAP5, in order to analyze SCWR design under supercritical pressure with the separated water coolant and moderator channels. This expansion is carried out on both codes. In PARCS, modification is focused on extending the water property tables to supercritical pressure, modifying the variable mapping input file and related code module for processing thermal-hydraulic information from separated coolant/moderator channels, and modifying neutronics feedback module to deal with the separated coolant/moderator channels. In RELAP5, modification is focused on incorporating more accurate water properties near SCWR operation/transient pressure and temperature in themore » code. Confirming tests of the modifications is presented and the major analyzing results from the extended codes package are summarized.« less

  14. Supercritical water gasification of biomass for H2 production: process design.

    PubMed

    Fiori, Luca; Valbusa, Michele; Castello, Daniele

    2012-10-01

    The supercritical water gasification (SCWG) of biomass for H(2) production is analyzed in terms of process development and energetic self-sustainability. The conceptual design of a plant is proposed and the SCWG process involving several substrates (glycerol, microalgae, sewage sludge, grape marc, phenol) is simulated by means of AspenPlus™. The influence of various parameters - biomass concentration and typology, reaction pressure and temperature - is analyzed. The process accounts for the possibility of exploiting the mechanical energy of compressed syngas (later burned to sustain the SCWG reaction) through expansion in turbines, while purified H(2) is fed to fuel cells. Results show that the SCWG reaction can be energetically self-sustained if minimum feed biomass concentrations of 15-25% are adopted. Interestingly, the H(2) yields are found to be maximal at similar feed concentrations. Finally, an energy balance is performed showing that the whole process could provide a net power of about 150 kW(e)/(1000 kg(feed)/h).

  15. Supercritical water gasification of biomass for H2 production: process design.

    PubMed

    Fiori, Luca; Valbusa, Michele; Castello, Daniele

    2012-10-01

    The supercritical water gasification (SCWG) of biomass for H(2) production is analyzed in terms of process development and energetic self-sustainability. The conceptual design of a plant is proposed and the SCWG process involving several substrates (glycerol, microalgae, sewage sludge, grape marc, phenol) is simulated by means of AspenPlus™. The influence of various parameters - biomass concentration and typology, reaction pressure and temperature - is analyzed. The process accounts for the possibility of exploiting the mechanical energy of compressed syngas (later burned to sustain the SCWG reaction) through expansion in turbines, while purified H(2) is fed to fuel cells. Results show that the SCWG reaction can be energetically self-sustained if minimum feed biomass concentrations of 15-25% are adopted. Interestingly, the H(2) yields are found to be maximal at similar feed concentrations. Finally, an energy balance is performed showing that the whole process could provide a net power of about 150 kW(e)/(1000 kg(feed)/h). PMID:22858478

  16. Supercritical Water Mixture (SCWM) Experiment in the High Temperature Insert-Reflight (HTI-R)

    NASA Technical Reports Server (NTRS)

    Hicks, Michael C.; Hegde, Uday G.; Garrabos, Yves; Lecoutre, Carole; Zappoli, Bernard

    2013-01-01

    Current research on supercritical water processes on board the International Space Station (ISS) focuses on salt precipitation and transport in a test cell designed for supercritical water. This study, known as the Supercritical Water Mixture Experiment (SCWM) serves as a precursor experiment for developing a better understanding of inorganic salt precipitation and transport during supercritical water oxidation (SCWO) processes for the eventual application of this technology for waste management and resource reclamation in microgravity conditions. During typical SCWO reactions any inorganic salts present in the reactant stream will precipitate and begin to coat reactor surfaces and control mechanisms (e.g., valves) often severely impacting the systems performance. The SCWM experiment employs a Sample Cell Unit (SCU) filled with an aqueous solution of Na2SO4 0.5-w at the critical density and uses a refurbished High Temperature Insert, which was used in an earlier ISS experiment designed to study pure water at near-critical conditions. The insert, designated as the HTI-Reflight (HTI-R) will be deployed in the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on the International Space Station (ISS). Objectives of the study include measurement of the shift in critical temperature due to the presence of the inorganic salt, assessment of the predominant mode of precipitation (i.e., heterogeneously on SCU surfaces or homogeneously in the bulk fluid), determination of the salt morphology including size and shapes of particulate clusters, and the determination of the dominant mode of transport of salt particles in the presence of an imposed temperature gradient. Initial results from the ISS experiments will be presented and compared to findings from laboratory experiments on the ground.

  17. Supercritical fluid extraction of chemical warfare agent simulants from soil.

    PubMed

    Griest, W H; Ramsey, R S; Ho, C H; Caldwell, W M

    1992-05-29

    Chemical warfare agent simulants are efficiently recovered from 2-ppm spikes in 1 g of Rocky Mountain Arsenal Standard Soil using methanol-carbon dioxide (5:95) at 300 atm for 2 min at 60 degrees C. Recoveries (n = 3) were 79 +/- 23% for dimethylmethylphosphonate, 93 +/- 14% for 2-chloroethylethyl sulfide, 92 +/- 13% for diisopropylfluorophosphate and 95 +/- 17% for diisopropylmethylphosphonate. Recoveries are higher than, but less precise than those achieved from a 5-min ultrasonic micro-scale extraction using methanol. Much less laboratory waste is generated than the current standard organic solvent extraction method (33 g of soil shaken with 100 ml of chloroform). PMID:1400849

  18. Supercritical fluid extraction and organic solvent microextraction of chemical agent simulants from soil

    SciTech Connect

    Griest, W.H.; Ramsey, R.S.; Ho, C.h.; Caldwell, W.M.

    1991-12-31

    Experiments with chemical warfare agent simulants suggest that supercritical fluid extraction can achieve good extraction recoveries of agents in soil and produce less laboratory waste than current organic solvent extraction methods. Two-ppm spikes in 1 g of Rocky Mountain Arsenal Standard Soil were extracted using 5% methanol in carbon dioxide at 300 atm for 2 min at 60{degrees}C. Recoveries (n=3) were 79{plus_minus}23% for dimethylmethylphosphonate, 93{plus_minus}14% for 2-chlorethylethylsulfide, 92{plus_minus}13% for diisopropylfluorophosphate, and 95{plus_minus}17% for diisopropylmethylphosphonate. A 5 min ultrasonic micro-scale extraction using methanol is more reproducible but less efficient.

  19. Supercritical fluid extraction and organic solvent microextraction of chemical agent simulants from soil

    SciTech Connect

    Griest, W.H.; Ramsey, R.S.; Ho, C.h.; Caldwell, W.M.

    1991-01-01

    Experiments with chemical warfare agent simulants suggest that supercritical fluid extraction can achieve good extraction recoveries of agents in soil and produce less laboratory waste than current organic solvent extraction methods. Two-ppm spikes in 1 g of Rocky Mountain Arsenal Standard Soil were extracted using 5% methanol in carbon dioxide at 300 atm for 2 min at 60{degrees}C. Recoveries (n=3) were 79{plus minus}23% for dimethylmethylphosphonate, 93{plus minus}14% for 2-chlorethylethylsulfide, 92{plus minus}13% for diisopropylfluorophosphate, and 95{plus minus}17% for diisopropylmethylphosphonate. A 5 min ultrasonic micro-scale extraction using methanol is more reproducible but less efficient.

  20. Prospects for development of an innovative water-cooled nuclear reactor for supercritical parameters of coolant

    NASA Astrophysics Data System (ADS)

    Kalyakin, S. G.; Kirillov, P. L.; Baranaev, Yu. D.; Glebov, A. P.; Bogoslovskaya, G. P.; Nikitenko, M. P.; Makhin, V. M.; Churkin, A. N.

    2014-08-01

    The state of nuclear power engineering as of February 1, 2014 and the accomplished elaborations of a supercritical-pressure water-cooled reactor are briefly reviewed, and the prospects of this new project are discussed based on this review. The new project rests on the experience gained from the development and operation of stationary water-cooled reactor plants, including VVERs, PWRs, BWRs, and RBMKs (their combined service life totals more than 15 000 reactor-years), and long-term experience gained around the world with operation of thermal power plants the turbines of which are driven by steam with supercritical and ultrasupercritical parameters. The advantages of such reactor are pointed out together with the scientific-technical problems that need to be solved during further development of such installations. The knowledge gained for the last decade makes it possible to refine the concept and to commence the work on designing an experimental small-capacity reactor.

  1. Direct Conversion of Cellulose into Ethyl Lactate in Supercritical Ethanol-Water Solutions.

    PubMed

    Yang, Lisha; Yang, Xiaokun; Tian, Elli; Lin, Hongfei

    2016-01-01

    Biomass-derived ethyl lactate is a green solvent with a growing market as the replacement for petroleum-derived toxic organic solvents. Here we report, for the first time, the production of ethyl lactate directly from cellulose with the mesoporous Zr-SBA-15 silicate catalyst in a supercritical mixture of ethanol and water. The relatively strong Lewis and weak Brønsted acid sites on the catalyst, as well as the surface hydrophobicity, were beneficial to the reaction and led to synergy during consecutive reactions, such as depolymerization, retro-aldol condensation, and esterification. Under the optimum reaction conditions, ∼33 % yield of ethyl lactate was produced from cellulose with the Zr-SBA-15 catalyst at 260 °C in supercritical 95:5 (w/w) ethanol/water.

  2. Design of an optical cell for pulse radiolysis of supercritical water

    SciTech Connect

    Takahashi, Kenji; Cline, Jason A.; Bartels, David M.; Jonah, Charles D.

    2000-09-01

    The design of a flow cell that is applicable to pulse radiolysis/transient absorption experiments on supercritical water is described. The cell is designed to minimize dead volume and prevent the accumulation of radiolytic products. It is also necessary to minimize emission and absorption of sapphire windows from high energy electron beam irradiation. To obtain an optical throughput of f/4, the inner diameter is 6 mm, and distance between windows is 25 mm. The effective optical path length is 20 mm for irradiation from the side through a thin Hastelloy wall. Belleville spring washers were used to keep a constant force on the 3 mm sapphire windows, which were sealed to the Hastelloy body with copper gaskets. An application of this cell to measurements of solvated electrons in supercritical water is demonstrated. (c) 2000 American Institute of Physics.

  3. Design of an optical cell for pulse radiolysis of supercritical water

    NASA Astrophysics Data System (ADS)

    Takahashi, Kenji; Cline, Jason A.; Bartels, David M.; Jonah, Charles D.

    2000-09-01

    The design of a flow cell that is applicable to pulse radiolysis/transient absorption experiments on supercritical water is described. The cell is designed to minimize dead volume and prevent the accumulation of radiolytic products. It is also necessary to minimize emission and absorption of sapphire windows from high energy electron beam irradiation. To obtain an optical throughput of f/4, the inner diameter is 6 mm, and distance between windows is 25 mm. The effective optical path length is 20 mm for irradiation from the side through a thin Hastelloy wall. Belleville spring washers were used to keep a constant force on the 3 mm sapphire windows, which were sealed to the Hastelloy body with copper gaskets. An application of this cell to measurements of solvated electrons in supercritical water is demonstrated.

  4. Kinetic analysis for destruction of municipal sewage sludge and alcohol distillery wastewater by supercritical water oxidation

    SciTech Connect

    Goto, Motonobu; Nada, Takatsugu; Kodama, Akio; Hirose, Tsutomu

    1999-05-01

    Supercritical water oxidation was applied to the destruction of municipal excess sewage sludge and alcohol distillery wastewater of molasses. The reaction was carried out in a batch reactor with hydrogen peroxide as an oxidant in the temperature range 673--773 K. Total organic carbon was measured as a function of reaction time. The dynamic data were analyzed by a first-order reaction model. The reaction rate constant coincides with those reported in the literature.

  5. Numerical simulation of supercritical heat transfer under severe axial density gradient in a narrow vertical tube

    SciTech Connect

    Bae, Y. Y.; Hong, S. D.; Kim, Y. W.

    2012-07-01

    A number of computational works have been performed so far for the simulation of heat transfer in a supercritical fluid. The simulations, however, faced a lot of difficulties when heat transfer deteriorates due either to buoyancy or by acceleration. When the bulk temperature approaches the pseudo-critical temperature the fluid experiences a severe axial density gradient on top of a severe radial one. Earlier numerical calculations showed, without exception, unrealistic over-predictions, as soon as the bulk temperature exceeded the pseudo-critical temperature. The over-predictions might have been resulted from an inapplicability of widely-used turbulence models. One of the major causes for the difficulties may probably be an assumption of a constant turbulent Prandtl number. Recent research, both numerical and experimental, indicates that the turbulent Prandtl number is never a constant when the gradient of physical properties is significant. This paper describes the applicability of a variable turbulent Prandtl number to the numerical simulation of heat transfer in supercritical fluids flowing in narrow vertical tubes. (authors)

  6. On the local environment surrounding pyrene in near- and supercritical water

    SciTech Connect

    Niemeyer, E.D.; Dunbar, R.A.; Bright, F.V.

    1997-10-01

    We use steady-state and time-resolved fluorescence spectroscopy to probe local solvent{endash}solute interactions between pyrene (the solute) and supercritical water (SCW). Toward this end, we have developed a new fiber-optic-based titanium high-pressure optical cell which can withstand the temperatures and pressure needed to generate supercritical water. Static fluorescence measurements indicate that there is an increase in the local water density surrounding the pyrene molecules (clustering) up to five times the bulk fluid density. This extent of clustering is most prevalent at about one-half the critical density. Consistent with previous work on more mild supercritical fluids (e.g., CO{sub 2}, CF{sub 3}H, C{sub 2}H{sub 6}), the extent of this solute-fluid clustering decreases as the system temperature and pressure are increased. Time-resolved fluorescence measurements show that the excited-state decay kinetics are exponentially activated and not themselves affected by this solute-fluid clustering process. {copyright} {ital 1997} {ital Society for Applied Spectroscopy}

  7. Glucose and fructose decomposition in subcritical and supercritical water: Detailed reaction pathway, mechanisms, and kinetics

    SciTech Connect

    Kabyemela, B.M.; Adschiri, T.; Malaluan, R.M.; Arai, K.

    1999-08-01

    The authors are developing a new catalyst-free process of cellulose decomposition in supercritical water. In their initial study on the cellulose decomposition in supercritical water, the main products of cellulose decomposition were found to be oligomers of glucose (cellobiose, cellotriose, etc.) and glucose at short residence times (400 C, 25 MPa, 0.05 s). The kinetics of glucose at these conditions can be useful in understanding the reaction pathways of cellulose. Experiments were performed on the products of glucose decomposition at short residence times to elucidate the reaction pathways and evaluate kinetics of glucose and fructose decomposition in sub- and supercritical water. The conditions were a temperature of 300--400 C and pressure of 25--40 MPa for extremely short residence times between 0.02 and 2 s. The products of glucose decomposition were fructose, a product of isomerization, 1,6-anhydroglucose, a product of dehydration, and erythrose and glyceraldehyde, products of C-C bond cleavage. Fructose underwent reactions similar to glucose except that it did not form 1,6-anhydroglucose and isomerization to glucose is negligible. The mechanism for the products formed from C-C bond cleavage could be explained by reverse aldol condensation and the double-bond rule of the respective enediols formed during the Lobry de Bruyn Alberda van Ekenstein transformation. The differential equations resulting from the proposed pathways were fit to experimental results to obtain the kinetic rate constants.

  8. Two-dimensional Numerical Simulations of Supercritical Accretion Flows Revisited

    NASA Astrophysics Data System (ADS)

    Yang, Xiao-Hong; Yuan, Feng; Ohsuga, Ken; Bu, De-Fu

    2014-01-01

    We study the dynamics of super-Eddington accretion flows by performing two-dimensional radiation-hydrodynamic simulations. Compared with previous works, in this paper we include the T θphi component of the viscous stress and consider various values of the viscous parameter α. We find that when T θphi is included, the rotational speed of the high-latitude flow decreases, while the density increases and decreases at the high and low latitudes, respectively. We calculate the radial profiles of inflow and outflow rates. We find that the inflow rate decreases inward, following a power law form of \\dot{M}_in\\propto r^s. The value of s depends on the magnitude of α and is within the range of ~0.4-1.0. Correspondingly, the radial profile of density becomes flatter compared with the case of a constant \\dot{M}(r). We find that the density profile can be described by ρ(r)vpropr -p and the value of p is almost same for a wide range of α ranging from α = 0.1 to 0.005. The inward decrease of inflow accretion rate is very similar to hot accretion flows, which is attributed to the mass loss in outflows. To study the origin of outflow, we analyze the convective stability of the slim disk. We find that depending on the value of α, the flow is marginally stable (when α is small) or unstable (when α is large). This is different from the case of hydrodynamical hot accretion flow, where radiation is dynamically unimportant and the flow is always convectively unstable. We speculate that the reason for the difference is because radiation can stabilize convection. The origin of outflow is thus likely because of the joint function of convection and radiation, but further investigation is required.

  9. On the oxidation of stainless steel alloy 304 in subcritical and supercritical water

    NASA Astrophysics Data System (ADS)

    Rodriguez, David; Merwin, Augustus; Chidambaram, Dev

    2014-09-01

    The oxidized surface of stainless steel 304 was studied after being subjected to constant tensile load creep tests in water at temperatures of 200, 315 and 450 °C and for 24 h at a pressure of 27 MPa. Post-exposure morphology was studied using scanning electron microscopy while surface chemistry was analyzed through Fourier transform-infrared, Raman and X-ray photoelectron spectroscopies. In subcritical water, the formation of hematite was observed; while magnetite was found to form at a higher rate on the surfaces of samples exposed to supercritical water.

  10. Large-eddy simulation of nitrogen injection at trans- and supercritical conditions

    NASA Astrophysics Data System (ADS)

    Müller, Hagen; Niedermeier, Christoph A.; Matheis, Jan; Pfitzner, Michael; Hickel, Stefan

    2016-01-01

    Large-eddy simulations (LESs) of cryogenic nitrogen injection into a warm environment at supercritical pressure are performed and real-gas thermodynamics models and subgrid-scale (SGS) turbulence models are evaluated. The comparison of different SGS models — the Smagorinsky model, the Vreman model, and the adaptive local deconvolution method — shows that the representation of turbulence on the resolved scales has a notable effect on the location of jet break-up, whereas the particular modeling of unresolved scales is less important for the overall mean flow field evolution. More important are the models for the fluid's thermodynamic state. The injected fluid is either in a supercritical or in a transcritical state and undergoes a pseudo-boiling process during mixing. Such flows typically exhibit strong density gradients that delay the instability growth and can lead to a redistribution of turbulence kinetic energy from the radial to the axial flow direction. We evaluate novel volume-translation methods on the basis of the cubic Peng-Robinson equation of state in the framework of LES. At small extra computational cost, their application considerably improves the simulation results compared to the standard formulation. Furthermore, we found that the choice of inflow temperature is crucial for the reproduction of the experimental results and that heat addition within the injector can affect the mean flow field in comparison to results with an adiabatic injector.

  11. Design and technology development of solid breeder blanket cooled by supercritical water in Japan

    NASA Astrophysics Data System (ADS)

    Enoeda, M.; Kosaku, Y.; Hatano, T.; Kuroda, T.; Miki, N.; Honma, T.; Akiba, M.; Konishi, S.; Nakamura, H.; Kawamura, Y.; Sato, S.; Furuya, K.; Asaoka, Y.; Okano, K.

    2003-12-01

    This paper presents results of conceptual design activities and associated R&D of a solid breeder blanket system for demonstration of power generation fusion reactors (DEMO blanket) cooled by supercritical water. The Fusion Council of Japan developed the long-term research and development programme of the blanket in 1999. To make the fusion DEMO reactor more attractive, a higher thermal efficiency of more than 40% was strongly recommended. To meet this requirement, the design of the DEMO fusion reactor was carried out. In conjunction with the reactor design, a new concept of a solid breeder blanket cooled by supercritical water was proposed and design and technology development of a solid breeder blanket cooled by supercritical water was performed. By thermo-mechanical analyses of the first wall, the tresca stress was evaluated to be 428 MPa, which clears the 3Sm value of F82H. By thermal and nuclear analyses of the breeder layers, it was shown that a net TBR of more than 1.05 can be achieved. By thermal analysis of the supercritical water power plant, it was shown that a thermal efficiency of more than 41% is achievable. The design work included design of the coolant flow pattern for blanket modules, module structure design, thermo-mechanical analysis and neutronics analysis of the blanket module, and analyses of the tritium inventory and permeation. Preliminary integration of the design of a solid breeder blanket cooled by supercritical water was achieved in this study. In parallel with the design activities, engineering R&D was conducted covering all necessary issues, such as development of structural materials, tritium breeding materials, and neutron multiplier materials; neutronics experiments and analyses; and development of the blanket module fabrication technology. Upon developing the fabrication technology for the first wall and box structure, a hot isostatic pressing bonded F82H first wall mock-up with embedded rectangular cooling channels was

  12. Gasification Mechanism of Carbon with Supercritical Water at Very High Pressures: Effects on H2 Production.

    PubMed

    Martin-Sanchez, Nicolas; Salvador, Francisco; Sanchez-Montero, M Jesus; Izquierdo, Carmen

    2014-08-01

    The scarce data concerning the gasification of carbonaceous solids with supercritical water (SCW) suggest the great potential of this method to produce a valuable green fuel such as H2. However, the extraordinary properties of SCW have not been properly applied to H2 production because the mechanism that governs gasification under these conditions remains unclear. Here, we present a study in which this reaction is explored within the largest pressure range ever assayed in this field, from 1 to 1000 bar. The amplitude of the experimental conditions investigated highlights the various pathways that govern gasification with steam and SCW. Under supercritical conditions, the clusters formed around the superficial groups of the solid reduce the energetic requirements for gasification and generate CO2 as a primary product of the reaction. Consequently, gasification with SCW is significantly faster than that using steam, and the produced gases are richer and more appropriate to obtain pure H2.

  13. Meeting Vision 21 goals with supercritical water gasification (SCWG) of biomass/coal slurries

    SciTech Connect

    Tolman, R.; Spritzer, M.; Hong, G.T.; Rickman, B.; Parkinson, W.J.

    2000-07-01

    In the Vapor Transmission Cycle (VTC), a special condensing expander turbine is planned to reduce temperature and pressure for low-temperature cleaning and to maintain quality and combustibility of the fuel vapor for a modern gas turbine. The VTC generates clean fuel gas and steam for gas turbines by feeding water slurries or emulsions above about 25% solids, including coal fines, coal water fuels, biomass, composted municipal refuse, sewage sludge, crumb rubber and pulp and paper wastes in patented HRSG tubes. A commercial method of particle scrubbing is used to improve heat transfer and prevent corrosion and deposition on heat transfer surfaces. Tests were conducted to produce clean fuels for gas turbines and fuel cells via supercritical water gasification (SCWG). The study includes lab-scale testing of composted packer truck refuse and sewage sludge made in an aerobic digester without shredding. A computer-based process simulation model has been prepared that includes material and energy balances that simulate commercial-scale operations of the VTC. Funded by DOE, pilot-scale data produced by General Atomics for sewage sludge shows that SCWG above 640 C and low residence time without an oxidizer can produce a gaseous mixture containing over 25 vol. % hydrogen in methane, carbon monoxide, carbon dioxide and higher light hydrocarbons. Excess hydrogen can be separated for use in fuel cells. Carbon can be separated up to the amount of fixed carbon in the proximate analysis of the solids in the feed. This carbon can be burned in an existing combustion system to help provide the heat required for SCWG, or it can be used to remove pollutants and hydrocarbons from water and air. Test and modeling results will be presented. Preliminary life cycle costs analyses will be presented that establish MSW and sludge disposal fees that improve operating economics over higher-cost fuels. Analyses show that the cost and schedule advantages of natural gas-fired combined cycle

  14. Preparative chromatography with supercritical fluids. Comparison of simulated moving bed and batch processes.

    PubMed

    Peper, Stephanie; Johannsen, Monika; Brunner, Gerd

    2007-12-28

    Preparative chromatography is a key technology for the separation of fine chemicals in production scale. Most of the published studies are carried out using liquid solvents as mobile phase. However, the used organic solvents can often be replaced by supercritical fluids. A reduction or renouncement of organic solvents does not only correspond to the trend of the so-called green chemistry--a sustainable, environmentally friendly production of chemical products. But a changeover to chromatography with supercritical fluids can also be reasonable under economic criteria. In this contribution a comparison between the Batch-supercritical fluid chromatography (Batch-SFC) process and the simulated moving bed (SMB)-SFC process is presented. Because of the minor importance of solvent consumption and solvent recovery in SFC, the separation systems were optimized primarily in terms of their specific productivity. For three of the four investigated model systems, the specific productivity of the SMB process is significantly higher than the productivity of the Batch process. Due to the fact, that the process with the higher specific productivity is not inevitably the more economical process, supplementary the costs of the process were considered. Therefore the comparison of the two processes was done from an economic point of view considering the minimum product price that has to be realized to fulfill the defined economic aim. It was found that although the optimized specific productivities of the SMB process were significantly higher than the productivities of the Batch process, the Batch process is the more profitable process for the investigated production rate range between 0.4 and 5t/a.

  15. RELAP5-3D Code for Supercritical-Pressure Light-Water-Cooled Reactors

    SciTech Connect

    Riemke, Richard Allan; Davis, Cliff Bybee; Schultz, Richard Raphael

    2003-04-01

    The RELAP5-3D computer program has been improved for analysis of supercritical-pressure, light-water-cooled reactors. Several code modifications were implemented to correct code execution failures. Changes were made to the steam table generation, steam table interpolation, metastable states, interfacial heat transfer coefficients, and transport properties (viscosity and thermal conductivity). The code modifications now allow the code to run slow transients above the critical pressure as well as blowdown transients (modified Edwards pipe and modified existing pressurized water reactor model) that pass near the critical point.

  16. Voltammetry of ferrocene in supercritical CO sub 2 containing water and tetrahexylammonium hexafluorophosphate

    SciTech Connect

    Niehaus, D.; Philips, M.; Michael, A.; Wightman, R.M. )

    1989-08-10

    The voltammetric oxidation of ferrocene has been examined with microdisk electrodes in supercritical CO{sub 2} containing small-amounts of added water. Voltammograms obtained under these conditions indicate a high rate of diffusion for ferrocene but exhibit considerable ohmic drop. The ohmic distortion of the voltammograms is reduced by the addition of tetrahexylammonium hexafluorophosphate ((THA)PF{sub 6}) to the cell. However, when large amounts of (THA)PF{sub 6} are added to the cell, visual inspection indicates a two-phase system under the conditions used. Near-infrared spectra show that the upper phase is supercritical CO{sub 2} and the lower phase is liquid (THA)PF{sub 6}. This result is obtained at a temperature that is 64{degree}C below the melting point of pure (THA)PF{sub 6} at atmospheric pressure. Ferrocene is found to have a much lower diffusion coefficient in the molten salt. However, the limiting current recorded in the molten salt is not attenuated relative to that in the upper phase, because ferrocene preferentially dissolves in the molten salt. It is shown that the molten salt, when added in small amounts to the cell, acts as an electrode-surface modifier that promotes ionic conductivity and allows the oxidation of ferrocene extracted from the supercritical CO{sub 2}. This occurs even when the electrode is placed in the upper CO{sub 2} phase.

  17. Kinetics of glucose epimerization and decomposition in subcritical and supercritical water

    SciTech Connect

    Kabyemela, B.M.; Adschiri, Tadafumi; Malaluan, R.M.; Arai, Kunio

    1997-05-01

    Glucose decomposition kinetics in subcritical and supercritical water were studied for the temperatures 573, 623, and 673 K, pressures between 25 and 40 MPa, and residence times between 0.02 and 2 s. Glucose decomposition products were fructose, saccharinic acids, erythrose, glyceraldehyde, 1,6-anhydroglucose, dihydroxyacetone, pyruvaldehyde, and small amounts of 5-hydroxymethylfurfural. Fructose was also studied and found to decompose to products similar to those of glucose, except that its epimerization to glucose was negligibly low and no formation of 1,6-anhydroglucose was detected. The authors concluded that only the forward epimerization of glucose to fructose was important. The glucose decomposition pathway could be described in terms of a forward epimerization rate, r{sub gf}, a fructose to decomposition products rate, r{sub f}, and a glucose to decomposition products rate, r{sub g}. A kinetic model based on this pathway gave good correlation of the experimental data. In the subcritical region, r{sub g}, r{sub f}, and r{sub gf} showed only small changes with pressure at a given temperature. In the supercritical region, the rate of glucose decomposition decreased with pressure at a given temperature. The reason for this decrease was mainly due to the decrease in r{sub gf}. The pressure effect in the supercritical region shows that there is a shift among the kinetic rates, which can lead to higher selectivity for glucose when decomposing cellulosic materials.

  18. Oxidation of phenolics in supercritical water. Quarterly technical progress report, March 1, 1994--May 31, 1994

    SciTech Connect

    Savage, P.E.

    1994-09-01

    An environmental hazard associated with coal liquefaction and gasification is the generation of aqueous waste streams containing phenolics and carcinogenic organics such as polynuclear aromatics. Oxidation in supercritical water (SCW) is an emerging technology for the ultimate destruction of phenolics and other organics in waste water streams. SCW oxidation involves the oxidation of organics in an aqueous medium at temperatures between 400-650{degrees}C and pressures around 250 atm. These conditions exceed the thermodynamic critical point of water, hence the water is said to be supercritical. Wastes can be converted by SCWO to benign products: carbon is converted to CO{sub 2}, hydrogen to H{sub 2}O, and nitrogen to N{sub 2} or N{sub 2}O (but not NO{sub X}). SCWO possesses several attractive features. (1) The effluents from the SCWO process can be collected or held in a recycle loop so the process can be easily {open_quotes}bottled up{close_quotes} with no uncontrolled emissions should an upset occur. (2) The oxidation reaction is exothermic, so it is possible to operate the SCWO reactor in an autothermal mode. That is, the oxidation of the organic material in the aqueous stream liberates sufficient heat to maintain the elevated reactor temperature and also preheat the feed. Thus, after start-up, the process would not require an external energy source and could even be used to produce energy provided the organics content in the feed stream was sufficiently high. (3) Operating at supercritical conditions also provides a single, homogeneous fluid phase in the reactor. Indeed, water above its critical point has a high solubility for organics, and it is totally miscible with oxygen. (4) The temperature in SCWO is high enough to provide rapid reaction rates but not so high that alloys begin to lose their mechanical strength. Thus, the oxidation of organics goes essentially to completion in a very short time (a few seconds).

  19. Burst wait time simulation of CALIBAN reactor at delayed super-critical state

    SciTech Connect

    Humbert, P.; Authier, N.; Richard, B.; Grivot, P.; Casoli, P.

    2012-07-01

    In the past, the super prompt critical wait time probability distribution was measured on CALIBAN fast burst reactor [4]. Afterwards, these experiments were simulated with a very good agreement by solving the non-extinction probability equation [5]. Recently, the burst wait time probability distribution has been measured at CEA-Valduc on CALIBAN at different delayed super-critical states [6]. However, in the delayed super-critical case the non-extinction probability does not give access to the wait time distribution. In this case it is necessary to compute the time dependent evolution of the full neutron count number probability distribution. In this paper we present the point model deterministic method used to calculate the probability distribution of the wait time before a prescribed count level taking into account prompt neutrons and delayed neutron precursors. This method is based on the solution of the time dependent adjoint Kolmogorov master equations for the number of detections using the generating function methodology [8,9,10] and inverse discrete Fourier transforms. The obtained results are then compared to the measurements and Monte-Carlo calculations based on the algorithm presented in [7]. (authors)

  20. A computer simulation study on self- and cross-aggregation of multiple polar species in supercritical carbon dioxide.

    PubMed

    Xu, Wenhao; Yang, Jichu

    2010-04-29

    The effect of hydrogen-bond cooperativity on self- and cross-aggregation of multiple polar species in supercritical carbon dioxide was investigated using both ab initio calculations and Monte Carlo simulations. Ab initio calculations indicate that hydrogen-bond cooperativity has a significant impact on the cluster size, but does not greatly influence the composition of clusters. The microscopic structures in the ethanol + CO(2) and acetic acid + CO(2) binary mixtures were first studied using Monte Carlo simulations with a strict set of criteria for hydrogen bonding, and a satisfactory agreement with experimental data was achieved. The state of microscopic phase separation in the ethanol + water + CO(2) and acetic acid + water + CO(2) ternary mixtures was then extensively investigated, indicating that the size and composition of aggregates are strongly dependent on the mixing ratio. Moreover, hydrogen-bond cooperativity must be considered to acquire more thorough understanding of the hydration process. On the basis of the detailed distributions of aggregate size and structure, a new two-staged hydration mechanism was finally proposed for the ternary solutions.

  1. Effect of sub- and supercritical water treatments on the physicochemical properties of crab shell chitin and its enzymatic degradation.

    PubMed

    Osada, Mitsumasa; Miura, Chika; Nakagawa, Yuko S; Kaihara, Mikio; Nikaido, Mitsuru; Totani, Kazuhide

    2015-12-10

    This study examined the effects of sub- and supercritical water pretreatments on the physicochemical properties of crab shell α-chitin and its enzymatic degradation to obtain N,N'-diacetylchitobiose (GlcNAc)2. Following sub- and supercritical water pretreatments, the protein in the crab shell was removed and the residue of crab shell contained α-chitin and CaCO3. Prolonged pretreatment led to α-chitin decomposition. The reaction of pure α-chitin in sub- and supercritical water pretreatments was investigated separately; we observed lower mean molecular weight and weaker hydrogen bonds compared with untreated α-chitin. (GlcNAc)2 yields from enzymatic degradation of subcritical (350 °C, 7 min) and supercritical water (400 °C, 2.5 min) pretreated crab shell were 8% and 6%, compared with 0% without any pretreatment. This study shows that sub- and supercritical water pretreatments of crab shell provide to an alternative method to the use of acid and base for decalcification and deproteinization of crab shell required for (GlcNAc)2 production.

  2. Supercritical water oxidation of polyvinyl alcohol and desizing wastewater: influence of NaOH on the organic decomposition.

    PubMed

    Zhang, Jie; Wang, Shuzhong; Guo, Yang; Xu, Donghai; Gong, Yanmeng; Tang, Xingying

    2013-08-01

    Polyvinyl alcohol is a refractory compound widely used in industry. Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition. However, it is difficult to implement complete degradation of organics even though polyvinyl alcohol can readily crack under supercritical water treatment. Sodium hydroxide had a significant catalytic effect during the supercritical water oxidation of polyvinyl alcohol. It appears that the OH- ion participated in the C-C bond cleavage of polyvinyl alcohol molecules, the CO2-capture reaction and the neutralization of intermediate organic acids, promoting the overall reactions moving in the forward direction. Acetaldehyde was a typical intermediate product during reaction. For supercritical water oxidation of desizing wastewater, a high destruction rate (98.25%) based on total organic carbon was achieved. In addition, cases where initial wastewater was alkaline were favorable for supercritical water oxidation treatment, but salt precipitation and blockage issues arising during the process need to be taken into account seriously.

  3. Recycling high-performance carbon fiber reinforced polymer composites using sub-critical and supercritical water

    NASA Astrophysics Data System (ADS)

    Knight, Chase C.

    complete recycling loop. After showing the feasibility and power of this technology, the third phase of the study was focused on the fundamentals on the degradation of highly cross-linked polymer network by sub- and near-critical water. A methodology framework was established to study the apparent kinetics of the degradation of epoxy in sub-critical water. The reaction rate was modeled by a phenomenological rate model of nth order, and the rate constant was modeled by taking into account of the contributions of important physical parameters, e.g., pressure, temperature and dielectric constants. The applicability of the established model to describe the degradation kinetics was confirmed by the validation runs. This model is a suitable starting point to gain the knowledge required for eventual industrial process design. The final phase of this research consisted of a preliminary foray into investigating the economic feasibility of this technology. A process model was designed around a reactor which was sized according to considerations of industrial relevancy. The simulation of the process was done using Aspen Plus, powerful and comprehensive process simulation software. Economic analysis of this pseudo-realistic process suggested that such technology was economically viable and competitive comparing to other recycling technologies. In summary, this dissertation work represents the first comprehensive investigation on recycling aerospace-grade, multilayer woven fabric composites using supercritical and sub-critical water. The fundamental knowledge gained and process technology developed during this research is anticipated to play an important role in advancing this recycling technology toward potential adoption and implementation by the recycling and composite industry.

  4. Hydrolysis of vegetable oils in sub- and supercritical water

    SciTech Connect

    Holliday, R.L.; King, J.W.; List, G.R.

    1997-03-01

    Water, in its subcritical state, can be used as both a solvent and reactant for the hydrolysis of triglycerides. In this study, soybean, linseed, and coconut oils were successfully and reproducibly hydrolyzed to free fatty acids with water at a density of 0.7 g/mL and temperatures of 260--280 C. Under these conditions the reaction proceeds quickly, with conversion of greater than 97% after 15--20 min. Some geometric isomerization of the linolenic acids was observed at reaction temperatures as low as 250 C. Reactions carried out at higher temperatures and pressures, up to the critical point of water, produced either/or degradation, pyrolysis, and polymerization, of the oils and resultant fatty acids.

  5. Generation of laser-induced plasma in supercritical water and vibrational spectroscopic study of accompanying stimulated Raman scattering

    NASA Astrophysics Data System (ADS)

    Yui, Hiroharu; Tomai, Takaaki; Sawada, Masayoshi; Terashima, Kazuo

    2011-08-01

    We have formed a laser-induced plasma (LIP) in supercritical water (SCW) and studied associated molecular vibrations using spectroscopic methods. The accompanying forward and backward stimulated Raman scattering (SRS) of water molecules showed anisotropic behavior at supercritical conditions (>647 K and >22.1 MPa). The Raman shift of the backward SRS indicated that attractive interactions between water molecules and excess electrons generated by the LIP were dominant in the SCW. The backward SRS spectrum provided a microscopic view of the hydration environment around an excess electron, which is useful for controlling electron-driven chemical reactions and materials processing in SCW.

  6. Generation of laser-induced plasma in supercritical water and vibrational spectroscopic study of accompanying stimulated Raman scattering

    SciTech Connect

    Yui, Hiroharu; Tomai, Takaaki; Sawada, Masayoshi; Terashima, Kazuo

    2011-08-29

    We have formed a laser-induced plasma (LIP) in supercritical water (SCW) and studied associated molecular vibrations using spectroscopic methods. The accompanying forward and backward stimulated Raman scattering (SRS) of water molecules showed anisotropic behavior at supercritical conditions (>647 K and >22.1 MPa). The Raman shift of the backward SRS indicated that attractive interactions between water molecules and excess electrons generated by the LIP were dominant in the SCW. The backward SRS spectrum provided a microscopic view of the hydration environment around an excess electron, which is useful for controlling electron-driven chemical reactions and materials processing in SCW.

  7. Molecular simulation of CO chemisorption on Co(0001) in presence of supercritical fluid solvent: A potential of mean force study

    NASA Astrophysics Data System (ADS)

    Asiaee, Alireza; Benjamin, Kenneth M.

    2016-08-01

    For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (no SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0-1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.

  8. Molecular simulation of CO chemisorption on Co(0001) in presence of supercritical fluid solvent: A potential of mean force study.

    PubMed

    Asiaee, Alireza; Benjamin, Kenneth M

    2016-08-28

    For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (no SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0-1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature. PMID:27586934

  9. Water Reactivity in the Liquid and Supercritical CO2 Phase: Has Half the Story Been Neglected?

    SciTech Connect

    McGrail, B. Peter; Schaef, Herbert T.; Glezakou, Vassiliki Alexandra; Dang, Liem X.; Owen, Antionette T.

    2009-02-01

    Aqueous-phase mediated chemical reactions with dissolved CO2 have long been considered the principal if not only reactive process supporting mineralization reactions with basalt and other reactive reservoir rocks and caprocks in deep geologic sequestration systems. This is not surprising given the quite high solubility of CO2 in the aqueous phase and ample evidence from natural systems of the reactivity of CO2-charged waters with a variety of silicate minerals. In contrast, comparatively scant attention has been directed at reactivity of water solvated in liquid and supercritical CO2, with the exception of interest in the impacts of water in CO2 on the corrosion of pipeline steels. The results presented in this paper show that the most interesting and important aspects of water reactivity with metal and oxide surfaces of interest in geologic sequestration systems actually occurs in the liquid or supercritical CO2 phase. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  10. Feasibility Study of Supercritical Light Water Cooled Fast Reactors for Actinide Burning and Electric Power Production

    SciTech Connect

    Mac Donald, Philip Elsworth; Buongiorno, Jacopo; Davis, Cliff Bybee; Weaver, Kevan Dean

    2002-01-01

    The use of supercritical temperature and pressure light water as the coolant in a direct-cycle nuclear reactor offers potential for considerable plant simplification and consequent capital and O&M cost reduction compared with current light water reactor (LWR) designs. Also, given the thermodynamic conditions of the coolant at the core outlet (i.e. temperature and pressure beyond the water critical point), very high thermal efficiencies of the power conversion cycle are possible (i.e. up to 46%). Because no change of phase occurs in the core, the need for steam separators and dryers as well as for BWR-type recirculation pumps is eliminated, which, for a given reactor power, results in a substantially shorter reactor vessel than the current BWRs. Furthermore, in a direct cycle the steam generators are not needed. If a tight fuel rod lattice is adopted, it is possible to significantly reduce the neutron moderation and attain fast neutron energy spectrum conditions. In this project a supercritical water reactor concept with a simple, blanket-free, pancake-shaped core will be developed. This type of core can make use of either fertile or fertile-free fuel and retain the hard spectrum to effectively burn plutonium and minor actinides from LWR spent fuel while efficiently generating electricity.

  11. Hydrogen production from high-moisture content biomass in supercritical water

    SciTech Connect

    Antal, M.J. Jr.; Adschiri, T.; Ekbom, T.

    1996-10-01

    Most hydrogen is produced by steam reforming methane at elevated pressures. The goal of this research is to develop commercial processes for the catalytic steam reforming of biomass and other organic wastes at high pressures. This approach avoids the high cost of gas compression and takes advantage of the unique properties of water at high pressures. Prior to this year the authors reported the ability of carbon to catalyze the decomposition of biomass and related model compounds in supercritical water. The product gas consists of hydrogen, carbon dioxide, carbon monoxide, methane, and traces of higher hydrocarbons. During the past year the authors have: (a) developed a method to extend the catalyst life, (b) begun studies of the role of the shift reaction, (c) completed studies of carbon dioxide absorption from the product effluent by high pressure water, (d) measured the rate of carbon catalyst gasification in supercritical water, (e) discovered the pumpability of oil-biomass slurries, and (f) completed the design and begun fabrication of a flow reactor that will steam reform whole biomass feedstocks (i.e. sewage sludge) and produce a hydrogen rich synthesis gas at very high pressure (>22 MPa).

  12. Development of porosity in a char during reaction with steam or supercritical water.

    PubMed

    Molina-Sabio, Miguel; Sánchez-Montero, M Jesús; Juarez-Galan, Juan M; Salvador, Francisco; Rodríguez-Reinoso, Francisco; Salvador, Aurelio

    2006-06-29

    Two series of activated carbon have been prepared by reaction of a char (from olive stones) with supercritical water (SCW) with the objective of studying the effect of temperature and residence time on the development of porosity. The results have been compared with those obtained using the same char but with classical activation with steam. Both procedures develop porosity, but (i) the reaction rate is critical in the development of porosity for steam but not for SCW activation, and (ii) SCW activation produces a larger development of microporosity at low degrees of burnoff, whereas steam produces more meso- and macroporosity. The differences have been explained by assuming that the mechanism for the carbon-water reaction is common but the transport properties of water in the supercritical state are more favorable to facilitate the access of water to the interior of the char particles. In contrast, when steam is used for the activation of the char, the diffusion of the molecules cannot keep up with the chemical rate and, consequently, the reaction is preferentially taking place at the most accessible surface sites, thus facilitating the development of larger pores and the widening of microporosity.

  13. Oxidative degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) in subcritical and supercritical waters.

    PubMed

    Hashimoto, M; Taniguchi, S; Takanami, R; Giri, R R; Ozaki, H

    2010-01-01

    Presence of chlorinated organic compounds in water bodies has become a concern among governments, health authorities and general public. Oxidation of organic compounds in water under high temperature and pressure is considered as a promising technique, but usefulness of the technique to mineralize 2,4-dichlorophenoxyacetic acid (2,4-D) is not well understood. This article aimed to elucidate degradation characteristics of 2,4-D in both subcritical and supercritical waters by laboratory batch experiments. 2,4-D degradation, total organic carbon (TOC) removal and dechlorination increased with increasing reaction time and temperature especially in subcritical waters, while dechlorination was a major step. 2,4-dichlorophenol (2,4-DCP) and acetic acid were the main degradation intermediates both in subcritical and supercritical waters. Though 2,4-D disappeared almost completely in subcritical waters near critical region ( approximately 99%), significant amounts of TOC and organic chlorine still remained as 2,4-DCP and acetic acid. But TOC removal and dechlorination were significantly enhanced ( approximately 95 and 91% respectively) in supercritical waters. Complete mineralization of 2,4-D in subcritical waters required a considerably longer reaction period, while the mineralization was almost complete within a short reaction period in supercritical waters. This is an important information of practical significance for oxidative degradation of chlorinated pesticides similar to 2,4-D.

  14. Evaluation of pretreatment processes for supercritical water oxidation

    SciTech Connect

    Barnes, C.M.

    1994-01-01

    This report evaluates processes to chemically treat US Department of Energy wastes to remove organic halogens, phosphorus, and sulfur. Chemical equilibrium calculations, process simulations, and responses from developers and licensors form the basis for comparisons. Gas-phase catalytic hydrogenation processes, strong base and base catalyzed processes, high pressure hydrolysis, and other emerging or commercial dehalogenation processes (both liquid and mixed phase) were considered. Cost estimates for full-scale processes and demonstration testing are given. Based on the evaluation, testing of a hydrogenation process and a strong base process are recommended.

  15. Final report on the oxidation of energetic materials in supercritical water. Final Air Force report

    SciTech Connect

    Buelow, S.J.; Allen, D.; Anderson, G.K.

    1995-04-03

    The objective of this project was to determine the suitability of oxidation in supercritical fluids (SCO), particularly water (SCWO), for disposal of propellants, explosives, and pyrotechnics (PEPs). The SCO studies of PEPs addressed the following issues: The efficiency of destruction of the substrate. The products of destruction contained in the effluents. Whether the process can be conducted safely on a large scale. Whether energy recovery from the process is economically practicable. The information essential for process development and equipment design was also investigated, including issues such as practical throughput of explosives through a SCWO reactor, reactor materials and corrosion, and models for process design and optimization.

  16. Advanced Computational Thermal Fluid Physics (CTFP) and Its Assessment for Light Water Reactors and Supercritical Reactors

    SciTech Connect

    D.M. McEligot; K. G. Condie; G. E. McCreery; H. M. McIlroy; R. J. Pink; L.E. Hochreiter; J.D. Jackson; R.H. Pletcher; B.L. Smith; P. Vukoslavcevic; J.M. Wallace; J.Y. Yoo; J.S. Lee; S.T. Ro; S.O. Park

    2005-10-01

    Background: The ultimate goal of the study is the improvement of predictive methods for safety analyses and design of Generation IV reactor systems such as supercritical water reactors (SCWR) for higher efficiency, improved performance and operation, design simplification, enhanced safety and reduced waste and cost. The objective of this Korean / US / laboratory / university collaboration of coupled fundamental computational and experimental studies is to develop the supporting knowledge needed for improved predictive techniques for use in the technology development of Generation IV reactor concepts and their passive safety systems. The present study emphasizes SCWR concepts in the Generation IV program.

  17. Supercritical water oxidation technology for DWPF. [Defense Waste Processing Facility (DWPF)

    SciTech Connect

    Carter, J.T.; Gentilucci, J.A.

    1992-02-07

    At the request of Mr. H.L. Brandt and others in the Savannah River Field Office High Level Waste Division office, DWPF, and SRL personnel have reviewed two potential applications for supercritical water oxidation technology in DWPF. The first application would replace the current hydrolysis process by destroying the organic fractions of the precipitated cesium / potassium tetraphenylborate slurry. The second application pertains to liquid benzene destruction. After a thorough evaluation the first application is not recommended. The second is ready to be tested if needed.

  18. Superior Corrosion Resistance Properties of TiN-Based Coatings on Zircaloy Tubes in Supercritical Water

    SciTech Connect

    Fauzia Khatkhatay; Liang Jiao; Jie Jian; Zhijie Jiao; Hongbin Zhang; Jian Gan; Haiyan Wang; Wenrui Zhang; Xinghang Zhang

    2014-08-01

    Thin films of TiN and Ti0.35Al0.65N nanocomposite were deposited on polished Zircaloy-4 tubes. After exposure to supercritical water for 48 h, the coated tubes are remarkably intact, while the bare uncoated tube shows severe oxidation and breakaway corrosion. X-ray diffraction patterns, secondary electron images, backscattered electron images, and energy dispersive X-ray spectroscopy data from the tube surfaces and cross-sections show that a protective oxide, formed on the film surface, effectively prevents further oxidation and corrosion to the Zircaloy-4 tubes. This result demonstrates the effectiveness of thin film ceramics as protective coatings under extreme environments.

  19. Wetting micro- and nanofluidic devices using supercritical water.

    PubMed

    Riehn, Robert; Austin, Robert H

    2006-08-15

    We describe a method for wetting micro- and nanofluidic devices with water or any other pure liquid. The process is performed by enclosing the fluidic device in a liquid-filled cell, heating the cell to a temperature above the critical point of the liquid, and subsequent cooling of the cell to room temperature. Because the process liquid is essentially a gas during wetting, arbitrary shapes can be wetted. We demonstrate wetting of micro- and nanostructures in a fused-silica device with only a single inlet. The process is low-cost, fast, safe, and very reliable. PMID:16906743

  20. Obtaining of gas, liquid, and upgraded solid fuel from brown coals in supercritical water

    NASA Astrophysics Data System (ADS)

    Vostrikov, A. A.; Fedyaeva, O. N.; Dubov, D. Yu.; Shishkin, A. V.; Sokol, M. Ya.

    2013-12-01

    Two new conversion methods of brown coals in water steam and supercritical water (SCW) are proposed and investigated. In the first method, water steam or SCW is supplied periodically into the array of coal particles and then is ejected from the reactor along with dissolved conversion products. The second method includes the continuous supply of water-coal suspension (WCS) into the vertically arranged reactor from above. When using the proposed methods, agglomeration of coal particles is excluded and a high degree of conversion of coal into liquid and gaseous products is provided. Due to the removal of the main mass of oxygen during conversion in the composition of CO2, the high heating value of fuels obtained from liquid substantially exceeds this characteristic of starting coal. More than half of the sulfur atoms transfer into H2S during the SCW conversion already at a temperature lower than 450°C.

  1. Supercritical water oxidation of Quinazoline: Effects of conversion parameters and reaction mechanism.

    PubMed

    Gong, Yanmeng; Guo, Yang; Wang, Shuzhong; Song, Wenhan

    2016-09-01

    The supercritical water oxidation reaction of quinazoline and a set of related reaction products were investigated in batch reactors by varying the temperature (T, 400-600 °C), time (t, 0-400 s), water density (ρ, 70.79-166.28  kg m(-3)) and oxidation coefficient (OC, 0-4.0). The TOC removal efficiency (CRE) increased significantly as the OC increased, whereas this effect was very limited at high OC (>2.0). Lack of oxygen resulted in low CRE and TN removal efficiency (NRE), also cause coke-formation, and giving high yield of NH3 and nitrogenous organic intermediates. Prolonging reaction time did not provide an appreciable improvement on CRE but remarkably increased NRE at temperature higher than 500 °C. Pyrimidines and pyridines as the nitrogenous intermediates were largely found in GC-MS spectrum. Polymerization among benzene, phenyl radical and benzyl radical played important roles in the formation of PAHs, such as naphthalene, biphenyl, phenanthrene. These collective results showed how the yield of intermediate products responded to changes in the process variables, which permitted the development of a potential reaction network for supercritical water oxidation of quinazoline. PMID:27179598

  2. Experimental study on heat transfer to supercritical water flowing through tubes

    SciTech Connect

    Zhao, M.; Gu, H.; Cheng, X.

    2012-07-01

    A test facility named SWAMUP (Supercritical Water Multi-Purpose Loop) has been constructed in Shanghai Jiao Tong Univ. to investigate heat transfer and pressure drop through tubes and rod bundles. SWAMUP is a closed loop with operating pressure up to 30 MPa, outlet-water temperature up to 550 deg. C, and mass flow rate up to 5 t/h. In this paper, experimental study has been carried out on heat transfer of supercritical water flowing vertically through tubes (ID=7.6 and 10 mm). A large number of test points in tubes has been obtained with a wide range of heat flux (200-1500 kw/m{sup 2}) and mass flux (450-2000 kg/m{sup 2}s). Test results showed that heat transfer deterioration (HTD) caused by buoyancy effect only appears in upward flow and HTD caused by acceleration effect appears both in upward flow and downward flow. The heat transfer coefficients (HTC) produced in tube tests were compared with existing heat transfer correlations. (authors)

  3. The first commercial supercritical water oxidation sludge processing plant.

    PubMed

    Griffith, James W; Raymond, Dennis H

    2002-01-01

    Final disposal of sludge continues to be one of the more pressing problems for the wastewater treatment industry. Present regulations for municipal sludge have favored beneficial use, primarily in land application. However, several agencies and entities have warned of potential health risks associated with these methods. Hydrothermal oxidation provides an alternative method that addresses the health concerns associated with sludge disposal by completely converting all organic matter in the sludge to carbon dioxide, water, and other innocuous materials. A hydrothermal oxidation system using HydroProcessing, L.L.C.'s HydroSolids process has been installed at Harlingen, Texas to process up to 9.8 dry tons per day of sludge. Based on a literature review, this system is the largest hydrothermal oxidation system in the world, and the only one built specifically to process a sludge. Start up of Unit 1 of two units of the HTO system began in April 2001. Early results have indicated COD conversion rates in excess of 99.9%. Harlingen Waterworks System estimates that the HydroSolids system will cost less than other alternatives such as autothermal thermophilic aerobic digestion and more traditional forms of digestion that still require dewatering and final disposal. The Waterworks intends to generate income from the sale of energy in the form of hot water and the use of carbon dioxide from the HydroSolids process for neutralization of high pH industrial effluent. The Waterworks also expects to generate income from the treatment of septage and grease trap wastes.

  4. Mass transfer in SCW extraction molecular diffusion and mass transfer coefficients of ketones and alkenes in sub- and supercritical water

    SciTech Connect

    Goemans, M.G.E.; Gloyna, E.F.

    1996-10-01

    The potential of sub- and supercritical water as extraction solvents has been demonstrated for the (reactive) extraction of coals, used car tires, organic species from residual aqueous solutions, and class selective extraction of organic pollutants with different polarities from solids. In addition, the potential of extraction of coal with supercritical aqueous solutions has been studied. However, physical transport in water at elevated temperature and pressures- and their impact on heterogenous reactions and (reactive) extraction -are not adequately understood. This situation is largely due to the limited data that is available for diffusion in high temperature, high pressure water mixture. Only the molecular diffusion of Iodine ions and hydroquinone in near-critical subcritical water and the self diffusion of coefficient of compressed supercritical water have been reported. In this paper, we present molecular diffusion coefficients of benzophenone, acetone, naphthalene, and anthracene in water at infinite dilution. Pressures ranged from 250 to 500 bar at temperatures ranging from 50{degrees}C to 500{degrees}C resulting in water densities ranging from 1000 to 150 kg/m{sup 3}. Diffusion coefficients were determined by the Taylor-Aris dispersion technique. The effects of increased diffusion on the mass transfer coefficients for emulsions and packed beds were quantified. Molecular division coefficients were 10 to 20 times faster in supercritical water than in water at ambient conditions. Experimental results were correlated with hydrodynamic and kinetic theory. This study and results to be published elsewhere show that diffusion-limited conditions are much more likely to be encountered in supercritical water than is commonly acknowledged.

  5. SCC and corrosion evaluations of the F/M steels for a supercritical water reactor

    NASA Astrophysics Data System (ADS)

    Hwang, Seong Sik; Lee, Byung Hak; Kim, Jung Gu; Jang, Jinsung

    2008-01-01

    As one of the Generation IV nuclear reactors, a supercritical water cooled reactor (SCWR) is being considered as a candidate reactor due to its high thermal efficiency and simple reactor design without steam generators and steam separators. For the application of a structural material to a core's internals and a fuel cladding, the material should be evaluated in terms of its corrosion and stress corrosion cracking susceptibility. Stress corrosion cracking and general corrosion tests of ferritic-martensitic (F/M) steels, high Ni alloys and an oxide dispersion strengthened (ODS) alloy were performed. Stress corrosion cracking (SCC) was not observed on the fractured surface of the T 91 steel in the supercritical water at 500, 550 and 600 °C. As the test temperature increased, the ultimate tensile strength (UTS) and yield strength (YS) of T 91 decreased, and a high dissolved oxygen level induced corrosion and low ductility. The F/M steels showed a high corrosion rate whereas the Ni base alloys showed a little corrosion at 500 and 550 °C. Corrosion rate of the F/M steels at 600 °C test was up to three times larger than that at 500 °C. A thin layer composed of Mo and Ni seems to retard the Cr diffusion into the out layer of the corrosion product of T 92 and T 122.

  6. Destruction of Representative Navy Wastes Using Supercritical Water Oxidation. Final report

    SciTech Connect

    Rice, S.F.; Steeper, R.R.; LaJeunesse, C.A.

    1993-10-01

    Supercritical water oxidation (SCWO) is a rapidly emerging technology that presents potential as a hazardous waste treatment method for a wide variety of industrial chemicals ranging from common organic solvents to complex formulations such as paints, lubricating oils, and degreasers. The Naval Civil Engineering Laboratory is contributing to the development of this technology for application to waste materials generated at naval shipyards and bases. These wastes include paint stripping and changeout fluids generated from equipment service procedures as well as herbicides, pesticides, paint, and numerous other materials associated with base facility maintenance. An important design consideration in the development of SCWO systems centers on choosing a reactor operating temperature such that the destruction of the waste organic is sufficiently complete. This report examines the temperature dependence of the oxidation in supercritical water of seven common organic compounds and three industrial commercial materials over the temperature range of 430{degree}C to 585{degree}C and reaction times ranging from seven to thirty seconds at a pressure of 27.5 MPa (4000 psi). The materials studies are methanol, phenol, methyl ethyl ketone, ethylene glycol, acetic acid, methylene chloride, 1,1,1-tichloroethane (TCA), latex paint, motor oil, and Roundup, a commercial general purpose herbicide. The results indicate that for most materials, temperatures over 530{degree}C and residence times near 20 seconds afford destruction efficiencies of greater than 99.95%

  7. Total organic carbon disappearance kinetics for the supercritical water oxidation of monosubstituted phenols

    SciTech Connect

    Martino, C.J.; Savage, P.E.

    1999-06-01

    Supercritical water oxidation (SCWO) is a process technology for destroying organic compounds present in aqueous waste streams. The authors oxidized phenols bearing single -CH{sub 3}, -C{sub 2}H{sub 5}, -COCH{sub 3}, -CHO, -OH, -OCH{sub 3}, and -NO{sub 2} substituents in supercritical water at 460 C and 25.3 MPa. The observed effects of the concentrations of total organic carbon (TOC) and oxygen on the global disappearance rates for TOC were correlated by using power-law rate expressions. This kinetics study revealed that the rate of TOC disappearance is more sensitive to the oxygen concentration than is the rate of reactant disappearance. Additionally, the rate of TOC disappearance is always slower than the rate of reactant disappearance, with the ratio of these rates ranging from 0.10 to 0.65 for the different phenols at the conditions studied. The rates of TOC disappearance during SCWO of these substituted phenols varied by nearly 2 orders of magnitude, showing significant effects from both the identity and location of the substituent. These substituent effects are greater for TOC disappearance kinetics than for reactant disappearance kinetics. Additionally, all of the substituted phenols exhibit faster TOC disappearance rates than does phenol. Accordingly, phenol is a good worst case model compound for SCWO studies. The pronounced substituent effects for TOC disappearance rates indicate that the oxidation of a common refractory intermediate is not an important feature of the SCWO networks for these phenols at the conditions studied.

  8. Fundamental Understanding of Crack Growth in Structural Components of Generation IV Supercritical Light Water Reactors

    SciTech Connect

    Iouri I. Balachov; Takao Kobayashi; Francis Tanzella; Indira Jayaweera; Palitha Jayaweera; Petri Kinnunen; Martin Bojinov; Timo Saario

    2004-11-17

    This work contributes to the design of safe and economical Generation-IV Super-Critical Water Reactors (SCWRs) by providing a basis for selecting structural materials to ensure the functionality of in-vessel components during the entire service life. During the second year of the project, we completed electrochemical characterization of the oxide film properties and investigation of crack initiation and propagation for candidate structural materials steels under supercritical conditions. We ranked candidate alloys against their susceptibility to environmentally assisted degradation based on the in situ data measure with an SRI-designed controlled distance electrochemistry (CDE) arrangement. A correlation between measurable oxide film properties and susceptibility of austenitic steels to environmentally assisted degradation was observed experimentally. One of the major practical results of the present work is the experimentally proven ability of the economical CDE technique to supply in situ data for ranking candidate structural materials for Generation-IV SCRs. A potential use of the CDE arrangement developed ar SRI for building in situ sensors monitoring water chemistry in the heat transport circuit of Generation-IV SCWRs was evaluated and proved to be feasible.

  9. Core design study of a supercritical light water reactor with double row fuel rods

    SciTech Connect

    Zhao, C.; Wu, H.; Cao, L.; Zheng, Y.; Yang, J.; Zhang, Y.

    2012-07-01

    An equilibrium core for supercritical light water reactor has been designed. A novel type of fuel assembly with dual rows of fuel rods between water rods is chosen and optimized to get more uniform assembly power distributions. Stainless steel is used for fuel rod cladding and structural material. Honeycomb structure filled with thermal isolation is introduced to reduce the usage of stainless steel and to keep moderator temperature below the pseudo critical temperature. Water flow scheme with ascending coolant flow in inner regions is carried out to achieve high outlet temperature. In order to enhance coolant outlet temperature, the radial power distributions needs to be as flat as possible through operation cycle. Fuel loading pattern and control rod pattern are optimized to flatten power distribution at inner regions. Axial fuel enrichment is divided into three parts to control axial power peak, which affects maximum cladding surface temperature. (authors)

  10. Numerical Simulations Studies of the Convective Instability Onset in a Supercritical Fluid

    NASA Technical Reports Server (NTRS)

    Furukawa, A.; Meyer, H.; Onuki, A.

    2004-01-01

    Numerical simulation studies are reported for the convection of a supercritical fluid, He-3, in a Rayleigh-Benard cell. The calculations provide the temporal profile DeltaT(t) of the temperature drop across the fluid layer. In a previous article, systematic delays in the onset of the convective instability in simulations relative to experiments were reported, as seen from the DeltaT(t) profiles. They were attributed to the smallness of the noise which is needed to start the instability. Therefore i) homogeneous temperature noise and ii) spatial lateral periodic temperature variations in the top plate were programmed into the simulations, and DeltaT(t) compared with that of an experiment with the same fluid parameters. An effective speed-up in the instability onset was obtained, with the best results obtained through the spatial temperature variations with a period of 2L, close to the wavelength of a pair of convections rolls. For a small amplitude of 0.5 micro-K, this perturbation gave a semiquantitative agreement with experimental observations. Results for various noise amplitudes are presented and discussed in relation to predictions by El Khouri and Carl es.

  11. Effects of water on reactions for waste treatment, organic synthesis, and bio-refinery in sub- and supercritical water.

    PubMed

    Akizuki, Makoto; Fujii, Tatsuya; Hayashi, Rumiko; Oshima, Yoshito

    2014-01-01

    Current research analyzing the effects of water in the field of homogeneous and heterogeneous reactions of organics in sub- and supercritical water are reviewed in this article. Since the physical properties of water (e.g., density, ion product and dielectric constants) can affect the reaction rates and mechanisms of various reactions, understanding the effects that water can have is important in controlling reactions. For homogeneous reactions, the effects of water on oxidation, hydrolysis, aldol condensation, Beckman rearrangement and biomass refining were introduced including recent experimental results up to 100 MPa using special pressure-resistance equipment. For heterogeneous reactions, the effects of ion product on acid/base-catalyzed reactions, such as hydrothermal conversion of biomass-related compounds, organic synthesis in the context of bio-refinery, and hydration of olefins were described and how the reaction paths are controlled by the concentration of water and hydrogen ions was summarized.

  12. Supercritical Water Reactor (SCWR) - Survey of Materials Research and Development Needs to Assess Viability

    SciTech Connect

    Philip E. MacDonald

    2003-09-01

    Supercritical water-cooled reactors (SCWRs) are among the most promising advanced nuclear systems because of their high thermal efficiency [i.e., about 45% vs. 33% of current light water reactors (LWRs)] and considerable plant simplification. SCWRs achieve this with superior thermodynamic conditions (i.e., high operating pressure and temperature), and by reducing the containment volume and eliminating the need for recirculation and jet pumps, pressurizer, steam generators, steam separators and dryers. The reference SCWR design in the U.S. is a direct cycle, thermal spectrum, light-water-cooled and moderated reactor with an operating pressure of 25 MPa and inlet/outlet coolant temperature of 280/500 °C. The inlet flow splits, partly to a down-comer and partly to a plenum at the top of the reactor pressure vessel to flow downward through the core in special water rods to the inlet plenum. This strategy is employed to provide good moderation at the top of the core, where the coolant density is only about 15-20% that of liquid water. The SCWR uses a power conversion cycle similar to that used in supercritical fossil-fired plants: high- intermediate- and low-pressure turbines are employed with one moisture-separator re-heater and up to eight feedwater heaters. The reference power is 3575 MWt, the net electric power is 1600 MWe and the thermal efficiency is 44.8%. The fuel is low-enriched uranium oxide fuel and the plant is designed primarily for base load operation. The purpose of this report is to survey existing materials for fossil, fission and fusion applications and identify the materials research and development needed to establish the SCWR viabilitya with regard to possible materials of construction. The two most significant materials related factors in going from the current LWR designs to the SCWR are the increase in outlet coolant temperature from 300 to 500 °C and the possible compatibility issues associated with the supercritical water environment.

  13. Comparison between Radiation-Hydrodynamic Simulation of Supercritical Accretion Flows and a Steady Model with Outflows

    NASA Astrophysics Data System (ADS)

    Jiao, Cheng-Liang; Mineshige, Shin; Takeuchi, Shun; Ohsuga, Ken

    2015-06-01

    We apply our two-dimensional (2D), radially self-similar steady-state accretion flow model to the analysis of hydrodynamic simulation results of supercritical accretion flows. Self-similarity is checked and the input parameters for the model calculation, such as advective factor and heat capacity ratio, are obtained from time-averaged simulation data. Solutions of the model are then calculated and compared with the simulation results. We find that in the converged region of the simulation, excluding the part too close to the black hole, the radial distributions of azimuthal velocity {{v}φ }, density ρ and pressure p basically follow the self-similar assumptions, i.e., they are roughly proportional to {{r}-0.5}, {{r}-n}, and {{r}-(n+1)}, respectively, where n∼ 0.85 for the mass injection rate of 1000{{L}E}/{{c}2}, and n∼ 0.74 for 3000{{L}E}/{{c}2}. The distribution of vr and {{v}θ } agrees less with self-similarity, possibly due to convective motions in the rθ plane. The distribution of velocity, density, and pressure in the θ direction obtained by the steady model agrees well with the simulation results within the calculation boundary of the steady model. Outward mass flux in the simulations is overall directed toward a polar angle of 0.8382 rad (∼ 48\\buildrel{\\circ}\\over{.} 0) for 1000{{L}E}/{{c}2} and 0.7852 rad (∼ 43\\buildrel{\\circ}\\over{.} 4) for 3000{{L}E}/{{c}2}, and ∼94% of the mass inflow is driven away as outflow, while outward momentum and energy fluxes are focused around the polar axis. Parts of these fluxes lie in the region that is not calculated by the steady model, and special attention should be paid when the model is applied.

  14. Gasification characteristics of an activated carbon catalyst during the decomposition of hazardous waste material in supercritical water

    SciTech Connect

    Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

    1996-12-31

    Recently, carbonaceous materials including activated carbon were proven to be effective catalysts for hazardous waste gasification in supercritical water. Using coconut shell activated carbon catalyst, complete decomposition of industrial organic wastes including methanol and acetic acid was achieved. During this process, the total mass of the activated carbon catalyst changes by two competing processes: a decrease in weight via gasification of the carbon by supercritical water, or an increase in weight by deposition of carbonaceous materials generated by incomplete gasification of the biomass feedstocks. The deposition of carbonaceous materials does not occur when complete gasification is realized. Gasification of the activated carbon in supercritical water is often favored, resulting in changes in the quality and quantity of the catalyst. To thoroughly understand the hazardous waste decomposition process, a more complete understanding of the behavior of activated carbon in pure supercritical water is needed. The gasification rate of carbon by water vapor at subcritical pressures was studied in relation to coal gasification and generating activated carbon.

  15. Simulation of Oxygen Disintegration and Mixing With Hydrogen or Helium at Supercritical Pressure

    NASA Technical Reports Server (NTRS)

    Bellan, Josette; Taskinoglu, Ezgi

    2012-01-01

    The simulation of high-pressure turbulent flows, where the pressure, p, is larger than the critical value, p(sub c), for the species under consideration, is relevant to a wide array of propulsion systems, e.g. gas turbine, diesel, and liquid rocket engines. Most turbulence models, however, have been developed for atmospheric-p turbulent flows. The difference between atmospheric-p and supercritical-p turbulence is that, in the former situation, the coupling between dynamics and thermodynamics is moderate to negligible, but for the latter it is very significant, and can dominate the flow characteristics. The reason for this stems from the mathematical form of the equation of state (EOS), which is the perfect-gas EOS in the former case, and the real-gas EOS in the latter case. For flows at supercritical pressure, p, the large eddy simulation (LES) equations consist of the differential conservation equations coupled with a real-gas EOS. The equations use transport properties that depend on the thermodynamic variables. Compared to previous LES models, the differential equations contain not only the subgrid scale (SGS) fluxes, but also new SGS terms, each denoted as a correction. These additional terms, typically assumed null for atmospheric pressure flows, stem from filtering the differential governing equations, and represent differences between a filtered term and the same term computed as a function of the filtered flow field. In particular, the energy equation contains a heat-flux correction (q-correction) that is the difference between the filtered divergence of the heat flux and the divergence of the heat flux computed as a function of the filtered flow field. In a previous study, there was only partial success in modeling the q-correction term, but in this innovation, success has been achieved by using a different modeling approach. This analysis, based on a temporal mixing layer Direct Numerical Simulation database, shows that the focus in modeling the q

  16. Effect of microstructure on the corrosion of CVD-SiC exposed to supercritical water

    NASA Astrophysics Data System (ADS)

    Tan, L.; Allen, T. R.; Barringer, E.

    2009-10-01

    Silicon carbide (SiC) is an important engineering material being studied for potential use in multiple nuclear energy systems including high-temperature gas-cooled reactors and water-cooled reactors. The corrosion behavior of SiC exposed to supercritical water (SCW) is critical for examining its applications in nuclear reactors. Although the hydrothermal corrosion of SiC has been the subject of many investigations, the study on the microstructural effects on the corrosion is limited. This paper presents the effect of residual strain, grain size, grain boundary types, and surface orientations on the corrosion of chemical vapor deposited (CVD) β-SiC exposed to SCW at 500 °C and 25 MPa. Weight loss occurred on all the samples due to localized corrosion. Residual strains associated with small grains showed the most significant effect on the corrosion compared to the other factors.

  17. Magnetic ramp scale at supercritical perpendicular collisionless shocks: Full particle electromagnetic simulations

    SciTech Connect

    Yang, Zhongwei; Lu, Quanming; Gao, Xinliang; Huang, Can; Yang, Huigen; Hu, Hongqiao; Han, Desheng; Liu, Ying

    2013-09-15

    Supercritical perpendicular collisionless shocks are known to exhibit foot, ramp, and overshoot structures. The shock ramp structure is in a smaller scale in contrast to other microstructures (foot and overshoot) within the shock front. One-dimensional full particle simulations of strictly perpendicular shocks over wide ranges of ion beta β{sub i}, Alfvén Mach number M{sub A}, and ion-to-electron mass ratio m{sub i}/m{sub e} are presented to investigate the impact of plasma parameters on the shock ramp scale. Main results are (1) the ramp scale can be as small as several electron inertial length. (2) The simulations suggest that in a regime below the critical ion beta value, the shock front undergoes a periodic self-reformation and the shock ramp scale is time-varying. At higher ion beta values, the shock front self-reformation is smeared. At still higher ion beta value, the motion of reflected ions is quite diffuse so that they can lead to a quasi-steady shock ramp. Throughout the above three conditions, the shock ramp thickness increases with β{sub i}. (3) The increase (decrease) in Mach number and the decrease (increase) in the beta value have almost equivalent impact on the state (i.e., stationary or nonstationary) of the shock ramp. Both of front and ramp thicknesses are increased with M{sub A}.

  18. Recycling of woven carbon-fibre-reinforced polymer composites using supercritical water.

    PubMed

    Knight, Chase C; Zeng, Changchun; Zhang, Chuck; Wang, Ben

    2012-01-01

    Over the past few years, there has been great deal of interest in recycling carbon-fibre-reinforced polymer composites. One method that has shown promising results involves the use of supercritical fluids to achieve separation between matrix and fibres by effectively degrading the resin into lower molecular weight compounds. In addition, the solvents used are environmentally benign and can also be recovered and reused. In this study, supercritical water with 0.05 M KOH as the catalyst was used for the recycling of an aerospace-grade high-performance epoxy carbon fibre composite (Hexcel 8552/IM7). The morphology of the reclaimed fibres was observed by scanning electron microscopy, and the tensile properties of the fibres were measured by single filament testing. The effects of processing time on the resin elimination efficiency and fibre property retention were investigated. With the process developed in this research, as much as 99.2 wt% resin elimination was achieved, resulting in the recovery of clean, undamaged fibres. The reclaimed fibres retained the original tensile strength. The feasibility of recycling multiple layer composites was also explored.

  19. Effect of impurities on the corrosion behavior of CO2 transmission pipeline steel in supercritical CO2-water environments.

    PubMed

    Choi, Yoon-Seok; Nesic, Srdjan; Young, David

    2010-12-01

    The corrosion property of carbon steel was evaluated using an autoclave under CO(2)-saturated water phase and water-saturated CO(2) phase with impurities (O(2) and SO(2)) at 80 bar CO(2) and 50 °C to simulate the condition of CO(2) transmission pipeline in the carbon capture and storage (CCS) applications. The results showed that the corrosion rate of carbon steel in CO(2)-saturated water was very high and it increased with adding O(2) in the system due to the inhibition effect of O(2) on the formation of protective FeCO(3). It is noteworthy that corrosion took place in the water-saturated CO(2) phase under supercritical condition when no free water is present. The addition of O(2) increased the corrosion rates of carbon steel in water-saturated CO(2) phase. The addition of 0.8 bar SO(2) (1%) in the gas phase dramatically increased the corrosion rate of carbon steel from 0.38 to 5.6 mm/y. This then increased to more than 7 mm/y with addition of both O(2) and SO(2). SO(2) can promote the formation of iron sulfite hydrate (FeSO(3)·3H(2)O) on the steel surface which is less protective than iron carbonate (FeCO(3)), and it is further oxidized to become FeSO(4) and FeOOH when O(2) is present with SO(2) in the CO(2)-rich phase. The corrosion rates of 13Cr steel were very low compared with carbon steel in CO(2)-saturated water environments with O(2), whereas it was as high as carbon steel in a water-saturated CO(2) phase with O(2) and SO(2).

  20. Determination of pure neutron radiolysis yields for use in chemical modeling of supercritical water

    NASA Astrophysics Data System (ADS)

    Edwards, Eric J.

    This work has determined pure neutron radical yields at elevated temperature and pressure up to supercritical conditions using a reactor core radiation. The data will be necessary to provides realistic conditions for material corrosion experiments for the supercritical water reactor (SCWR) through water chemistry modeling. The work has been performed at the University of Wisconsin Nuclear Reactor using an apparatus designed to transport supercritical water near the reactor core. Low LET yield data used in the experiment was provided by a similar project at the Notre Dame Radiation Lab. Radicals formed by radiolysis were measured through chemical scavenging reactions. The aqueous electron was measured by two methods, a reaction with N2O to produce molecular nitrogen and a reaction with SF6 to produce fluoride ions. The hydrogen radical was measured through a reaction with ethanol-D6 (CD3CD2OD) to form HD. Molecular hydrogen was measured directly. Gaseous products were measured with a mass spectrometer and ions were measured with an ion selective electrode. Radiation energy deposition was calibrated for neutron and gamma radiation separately with a neutron activation analysis and a radiolysis experiment. Pure neutron yields were calculated by subtracting gamma contribution using the calibrated gamma energy deposition and yield results from work at the Notre Dame Radiation Laboratory. Pure neutron yields have been experimentally determined for aqueous electrons from 25°C to 400°C at 248 bar and for the hydrogen radical from 25°C to 350°C at 248 bar, Isothermal data has been acquired for the aqueous electron at 380°C and 400°C as a function of density. Molecular hydrogen yields were measured as a function of temperature and pressure, although there was evidence that chemical reactions with the walls of the water tubing were creating molecular hydrogen in addition to that formed through radiolysis. Critical hydrogen concentration behavior was investigated but a

  1. Hydrogen production from high-moisture content biomass in supercritical water

    SciTech Connect

    Antal, M.J. Jr.; Matsumura, Y.; Onuma, M.T.

    1995-09-01

    Wet biomass (water hyacinth, banana trees, cattails, green algae, kelp, etc.) grows rapidly and abundantly around the world. However, wet biomass is not regarded as a promising feedstock for conventional thermochemical conversion processes because the cost of drying the material is too high. Prior work has shown that low concentrations of glucose (a model compound for whole biomass) and various wet biomass species (water hyacinth, algae) can be completely gasified in supercritical water at 600{degrees}C and 34.5 MPa after a 30 s residence time. But higher concentrations of glucose evidenced incomplete conversion. For this reason, flow reactors were fabricated which could accommodate packed beds of catalyst, and studies were initiated of the steam reforming (gasification) reactions in the presence of various candidate heterogeneous catalysts. The goal is to identify active catalysts for steam reforming biomass slurries in supercritical water. Soon after tests began, a suitable class of carbon-based catalysts was discovered. These catalysts effect complete (>99%) conversion of high-concentration glucose (up to 22% by weight) to a hydrogen-rich synthesis gas. High space velocities are realized [>20 (g/hr)/g], and the catalyst is stable over a period of several hours. The carbon catalyst is not expensive, and exists in a wide variety of forms and compositions. After this discovery, work has focused on four interrelated tasks: (1) tests to identify the most active form and composition of the catalyst; (2) tests employing the preferred catalyst to study the effect of feedstock composition on carbon conversion and gas composition; (3) studies of catalyst deactivation and subsequent reactivation, including the in-house synthesis of bifunctional catalysts which incorporate promoters and stabilizers; and (4) the design and fabrication of a larger, new reactor with a slurry feeder intended to handle high-concentration, wet biomass feeds.

  2. The thermal circuit of a nuclear power station's unit built around a supercritical-pressure water-cooled reactor

    NASA Astrophysics Data System (ADS)

    Silin, V. A.; Zorin, V. M.; Tagirov, A. M.; Tregubova, O. I.; Belov, I. V.; Povarov, P. V.

    2010-12-01

    Main results obtained from calculations of the steam generator and thermal circuit of the steam turbine unit for a nuclear power unit with supercritical-pressure water coolant and integral layout are presented. The obtained characteristics point to the advisability of carrying out further developments of this promising nuclear power technology.

  3. Three-dimensional simulations of supercritical black hole accretion discs - luminosities, photon trapping and variability

    NASA Astrophysics Data System (ADS)

    Sądowski, Aleksander; Narayan, Ramesh

    2016-03-01

    We present a set of four three-dimensional, general relativistic, radiation magnetohydrodynamical simulations of black hole accretion at supercritical mass accretion rates, dot{M} > dot{M}_Edd. We use these simulations to study how disc properties are modified when we vary the black hole mass, the black hole spin, or the mass accretion rate. In the case of a non-rotating black hole, we find that the total efficiency is of the order of 3 per cent dot{M} c^2, approximately a factor of 2 less than the efficiency of a standard thin accretion disc. The radiation flux in the funnel along the axis is highly super-Eddington, but only a small fraction of the energy released by accretion escapes in this region. The bulk of the 3 per cent dot{M} c^2 of energy emerges farther out in the disc, either in the form of photospheric emission or as a wind. In the case of a black hole with a spin parameter of 0.7, we find a larger efficiency of about 8 per cent dot{M} c^2. By comparing the relative importance of advective and diffusive radiation transport, we show that photon trapping is effective near the equatorial plane. However, near the disc surface, vertical transport of radiation by diffusion dominates. We compare the properties of our fiducial three-dimensional run with those of an equivalent two-dimensional axisymmetric model with a mean-field dynamo. The latter simulation runs nearly 100 times faster than the three-dimensional simulation, and gives very similar results for time-averaged properties of the accretion flow, but does not reproduce the time-variability.

  4. Effects of water on enzyme performance with an emphasis on the reactions in supercritical fluids.

    PubMed

    Rezaei, K; Jenab, E; Temelli, F

    2007-01-01

    Enzymes require a certain level of water in their structures in order to maintain their natural conformation, allowing them to deliver their full functionality. Furthermore, as a modifier of the solvent, up to a certain level, water can modify the solvent properties such as polarity/polarizability as well as the solubility of the reactants and the products. In addition, depending on the type of the reaction, water can be a substrate (e.g., in hydrolysis) or a product (e.g., in esterolysis) of the enzymatic reaction, influencing the enzyme turnover in different ways. It is found that regardless of the type of reaction, the functionality of enzyme itself is maximum at an optimum level of water, beyond which the enzyme performance is declined due to the loss in enzyme stability. Furthermore, mass transfer limitations caused by pathway blockage and/or by reduced solubilities of the reactants and/or products can also affect the enzyme performance at higher water levels. Controlling water content of ingoing CO2 and substrates as well as precise management of enzyme support and salt hydrates are important strategies to adjust water level in reaction media, especially in supercritical environments. PMID:18085461

  5. Simulated distillation of petroleum and coal-derived products by packed capillary supercritical fluid chromatography

    SciTech Connect

    Robson, M.; Johnson, B.R.; Mitchell, S.C.

    1995-12-31

    The advantages of simulated distillation (SD) of petroleum compounds by super-critical fluid chromatography (SFC) over high temperature gas chromatography (HTGC) are well recognised. Most of the research performed using this technique has employed conventional open tubular columns but the use of packed capillary columns which offer high sample capacities, greater efficiency of separation and a shorter analysis time has recently received much attention. Previous work at Leeds using a variety of column packings (C{sub 1}-C{sub 18} alkyl groups bonded to silica) has demonstrated that high molecular weight hydrocarbons with boiling points up to 800{degrees}C can be successfully eluted with pure CO{sub 2} as a mobile phase. However, the high compositional variability of coal-derived samples increases the difficulty of SD-SFC of coal fractions as compared to petroleum derived fractions. In this study, a number of coal samples have been investigated to determine the suitability of packed capillary SD-SFC for heavy coal products.

  6. Catalysis of CuSO4 for total organic carbon detection based on supercritical water oxidation.

    PubMed

    Hui, Zhang; Dongdong, Han; Yi, Chen; Chunmian, Lin

    2016-01-01

    The catalytic effects of CuSO4 in total organic carbon (TOC) detecting processes based on supercritical water oxidation have been investigated. Using benzoic acid as a model pollutant, the presence of a CuSO4 catalyst can significantly decrease the reaction temperature and H2O2 multiple during the TOC detection processes. A better TOC conversion efficiency was obtained at a much lower temperature in the catalytic system compared with the non-catalytic condition. The use of the catalyst effectively lowered the necessary H2O2 multiple from 20.0 without catalyst to 3.0 in the catalytic system. The established device could detect the TOC concentration precisely in model wastewater without inorganic carbon (IC). Moreover, the detection of the practical wastewater was studied. Detection results were total carbon of wastewater rather than TOC of practical wastewater. A detection or removal unit of IC is necessary before it can be practically utilized. PMID:27438232

  7. Sterilization of biological pathogens using supercritical fluid carbon dioxide containing water and hydrogen peroxide.

    PubMed

    Checinska, Aleksandra; Fruth, Ingrid A; Green, Tonia L; Crawford, Ronald L; Paszczynski, Andrzej J

    2011-10-01

    Novel noninvasive techniques for the removal of biological contaminants to generate clean or sterile materials are in demand by the medical, pharmaceutical and food industries. The sterilization method described here uses supercritical fluid carbon dioxide (SF-CO(2)) containing 3.3% water and 0.1% hydrogen peroxide (v/v/v) to achieve from four to eight log viability reduction of all tested microbial species, including vegetative cells, spores and biofilms. The sterilization method employs moderate pressure and temperature (80 atm, 50°C) and a short (30-minute) treatment time. The procedure kills various opportunistic pathogens that often persist in biofilm structures, fungal spores commonly associated with nosocomial infections, and Bacillus pumilus SAFR-032 endospores that are notoriously hard to eradicate by conventional sterilization techniques.

  8. Oxidation kinetics of model compounds of metabolic waste in supercritical water

    NASA Technical Reports Server (NTRS)

    Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.

    1990-01-01

    In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

  9. A parametric study on supercritical water gasification of Laminaria hyperborea: a carbohydrate-rich macroalga.

    PubMed

    Cherad, Ramzi; Onwudili, Jude A; Williams, Paul T; Ross, Andrew B

    2014-10-01

    The potential of supercritical water gasification (SCWG) of macroalgae for hydrogen and methane production has been investigated in view of the growing interest in a future macroalgae biorefinery concept. The compositions of syngas from the catalytic SCWG of Laminaria hyperborea under varying parameters including catalyst loading, feed concentration, hold time and temperature have been investigated. Their effects on gas yields, gasification efficiency and energy recovery are presented. Results show that the carbon gasification efficiencies increased with reaction temperature, reaction hold time and catalyst loading but decreased with increasing feed concentrations. In addition, the selectivity towards hydrogen and/or methane production from the SCWG tests could be controlled by the combination of catalysts and varying reaction conditions. For instance, Ru/Al2O3 gave highest carbon conversion and highest methane yield of up to 11 mol/kg, whilst NaOH produced highest hydrogen yield of nearly 30 mol/kg under certain gasification conditions.

  10. Experimental study of crossover from capillary to viscous fingering for supercritical CO2-water displacement in a homogeneous pore network.

    PubMed

    Wang, Ying; Zhang, Changyong; Wei, Ning; Oostrom, Mart; Wietsma, Thomas W; Li, Xiaochun; Bonneville, Alain

    2013-01-01

    Carbon sequestration in saline aquifers involves displacing brine from the pore space by supercritical CO(2) (scCO(2)). The displacement process is considered unstable due to the unfavorable viscosity ratio between the invading scCO(2) and the resident brine. The mechanisms that affect scCO(2)-water displacement under reservoir conditions (41 °C, 9 MPa) were investigated in a homogeneous micromodel. A large range of injection rates, expressed as the dimensionless capillary number (Ca), was studied in two sets of experiments: discontinuous-rate injection, where the micromodel was saturated with water before each injection rate was imposed, and continuous-rate injection, where the rate was increased after quasi-steady conditions were reached for a certain rate. For the discontinuous-rate experiments, capillary fingering and viscous fingering are the dominant mechanisms for low (logCa ≤ -6.61) and high injection rates (logCa ≥ -5.21), respectively. Crossover from capillary to viscous fingering was observed for logCa = -5.91 to -5.21, resulting in a large decrease in scCO(2) saturation. The discontinuous-rate experimental results confirmed the decrease in nonwetting fluid saturation during crossover from capillary to viscous fingering predicted by numerical simulations by Lenormand et al. (J. Fluid Mech.1988, 189, 165-187). Capillary fingering was the dominant mechanism for all injection rates in the continuous-rate experiment, resulting in monotonic increase in scCO(2) saturation.

  11. Oxidation of ferritic martensitic alloys T91, HCM12A and HT-9 in supercritical water

    NASA Astrophysics Data System (ADS)

    Ampornrat, Pantip; Was, Gary S.

    2007-09-01

    The oxidation behavior of ferritic-martensitic (F-M) alloys in supercritical water (SCW) was studied in order to evaluate the suitability of these alloys for use in the Gen IV supercritical water reactor (SCWR) concept. A series of exposure tests in SCW were performed with three F-M alloys: T91, HCM12A, and HT-9. The effect of temperature was evaluated over the range of 400-600 °C and the dissolved oxygen concentration was controlled at <10 ppb (deaerated condition), 100 and 300 ppb. The oxidation behavior was determined from weight gain measurements along with oxide structure analysis. The results indicated that the oxidation rate was strongly dependent on temperature and followed an Arrhenius behavior. Activation energies for oxidation were 172, 177, and 189 kJ/mol for HT-9, HCM12A, and T91, respectively. The time dependence of the oxidation rate followed an exponential law with time exponents ˜0.3-0.42. Reduction in oxidation rate was observed at intermediate values (100-300 ppb) of dissolved oxygen concentration. The oxide formed on the alloy surface consisted of an outer layer of porous magnetite (Fe 3O 4) and an inner layer of iron chromium oxide, (Fe, Cr) 3O 4 with spinel structure. A transition region lies beneath the inner oxide in which the metal content increases to bulk values and the oxygen content decreases to nearly zero. Iron chromium oxide, (Fe, Cr)O, with the wustite structure was observed in the transition layer at 600 °C. The relatively good agreement between the activation energies for oxidation and that for grain boundary diffusion of oxygen support an oxidation mechanism based on short circuit oxygen diffusion to the oxide-metal interface.

  12. Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology

    SciTech Connect

    Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong; Guo, Yang; Tang, Xingying

    2015-09-15

    Highlights: • Partial oxidation of landfill leachate in supercritical water was investigated. • The process was optimized by Box–Behnken design and response surface methodology. • GY{sub H2}, TRE and CR could exhibit up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56%. • Small amounts of oxidant can decrease the generation of tar and char. - Abstract: To achieve the maximum H{sub 2} yield (GY{sub H2}), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models for GY{sub H2}, CR and TRE were established with Box–Behnken design. GY{sub H2}, CR and TRE reached up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO{sub 2} and H{sub 2} were the most abundant gaseous products. As a product of nitrogen-containing organics, NH{sub 3} has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient.

  13. SUPERCRITICAL WATER PARTIAL OXIDATION PHASE I - PILOT-SCALE TESTING / FEASIBILITY STUDIES FINAL REPORT

    SciTech Connect

    SPRITZER,M; HONG,G

    2005-01-01

    Under Cooperative Agreement No. DE-FC36-00GO10529 for the Department of Energy, General Atomics (GA) is developing Supercritical Water Partial Oxidation (SWPO) as a means of producing hydrogen from low-grade biomass and other waste feeds. The Phase I Pilot-scale Testing/Feasibility Studies have been successfully completed and the results of that effort are described in this report. The Key potential advantages of the SWPO process is the use of partial oxidation in-situ to rapidly heat the gasification medium, resulting in less char formation and improved hydrogen yield. Another major advantage is that the high-pressure, high-density aqueous environment is ideal for reaching and gasifying organics of all types. The high water content of the medium encourages formation of hydrogen and hydrogen-rich products and is especially compatible with high water content feeds such as biomass materials. The high water content of the medium is also effective for gasification of hydrogen-poor materials such as coal. A versatile pilot plant for exploring gasification in supercritical water has been established at GA's facilities in San Diego. The Phase I testing of the SWPO process with wood and ethanol mixtures demonstrated gasification efficiencies of about 90%, comparable to those found in prior laboratory-scale SCW gasification work carreid out at the University of Hawaii at Manoa (UHM) as well as other biomass gasification experience with conventional gasifiers. As in the prior work at UHM, a significant amount of the hydrogen found in the gas phase products is derived from the water/steam matrix. The studies at UHM utilized an indirectly heated gasifier with an acitvated carbon catalyst. In contrast, the GA studies utilized a directly heated gasifier without catalyst, plus a surrogate waste fuel. Attainment of comparable gasification efficiencies without catalysis is an important advancement for the GA process, and opens the way for efficient hydrogen production from low

  14. Experimental investigation of inclination effect on subcritical and supercritical water flows heat transfer in an internally ribbed tube

    NASA Astrophysics Data System (ADS)

    Taklifi, Alireza; Akhavan-Behabadi, Mohammad Ali; Hanafizadeh, Pedram; Aliabadi, Abbas

    2016-06-01

    The effect of various inclination angles on heat transfer of water at subcritical and supercritical operating pressures is investigated experimentally. The test section was a SA213T12 steel six-headed internally ribbed tube with minimum inner diameter of 19.5 mm. The operating test pressures were 15, 21.5, 22.5, 25 and 28 MPa, the mass flux was 800 kg/m2 s and the heat flux was 400 kW/m2. To keep the mass flux to heat flux ratio equal to 2 kg/kJ. These operating conditions covered subcritical, near critical and supercritical water flows and also refers to low mass flux conditions. The inclination angles were 5, 20, 30, 45 and 90 (vertical) degrees respecting to horizontal plane. The heat flux was kept constant along the test tube by controlling of electric heating. As a result the inner wall temperature and convective heat transfer coefficient variations with respect to heated length and bulk enthalpy of fluid were considered in order to study the heat transfer characteristics of various flows at different inclinations. The corresponding correlation for heat transfer coefficient was developed which is applicable for wide range of inclination angles. The heat transfer enhancement was obvious for inclination angles other than 90°, however, this effect was more obvious in 5° and 20° in some operating conditions. It was also concluded that the effect of inclination on heat transfer of water was more considerable in subcritical flow conditions than supercritical ones. Also, it was observed that angle of 20° seems to be the best for subcritical flows from heat transfer point of view, but for supercritical flows 5 or 45 seem to be more advantageous. These differences could be related to different heat transfer mechanisms of subcritical and supercritical flows.

  15. Effect of Sub- and Super-critical Water Treatment on Physicochemical Properties of Porcine Skin

    PubMed Central

    2015-01-01

    Super- and sub-critical water treatments have been of interest as novel methods for protein hydrolysis. In the present study, we studied the effect of sub-critical water (Sub-H2O, 300℃, 80 bar) treatment as well as super-critical water (Super-H2O, 400℃, 280 bar) treatment on the physicochemical properties of porcine skin (PS), which has abundant collagen. Porcine skin was subjected to pre-thermal treatment by immersion in water at 70℃, and then treated with sub- or super-critical water. Physicochemical properties of the hydrolysates, such as molecular weight distribution, free amino acid content, amino acid profile, pH, color, and water content were determined. For the molecular weight distribution analysis, 1 kDa hydrolyzed porcine skin (H-PS) was produced by Super-H2O or Sub-H2O treatment. The free amino acid content was 57.18 mM and 30.13 mM after Sub-H2O and Super-H2O treatment, respectively. Determination of amino acid profile revealed that the content of Glu (22.5%) and Pro (30%) was higher after Super-H2O treatment than after Sub-H2O treatment, whereas the content of Gly (28%) and Ala (13.1%) was higher after Sub-H2O treatment. Super-H2O or Sub-H2O treatment affected the pH of PS, which changed from 7.29 (Raw) to 9.22 (after Sub-H2O treatment) and 9.49 (after Super-H2O treatment). Taken together, these results showed that Sub-H2O treatment was slightly more effective for hydrolysis than Super-H2O was. However, both Sub-H2O and Super-H2O treatments were effective processing methods for hydrolysis of PS collagen in a short time and can be regarded as a green chemistry technology. PMID:26761798

  16. Water under Hydrothermal, Supercritical, and High Pressure Conditions as Key to Developing Green Processes and New Technologies

    NASA Astrophysics Data System (ADS)

    Smith, Richard L.

    2010-11-01

    In this work, an overview of research and activity in the hydrothermal and supercritical fields is given. Properties and characteristics of water are reviewed in relation to separations, materials, and chemical conversion processes. Examples that are discussed include biomass fractionation, natural product extraction, material formation, biomass oxidation, biomass conversions, waste treatment, flames, and hydrocarbon upgrading. In the field of chromatography, water under hydrothermal conditions can be used to replace many organic solvents. As a solvent for separation processes, hot water can be used to achieve rapid and efficient fractionation of biomass or isolation of chemical compounds. In the field of materials, water in its supercritical state can be used to synthesize practical materials and to develop processes with low environmental burden. In the field of chemical processing, water can be used under oxidizing conditions to generate clean and renewable energy and to reduce the number of chemical steps for producing chemical products. A few other technological applications such as flames and hydrocarbon upgrading will be discussed. Water under hydrothermal, supercritical and high pressure conditions has many favorable properties that allow the development of green chemical processes and new technologies.

  17. Structural Properties and Dynamics of Thiophene in Sub/Supercritical Carbon Dioxide from Car-Parrinello Molecular Dynamics Simulations.

    PubMed

    Zeng, Yongping; Wang, Chunfeng; Xu, Yueyang; Xu, WenLin; Ju, Shengui

    2015-07-01

    Structrual and dynamic properties of thiophene (C4H4S) in supercritical carbon dioxide were studied using Car-Parrinello molecular dynamics simulations. The geometries and energies optimized for the thiophene-CO2 complex show a stable C-H···O hydrogen bond interactions both in gas phase and in supercritical CO2. The radial distribution functions of CO2 around thiophene in the supercritical phase state show a correlation suggesting C-H···O hydrogen bond and S···C interaction. Local structural properties of the mixtures were investigated by angular-radial distributions and spatial distribution functions. The results show a mutually parallel arrangement between the thiophene plane and CO2 molecules at short distances and a high probability of the thiophene being located in the radial directions of the CO2 molecules. The decay of orientational correlations at 318.15 K shows slower relaxation compared to those of 298.15 K for first and second rank correlations. The vibrations of CO2 and thiophene molecules have been examined through an analysis of the velocity autocorrelation functions of the atoms. The C-H stretching modes of thiophene in the isolated configuration are less red-shifted and have a much narrower frequency range than that in the mixtures.

  18. The use of supercritical parameters of a coolant—A promising path to development of nuclear power plant water-cooled reactors in the 21st century

    NASA Astrophysics Data System (ADS)

    Gabaraev, B. A.; Smolin, V. N.; Solov'ev, S. L.

    2006-09-01

    A modern concept of the development of water-cooled reactors of nuclear power plants (NPPs) is considered. Data on the design of NPPs with supercritical-parameters coolant and the results of experimental studies are presented.

  19. Exploration of the effect of process variables on the production of high-value fuel gas from glucose via supercritical water gasification.

    PubMed

    Hendry, Doug; Venkitasamy, Chandrasekar; Wilkinson, Nikolas; Jacoby, William

    2011-02-01

    A new continuous supercritical water gasification reactor was designed to investigate glucose gasification in supercritical water at high temperatures and low residence times. A 2(3) full factorial experiment was performed to determine the effects of feed concentration, temperature, and residence time on glucose gasification. The temperature levels (750°C and 800°C) were higher than ever used, while the residence times (4 and 6.5s) were shorter than ever used in previous supercritical water gasification studies. The reactor proved capable of attaining higher gasification rates than previously shown with high efficiencies and yields. In addition, the glucose gasification reaction was modeled by estimating activation energy and reaction order of glucose gasification in supercritical water.

  20. Destruction of an industrial wastewater by supercritical water oxidation in a transpiring wall reactor.

    PubMed

    Bermejo, M D; Cocero, M J

    2006-09-21

    The supercritical water oxidation (SCWO) is a technology that takes advantage of the special properties of water in the surroundings of critical point of water to completely oxidize wastes in residence times lower than 1 min. The problems caused by the harsh operational conditions of the SCWO process are being solved by new reactor designs, such as the transpiring wall reactor (TWR). In this work, the operational parameters of a TWR have been studied for the treatment of an industrial wastewater. As a result, the process has been optimized for a feed flow of 16 kg/h with feed inlet temperatures higher than 300 degrees C and transpiring flow relation (R) between 0.2 and 0.6 working with an 8% (w/w) isopropanol (IPA) as a fuel. The experimental data and a mathematical model have been applied for the destruction of an industrial waste containing acetic acid and crotonaldehyde as main compounds. As the model predicted, removal efficiencies higher than 99.9% were obtained, resulting in effluents with 2 ppm total organic carbon (TOC) at feed flow of 16 kg/h, 320 degrees C of feed temperature and R = 0.32. An effluent TOC of 35 ppm under conditions feed flow of 18 kg/h, feed inlet temperatures of 290 degrees C, reaction temperatures of 570 degrees C and R = 0.6.

  1. Oxidation of phenolics in supercritical water. Quarterly technical progress report, September 1, 1993--November 30, 1993

    SciTech Connect

    Savage, P.E.

    1993-12-31

    Oxidation reactions are accomplished in an isothermal, high-pressure, flow reactor designed specifically for operation at supercritical water conditions. The reactor feed stream is prepared by mixing two separate streams. One stream is an aqueous solution of the phenolic reactant and the second stream is water with dissolved oxygen. Controlling the flow rates of these two streams allows us to control the reactor residence time and the relative amounts of the phenol and oxygen fed to the reactor. The reactor effluent is cooled and depressorized and then collected for analysis. The gaseous products are analyzed by gas chromatography (GC). The liquid-phase products are analyzed by GC, high-performance liquid chromatography, and GC-mass spectrometry. Our work to date has focused on the oxidation of cresols in SCW. We have explored the effects of temperature, pressure, and the concentrations of o-cresol, oxygen, and water. Table I gives these experimental conditions and the resulting ocresol conversions. We reported a portion of this data in our previous quarterly report. New information is given in the last three columns where we report the molar yields of phenol, CO{sub 2}, and CO. Molar yields were calculated as the molar flow rate of a given product divided by the initial molar flow rate of o-cresol and normalized by the stoichiometric coefficient. Earlier, we used the o-cresol conversion data to determine the parameters in a global reaction rate law for o-cresol disappearance.

  2. Energy conversion of biomass with supercritical and subcritical water using large-scale plants.

    PubMed

    Okajima, Idzumi; Sako, Takeshi

    2014-01-01

    Exploiting unused or waste biomass as an alternative fuel is currently receiving much attention because of the potential reductions in CO2 emissions and the lower cost in comparison to expensive fossil fuels. If we are to use biomass domestically or industrially, we must be able to convert biomass to high-quality and easy-to-use liquid, gas, or solid fuels that have high-calorific values, low moisture and ash contents, uniform composition, and suitable for stored over long periods. In biomass treatment, hot and high-pressure water including supercritical and subcritical water is an excellent solvent, as it is clean and safe and its action on biomass can be optimized by varying the temperature and pressure. In this article, the conversion of waste biomass to fuel using hot and high-pressure water is reviewed, and the following examples are presented: the production of large amounts of hydrogen from waste biomass, the production of cheap bioethanol from non-food raw materials, and the production of composite powder fuel from refractory waste biomass in the rubble from the Great East Japan Earthquake. Several promising techniques for the conversion of biomass have been demonstrated in large-scale plants and commercial deployment is expected in the near future. PMID:23867098

  3. Energy conversion of biomass with supercritical and subcritical water using large-scale plants.

    PubMed

    Okajima, Idzumi; Sako, Takeshi

    2014-01-01

    Exploiting unused or waste biomass as an alternative fuel is currently receiving much attention because of the potential reductions in CO2 emissions and the lower cost in comparison to expensive fossil fuels. If we are to use biomass domestically or industrially, we must be able to convert biomass to high-quality and easy-to-use liquid, gas, or solid fuels that have high-calorific values, low moisture and ash contents, uniform composition, and suitable for stored over long periods. In biomass treatment, hot and high-pressure water including supercritical and subcritical water is an excellent solvent, as it is clean and safe and its action on biomass can be optimized by varying the temperature and pressure. In this article, the conversion of waste biomass to fuel using hot and high-pressure water is reviewed, and the following examples are presented: the production of large amounts of hydrogen from waste biomass, the production of cheap bioethanol from non-food raw materials, and the production of composite powder fuel from refractory waste biomass in the rubble from the Great East Japan Earthquake. Several promising techniques for the conversion of biomass have been demonstrated in large-scale plants and commercial deployment is expected in the near future.

  4. Packed column supercritical fluid chromatography using stainless steel particles and water as a stationary phase.

    PubMed

    Murakami, Jillian N; Thurbide, Kevin B

    2015-09-15

    Stainless steel (SS) particles were demonstrated as a novel useful support for a water stationary phase in packed column supercritical fluid chromatography using a CO2 mobile phase. Separations employed flame ionization detection, and the system was operated over a range of temperatures and pressures. Retention times reproduced well with RSD values of 2.6% or less. Compared to analogous separations employing a water stationary phase coated onto a SS capillary column, the packed column method provided separations that were about 10× faster, with nearly 8-fold larger analyte retention factors, while maintaining good peak shape and comparable column efficiency. Under normal operating conditions, the packed column contains about 131 ± 4 μL/m of water phase (around a 5% m/m coating), which is over 25× greater than the capillary column and also affords it a 20-fold larger sample capacity. Several applications of the packed column system are examined, and the results indicate that it is a useful alternative to the capillary column mode, particularly where analyte loads or sample matrix interference is a concern. Given its high sample capacity, this packed column method may also be useful to explore on a more preparative scale in the future.

  5. Supercritical water treatment for cello-oligosaccharide production from microcrystalline cellulose.

    PubMed

    Tolonen, Lasse K; Juvonen, Minna; Niemelä, Klaus; Mikkelson, Atte; Tenkanen, Maija; Sixta, Herbert

    2015-01-12

    Microcrystalline cellulose was treated in supercritical water at 380 °C and at a pressure of 250 bar for 0.2, 0.4, and 0.6s. The yield of the ambient-water-insoluble precipitate and its average molar mass decreased with an extended treatment time. The highest yield of 42 wt% for DP2-9 cello-oligosaccharides was achieved after the 0.4s treatment. The reaction products included also 11 wt% ambient-water-insoluble precipitate with a DP(w) of 16, and 6.1 wt% monomeric sugars, and 37 wt% unidentified degradation products. Oligo- and monosaccharide-derived dehydration and retro-aldol fragmentation products were analyzed via a combination of HPAEC-PAD-MS, ESI-MS/MS, and GC-MS techniques. The total amount of degradation products increased with treatment time, and fragmented (glucosyl(n)-erythrose, glucosyl(n)-glycolaldehyde), and dehydrated (glucosyl(n)-levoglucosan) were identified as the main oligomeric degradation products from the cello-oligosaccharides. PMID:25464077

  6. Hydrothermal liquefaction of Spirulina and Nannochloropsis salina under subcritical and supercritical water conditions.

    PubMed

    Toor, Saqib S; Reddy, Harvind; Deng, Shuguang; Hoffmann, Jessica; Spangsmark, Dorte; Madsen, Linda B; Holm-Nielsen, Jens Bo; Rosendahl, Lasse A

    2013-03-01

    Six hydrothermal liquefaction experiments on Nannochloropsis salina and Spirulina platensis at subcritical and supercritical water conditions (220–375 °C, 20–255 bar) were carried out to explore the feasibility of extracting lipids from wet algae, preserving nutrients in lipid-extracted algae solid residue, and recycling process water for algae cultivation. GC–MS, elemental analyzer, FT-IR, calorimeter and nutrient analysis were used to analyze bio-crude, lipid-extracted algae and water samples produced in the hydrothermal liquefaction process. The highest bio-crude yield of 46% was obtained on N. salina at 350 °C and 175 bar. For S. platensis algae sample, the optimal hydrothermal liquefaction condition appears to be at 310 °C and 115 bar, while the optimal condition for N. salina is at 350 °C and 175 bar. Preliminary data also indicate that a lipid-extracted algae solid residue sample obtained in the hydrothermal liquefaction process contains a high level of proteins.

  7. Oxidation behavior of ferritic-martensitic and ODS steels in supercritical water

    NASA Astrophysics Data System (ADS)

    Bischoff, Jeremy

    Ferritic-martensitic and ODS alloys are primary candidates for application as cladding and structural material in Generation IV nuclear power plants, especially the supercritical water reactor. One of the main in-service degradation mechanisms for these alloys is uniform corrosion, thus this project focuses on understanding the oxidation behavior of these alloys in the supercritical water (SCW) environment. This understanding is acquired through the analysis of the oxide microstructure using microbeam synchrotron radiation diffraction and fluorescence associated with electron microscopy (both SEM and TEM). The microbeam synchrotron radiation diffraction and fluorescence technique provides unique microstructural data of the oxide. This technique simultaneously probes elemental and phase information step by step with a sub-micron spatial resolution throughout the oxide layers. Thus we were able to locate specific phases, such as Cr2O3, at specific locations in the oxide layer, mainly the interfaces. The electron microscopy complemented this analysis by imaging the oxide layers, to yield detailed information on the oxide morphology. All the alloys studied exhibited the same three-layer structure with an outer layer containing only Fe3O4, an inner layer containing a mixture of Fe3O4 and FeCr2O 4, and a diffusion layer containing a mixture of chromium-rich precipitates (Cr2O3 and FeCr2O4) and metal grains. By analyzing samples with various exposure times, we were able to follow the evolution of the oxide microstructure with exposure time. To obtain the corroded samples, several corrosion experiments were performed: some in supercritical water (at 500°C and 600°C) and one experiment in 500°C steam. The test in steam was undertaken to obtain more data points in the kinetic curves, because we thought the corrosion in steam and supercritical water at the same temperature would result in similar kinetics. This turned out not to be the case and the samples in supercritical

  8. Advanced Supercritical Carbon Dioxide Brayton Cycle Development

    SciTech Connect

    Anderson, Mark; Sienicki, James; Moisseytsev, Anton; Nellis, Gregory; Klein, Sanford

    2015-10-21

    Fluids operating in the supercritical state have promising characteristics for future high efficiency power cycles. In order to develop power cycles using supercritical fluids, it is necessary to understand the flow characteristics of fluids under both supercritical and two-phase conditions. In this study, a Computational Fluid Dynamic (CFD) methodology was developed for supercritical fluids flowing through complex geometries. A real fluid property module was implemented to provide properties for different supercritical fluids. However, in each simulation case, there is only one species of fluid. As a result, the fluid property module provides properties for either supercritical CO2 (S-CO2) or supercritical water (SCW). The Homogeneous Equilibrium Model (HEM) was employed to model the two-phase flow. HEM assumes two phases have same velocity, pressure, and temperature, making it only applicable for the dilute dispersed two-phase flow situation. Three example geometries, including orifices, labyrinth seals, and valves, were used to validate this methodology with experimental data. For the first geometry, S-CO2 and SCW flowing through orifices were simulated and compared with experimental data. The maximum difference between the mass flow rate predictions and experimental measurements is less than 5%. This is a significant improvement as previous works can only guarantee 10% error. In this research, several efforts were made to help this improvement. First, an accurate real fluid module was used to provide properties. Second, the upstream condition was determined by pressure and density, which determines supercritical states more precise than using pressure and temperature. For the second geometry, the flow through labyrinth seals was studied. After a successful validation, parametric studies were performed to study geometric effects on the leakage rate. Based on these parametric studies, an optimum design strategy for the see

  9. Hydrodynamic analysis and calculation of metal temperature distribution in spiral water wall of ultra supercritical tower boiler

    NASA Astrophysics Data System (ADS)

    Shen, Chengwu; Yang, Dong; Yao, Danhua; Zhu, Yufeng; Xu, Xueyuan

    2013-07-01

    In this paper, the spiral water wall system of a 1000MW ultra supercritical tower boiler is simplified as a network system, consisting of circuits, pressure grids and connecting tubes. The establishment of the mathematical model for calculating the mass flux distribution and metal temperature in water wall is based on the mass, momentum and energy conservation equations. The water wall flow distribution and temperature profile of the boiler were computed. The result shows that the differences of outlet temperature and mass flux are small in spiral tube water wall at BMCR, 75%BMCR load and 40%BMCR load. The metal temperatures are all in the allowable ranger.

  10. Hydrogen bond driven chemical reactions: Beckmann rearrangement of cyclohexanone oxime into epsilon-caprolactam in supercritical water.

    PubMed

    Boero, Mauro; Ikeshoji, Tamio; Liew, Chee Chin; Terakura, Kiyoyuki; Parrinello, Michele

    2004-05-26

    Recent experiments have shown that supercritical water (SCW) has the ability to accelerate and make selective synthetic organic reactions, thus replacing the common but environmentally harmful acid and basic catalysts. In an attempt to understand the intimate mechanism behind this observation, we analyze, via first-principles molecular dynamics, the Beckmann rearrangement of cyclohexanone oxime into epsilon-caprolactam in supercritical water, for which accurate experimental evidence has been reported. Differences in the wetting of the hydrophilic parts of the solute, enhanced by SCW, and the disrupted hydrogen bond network are shown to be crucial in triggering the reaction and in making it selective. Furthermore, the enhanced concentrations of H(+) in SCW play an important role in starting the reaction.

  11. Macroemulsions of liquid and supercritical CO{sub 2}-in-water and water-in-liquid CO{sub 2} stabilized by fine particles

    SciTech Connect

    Golomb, D.; Barry, E.; Ryan, D.; Swett, P.; Duan, H.

    2006-04-12

    Liquid and supercritical carbon dioxide-in-water (C/W) and water-in-carbon dioxide (W/C) macroemulsions (Pickering emulsions) stabilized by fine particles were created in a high-pressure batch reactor. C/W macroemulsions form when hydrophilic particles, such as pulverized limestone, sand, flyash, shale, and lizardite, a rock rich in magnesium silicate, are used as stabilizers; W/C macroemulsions form when hydrophobic particles, such as Teflon powder, activated carbon, carbon black, and pulverized coal, are used as stabilizers. C/W macroemulsions form with both liquid and supercritical CO{sub 2}, C/W macroemulsions consist of dispersed droplets of liquid or supercritical CO{sub 2} sheathed with particles in water; W/C macroemulsions consist of droplets of water sheathed with particles dispersed in liquid CO{sub 2}. The sheathed droplets are called globules. The globule diameter is largely dependent on the shear force imparted by mixing the two fluids, CO{sub 2} and H{sub 2O. The particle size needs to be adjusted to the dispersed droplet diameter; a practical ratio was found to be 1:20. In a batch reactor with a magnetic stir bar rotating at 1300 rpm, liquid CO{sub 2} produced typical globule diameters in the 200-300 mu m range, whereas supercritical CO{sub 2} produced smaller globules, in the 100-150 mu m range.

  12. Analyses of oxide films grown on AISI 304L stainless steel and Incoloy 800HT exposed to supercritical water environment

    NASA Astrophysics Data System (ADS)

    Fulger, Manuela; Mihalache, Maria; Ohai, Dumitru; Fulger, Stefan; Valeca, Serban Constantin

    2011-08-01

    Supercritical water (SCW) is being considered as a cooling medium for the next generation nuclear reactors because it provides high thermal efficiency and plant simplification. However, materials corrosion has been identified as a critical problem due to the oxidative nature of supercritical water. Thus, for safety using of these nuclear reactor systems a systematic study of candidate materials corrosion is needed. As in other high temperature environments, corrosion in SCW occurs by the growth of an oxide layer on the materials surface. The current work aims to evaluate oxidation behavior of AISI 304L SS and Incoloy 800HT in water at supercritical temperatures in the range 723-873 K under a pressure of 25 MPa for up to 1680 h. After exposure to deaerated supercritical water, the samples were investigated using gravimetry, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS). Oxide films grown on these materials have a layered structure with an outer layer consisting of a mixture of iron oxide/iron-nickel spinel oxides and an inner layer consisting of chromium oxide in the case of Incoloy 800HT and nickel-chromium spinel oxide in the case of AISI 304L SS. The mass gains for Incoloy 800HT at all temperatures were small, while comparatively with AISI 304L SS which exhibited higher oxidation rates. In the same time the results obtained by EIS indicate the best corrosion resistance of oxides grown on Incoloy 800HT surface.

  13. Antioxidation Properties and Surface Interactions of Polyvinylpyrrolidone-Capped Zerovalent Copper Nanoparticles Synthesized in Supercritical Water.

    PubMed

    Morioka, Takuya; Takesue, Masafumi; Hayashi, Hiromichi; Watanabe, Masaru; Smith, Richard L

    2016-01-27

    Zerovalent copper nanoparticles (CuNPs) (diameter, 26.5 ± 9 nm) capped with polyvinylpyrrolidone (PVP) were synthesized in supercritical water at 400 °C and 30 MPa with a continuous flow reactor. The PVP-capped CuNPs were dispersed in distilled water, methanol, ethanol, 1-propanol, 2-propanol, butanol, and their mixed solvents to study their long-term stability. Temporal variation of UV-vis spectra and surface plasmon resonance were measured and showed that ethanol, the propanols, and butanol solvents provided varying degrees of oxidative protection for Cu(0). Fourier transform infrared spectroscopy showed that PVP adsorbed onto the surface of the CuNPs with a pyrrolidone ring of PVP even if the CuNPs were oxidized. Intrinsic viscosities of PVP were higher for solvents that provided antioxidation protection than those that give oxidized CuNPs. In solvents that provided Cu(0) with good oxidative protection (ethanol, the propanols, and butanol), PVP polymer chains formed large radii of gyration and coil-like conformations in the solvents so that they were arranged uniformly and orderly on the surface of the CuNPs and could provide protection of the Cu(0) surface against dissolved oxygen. In solvents that provided poor oxidative protection for Cu(0) (water, alcohol-water mixed solvents with 30% water), PVP polymer chains had globular-like conformations due to their relatively high hydrogen-bonding interactions and sparse adsorption onto the CuNP surface. Antioxidative properties of PVP-capped CuNPs in a solvent can be ascribed to the conformation of PVP polymer chains on the Cu(0) particle surface that originates from the interaction between polymer chains and its interaction with the solvent. PMID:26716468

  14. Recovery of metals from waste printed circuit boards by supercritical water pre-treatment combined with acid leaching process.

    PubMed

    Xiu, Fu-Rong; Qi, Yingying; Zhang, Fu-Shen

    2013-05-01

    Waste printed circuit boards (PCBs) contain a large number of metals such as Cu, Sn, Pb, Cd, Cr, Zn, and Mn. In this work, an efficient and environmentally friendly process for metals recovery from waste PCBs by supercritical water (SCW) pre-treatment combined with acid leaching was developed. In the proposed process, waste PCBs were pre-treated by SCW, then the separated solid phase product with concentrated metals was subjected to an acid leaching process for metals recovery. The effect of SCW pre-treatment on the recovery of different metals from waste PCBs was investigated. Two methods of SCW pre-treatment were studied: supercritical water oxidation (SCWO) and supercritical water depolymerization (SCWD). Experimental results indicated that SCWO and SCWD pre-treatment had significant effect on the recovery of different metals. SCWO pre-treatment was highly efficient for enhancing the recovery of Cu and Pb, and the recovery efficiency increased significantly with increasing pre-treatment temperature. The recovery efficiency of Cu and Pb for SCWO pre-treatment at 420°C was 99.8% and 80%, respectively, whereas most of the Sn and Cr were immobilized in the residue. The recovery of all studied metals was enhanced by SCWD pre-treatment and increased along with pre-treatment temperature. Up to 90% of Sn, Zn, Cr, Cd, and Mn could be recovered for SCWD pre-treatment at 440°C.

  15. Oxidation of phenolics in supercritical water. Combined quarterly technical progress report, December 1, 1995--May 31, 1996

    SciTech Connect

    1996-11-01

    Over the past two quarters, our work has focused on three main areas. The first area of interest involved a reexamination of the rate laws that were formed in past quarters. A possible error was discovered for the analytical methods used in the o-cresol oxidation study and the data were corrected, yielding a new rate equation. The data for hydroxybenzaldehydes were studied again, this time as a system of parallel oxidation and thermolysis reactions. The second area in which progress was made was the study of the thermolysis of nitrophenols and dihydroxybenzenes in supercritical water. These investigations were needed to determine the effect that pyrolysis or hydrolysis had on our previous supercritical water oxidation experiments. Thirdly, we have continued to investigate the use of molecular orbital theory in the determination reactivity indices. A reactivity index, such as the enthalpy of formation, may be used in a structure-reactivity relationship to summarize the kinetics for the oxidation of phenolics in supercritical water. Progress in each of these areas is summarized.

  16. Preparation of highly pure zeaxanthin particles from sea water-cultivated microalgae using supercritical anti-solvent recrystallization.

    PubMed

    Chen, Chao-Rui; Hong, Siang-En; Wang, Yuan-Chuen; Hsu, Shih-Lan; Hsiang, Daina; Chang, Chieh-Ming J

    2012-01-01

    Xanthophylls, including zeaxanthin, are considered dietary supplements with a potentially positive impact on age-related macular degeneration. Using pilot-scale column fractionation coupled with supercritical anti-solvent (SAS) recrystallization, highly pure zeaxanthin particulates were prepared from ultrasonic extracts of the microalgae, Nannochloropsis oculata, grown in sea water. Column partition chromatography increased the concentration of zeaxanthin from 36.2 mg/g of the ultrasonic extracts to 425.6 mg/g of the collected column fractions. A response surface methodology was systematically designed for the SAS process by changing feed concentration, CO(2) flow rate and anti-solvent pressure. Zeaxanthin-rich particles with a purity of 84.2% and a recovery of 85.3% were produced using supercritical anti-solvent recrystallization from the column eluate at a feed concentration of 1.5 mg/mL, CO(2) flow rate of 48.6 g/min and pressure of 135 bar.

  17. Characterization of Ni-20Cr-5Al model alloy in supercritical water

    NASA Astrophysics Data System (ADS)

    Huang, Xiao; Guzonas, D.

    2014-02-01

    MCrAlY is a class of coating materials that provide corrosion and oxidation resistance to many Ni and Fe based alloys by forming dense alumina layer on the surface. In order to assess its potential as corrosion resistant coatings on components in supercritical water cooled nuclear reactors (SWCR), a Ni-20Cr-5Al model alloy is tested in SCW (500 °C and 25 MPa) for over 6000 h. The long term corrosion behavior of the samples with various surface preparations is evaluated by measuring weight change and examining surface microstructure and oxide formation. The results show that surface preparation alone can lead to changes in weight gain as great as an order of magnitude. Smooth and near stress free surface allows for more oxidation to take place in SCW, hence more weight change. Simple grinding with abrasive paper yields the least and most stable weight change while grit blasting has some effect in reducing weight gain. Comparing to other alloys tested under similar condition, Ni-20Cr-5Al has the lowest weight change. Although not detected, the formation of Al2O3 or an Al modified Cr2O3 superficial layer is likely the reason for such low weight change.

  18. Destruction of OPA from munitions demilitarization in supercritical water oxidation: kinetics of total organic carbon disappearance.

    PubMed

    Veriansyah, Bambang; Kim, Jae-Duck; Lee, Jong-Chol; Hong, Deasik

    2006-01-01

    The destruction of OPA from munitions demilitarization has been accomplished in supercritical water oxidation (SCWO) with oxygen as oxidant in an isothermal continuous-flow reactor. The experiments were conducted at a temperature of 689-887 K and a fixed pressure of 25 MPa, with a residence time that ranged from 7 s to 14 s. The destruction efficiency was measured by total organic carbon (TOC) conversion. At the reaction condition, the initial TOC concentrations of OPA were varied from 1.41 mmol/L to 19.57 mmol/L and the oxygen concentrations were varied from 15.03 mmol/L to 81.85 mmol/L. Experimental data showed that all the TOC conversions were >80% under the above experimental conditions. The kinetics of TOC disappearance, which is essential for the design, optimization, and control of reliable commercial SCWO reactor was developed by taking into account the dependence of the oxidant and TOC concentration on the reaction rate. A global TOC disappearance rates expression was regressed from the data of 38 experiments, to a 95% confidence level. The resulting activation energy was determined to be 44.01 +/- 1.52 kJ/mol, and the pre-exponential factor was (1.67 +/- 0.45) x 10(2) L(1.14) mmol(-0.14) s(-1). The reaction orders for the TOC and the oxidant were 0.98 +/- 0.01 and 0.16 +/- 0.02, respectively.

  19. Supercritical water oxidation of colored smoke, dye, and pyrotechnic compositions. Final report: Pilot plant conceptual design

    SciTech Connect

    LaJeunesse, C.A.; Chan, Jennifer P.; Raber, T.N.; Macmillan, D.C.; Rice, S.F.; Tschritter, K.L.

    1993-11-01

    The existing demilitarization stockpile contains large quantities of colored smoke, spotting dye, and pyrotechnic munitions. For many years, these munitions have been stored in magazines at locations within the continental United States awaiting completion of the life-cycle. The open air burning of these munitions has been shown to produce toxic gases that are detrimental to human health and harmful to the environment. Prior efforts to incinerate these compositions have also produced toxic emissions and have been unsuccessful. Supercritical water oxidation (SCWO) is a rapidly developing hazardous waste treatment method that can be an alternative to incineration for many types of wastes. The primary advantage SCWO affords for the treatment of this selected set of obsolete munitions is that toxic gas and particulate emissions will not occur as part of the effluent stream. Sandia is currently designing a SCWO reactor for the US Army Armament Research, Development & Engineering Center (ARDEC) to destroy colored smoke, spotting dye, and pyrotechnic munitions. This report summarizes the design status of the ARDEC reactor. Process and equipment operation parameters, process flow equations or mass balances, and utility requirements for six wastes of interest are developed in this report. Two conceptual designs are also developed with all process and instrumentation detailed.

  20. Experimental study of the supercritical water oxidation of recalcitrant compounds under hydrothermal flames using tubular reactors.

    PubMed

    Cabeza, Pablo; Bermejo, M Dolores; Jiménez, Cristina; Cocero, M José

    2011-04-01

    The hydrothermal flame is a new method of combustion that takes place in supercritical water oxidation reactions when the temperature is higher than the autoignition temperature. In these conditions, waste can be completely mineralized in residence times of milliseconds without the formation of by-products typical of conventional combustion. The object of this work is to study the hydrothermal flame formation in aqueous streams with high concentrations of recalcitrant compounds: an industrial waste with a high concentration of acetic acid and various concentrated solutions of ammonia. A tubular reactor with a residence time of 0.7 s was used. Oxygen was used as the oxidant and isopropyl alcohol (IPA) as co-fuel to reach the operation temperature required. The increase of IPA concentrations in the feeds resulted in a better TOC removal. For mixtures containing acetic acid, 99% elimination of TOC was achieved at temperatures higher than 750 °C. In the case of mixtures containing ammonia, TOC removals reached 99% while maximum total nitrogen removals were never higher than 94%, even for reaction temperatures higher than 710 °C. Ignition was observed at concentrations as high as 6% wt NH(3) with 2% wt IPA while at IPA concentrations below 2% wt IPA, the ammonia did not ignite.

  1. Solubility behavior of quartz and corundum in supercritical water: A quantitative thermodynamic interpretation

    SciTech Connect

    Ziemniak, S.E.

    1995-05-01

    Dissolution reaction equilibria for {alpha}-quartz (SiO{sub 2}) and corundum ({alpha}-Al{sub 2}0{sub 3}) in pure, supercritical water are quantified using a density-dependent thermodynamic model. The database of existing solubility literature for {alpha}-quartz (0.2-10 kb, 200--575{degrees}C) is shown to be consistent with the presence of two hydrolyzed SI(IV) ion forms: Si(OH){sub 4}(aq) and Si{sub 2}O(OH){sub 6}(aq); the corundum database (1-20 kb, 400--700{degrees}C) is consistent with Al(OH){sub 3}(aq) and Al(OH){sub 4}{sup {minus}}. A third Si(IV) ion hydroxocomplex, Si{sub 2}O{sub 2}(OH){sub 5}{sup {minus}}, is indicated at lower pressures (0.03-0.10 kb). The characteristic sigmoidal nature of the solubility isobars is explained by dimerization of Si(OH){sub 4}(aq) (at high densities) or the formation of anionic hydrolysis products, Si{sub 2}0{sub 2}(OH){sub 5}{sup {minus}} and Al(OH){sub 4}{sup {minus}}, in the low density region (p < 0.01 gm/cc). By means of the evaluated equilibria, thermochemical properties of Si{sub 2}O(OH){sub 6}(aq) and Si{sub 2}O{sub 2}(OH){sub 5}{sup {minus}} are made available for the first time.

  2. Supercritical water gasification of Eucalyptus grandis and related pyrolysis char: Effect of feedstock composition.

    PubMed

    Louw, Jeanne; Schwarz, Cara E; Burger, Andries J

    2016-09-01

    Eucalyptus grandis (E. grandis) wood and char products derived from pyrolysis of E. grandis wood, were gasified in supercritical water at 450°C - with and without the use of a homogeneous (K2CO3) and heterogeneous (Ni/Al2O3-SiO2) catalyst. Gas yields and gasification efficiencies were measured experimentally and compared to calculated thermodynamic equilibrium values, specifically considering the effects of the O/C ratio and volatile matter content of the feed material. Thermodynamically, feed material with lower O/C ratios (0.22) typically resulted in higher CH4 yields (30mol/kgfeed,dry) and gasification efficiencies (188%). However, experimentally, feed material with lower O/C ratios and lower volatile matter resulted in the lowest CH4 yields and gasification efficiencies. Furthermore, a linear relationship between the carbon efficiency (CE) and both the volatile matter content and O/C ratio of the feed material was found to hold true in both catalytic and non-catalytic experiments. PMID:27343456

  3. Supercritical water oxidation of colored smoke, dye, and pyrotechnic compositions. Phase 1, Final report

    SciTech Connect

    Rice, S.F.; LaJeunesse, C.A.; Hanush, R.G.; Aiken, J.D.; Johnston, S.C.

    1994-01-01

    The US military stockpile has large quantities of obsolete munitions awaiting disposal. Although suitable means for the safe dismantlement of much of this stockpile have been identified, there are still considerable quantities of specialty materials for which existing methods have been deemed inappropriate from an environmental standpoint. Among these munitions are colored spotting dyes and a wide assortment of pyrotechnics, including colored smokes and flares. In open bum or incineration treatment processes these materials produce large quantities of toxic, and possibly carcinogenic, gases and particulate matter. The U.S Army Armament Research, Development and Engineering Center at Picatinny Arsenal, NJ is interested in developing a method of treatment that will dispose of these munitions without the difficulties identified above. This report examines the feasibility of supercritical water oxidation, an emerging waste treatment technology, to process these materials. Four colored dyes and one pyrotechnic smoke composition were processed in a flow reactor, and the effluent was analyzed to determine the effectiveness of the processing. The tests showed that all of these materials could by oxidized to much less hazardous compounds in less than 10 seconds with a destruction and removal efficiency (DRE) typically > 99.5%. Two technical issues were identified as needing more attention in Phase II of this project: formation of sulfate and chloride salt deposits within the flow reactor and corrosion of the materials of construction.

  4. Degradation of SPS-Fabricated YSZ and Nd2O3-YSZ Ceramics in Supercritical Water

    NASA Astrophysics Data System (ADS)

    Siebert-Timmer, A.; Bichler, L.

    2016-04-01

    Zirconia (ZrO2) ceramics are being considered as a candidate material for thermal insulating barriers in pressure tubes used in the supercritical water (SCW) nuclear reactors. However, the literature suggests that zirconia may undergo a detrimental phase transformation which is accelerated in aqueous environments. In this research, 8 mol% Yttria-Stabilized Zirconia (YSZ) ceramics with the addition of 5 and 10 mol% Nd2O3 were manufactured via spark plasma sintering (SPS) process and subsequently subjected to a SCW environment. The weight losses and microstructural evolutions of these materials during SCW exposure were studied. The results suggest that doping YSZ with Nd2O3 significantly decreased the degradation rate of the YSZ ceramic and improved its structural stability. X-ray diffraction studies revealed that after degradation testing, the Nd2O3 helped to retain the desirable cubic phase of YSZ matrix. In the case of pure YSZ ceramic, a phase change of the matrix toward the monoclinic lattice was observed and likely contributed to the ceramic's disintegration in SCW environment.

  5. Energy recovery from secondary pulp/paper-mill sludge and sewage sludge with supercritical water treatment.

    PubMed

    Zhang, Linghong; Xu, Chunbao Charles; Champagne, Pascale

    2010-04-01

    Secondary pulp/paper-mill sludge (SPP) and sewage sludges (primary, secondary, and digested sewage sludges) were treated in supercritical water at temperatures ranging between 400 degrees Celsius and 550 degrees Celsius over 20-120 min for energy recovery. Low temperature and short reaction time favored the formation of heavy oil (HO) products, which were mainly composed of a variety of phenol and phenolic compounds, as well as some nitrogen-containing compounds, long-chain alkenes and alcohols, etc., with high gross calorific values (>36 MJ/kg). By contrast, the formation of synthetic gases, a mixture of hydrogen, carbon monoxide, carbon dioxide, methane, and other light hydrocarbons, were not significantly affected by reaction time but greatly enhanced with increasing temperature. The highest gas yield was obtained at 550 degrees Celsius, where 37.7 wt.% of the SPP (on dry basis) was converted into gases, with hydrogen yields as high as 14.5 mol H(2)/kg SPP (on a dry basis). In comparison to sewage sludges, SPP exhibited a greater capability for the production of HO and gases owing to its higher contents of volatiles and alkali metals, indicating a prospective utilization potential for SPP as a source of bio-energy.

  6. Environmental assessment of supercritical water oxidation and other sewage sludge handling options.

    PubMed

    Svanström, Magdalena; Fröling, Morgan; Olofsson, Mattias; Lundin, Margareta

    2005-08-01

    Sustainable development relies on the eco-efficient use of all flows in society; more value created out of each resource unit. Supercritical water oxidation (SCWO) can be used for treatment of wet organic waste. The technology has been under development for over 20 years but has not yet been fully commercialized. SCWO allows for complete oxidation of all organics in sewage sludge and almost complete recovery of the inherent energy, essentially without harmful emissions. In this paper, a life-cycle assessment (LCA) of sewage sludge SCWO (Aqua-Critox) is presented and the results are compared with LCA results for other sludge handling options: agricultural use, co-incineration with municipal solid waste, incineration with subsequent phosphorus extraction (Bio-Con) and sludge fractionation with phosphorus recovery (Cambi-KREPRO). For SCWO, beneficial utilization of the heat of reaction is of crucial importance for the outcome. The electricity consumed by pumping and the nitrous oxide produced are other important parameters. The best sludge handling option from an environmental point of view depends on what aspect is considered more important in the impact assessment. Regarding global warming, the energy recovery methods perform better than agricultural use.

  7. Computational Thermodynamics for Interpreting Oxidation of Structural Materials in Supercritical Water

    SciTech Connect

    Tan, Lizhen; Yang, Ying; Allen, Todd R.; Busby, Jeremy T

    2011-01-01

    Supercritical water-cooled reactor (SCWR) is one of the advanced nuclear reactors being developed to meet the soaring energy demand. The corrosion resistance of structural materials used in SCWR becomes one of the major concerns as the operation conditions being raised up to {approx}600 C and {approx}25 MPa. Oxidation has been observed as the major corrosion behavior. To mitigate the oxidation corrosion, stabilities of metals and oxides need to be understood with respect to environmental temperature and oxygen partial pressure. Computational thermodynamics provides a practical approach to assess phase stabilities of such multi-component multi-variable systems. In this study, calculated phase stability diagrams of alloys and corresponding oxides were used to guide the interpretation of oxidation behaviors of SCW-exposed structural materials. Examples include ferritic-martensitic steel, austenitic steels and Ni-base alloy, e.g., HCM12A (Fe-12Cr), D9 (Fe-15Cr-15Ni), 800H (Fe-21Cr-32Ni), and 690 (Ni-30Cr-10Fe). Calculated results are in good overall consistence with the experimental data.

  8. Supercritical water gasification of Eucalyptus grandis and related pyrolysis char: Effect of feedstock composition.

    PubMed

    Louw, Jeanne; Schwarz, Cara E; Burger, Andries J

    2016-09-01

    Eucalyptus grandis (E. grandis) wood and char products derived from pyrolysis of E. grandis wood, were gasified in supercritical water at 450°C - with and without the use of a homogeneous (K2CO3) and heterogeneous (Ni/Al2O3-SiO2) catalyst. Gas yields and gasification efficiencies were measured experimentally and compared to calculated thermodynamic equilibrium values, specifically considering the effects of the O/C ratio and volatile matter content of the feed material. Thermodynamically, feed material with lower O/C ratios (0.22) typically resulted in higher CH4 yields (30mol/kgfeed,dry) and gasification efficiencies (188%). However, experimentally, feed material with lower O/C ratios and lower volatile matter resulted in the lowest CH4 yields and gasification efficiencies. Furthermore, a linear relationship between the carbon efficiency (CE) and both the volatile matter content and O/C ratio of the feed material was found to hold true in both catalytic and non-catalytic experiments.

  9. Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids: Implications for Geologic Carbon Sequestration

    NASA Astrophysics Data System (ADS)

    Miller, Q. R.; Schaef, T.; Thompson, C.; Loring, J. S.; Windisch, C. F.; Bowden, M. E.; Arey, B. W.; McGrail, P.

    2012-12-01

    Global climate change is viewed by many as an anthropogenic phenomenon that could be mitigated through a combination of conservation efforts, alternative energy sources, and the development of technologies capable of reducing carbon dioxide (CO2) emissions. Continued increases of atmospheric CO2 concentrations are projected over the next decade, due to developing nations and growing populations. One economically favorable option for managing CO2 involves subsurface storage in deep basalt formations. The silicate minerals and glassy mesostasis basalt components act as metal cation sources, reacting with the CO2 to form carbonate minerals. Most prior work on mineral reactivity in geologic carbon sequestration settings involves only aqueous dominated reactions. However, in most sequestration scenarios, injected CO2 will reside as a buoyant fluid in contact with the sealing formation (caprock) and slowly become water bearing. Comparatively little laboratory research has been conducted on reactions occurring between minerals in the host rock and the wet scCO2. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably wet supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) in order to gain insight into reaction processes. Mineral transformation reactions were followed by two novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the scCO2 resulted in increased carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared (IR) spectroscopy and indirectly with 18O isotopic labeling techniques (Raman spectroscopy). The thin water films were determined to be critical for facilitating carbonation processes in wet scCO2. Even in extreme low water conditions, the IR technique detected the formation of

  10. Thermal Aspects of Using Alternative Nuclear Fuels in Supercritical Water-Cooled Reactors

    NASA Astrophysics Data System (ADS)

    Grande, Lisa Christine

    A SuperCritical Water-cooled Nuclear Reactor (SCWR) is a Generation IV concept currently being developed worldwide. Unique to this reactor type is the use of light-water coolant above its critical point. The current research presents a thermal-hydraulic analysis of a single fuel channel within a Pressure Tube (PT)-type SCWR with a single-reheat cycle. Since this reactor is in its early design phase many fuel-channel components are being investigated in various combinations. Analysis inputs are: steam cycle, Axial Heat Flux Profile (AHFP), fuel-bundle geometry, and thermophysical properties of reactor coolant, fuel sheath and fuel. Uniform and non-uniform AHFPs for average channel power were applied to a variety of alternative fuels (mixed oxide, thorium dioxide, uranium dicarbide, uranium nitride and uranium carbide) enclosed in an Inconel-600 43-element bundle. The results depict bulk-fluid, outer-sheath and fuel-centreline temperature profiles together with the Heat Transfer Coefficient (HTC) profiles along the heated length of fuel channel. The objective is to identify the best options in terms of fuel, sheath material and AHFPS in which the outer-sheath and fuel-centreline temperatures will be below the accepted temperature limits of 850°C and 1850°C respectively. The 43-element Inconel-600 fuel bundle is suitable for SCWR use as the sheath-temperature design limit of 850°C was maintained for all analyzed cases at average channel power. Thoria, UC2, UN and UC fuels for all AHFPs are acceptable since the maximum fuel-centreline temperature does not exceed the industry accepted limit of 1850°C. Conversely, the fuel-centreline temperature limit was exceeded for MOX at all AHFPs, and UO2 for both cosine and downstream-skewed cosine AHFPs. Therefore, fuel-bundle modifications are required for UO2 and MOX to be feasible nuclear fuels for SCWRs.

  11. Fayalite Dissolution and Siderite Formation in Water-Saturated Supercritical CO2

    SciTech Connect

    Qafoku, Odeta; Kovarik, Libor; Kukkadapu, Ravi K.; Ilton, Eugene S.; Arey, Bruce W.; Tucek, Jiri; Felmy, Andrew R.

    2012-11-25

    Olivines, a significant constituent of basaltic rocks, have the potential to immobilize permanently CO2 after it is injected in the deep subsurface, due to carbonation reactions occurring between CO2 and the host rock. To investigate the reactions of fayalitic olivine with supercritical CO2 (scCO2) and formation of mineral carbonates, experiments were conducted at temperatures of 35 °C to 80 °C, 90 atm pressure and anoxic conditions. For every temperature, the dissolution of fayalite was examined both in the presence of liquid water and H2O-saturated scCO2. The experiments were conducted in a high pressure batch reactor at reaction time extending up to 85 days. The newly formed products were characterized using a comprehensive suite of bulk and surface characterization techniques X-ray diffraction, Transmission/Emission Mössbauer Spectroscopy, Scanning Electron Microscopy coupled with Focused Ion Beam, and High Resolution Transmission Electron Microscopy. Siderite with rhombohedral morphology was formed at 35 °C, 50 °C, and 80 °C in the presence of liquid water and scCO2. In H2O-saturated scCO2, the formation of siderite was confirmed only at high temperature (80 °C). Characterization of reacted samples in H2O-saturated scCO2 with high resolution TEM indicated that siderite formation initiated inside voids created during the initial steps of fayalite dissolution. Later stages of fayalite dissolution result in the formation of siderite in layered vertical structures, columns or pyramids with a rhombus base morphology.

  12. Research on the Hydrodynamic Characteristics and Metal Temperature Distribution in Spiral tube Water Wall of an Ultra Supercritical Boiler

    NASA Astrophysics Data System (ADS)

    Zhang, Weijing; Yang, Dong; Pan, Jie; Zhou, Xu

    2010-03-01

    On the basis of a 350 MW supercritical pressure OTSC boiler, established the mathematical model for the circulation loop flow and grid pressure in a complex flow network system, and an iteration method was used to solve the nonlinear equations. The water wall flow distribution and temperature profile of the boiler were computed. The results show that the flow difference and heat difference are small in spiral tube water wall at BMCR, 75%BMCR load and 30%BMCR load. The metal temperatures are all in the range of allowable range, and the operation of boil is safe and reliable.

  13. An application of the novel quantum mechanical/molecular mechanical method combined with the theory of energy representation: An ionic dissociation of a water molecule in the supercritical water.

    PubMed

    Takahashi, Hideaki; Satou, Wataru; Hori, Takumi; Nitta, Tomoshige

    2005-01-22

    A novel quantum chemical approach recently developed has been applied to an ionic dissociation of a water molecule (2H(2)O-->H(3)O(+)+OH(-)) in ambient and supercritical water. The method is based on the quantum mechanical/molecular mechanical (QM/MM) simulations combined with the theory of energy representation (QM/MM-ER), where the energy distribution function of MM solvent molecules around a QM solute serves as a fundamental variable to determine the hydration free energy of the solute according to the rigorous framework of the theory of energy representation. The density dependence of the dissociation free energy in the supercritical water has been investigated for the density range from 0.1 to 0.6 g/cm(3) with the temperature fixed at a constant. It has been found that the product ionic species significantly stabilizes in the high density region as compared with the low density. Consequently, the dissociation free energy decreases monotonically as the density increases. The decomposition of the hydration free energy has revealed that the entropic term (-TDeltaS) strongly depends on the density of the solution and dominates the behavior of the dissociation free energy with respect to the variation of the density. The increase in the entropic term in the low density region can be attributed to the decrease in the translational degrees of freedom brought about by the aggregation of solvent water molecules around the ionic solute.

  14. A Priori Analysis of Subgrid-Scale Models for Large Eddy Simulations of Supercritical Binary-Species Mixing Layers

    NASA Technical Reports Server (NTRS)

    Okong'o, Nora; Bellan, Josette

    2005-01-01

    Models for large eddy simulation (LES) are assessed on a database obtained from direct numerical simulations (DNS) of supercritical binary-species temporal mixing layers. The analysis is performed at the DNS transitional states for heptane/nitrogen, oxygen/hydrogen and oxygen/helium mixing layers. The incorporation of simplifying assumptions that are validated on the DNS database leads to a set of LES equations that requires only models for the subgrid scale (SGS) fluxes, which arise from filtering the convective terms in the DNS equations. Constant-coefficient versions of three different models for the SGS fluxes are assessed and calibrated. The Smagorinsky SGS-flux model shows poor correlations with the SGS fluxes, while the Gradient and Similarity models have high correlations, as well as good quantitative agreement with the SGS fluxes when the calibrated coefficients are used.

  15. Utilization of geopressured resources in the oxidation of organic waste in supercritical water. Phase I, Final report

    SciTech Connect

    Diaz, Alexander F.; Herzog, Howard J.; Tester, Jefferson W.

    1992-11-01

    that concept, the waste, brine and oxidant (air or oxygen) are introduced into the SCWO reactor at the system pressure of 234 bar (3400 psia). The heat of oxidation raises the temperature of the system to about 600 C (1100 F). Due to the low solubility of inorganic salts in supercritical water (about 200 ppm or less) (Armellini and Tester, 1990, 1991a, 1991b), solid salt forms and falls to the lower section of the reactor, where it is cooled and quenched with water, creating a concentrated (organic-free) brine that would be mixed with brackish water and reinjected back to the geopressured well. Power is generated by the expansion of the products of the SCWO process through a series of multi-stage turboexpanden. A processing capacity of 100,000 gallons per day (gpd) was initially taken as the design basis, following some investigations carried out at the Idaho National Engineering Laboratory (Propp et al., 1990). The process was modeled using the ASPEN PLUS{trademark} process flowsheet simulator and material and energy balances were determined. Both the cases of using air and oxygen as oxidant were investigated. Toluene was chosen as the model compound to represent the organic waste. Turbine design calculations based on the volumetric flowrates obtained for a 100,000 gpd capacity resulted in unrealistically high rotor rotational speeds and small wheel pitch diameters to achieve optimum efficiencies. Higher SCWO effluent flowrates would lower rotor rotational speeds and increase wheel pitch diameters to more practical levels. Thus, a 42-fold larger design capacity of 100,000 barrels per day (bpd) was adopted as the basis for an above-ground base case. The results for the material and energy balances for a processing capacity of 100,000 bpd using air and oxygen as oxidant scale up linearly from the results for the 100,000 gpd case. The best case flowsheet corresponding to a 100,000 bpi case using oxygen as oxidant is given in Figure 1. Our conceptual design study suggests

  16. Numerical simulation of the solvate structures of acetylsalicylic acid in supercritical carbon dioxide containing polar co-solvents

    NASA Astrophysics Data System (ADS)

    Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.; Kumeev, R. S.; Golubev, V. A.

    2016-07-01

    Hydrogen-bonded complexes of acetylsalicylic acid with polar co-solvents in supercritical carbon dioxide, modified by methanol, ethanol, and acetone of 0.03 mole fraction concentration, are studied by numerical methods of classical molecular dynamics simulation and quantum chemical calculations. The structure, energy of formation, and lifetime of hydrogen-bonded complexes are determined, along with their temperature dependences (from 318 to 388 K at constant density of 0.7 g cm-3). It is shown that the hydrogen bonds between acetylsalicylic acid and methanol are most stable at 318 K and are characterized by the highest value of absolute energy. At higher supercritical temperatures, however, the longest lifetime is observed for acetylsalicylic acid-ethanol complexes. These results correlate with the known literature experimental data showing that the maximum solubility of acetylsalicylic acid at density values close to those considered in this work and at temperatures of 318 and 328 K is achieved when using methanol and ethanol as co-solvents, respectively.

  17. Radiation hydrodynamics simulations of wide-angle outflows from super-critical accretion disks around black holes

    NASA Astrophysics Data System (ADS)

    Hashizume, Katsuya; Ohsuga, Ken; Kawashima, Tomohisa; Tanaka, Masaomi

    2015-08-01

    By performing two-dimensional radiation hydrodynamics simulations with a large computational domain of 5000 times the Schwarzschild radius, we revealed that wide-angle outflow is launched via the radiation force from the super-critical accretion flows around black holes. The angular size of the outflow, where the radial velocity (vr) exceeds the escape velocity (vesc), increases with an increase of the distance from the black hole. As a result, the mass is blown away with speed of vr > vesc in all directions except for in the vicinity of the equatorial plane, θ = 0°-85°, where θ is the polar angle. The mass ejected from the outer boundary per unit time by the outflow is larger than the mass accretion rate onto the black hole, ˜ 150 LEdd/c2, where LEdd and c are the Eddington luminosity and the speed of light. The kinetic power of such wide-angle high-velocity outflow is comparable to the photon luminosity and is a few times larger than the Eddington luminosity. This corresponds to ˜ 1039-1040 erg s-1 for the stellar mass black holes. Our model is consistent with the observations of shock excited bubbles observed in some ultra-luminous X-ray sources (ULXs), supporting a hypothesis that ULXs are powered by the super-critical accretion onto stellar mass black holes.

  18. Oxidation of phenolics in supercritical water. Quarterly technical progress report, 1 December 1993--28 February 1994

    SciTech Connect

    Not Available

    1994-05-01

    An environmental hazard associated with coal liquefaction and gasification is the generation of aqueous waste streams containing phenolics and carcinogenic organics such as polynuclear aromatics. Oxidation in supercritical water (SCW) is an emerging technology for the ultimate destruction of phenolics and other organics in waste water streams. SCW oxidation involves the oxidation of organics in an aqueous medium at temperatures between 400--650 C and pressures around 250 atm. These conditions exceed the thermodynamic critical point of water, hence the water is said to be supercritical. Wastes can be converted by SCWO to benign products: carbon is converted to CO{sub 2}, hydrogen to H{sub 2}O, and nitrogen to N{sub 2} or N{sub 2}O (but not NO{sub x}). The objective of this project is to oxidize selected phenolics in SCW and then determine the reaction kinetics (rate constants, reaction orders, activation energies) and the reaction pathways. These reaction fundamentals can then be used to evaluate, design, optimize, and control coal-conversion waste water treatment processes based on SCWO.

  19. Investigation of parameter estimation and impact of injection rate on relative permeability measurements for supercritical CO2 and water by unsteady-state method

    NASA Astrophysics Data System (ADS)

    Hiratsuka, Y.; Yamamoto, H.

    2014-12-01

    CCS (Carbon dioxide Capture and Storage) is a promising option for mitigating climate changes. To predict the behavior of injected CO2 in a deep reservoir, relative permeability of supercritical CO2 and water of the reservoir rock is one of the most fundamental and influential properties. For determining the relative permeability, we employed the unsteady state method, in which the relative permeability is determined based on history matching of transient monitoring data with a multi-phase flow model. The unsteady-state method is relatively simple and short, but obviously its accuracy strongly depends on the flow model assumed in the history matching. In this study, we conducted relative permeability measurements of supercritical CO2-water system for Berea sandstone with the unsteady-state method under a reservoir condition at a 1km depth (P= 9.5MPa, T = 44˚C). Automatic history matching was performed with an inversion simulator iTOUGH2/ECO2N for multi-phase flow system of supercritical CO2, NaCl, and water. A sensitivity analysis of relative permeability parameters for CO2 and water was carried out to better understand the uniqueness and the uncertainty of the optimum solution estimated by the history matching. Among the parameters of the Corey-type curve employed in this study, while the end-point permeability could be optimized in a limited range, the other parameters were correlated and their combinations were not unique. However it was found that any combination of these parameters results in nearly identical shapes of the curve in the range of CO2 saturation in this study (0 to 60%). The optimally estimated curve from the unsteady-method was well comparable with those from the steady-state method acquired in the previous studies. Our experiment also focuses on the impact of injection rate on the estimates of relative permeability, as it is known that the injection rate could have a significant effect on fluid distribution such as viscous fingering with

  20. Wettability of supercritical carbon dioxide/water/quartz systems: simultaneous measurement of contact angle and interfacial tension at reservoir conditions.

    PubMed

    Saraji, Soheil; Goual, Lamia; Piri, Mohammad; Plancher, Henry

    2013-06-11

    Injection of carbon dioxide in deep saline aquifers is considered as a method of carbon sequestration. The efficiency of this process is dependent on the fluid-fluid and rock-fluid interactions inside the porous media. For instance, the final storage capacity and total amount of capillary-trapped CO2 inside an aquifer are affected by the interfacial tension between the fluids and the contact angle between the fluids and the rock mineral surface. A thorough study of these parameters and their variations with temperature and pressure will provide a better understanding of the carbon sequestration process and thus improve predictions of the sequestration efficiency. In this study, the controversial concept of wettability alteration of quartz surfaces in the presence of supercritical carbon dioxide (sc-CO2) was investigated. A novel apparatus for measuring interfacial tension and contact angle at high temperatures and pressures based on Axisymmetric Drop Shape Analysis with no-Apex (ADSA-NA) method was developed and validated with a simple system. Densities, interfacial tensions, and dynamic contact angles of CO2/water/quartz systems were determined for a wide range of pressures and temperatures relevant to geological sequestration of CO2 in the subcritical and supercritical states. Image analysis was performed with ADSA-NA method that allows the determination of both interfacial tensions and contact angles with high accuracy. The results show that supercritical CO2 alters the wettability of quartz surface toward less water-wet conditions compared to subcritical CO2. Also we observed an increase in the water advancing contact angles with increasing temperature indicating less water-wet quartz surfaces at higher temperatures.

  1. Solubilization of the poorly water soluble drug, telmisartan, using supercritical anti-solvent (SAS) process.

    PubMed

    Park, Junsung; Cho, Wonkyung; Cha, Kwang-Ho; Ahn, Junhyun; Han, Kang; Hwang, Sung-Joo

    2013-01-30

    Telmisartan is a biopharmaceutical classification system (BCS) class II drug that has extremely low water solubility but is freely soluble in highly alkalized solutions. Few organic solvents can dissolve telmisartan. This solubility problem is the main obstacle achieving the desired bioavailability. Because of its unique characteristics, the supercritical anti-solvent (SAS) process was used to BCS class II drug in a variety of ways including micronization, amorphization and solid dispersion. Solid dispersions were prepared using hydroxypropylmethylcellulose/polyvinylpyrrolidone (HPMC/PVP) at 1:0.5, 1:1, and 1:2 weight ratios of drug to polymer, and pure telmisartan was also treated using the SAS process. Processed samples were characterized for morphology, particle size, crystallinity, solubility, dissolution rate and polymorphic stability. After the SAS process, all samples were converted to the amorphous form and were confirmed to be hundreds nm in size. Solubility and dissolution rate were increased compared to the raw material. Solubility tended to increase with increases in the amount of polymer used. However, unlike the solubility results, the dissolution rate decreased with increases in polymer concentration due to gel layer formation of the polymer. Processed pure telmisartan showed the best drug release even though it had lower solubility compared to other solid dispersions; however, because there were no stabilizers in processed pure telmisartan, it recrystallized after 1 month under severe conditions, while the other solid dispersion samples remained amorphous form. We conclude that after controlling the formulation of solid dispersion, the SAS process could be a promising approach for improving the solubility and dissolution rate of telmisartan.

  2. Mass transfer of SCWO processes: Molecular diffusion and mass transfer coefficients of inorganic nitrate species in sub- and supercritical water

    SciTech Connect

    Goemans, M.G.E.; Gloyna, E.F.; Buelow, S.J.

    1996-04-01

    Molecular diffusion coefficients of lithium-, sodium-, potassium-, cesium-, calcium-, and strontium nitrate in subcritical water were determined by analysis of Taylor dispersion profiles. Pressures ranged from 300 to 500 bar at temperatures ranging from 25{degrees}C to 300{degrees}C. The reported diffusion values were determined at infinite dilution. Molecular diffusion coefficients were 10 to 20 times faster in near-critical subcritical water than in water at ambient temperature and pressure (ATP). These findings implied that the diffusion rates were more liquid like than they were gas like, hence experimental results were correlated with diffusion models for liquids. The subcritical diffusion data presented in this work, and supercritical diffusion results published elsewhere were correlated with hydrodynamic diffusion equations. Both the Wilke-Chang correlation and the Stokes-Einstein equation yielded predictions within 10% of the experimental results if the structure of the diffusing species could be estimated. The effect of the increased diffusion rates on mass transfer rates in supercritical water oxidation applications was quantified, with emphasis on heterogeneous oxidation processes. This study and results published elsewhere showed that diffusion limited conditions are much more likely to be encountered in SCWO processes than commonly acknowledged.

  3. Recycling high-performance carbon fiber reinforced polymer composites using sub-critical and supercritical water

    NASA Astrophysics Data System (ADS)

    Knight, Chase C.

    Carbon fiber reinforced plastics (CFRP) are composite materials that consist of carbon fibers embedded in a polymer matrix, a combination that yields materials with properties exceeding the individual properties of each component. CFRP have several advantages over metals: they offer superior strength to weight ratios and superior resistance to corrosion and chemical attack. These advantages, along with continuing improvement in manufacturing processes, have resulted in rapid growth in the number of CFRP products and applications especially in the aerospace/aviation, wind energy, automotive, and sporting goods industries. Due to theses well-documented benefits and advancements in manufacturing capabilities, CFRP will continue to replace traditional materials of construction throughout several industries. However, some of the same properties that make CFRP outstanding materials also pose a major problem once these materials reach the end of service life. They become difficult to recycle. With composite consumption in North America growing by almost 5 times the rate of the US GDP in 2012, this lack of recyclability is a growing concern. As consumption increases, more waste will inevitably be generated. Current composite recycling technologies include mechanical recycling, thermal processing, and chemical processing. The major challenge of CFRP recycling is the ability to recover materials of high-value and preserve their properties. To this end, the most suitable technology is chemical processing, where the polymer matrix can be broken down and removed from the fiber, with limited damage to the fibers. This can be achieved using high concentration acids, but such a process is undesirable due to the toxicity of such materials. A viable alternative to acid is water in the sub-critical and supercritical region. Under these conditions, the behavior of this abundant and most environmentally friendly solvent resembles that of an organic compound, facilitating the breakdown

  4. SUPERCRITICAL WATER PARTIAL OXIDATION PHASE I - PILOT-SCALE TESTING/FEASIBILTY SUDIES FINAL REPORT

    SciTech Connect

    SPRITZER.M; HONG,G

    2005-01-01

    General Atomics (GA) is developing Supercritical Water Partial Oxidation (SWPO) as a means of producing hydrogen from low-grade biomass and other waste feeds. The Phase I Pilot-scale Testing/Feasibility Studies have been successfully completed and the results of that effort are described in this report. The key potential advantage of the SWPO process is the use of partial oxidation in-situ to rapidly heat the gasification medium, resulting in less char formation and improved hydrogen yield. Another major advantage is that the high-pressure, high-density aqueous environment is ideal for reacting and gasifying organics of all types. The high water content of the medium encourages formation of hydrogen and hydrogen-rich products and is especially compatible with high water content feeds such as biomass materials. The high water content of the medium is also effective for gasification of hydrogen-poor materials such as coal. A versatile pilot plant for exploring gasification in supercritical water has been established at GA's facilities in San Diego. The Phase I testing of the SWPO process with wood and ethanol mixtures demonstrated gasification efficiencies of about 90%, comparable to those found in prior laboratory-scale SCW gasification work carried out at the University of Hawaii at Manoa (UHM), as well as other biomass gasification experience with conventional gasifiers. As in the prior work at UHM, a significant amount of the hydrogen found in the gas phase products is derived from the water/steam matrix. The studies at UHM utilized an indirectly heated gasifier with an activated carbon catalyst. In contrast, the GA studies utilized a directly heated gasifier without catalyst, plus a surrogate waste fuel. Attainment of comparable gasification efficiencies without catalysis is an important advancement for the GA process, and opens the way for efficient hydrogen production from low-value, dirty feed materials. The Phase I results indicate that a practical means to

  5. MIF-SKD computation code for thermohydraulic design of a reactor core cooled by supercritical-pressure water

    NASA Astrophysics Data System (ADS)

    Bogoslovskaya, G. P.; Karpenko, A. A.; Kirillov, P. L.; Sorokin, A. P.

    2009-03-01

    Presented here is the MIF-SKD computation code for channel-by-channel thermohydraulic calculations of fuel-rod assemblies cooled by supercritical-pressure water. The code allows one to calculate distributions of temperature and velocity of the coolant in channels of fuel-rod assemblies and temperatures of fuel-rod claddings and fuel-rod assembly casings with regular and irregular geometrical characteristics at various distributions of energy release along the length and the radius of fuel-rod assemblies.

  6. Numerical simulation and comparison of symmetrical/supercritical airfoils for the near tip region of a helicopter in forward flight

    NASA Technical Reports Server (NTRS)

    Badavi, F. F.

    1989-01-01

    Aerodynamic loads on a multi-bladed helicopter rotor in forward flight at transonic tip conditions are calculated. The unsteady, three-dimensional, time-accurate compressible Reynolds-averaged thin layer Navier-Stokes equations are solved in a rotating coordinate system on a body-conformed, curvilinear grid of C-H topology. Detailed boundary layer and global numerical comparisons of NACA-0012 symmetrical and CAST7-158 supercritical airfoils are made under identical forward flight conditions. The rotor wake effects are modeled by applying a correction to the geometric angle of attack of the blade. This correction is obtained by computing the local induced downwash velocity with a free wake analysis program. The calculations are performed on the Numerical Aerodynamic Simulation Cray 2 and the VPS32 (a derivative of a Cyber 205 at the Langley Research Center) for a model helicopter rotor in forward flight.

  7. Application of high-temperature simulated distillation to the residuum oil supercritical extraction process in petroleum refining

    PubMed

    Raia; Villalanti; Subramanian; Williams

    2000-01-01

    The gas chromatographic method of high-temperature simulated distillation (HTSD) is described, and the results are presented for the application of HTSD to the characterization of petroleum refinery feed and products from solvent deasphalting operations. Results are presented for refinery residual feed, deasphalted oil, and asphaltene fractions from the residual oil supercritical extraction process. Asphaltene removal from petroleum residuum using solvent deasphalting results in the improved quality and high recovery of deasphalted oil product for use as lube oil, fluid catalytic cracking, or hydrocracker feedstocks. The HTSD procedure presented here proves valuable for characterizing the fractions from the deasphalting process to obtain the percentage yield with boiling point data over the range from approximately 36 degrees C (97 degrees F) to 733 degrees C (1352 degrees F), which covers the boiling range of n-paraffins of carbon number C5 to C108.

  8. Corrosion of ferritic-martensitic steels and nickel-based alloys in supercritical water

    NASA Astrophysics Data System (ADS)

    Ren, Xiaowei

    The corrosion behavior of ferritic/martensitic (F/M) steels and Ni-based alloys in supercritical water (SCW) has been studied due to their potential applications in future nuclear reactor systems, fossil fuel power plants and waste treatment processes. 9˜12% chromium ferritic/martensitic steels exhibit good radiation resistance and stress corrosion cracking resistance. Ni-based alloys with an austenitic face-centered cubic (FCC) structure are designed to retain good mechanical strength and corrosion/oxidation resistance at elevated temperatures. Corrosion tests were carried out at three temperatures, 360°C, 500°C and 600°C, with two dissolved oxygen contents, 25 ppb and 2 ppm for up to 3000 hours. Alloys modified by grain refinement and reactive element addition were also investigated to determine their ability to improve the corrosion resistance in SCW. A duplex oxide structure was observed in the F/M steels after exposure to 25 ppb oxygen SCW, including an outer oxide layer with columnar magnetite grains and an inner oxide layer constituted of a mixture of spinel and ferrite phases in an equiaxed grain structure. An additional outermost hematite layer formed in the SCW-exposed samples when the oxygen content was increased to 2 ppm. Weight gain in the F/M steels increased with exposure temperatures and times, and followed parabolic growth kinetics in most of the samples. In Ni-based alloys after exposure to SCW, general corrosion and pitting corrosion were observed, and intergranular corrosion was found when exposed at 600°C due to formation of a local healing layer. The general oxide structure on the Ni-based alloys was characterized as NiO/Spinel/(CrxFe 1-x)2O3/(Fe,Ni). No change in oxidation mechanism was observed in crossing the critical point despite the large change in water properties. Corrosion resistance of the F/M steels was significantly improved by plasma-based yttrium surface treatment because of restrained outward diffusion of iron by the

  9. Nonthermal inactivation of Escherichia coli K12 in buffered peptone water using a pilot-plant scale supercritical carbon dioxide system with gas-liquid porous metal contractor

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study evaluated the effectiveness of a supercritical carbon dioxide (SCCO2) system, with a gas-liquid CO2 contactor, for reducing Escherichia coli K12 in diluted buffered peptone water. 0.1% (w/v) buffered peptone water inoculated with E. coli K12 was processed using the SCCO2 system at CO2 con...

  10. Molecular dynamics simulation of diffusion coefficients and structural properties of some alkylbenzenes in supercritical carbon dioxide at infinite dilution.

    PubMed

    Wang, Jinyang; Zhong, Haimin; Feng, Huajie; Qiu, Wenda; Chen, Liuping

    2014-03-14

    The binary infinite dilute diffusion coefficients, D₁₂(∞), of some alkylbenzenes (Ph-C(n), from Ph-H to Ph-C12) from 313 K to 333 K at 15 MPa in supercritical carbon dioxide (scCO2) have been studied by molecular dynamics (MD) simulation. The MD values agree well with the experimental ones, which indicate MD simulation technique is a powerful way to predict and obtain diffusion coefficients of solutes in supercritical fluids. Besides, the local structures of Ph-C(n)/CO2 fluids are further investigated by calculating radial distribution functions and coordination numbers. It qualitatively convinces that the first solvation shell of Ph-C(n) in scCO2 is significantly influenced by the structure of Ph-C(n) solute. Meanwhile, the mean end-to-end distance, the mean radius of gyration and dihedral angle distribution are calculated to gain an insight into the structural properties of Ph-C(n) in scCO2. The abnormal trends of radial distribution functions and coordination numbers can be reasonably explained in term of molecular flexibility. Moreover, the computed results of dihedral angle clarify that flexibility of long-chain Ph-C(n) is the result of internal rotation of C-C single bond (σ(c-c)) in alkyl chain. It is interesting that compared with n-alkane, because of the existence of benzene ring, the flexibility of alkyl chain in Ph-C(n) with same carbon atom number is significantly reduced, as a result, the carbon chain dependence of diffusion behaviors for long-chain n-alkane (n ≥ 5) and long-chain Ph-C(n) (n ≥ 4) in scCO2 are different.

  11. Molecular dynamics simulation of diffusion coefficients and structural properties of some alkylbenzenes in supercritical carbon dioxide at infinite dilution

    SciTech Connect

    Wang, Jinyang; Zhong, Haimin; Qiu, Wenda; Chen, Liuping; Feng, Huajie

    2014-03-14

    The binary infinite dilute diffusion coefficients, D{sub 12}{sup ∞}, of some alkylbenzenes (Ph-C{sub n}, from Ph-H to Ph-C{sub 12}) from 313 K to 333 K at 15 MPa in supercritical carbon dioxide (scCO{sub 2}) have been studied by molecular dynamics (MD) simulation. The MD values agree well with the experimental ones, which indicate MD simulation technique is a powerful way to predict and obtain diffusion coefficients of solutes in supercritical fluids. Besides, the local structures of Ph-C{sub n}/CO{sub 2} fluids are further investigated by calculating radial distribution functions and coordination numbers. It qualitatively convinces that the first solvation shell of Ph-C{sub n} in scCO{sub 2} is significantly influenced by the structure of Ph-C{sub n} solute. Meanwhile, the mean end-to-end distance, the mean radius of gyration and dihedral angle distribution are calculated to gain an insight into the structural properties of Ph-C{sub n} in scCO{sub 2}. The abnormal trends of radial distribution functions and coordination numbers can be reasonably explained in term of molecular flexibility. Moreover, the computed results of dihedral angle clarify that flexibility of long-chain Ph-C{sub n} is the result of internal rotation of C-C single bond (σ{sub c-c}) in alkyl chain. It is interesting that compared with n-alkane, because of the existence of benzene ring, the flexibility of alkyl chain in Ph-C{sub n} with same carbon atom number is significantly reduced, as a result, the carbon chain dependence of diffusion behaviors for long-chain n-alkane (n ≥ 5) and long-chain Ph-C{sub n} (n ≥ 4) in scCO{sub 2} are different.

  12. Stability of Chromium Carbide/Chromium Oxide Based Porous Ceramics in Supercritical Water

    NASA Astrophysics Data System (ADS)

    Dong, Ziqiang

    This research was aimed at developing porous ceramics as well as ceramic-metal composites that can be potentially used in Gen-IV supercritical water reactors (SCWR). The research mainly includes two parts: 1) fabricating and engineering the porous ceramics and porous ceramic-metal composite; 2) Evaluating the stability of the porous ceramics in SCW environments. Reactive sintering in carbonaceous environments was used to fabricate porous Cr3C2/Cr2O3-based ceramic. A new process consisting of freeze casting and reactive sintering has also been successfully developed to fabricate highly porous Cr3C 2 ceramics with multiple interconnected pores. Various amounts of cobalt powders were mixed with ceramic oxides in order to modify the porous structure and property of the porous carbide obtained by reactive sintering. The hardness of the M(Cr,Co)7C3-Co composite has been evaluated and rationalized based on the solid solution of cobalt in the ceramic phase, the composite effect of soft Co metal and the porous structure of the ceramic materials. Efforts have also been made in fabricating and evaluating interpenetrating Cr3C2-Cu composites formed by infiltrating liquid copper into porous Cr3C2. The corrosion evaluation mainly focused on assessing the stability of porous Cr3C2 and Cr2O3 under various SCW conditions. The corrosion tests showed that the porous Cr3C 2 is stable in SCW at temperatures below 425°C. However, cracking and disintegrating of the porous Cr3C2 occurred when the SCW temperature increased above 425°C. Mechanisms of the corrosion attack were also investigated. The porous Cr2O3 obtained by oxidizing the porous Cr3C2 was exposed to various SCW environments. It was found that the stability of Cr 2O 3 was dependent on its morphology and the SCW testing conditions. Increasing SCW temperature increased the dissociation rate of the Cr2O 3. Adding proper amount of Y2O3 can increase the stability of the porous Cr2O3 in SCW. It was also concluded that decreasing

  13. Effect of thermal treatment on the corrosion resistance of Type 316L stainless steel exposed in supercritical water

    NASA Astrophysics Data System (ADS)

    Jiao, Y.; Zheng, W.; Guzonas, D. A.; Cook, W. G.; Kish, J. R.

    2015-09-01

    There are still unknown aspects about the growth mechanism of oxide scales formed on candidate stainless steel fuel cladding materials during exposure in supercritical water (SCW) under the conditions relevant to the Canadian supercritical water-cooled reactor (SCWR). The tendency for intermetallic precipitates to form within the grains and on grain boundaries during prolonged exposure at high temperatures represents an unknown factor to corrosion resistance, since they tend to bind alloyed Cr. The objective of this study was to better understand the extent to which intermetallic precipitates affects the mode and extent of corrosion in SCW. Type 316L stainless steel, used as a model Fe-Cr-Ni-Mo alloy, was exposed to 25 MPa SCW at 550 °C for 500 h in a static autoclave for this purpose. Mechanically-abraded samples were tested in the mill-annealed (MA) and a thermally-treated (TT) condition. The thermal treatment was conducted at 815 °C for 1000 h to precipitate the carbide (M23C6), chi (χ), laves (η) and sigma (σ) phases. It was found that although relatively large intermetallic precipitates formed at the scale/alloy interface locally affected the oxide scale formation, their discontinuous formation did not affect the short-term overall apparent corrosion resistance.

  14. Recovery of copper and lead from waste printed circuit boards by supercritical water oxidation combined with electrokinetic process.

    PubMed

    Xiu, Fu-Rong; Zhang, Fu-Shen

    2009-06-15

    An effective and benign process for copper and lead recovery from waste printed circuit boards (PCBs) was developed. In the process, the PCBs was pre-treated in supercritical water, then subjected to electrokinetic (EK) process. Experimental results showed that supercritical water oxidation (SCWO) process was strong enough to decompose the organic compounds of PCBs, and XRD spectra indicated that copper and lead were oxidized into CuO, Cu(2)O and beta-PbO(2) in the process. The optimum SCWO treatment conditions were 60 min, 713 K, 30 MPa, and EK treatment time, constant current density were 11h, 20 mA cm(-2), respectively. The recovery percentages of copper and lead under optimum SCWO+EK treatment conditions were around 84.2% and 89.4%, respectively. In the optimized EK treatment, 74% of Cu was recovered as a deposit on the cathode with a purity of 97.6%, while Pb was recovered as concentrated solutions in either anode (23.1%) or cathode (66.3%) compartments but little was deposited on the electrodes. It is believed that the process is effective and practical for Cu and Pb recovery from waste electric and electronic equipments.

  15. Application of the GRI 1.2 methane oxidation model to methane and methanol oxidation in supercritical water

    SciTech Connect

    Rice, S.F.

    1996-05-01

    The GRI 1.2 mechanism is used to predict the oxidation rates of methane and methanol by oxygen in supercritical water at 250 bar and temperatures ranging from 420--630 C. Using the Chemkin II computational package which assumes an ideal gas equation of state, the GRI model does very well in representing the available experimental results on methane over a wide temperature and concentration rate. However, the model may lack key CH{sub 3}O{sub 2} reactions needed for a complete description in the < 450 C region. The oxidation of methanol and formation of formaldehyde is not well represented by the GRI mechanism when left unchanged. If two important modifications are made to the reactivity of HO{sub 2}, good agreement with the methanol oxidation results is achieved. This paper illustrates that the carefully-assembled GRI 1.2 mechanism, although designed for conventional combustion conditions, can be successfully extended with very little modification to much lower temperature and extreme pressure conditions. The purpose of this study is to understand the operative chemical kinetics of supercritical water oxidation required for the more efficient application of this technology to treatment of hazardous wastes, obsolete munitions, rocket motors, and chemical warfare agents.

  16. Recycling acetic acid from polarizing film of waste liquid crystal display panels by sub/supercritical water treatments.

    PubMed

    Wang, Ruixue; Chen, Ya; Xu, Zhenming

    2015-05-19

    Waste liquid crystal display (LCD) panels mainly contain inorganic materials (glass substrate) and organic materials (polarizing film and liquid crystal). The organic materials should be removed first since containing polarizing film and liquid crystal is to the disadvantage of the indium recycling process. In the present study, an efficient and environmentally friendly process to obtain acetic acid from waste LCD panels by sub/supercritical water treatments is investigated. Furthermore, a well-founded reaction mechanism is proposed. Several highlights of this study are summarized as follows: (i) 99.77% of organic matters are removed, which means the present technology is quite efficient to recycle the organic matters; (ii) a yield of 78.23% acetic acid, a quite important fossil energy based chemical product is obtained, which can reduce the consumption of fossil energy for producing acetic acid; (iii) supercritical water acts as an ideal solvent, a requisite reactant as well as an efficient acid-base catalyst, and this is quite significant in accordance with the "Principles of Green Chemistry". In a word, the organic matters of waste LCD panels are recycled without environmental pollution. Meanwhile, this study provides new opportunities for alternating fossil-based chemical products for sustainable development, converting "waste" into "fossil-based chemicals".

  17. Hydrogen production by supercritical water gasification of biomass. Phase 1 -- Technical and business feasibility study, technical progress report

    SciTech Connect

    1997-12-01

    The nine-month Phase 1 feasibility study was directed toward the application of supercritical water gasification (SCWG) for the economical production and end use of hydrogen from renewable energy sources such as sewage sludge, pulp waste, agricultural wastes, and ultimately the combustible portion of municipal solid waste. Unique in comparison to other gasifier systems, the properties of supercritical water (SCW) are ideal for processing biowastes with high moisture content or contain toxic or hazardous contaminants. During Phase I, an end-to-end SCWG system was evaluated. A range of process options was initially considered for each of the key subsystems. This was followed by tests of sewage sludge feed preparation, pumping and gasification in the SCW pilot plant facility. Based on the initial process review and successful pilot-scale testing, engineering evaluations were performed that defined a baseline system for the production, storage and end use of hydrogen. The results compare favorably with alternative biomass gasifiers currently being developed. The results were then discussed with regional wastewater treatment facility operators to gain their perspective on the proposed commercial SCWG systems and to help define the potential market. Finally, the technical and business plans were developed based on perceived market needs and the projected capital and operating costs of SCWG units. The result is a three-year plan for further development, culminating in a follow-on demonstration test of a 5 MT/day system at a local wastewater treatment plant.

  18. Comparison of Performance and Oxidation of Nitronic-50 and Stainless Steel 316 in Subcritical and Supercritical Water Environments

    NASA Astrophysics Data System (ADS)

    Karmiol, Zachary; Chidambaram, Dev

    2016-05-01

    This work investigates two austenitic stainless steels, Nitronic-50 and stainless steel 316, for use in both subcritical and supercritical water (SCW) conditions. The mechanical characteristics of the materials were investigated using slow strain rate testing in a SCW test loop under the following conditions: nitrogen at ambient temperature and pressure, liquid water at 473 K (200 °C) and 8 MPa, liquid water at 573 K (300 °C) and 15 MPa, and SCW at 698 K (425 °C) and 27 MPa. The surfaces of the failed samples were characterized using Raman spectroscopy, and X-ray photoelectron spectroscopy. Nitronic-50 was found to have superior mechanical strength characteristics at all conditions compared to stainless steel 316. At all elevated temperature conditions, stainless steel 316 was found to have a surface film consisting of iron oxides, while the surface film of Nitronic-50 predominantly consisted of nickel-iron spinel.

  19. Sensitivity Analysis of Fuel Centerline Temperatures in SuperCritical Water-cooled Reactors (SCWRs)

    NASA Astrophysics Data System (ADS)

    Abdalla, Ayman

    SuperCritical Water-cooled Reactors (SCWRs) are one of the six nuclear-reactor concepts currently being developed under the Generation-IV International Forum (GIF). A main advantage of SCW Nuclear Power Plants (NPPs) is that they offer higher thermal efficiencies compared to those of current conventional NPPs. Unlike today's conventional NPPs, which have thermal efficiencies between 30 - 35%, SCW NPPs will have thermal efficiencies within a range of 45 - 50%, owing to high operating temperatures and pressures (i.e., coolant temperatures as high as 625°C at 25 MPa pressure). The use of current fuel bundles with UO2 fuel at the high operating parameters of SCWRs may cause high fuel centerline temperatures, which could lead to fuel failure and fission gas release. Studies have shown that when the Variant-20 (43-element) fuel bundle was examined at SCW conditions, the fuel centerline temperature industry limit of 1850°C for UO2 and the sheath temperature design limit of 850°C might be exceeded. Therefore, new fuel-bundle designs, which comply with the design requirements, are required for future use in SCWRs. The main objective of this study to conduct a sensitivity analysis in order to identify the main factors that leads to fuel centerline temperature reduction. Therefore, a 54-element fuel bundle with smaller diameter of fuel elements compared to that of the 43-element bundle was designed and various nuclear fuels are examined for future use in a generic Pressure Tube (PT) SCWR. The 54-element bundle consists of 53 heated fuel elements with an outer diameter of 9.5 mm and one central unheated element of 20-mm outer diameter which contains burnable poison. The 54-element fuel bundle has an outer diameter of 103.45 mm, which is the same as the outer diameter of the 43-element fuel bundle. After developing the 54-element fuel bundle, one-dimensional heat-transfer analysis was conducted using MATLAB and NIST REFPROP programs. As a result, the Heat Transfer

  20. Solar Hot Water Hourly Simulation

    2009-12-31

    The Software consists of a spreadsheet written in Microsoft Excel which provides an hourly simulation of a solar hot water heating system (including solar geometry, solar collector efficiency as a function of temperature, energy balance on storage tank and lifecycle cost analysis).

  1. Clay hydration/dehydration in dry to water-saturated supercritical CO2: Implications for caprock integrity

    SciTech Connect

    Loring, John S.; Schaef, Herbert T.; Thompson, Christopher J.; Turcu, Romulus VF; Miller, Quin R.; Chen, Jeffrey; Hu, Jian Z.; Hoyt, David W.; Martin, Paul F.; Ilton, Eugene S.; Felmy, Andrew R.; Rosso, Kevin M.

    2013-01-01

    Injection of supercritical CO2 (scCO2) for the geologic storage of carbon dioxide will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Wet scCO2 is highly reactive and capable of carbonating and hydrating certain minerals, whereas anhydrous scCO2 can dehydrate water-containing minerals. Because these geochemical processes affect solid volume and thus porosity and permeability, they have the potential to affect the long-term integrity of the caprock seal. In this study, we investigate the swelling and shrinkage of an expandable clay found in caprock formations, montmorillonite (Ca-STx-1), when exposed to variable water-content scCO2 at 50 °C and 90 bar using a combination of in situ probes, including X-ray diffraction (XRD), in situ magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR), and in situ attenuated total reflection infrared spectroscopy (ATR-IR). We show that the extent of montmorillonite clay swelling/shrinkage is dependent not only on water hydration/dehydration, but also on CO2 intercalation reactions. Our results also suggest a competition between water and CO2 for interlayer residency where increasing concentrations of intercalated water lead to decreasing concentrations of intercalated CO2. Overall, this paper demonstrates the types of measurements required to develop fundamental knowledge that will enhance modeling efforts and reduce risks associated with subsurface storage of CO2.

  2. Processing of High Level Waste: Spectroscopic Characterization of Redox Reactions in Supercritical Water - Final Report

    SciTech Connect

    Arrington Jr., C. A.

    2000-11-15

    Current efforts are focused on the oxidative dissolution of chromium compounds found in Hanford tank waste sludge. Samples of chromium oxides and hydroxides with varying degrees of hydration are being characterized using Raman, FTIR, and XPS spectroscopic techniques. Kinetics of oxidation reactions at subcritical and supercritical temperatures are being followed by Raman spectroscopy using a high temperature stainless steel cell with diamond windows. In these reactions both hydrogen peroxide and nitrate anions are used as the oxidizing species with Cr(III) compounds and organic compounds as reducing agents.

  3. In situ high-energy synchrotron radiation study of boehmite formation, growth, and phase transformation to alumina in sub- and supercritical water.

    SciTech Connect

    Lock, N.; Bremholm, M.; Christensen, M.; Almer, J .D.; Chen, Y.-S.; Iverson, B. B.; Univ. of Aarhus; Univ. of Chicago; Princeton Univ.

    2009-01-01

    Boehmite (AlOOH) nanoparticles have been synthesized in subcritical (300 bar, 350 C) and supercritical (300 bar, 400 C) water. The formation and growth of AlOOH nanoparticles were studied in situ by small- and wide-angle X-ray scattering (SAXS and WAXS) using 80 keV synchrotron radiation. The SAXS/WAXS data were measured simultaneously with a time resolution greater than 10 s and revealed the initial nucleation of amorphous particles takes place within 10 s with subsequent crystallization after 30 s. No diffraction signals were observed from Al(OH){sub 3} within the time resolution of the experiment, which shows that the dehydration step of the reaction is fast and the hydrolysis step rate-determining. The sizes of the crystalline particles were determined as a function of time. The overall size evolution patterns are similar in sub- and supercritical water, but the growth is faster and the final particle size larger under supercritical conditions. After approximately 5 min, the rate of particle growth decreases in both sub- and supercritical water. Heating of the boehmite nanoparticle suspension allowed an in situ X-ray investigation of the phase transformation of boehmite to aluminium oxide. Under the wet conditions used in this work, the transition starts at 530 C and gives a two-phase product of hydrated and non-hydrated aluminium oxide.

  4. Effect of property variations on the mixing of turbulent supercritical water streams in a T-junction

    SciTech Connect

    Bu, L.; Zhao, J.

    2012-07-01

    The supercritical water mixing phenomenon is investigated with a wide range of conditions, i.e. the inlet temperature of the streams ranges from 323.15 K to 723.15 K and the pressure ranges from 25 MPa to 45 MPa. A sensitivity study is carried out for the jet and main flow velocity ratio (VR) which is varying from 1 to 40. In addition, the effect of the inject angles of branch flow to main flow on the mixing is conducted by varying the inject angle from 80 deg. to 100 deg.. The results show that the maximum temperature gradient appears on the wall of the upstream side in all the cases, and the inclined angles can be optimized to mitigate the thermal stress. (authors)

  5. Experimental and simulation studies of pore scale flow and reactive transport associated with supercritical CO2 injection into brine-filled reservoir rocks (Invited)

    NASA Astrophysics Data System (ADS)

    DePaolo, D. J.; Steefel, C. I.; Bourg, I. C.

    2013-12-01

    This talk will review recent research relating to pore scale reactive transport effects done in the context of the Department of Energy-sponsored Energy Frontier Research Center led by Lawrence Berkeley National Laboratory with several other laboratory and University partners. This Center, called the Center for Nanoscale Controls on Geologic CO2 (NCGC) has focused effort on the behavior of supercritical CO2 being injected into and/or residing as capillary trapped-bubbles in sandstone and shale, with particular emphasis on the description of nanoscale to pore scale processes that could provide the basis for advanced simulations. In general, simulation of reservoir-scale behavior of CO2 sequestration assumes a number of mostly qualitative relationships that are defensible as nominal first-order descriptions of single-fluid systems, but neglect the many complications that are associated with a two-phase or three-phase reactive system. The contrasts in properties, and the mixing behavior of scCO2 and brine provide unusual conditions for water-rock interaction, and the NCGC has investigated the underlying issues by a combination of approaches including theoretical and experimental studies of mineral nucleation and growth, experimental studies of brine films, mineral wetting properties, dissolution-precipitation rates and infiltration patterns, molecular dynamic simulations and neutron scattering experiments of fluid properties for fluid confined in nanopores, and various approaches to numerical simulation of reactive transport processes. The work to date has placed new constraints on the thickness of brine films, and also on the wetting properties of CO2 versus brine, a property that varies between minerals and with salinity, and may also change with time as a result of the reactivity of CO2-saturated brine. Mineral dissolution is dependent on reactive surface area, which can be shown to vary by a large factor for various minerals, especially when correlated with

  6. Understanding electrofreezing in water simulations

    NASA Astrophysics Data System (ADS)

    Yan, J. Y.; Overduin, S. D.; Patey, G. N.

    2014-08-01

    Molecular dynamics simulations are used to investigate why external electric fields promote the freezing of liquid water models. It is shown that the melting point of water at a pressure of 1 bar increases significantly when water is polarized by a uniform field. Fields of 1 V/nm and 2 V/nm increase the melting point by 24 K and 44 K, respectively. The increased melting point is mainly due to the favorable interaction of near perfectly polarized cubic ice with the applied field. For a fixed temperature, we demonstrate that the size of the critical ice nucleus decreases with field strength, mostly because the melting point, and hence the true degree of supercooling, is increasing with field. On simulation timescales, ice nucleation is observed at ˜40 K below the field-dependent melting point, independent of the particular value of the field applied. Indeed, we find that even quite highly polarized liquid water retains the characteristic local structures, and the related anomalous properties of water. Our results are obviously relevant to the mechanism of heterogeneous ice nucleation by local surface fields. Local fields will effectively increase the degree of supercooling of locally polarized liquid, decreasing the size of the critical nucleus in the region influenced by the field, hence facilitating ice nucleation.

  7. Microscopic structure and interaction analysis for supercritical carbon dioxide-ethanol mixtures: a Monte Carlo simulation study.

    PubMed

    Xu, Wenhao; Yang, Jichu; Hu, Yinyu

    2009-04-01

    Configurational-bias Monte Carlo simulations in the isobaric-isothermal ensemble using the TraPPE-UA force field were performed to study the microscopic structures and molecular interactions of mixtures containing supercritical carbon dioxide (scCO(2)) and ethanol (EtOH). The binary vapor-liquid coexisting curves were calculated at 298.17, 333.2, and 353.2 K and are in excellent agreement with experimental results. For the first time, three important interactions, i.e., EtOH-EtOH hydrogen bonding, EtOH-CO(2) hydrogen bonding, and EtOH-CO(2) electron donor-acceptor (EDA) bonding, in the mixtures were fully analyzed and compared. The EtOH mole fraction, temperature, and pressure effect on the three interactions was investigated and then explained by the competition of interactions between EtOH and CO(2) molecules. Analysis of the microscopic structures indicates a strong preference for the formation of EtOH-CO(2) hydrogen-bonded tetramers and pentamers at higher EtOH compositions. The distribution of aggregation sizes and types shows that a very large EtOH-EtOH hydrogen-bonded network exists in the mixtures, while only linear EtOH-CO(2) hydrogen-bonded and EDA-bonded dimers and trimers are present. Further analysis shows that EtOH-CO(2) EDA complex is more stable than the hydrogen-bonded one.

  8. Simulation of shock wave buffet and its suppression on an OAT15A supercritical airfoil by IDDES

    NASA Astrophysics Data System (ADS)

    Huang, JingBo; Xiao, ZhiXiang; Liu, Jian; Fu, Song

    2012-02-01

    In the present paper, extremely unsteady shock wave buffet induced by strong shock wave/boundary-layer interactions (SWBLI) on the upper surface of an OAT15A supercritical airfoil at Mach number of 0.73 and angle of attack of 3.5 degrees is first numerically simulated by IDDES, one of the most advanced RANS/LES hybrid methods. The results imply that conventional URANS methods are unable to effectively predict the buffet phenomenon on the wing surface; IDDES, which involves more flow physics, predicted buffet phenomenon. Some complex flow phenomena are predicted and demonstrated, such as periodical oscillations of shock wave in the streamwise direction, strong shear layer detached from the shock wave due to SWBLI and plenty of small scale structures broken down by the shear layer instability and in the wake. The root mean square (RMS) of fluctuating pressure coefficients and streamwise range of shock wave oscillation reasonably agree with experimental data. Then, two vortex generators (VG) both with an inclination angle of 30 degrees to the main flow directions are mounted in front of the shock wave region on the upper surface to suppress shock wave buffet. The results show that shock wave buffet can be significantly suppressed by VGs, the RMS level of pressure in the buffet region is effectively reduced, and averaged shock wave position is obviously pushed downstream, resulting in increased total lift.

  9. Lattice Monte Carlo simulations of phase separation and micellization in supercritical CO2/surfactant systems: effect of CO2 density.

    PubMed

    Scanu, Lauriane F; Gubbins, Keith E; Hall, Carol K

    2004-01-20

    Lattice Monte Carlo simulations are used to study the effect of nonionic surfactant concentration and CO2 density on the micellization and phase equilibria of supercritical CO2/surfactant systems. The interaction parameter for carbon dioxide is obtained by matching the critical temperature of the model fluid with the experimental critical temperature. Various properties such as the critical micelle concentration and the size, shape, and structure ofmicelles are calculated, and the phase diagram in the surfactant concentration-CO2 density space is constructed. On increasing the CO2 density, we find an increase in the critical micelle concentration and a decrease in the micellar size; this is consistent with existing experimental results. The variation of the micellar shape and structure with CO2 density shows that the micelles are spherical and that the extension of the micellar core increases with increasing micellar size, while the extension of the micellar corona increases with increasing CO2 density. The predicted phase diagram is in qualitative agreement with experimental phase diagrams for nonionic surfactants in carbon dioxide.

  10. Density dependence of the yield of hydrated electrons in the low-LET radiolysis of supercritical water at 400 °C: influence of the geminate recombination of subexcitation-energy electrons prior to thermalization.

    PubMed

    Meesungnoen, Jintana; Sanguanmith, Sunuchakan; Jay-Gerin, Jean-Paul

    2013-10-21

    Monte Carlo simulations were used to calculate the yield of hydrated electrons (eaq(-)) in the low-linear energy transfer radiolysis of supercritical water at 400 °C as a function of water density over the range of ~0.15 to 0.6 g cm(-3). Very good agreement was found between our calculations and picosecond pulse radiolysis experimental data at ~60 ps and 1 ns at high density (>0.35 g cm(-3)). At densities lower than ~0.35 g cm(-3), our eaq(-) yields were lower than the experimental data, especially at ~60 ps. However, if we incorporated into the simulations a prompt geminate electron-cation (H2O˙(+)) recombination (prior thermalization of the electron) that decreased as the density decreased, our computed eaq(-) yields at ~60 ps and 1 ns compared fairly well with the experimental data for the entire density range studied.

  11. Effect of transient thermal cycles in a supercritical water-cooled reactor on the microstructure and properties of ferritic martensitic steels

    NASA Astrophysics Data System (ADS)

    Totemeier, T. C.; Clark, D. E.

    2006-09-01

    Microstructural and mechanical property changes in modified 9Cr-1Mo and HCM12A ferritic-martensitic steels resulting from short-duration thermal transients that occur during loss of feedwater flow events in a supercritical water reactor (SCWR) were studied. Specimen blanks were exposed to reference transients with 810 and 840 °C maximum temperatures using a thermal cycle simulator, and the subsequent microstructure, hardness, and creep-rupture strength were evaluated. Exposure to five consecutive cycles at either temperature resulted in no significant changes - only very slight indications of overtempering. Subsequent study of a wider variety of transient conditions showed that significant ferrite-to-austenite transformation occurred during thermal transients whose maximum temperature exceeded 860 °C, or during transients with holds exceeding 10 s at 840 °C maximum temperature. The subsequent presence of untempered martensite in the microstructure, coupled with severe overtempering, resulted in an order of magnitude decrease in creep-rupture strength at 600 °C. The findings were consistent with measured Ac1 temperatures for the two steels and the dependence of Ac1 on heating rate.

  12. Supercritical fluid extraction of fat from ground beef: effects of water on gravimetric and GC-FAME fat determinations.

    PubMed

    Eller, F J; King, J W

    2001-10-01

    This study investigated the supercritical carbon dioxide (SC-CO(2)) extraction of fat from ground beef and the effects of several factors on the gravimetric determination of fat. The use of ethanol modifier with the SC-CO(2) was not necessary for efficient fat extraction; however, the ethanol did increase the coextraction of water. This coextraction of water caused a significant overestimation of gravimetric fat. Oven-drying ground beef samples prior to extraction inhibited the subsequent extraction of fat, whereas oven-drying the extract after collection decreased the subsequent gas chromatographic fatty acid methyl ester (GC-FAME) fat determination. None of the drying agents tested were able to completely prevent the coextraction of water, and silica gel and molecular sieves inhibited the complete extraction of fat. Measurements of collection vial mass indicated that CO(2) extraction/collection causes an initial increase in mass due to the density of CO(2) (relative to displaced air) followed by a decrease in vial mass due to the removal of adsorbed water from the collection vial. Microwave-drying of the empty collection vials removes approximately 3 mg of adsorbed water, approximately 15-20 min is required for readsorption of the displaced water. For collection vials containing collected fat, microwave-drying effectively removed coextracted water, and the vials reached equilibration after approximately 10-15 min. Silanizing collection vials did not significantly affect weight loss during microwave-drying. SC-CO(2) can be used to accurately determine fat gravimetrically for ground beef, and the presented method can also be followed by GC-FAME analysis to provide specific fatty acid information as well.

  13. New Linear Partitioning Models Based on Experimental Water: Supercritical CO2 Partitioning Data of Selected Organic Compounds.

    PubMed

    Burant, Aniela; Thompson, Christopher; Lowry, Gregory V; Karamalidis, Athanasios K

    2016-05-17

    Partitioning coefficients of organic compounds between water and supercritical CO2 (sc-CO2) are necessary to assess the risk of migration of these chemicals from subsurface CO2 storage sites. Despite the large number of potential organic contaminants, the current data set of published water-sc-CO2 partitioning coefficients is very limited. Here, the partitioning coefficients of thiophene, pyrrole, and anisole were measured in situ over a range of temperatures and pressures using a novel pressurized batch-reactor system with dual spectroscopic detectors: a near-infrared spectrometer for measuring the organic analyte in the CO2 phase and a UV detector for quantifying the analyte in the aqueous phase. Our measured partitioning coefficients followed expected trends based on volatility and aqueous solubility. The partitioning coefficients and literature data were then used to update a published poly parameter linear free-energy relationship and to develop five new linear free-energy relationships for predicting water-sc-CO2 partitioning coefficients. A total of four of the models targeted a single class of organic compounds. Unlike models that utilize Abraham solvation parameters, the new relationships use vapor pressure and aqueous solubility of the organic compound at 25 °C and CO2 density to predict partitioning coefficients over a range of temperature and pressure conditions. The compound class models provide better estimates of partitioning behavior for compounds in that class than does the model built for the entire data set.

  14. Near-infrared spectroscopic investigation of water in supercritical CO2 and the effect of CaCl2

    SciTech Connect

    Wang, Zheming; Felmy, Andrew R.; Thompson, Christopher J.; Loring, John S.; Joly, Alan G.; Rosso, Kevin M.; Schaef, Herbert T.; Dixon, David A.

    2013-01-01

    Near-infrared (NIR) spectroscopy was applied to investigate the dissolution and chemical interaction of water dissolved into supercritical carbon dioxide (scCO2) and the influence of CaCl2 in the co-existing aqueous phase at fo empe e : 40 50 75 nd 100 C at 90 atm. Consistent with the trend of the vapor pressure of water, the solubility of pure water in scCO2 inc e ed f om 40 °C (0.32 mole%) o 100 °C (1.61 mole%). The presence of CaCl2 negatively affects the solubility of water in scCO2: at a given temperature and pressure the solubility of water decreased as the concentration of CaCl2 in the aqueous phase increased, following the trend of the activity of water. A 40 °C, the water concentration in scCO2 in contact with saturated CaCl2 aqueous solution was only 0.16 mole%, a drop of more than 50% as compared to pure water while that a 100 °C was 1.12 mole%, a drop of over 30% as compared to pure water, under otherwise the same conditions. Analysis of the spectral profiles suggested that water dissolved into scCO2 exists in the monomeric form under the evaluated temperature and pressure conditions, for both neat water and CaCl2 solutions. However, its rotational degrees of freedom decrease at lower temperatures due to higher fluid densities, leading to formation of weak H2O:CO2 Lewis acid-base complexes. Similarly, the nearly invariant spectral profiles of dissolved water in the presence and absence of saturated CaCl2 under the same experimental conditions was taken as evidence that CaCl2 dissolution in scCO2 was limited as the dissolved Ca2+/CaCl2 would likely be highly hydrated and would alter the overall spectra of waters in the scCO2 phase.

  15. The effect of oxidation treatment with supercritical water/hydrogen peroxide system on intersurface performance for polyacrylonitrile-based carbon fibers

    NASA Astrophysics Data System (ADS)

    Meng, Linghui; Fan, Dapeng; Zhang, Chunhua; Jiang, Zaixing; Huang, Yudong

    2013-05-01

    In order to improve the interfacial properties between carbon fibers and epoxy matrix, supercritical water and hydrogen peroxide were used as oxidation medium for the oxidation treatment for carbon fibers. Analysis results of X-ray photoelectron spectroscopy suggest that the oxygen content on the carbon fibers' surfaces increases by these oxidation treatments. Scanning electron microscope and atomic force microscopy images indicate that the surface appearance of oxidized carbon fibers obviously changed. The maximal interlaminar shear strength and interface shear strength of carbon fiber/epoxy resin composite in which the fibers were treated by the supercritical water and hydrogen peroxide systems reaches 70.46 MPa and 106.66 MPa, increases by 13.4% and 29.6% respectively compared with untreated carbon fibers.

  16. Continuous production of phosphor YAG:Tb nanoparticles by hydrothermal synthesis in supercritical water

    SciTech Connect

    Hakuta, Yukiya; Haganuma, Tsukasa; Sue, Kiwamu; Adschiri, Tadafumi; Arai, Kunio

    2003-06-19

    Phosphor YAG:Tb ((Y{sub 2.7}Tb{sub 0.3})Al{sub 5}O{sub 12}) nano particles were synthesized by a hydrothermal method at supercritical conditions (400 deg. C and 30 MPa) using a flow reactor. Hydroxide sol solutions formed by stoichiometric aluminum nitrate, yttrium nitrate, terbium nitrate and potassium hydroxide solutions. The relationship between particle size and experimental variables including pH, concentration of coexistent ions and hydroxide sol were investigated. Particles were characterized by XRD, TEM and photo-luminescence measurements. Particle size of YAG:Tb became finer as pH was increased or potassium nitrate concentration of the starting metal salt solution was increased. By removing the coexisting ions (NO{sub 3}{sup -}, K{sup +}) from the metal salt solution, single phase YAG:Tb particles with 20 nm particle size were obtained. The emission spectra of YAG:Tb particles of 14 nm shows a blue shift.

  17. Modeling the radiolysis of supercritical water by fast neutrons: density dependence of the yields of primary species at 400°c.

    PubMed

    Butarbutar, Sofia Loren; Meesungnoen, Jintana; Guzonas, David A; Stuart, Craig R; Jay-Gerin, Jean-Paul

    2014-12-01

    A reliable understanding of radiolysis processes in supercritical water (SCW)-cooled reactors is crucial to developing chemistry control strategies that minimize the corrosion and degradation of materials. However, directly measuring the chemistry in reactor cores is difficult due to the extreme conditions of high temperature and pressure and mixed neutron and gamma-radiation fields, which are incompatible with normal chemical instrumentation. Thus, chemical models and computer simulations are an important route of investigation for predicting the detailed radiation chemistry of the coolant in a SCW reactor and the consequences for materials. Surprisingly, information on the fast neutron radiolysis of water at high temperatures is limited, and even more so for fast neutron irradiation of SCW. In this work, Monte Carlo simulations were used to predict the G values for the primary species e(-)aq, H(•), H2, (•)OH and H2O2 formed from the radiolysis of pure, deaerated SCW (H2O) by 2 MeV monoenergetic neutrons at 400°C as a function of water density in the range of ∼0.15-0.6 g/cm(3). The 2 MeV neutron was taken as representative of a fast neutron flux in a reactor. For light water, the moderation of these neutrons after knock-on collisions with water molecules generated mostly recoil protons of 1.264, 0.465, 0.171 and 0.063 MeV. Neglecting oxygen ion recoils and assuming that the most significant contribution to the radiolysis came from these first four recoil protons, the fast neutron yields were estimated as the sum of the G values for these protons after appropriate weightings were applied according to their energy. Calculated yields were compared with available experimental data and with data obtained for low-LET radiation. Most interestingly, the reaction of H(•) atoms with water was found to play a critical role in the formation yields of H2 and (•)OH at 400°C. Recent work has underscored the potential importance of this reaction above 200°C, but its

  18. Molecular dynamics simulation of diffusion and structure of some n-alkanes in near critical and supercritical carbon dioxide at infinite dilution.

    PubMed

    Feng, Huajie; Gao, Wei; Sun, Zhenfan; Lei, Bingxin; Li, Gaonan; Chen, Liuping

    2013-10-17

    The diffusion coefficients of n-alkanes (from CH4 to C14H30) in near critical and supercritical carbon dioxide at infinite dilution have been studied by molecular dynamics simulation. The simulation results agree well with experiment, which suggests that the simulation method is a powerful tool to obtain diffusion coefficients of solutes in fluids at high pressures. The local structures of such fluids are further investigated by calculating radial distribution functions and coordination numbers. Meanwhile, the dihedral, end-to-end distance and radius of gyration, which are calculated to characterize the flexibility of n-alkanes, are used to reasonably explain the abnormal trends on radial distribution functions and coordination numbers. Moreover, it is found that the flexibility effects on diffusion in pure n-alkanes and infinitely dilute n-alkane/CO2 system are different. The differences in MD simulation results of molecular diffusion in such systems could be qualitatively explained by the flexibility.

  19. Numerical simulations of mixing under supercritical pressures of a shear coaxial injector using a high-order method: effect of outer jet temperature

    NASA Astrophysics Data System (ADS)

    Terashima, H.; Koshi, M.

    2016-07-01

    A three-dimensional (3D) simulation of N2/H2 mixing for a coaxial injector under a supercritical pressure of 10 MPa is conducted using a highorder numerical method. Two outer H2 jets with injection temperatures of approximately 52 and 462 K are applied while an inner N2 jet with an injection temperature of approximately 97 K is applied. The mean and fluctuation properties and instantaneous flow fields are discussed in order to characterize the detailed mixing features for the two injection conditions. A clear dependence of dense-core length on the momentum flux ratio is also demonstrated.

  20. Direct numerical simulation of heated CO2 flows at supercritical pressure in a vertical annulus at Re =8900

    NASA Astrophysics Data System (ADS)

    Bae, Joong Hun; Yoo, Jung Yul; McEligot, Donald M.

    2008-05-01

    The present study is concerned with thermal physics of the fluid at supercritical pressure (SCP) where many singular phenomena are observed in turbulent heat transfer due to severe property variations of the fluid. Direct numerical simulation is conducted for upward annular flows of CO2 at a pressure of 8MPa with a constant-heat-flux boundary condition imposed on the inner wall. All simulations are made at the inlet bulk Reynolds number of 8900 with particular attention being paid to the structure of the heated boundary layers at SCP. It is shown that most singular phenomena at SCP occur when the pseudocritical temperature arises between the heated wall and bulk fluid temperatures. The mean velocity profile near the heated wall shows no logarithmic distribution in the inertial subrange because a large reduction in the Reynolds shear stress occurs in the viscous region. The computational flow visualization reveals that alternating low- and high-speed streaks in the viscous region are not clearly observed when the wall temperature peak is realized due to significant heat transfer deterioration. These results strongly suggest that the ejection and sweep motions of the fluid in the viscous region become so weakened that turbulent boundary layers at SCP cannot be self-sustained in the presence of strong stabilizing effects of the variable-property and buoyancy. It is also shown that streaky thermal pattern remains no longer similar to that of the velocity boundary layer when these coherent motions are reduced in the viscous region. In the meanwhile, the predicted normalized temperature profile at SCP shows a nearly flat distribution outside the viscous region although substantial amount of the radial turbulent heat flux is predicted there. This singular phenomenon at SCP can be considered as comparable to a phase change phenomenon at subcritical pressure, where the internal energy of the fluid is increased without changing the fluid temperature. At SCP, this transition

  1. Evaluating stress corrosion and corrosion aspects in supercritical water oxidation systems for the destruction of hazardous waste

    SciTech Connect

    Mitton, D.B.; Zhang, S.H.; Hautanen, K.E.; Cline, J.A.; Han, E.H.; Latanision, R.M.

    1997-08-01

    There is, currently, simultaneous public resistance to traditional waste handling procedures and a compelling need to destroy both military and civilian hazardous waste. Supercritical water oxidation (SCWO) is one developing technology particularly appropriate for treating a broad range of dilute aqueous organic wastes. Above its critical point (374 C and 221 atm) water is a low density fluid possessing properties intermediate between those of a liquid and a gas, and solvation characteristics more typical of a low polarity organic than water. Although this is a promising technology, a critical issue in its development will be the ability to overcome severe degradation problems of the materials of construction. While titanium and platinum liners have shown promise for some hazardous military feed streams, costs are high. Although nickel alloys are considered important for severe service, the indication is that they will not survive certain SCWO environments. Nevertheless, there is evidence that judicious feed modification may be employed to mitigate corrosion and reduce fabrication cost. Exposure studies have been accomplished for various alloys over a range of temperatures from 300--600 C. Experiments have been carried out in environments as innocuous as deionized water and as aggressive as highly chlorinated aqueous organic feed streams. Analysis of a number of failed components has provided enlightenment on degradation mechanisms and cracking, pitting and elevated corrosion rates are all observed in these systems. For chlorinated feed streams, both dealloying and cracking have been observed for alloy C-276. Samples exposed to a highly chlorinated organic indicate that the high-nickel alloys behave significantly better at 600 C than stainless steel type 316.

  2. Geologic controls on supercritical geothermal resources above magmatic intrusions

    PubMed Central

    Scott, Samuel; Driesner, Thomas; Weis, Philipp

    2015-01-01

    A new and economically attractive type of geothermal resource was recently discovered in the Krafla volcanic system, Iceland, consisting of supercritical water at 450 °C immediately above a 2-km deep magma body. Although utilizing such supercritical resources could multiply power production from geothermal wells, the abundance, location and size of similar resources are undefined. Here we present the first numerical simulations of supercritical geothermal resource formation, showing that they are an integral part of magma-driven geothermal systems. Potentially exploitable resources form in rocks with a brittle–ductile transition temperature higher than 450 °C, such as basalt. Water temperatures and enthalpies can exceed 400 °C and 3 MJ kg−1, depending on host rock permeability. Conventional high-enthalpy resources result from mixing of ascending supercritical and cooler surrounding water. Our models reproduce the measured thermal conditions of the resource discovered at Krafla. Similar resources may be widespread below conventional high-enthalpy geothermal systems. PMID:26211617

  3. Geologic controls on supercritical geothermal resources above magmatic intrusions.

    PubMed

    Scott, Samuel; Driesner, Thomas; Weis, Philipp

    2015-01-01

    A new and economically attractive type of geothermal resource was recently discovered in the Krafla volcanic system, Iceland, consisting of supercritical water at 450 °C immediately above a 2-km deep magma body. Although utilizing such supercritical resources could multiply power production from geothermal wells, the abundance, location and size of similar resources are undefined. Here we present the first numerical simulations of supercritical geothermal resource formation, showing that they are an integral part of magma-driven geothermal systems. Potentially exploitable resources form in rocks with a brittle-ductile transition temperature higher than 450 °C, such as basalt. Water temperatures and enthalpies can exceed 400 °C and 3 MJ kg(-1), depending on host rock permeability. Conventional high-enthalpy resources result from mixing of ascending supercritical and cooler surrounding water. Our models reproduce the measured thermal conditions of the resource discovered at Krafla. Similar resources may be widespread below conventional high-enthalpy geothermal systems. PMID:26211617

  4. Geologic controls on supercritical geothermal resources above magmatic intrusions.

    PubMed

    Scott, Samuel; Driesner, Thomas; Weis, Philipp

    2015-07-27

    A new and economically attractive type of geothermal resource was recently discovered in the Krafla volcanic system, Iceland, consisting of supercritical water at 450 °C immediately above a 2-km deep magma body. Although utilizing such supercritical resources could multiply power production from geothermal wells, the abundance, location and size of similar resources are undefined. Here we present the first numerical simulations of supercritical geothermal resource formation, showing that they are an integral part of magma-driven geothermal systems. Potentially exploitable resources form in rocks with a brittle-ductile transition temperature higher than 450 °C, such as basalt. Water temperatures and enthalpies can exceed 400 °C and 3 MJ kg(-1), depending on host rock permeability. Conventional high-enthalpy resources result from mixing of ascending supercritical and cooler surrounding water. Our models reproduce the measured thermal conditions of the resource discovered at Krafla. Similar resources may be widespread below conventional high-enthalpy geothermal systems.

  5. Experimental study of crossover from capillary to viscous fingering for supercritical CO2 - water displacement in a homogeneous pore network

    SciTech Connect

    Wang, Ying; Zhang, Changyong; Wei, Ning; Oostrom, Martinus; Wietsma, Thomas W.; Li, Xiaochun; Bonneville, Alain

    2012-06-05

    Carbon sequestration in saline aquifers involves displacing resident brine from the pore space by supercritical CO2 (scCO2 ). The displacement process is considered unstable due to the unfavorable viscosity ratio (logM < 0). The unstable mechanisms that affect scCO2 - water displacement under reservoir conditions (i.e., 41 °C, 9 MPa) were investigated in a homogeneous micromodel. A wide range of injection rates (logCa = -7.61~-4.73) was studied in two sets of experiments: discontinuous-rate injection, where the micromodel was first cleaned and saturated with water before each injection rate was imposed, and continuous-rate injection, where the rate was increased after quasi-steady conditions were reached for a certain rate. For the discontinuous-rate experiments, capillary fingering and viscous fingering are the dominant mechanisms for low (logCa <= -6.61) and high injection rates (logCa >= -5.21), respectively. Crossover from capillary to viscous fingering was observed for logCa = -5.91~-5.21, resulting in a large decrease in scCO2 saturation. The discontinuous-rate experimental results confirmed the decrease in nonwetting fluid saturation during crossover from capillary to viscous fingering predicted by numerical simulations by Lenormand et al. (1988).1 Capillary fingering was the only mechanism that dominates all injection rates in the continuous-rate experiment, and resulted in monotonic increase in scCO2 saturation.

  6. Atomistic molecular dynamics simulations of H2O diffusivity in liquid and supercritical CO2

    NASA Astrophysics Data System (ADS)

    Moultos, Othonas A.; Orozco, Gustavo A.; Tsimpanogiannis, Ioannis N.; Panagiotopoulos, Athanassios Z.; Economou, Ioannis G.

    2015-09-01

    Molecular dynamics simulations were employed for the calculation of diffusion coefficients of pure CO2 and of H2O in CO2 over a wide range of temperatures (298.15 K < T < 523.15 K) and pressures (5.0 MPa < P < 100.0 MPa), that are of interest to CO2 capture-and-sequestration processes. Various combinations of existing fixed-point-charge force-fields for H2O (TIP4P/2005 and Exponential-6) and CO2 (elementary physical model 2 [EPM2], transferable potentials for phase equilibria [TraPPE], and Exponential-6) were tested. All force-field combinations qualitatively reproduce the trends of the experimental data for infinitely diluted H2O in CO2; however, TIP4P/2005-EPM2, TIP4P/2005-TraPPE and Exponential-6-Exponential-6 were found to be the most consistent. Additionally, for H2O compositions ranging from infinite dilution to ?, the Maxwell-Stefan diffusion coefficient is shown to have a weak non-linear composition dependence.

  7. A Parametric Study of the Thermal-Hydraulic Response of Supercritical Light Water Reactors During Loss-of-Feedwater and Turbine-Trip Events

    SciTech Connect

    Cliff B. Davis; Jacopo Buongiorno; Philip E. MacDonald

    2003-09-01

    The Idaho National Engineering and Environmental Laboratory in investigating the feasibility of supercritical light water reactors for low-cost electric power production through a Nuclear Energy Research Initiative Project sponsored by the United State Department of Energy. The project is evaluating a variety of technical issues related to the fuel and reactor design, material corrosion, and safety characteristics. This paper presents the results of parametric calculations using the RELAP5 computer code to characterize the thermal-hydraulic response of supercritical reactors to transients initiated by loss-of-feedwater and turbine-trip events. The purpose of the calculations was to aid in the design of the safety systems by determining the time available for the safety systems to respond and their required capacities.

  8. Characterization of TiO2-Doped Yttria-Stabilized Zirconia (YSZ) for Supercritical Water-Cooled Reactor Insulator Application

    NASA Astrophysics Data System (ADS)

    Barrett, F.; Huang, X.; Guzonas, Dave

    2013-06-01

    In this study, TiO2-doped YSZ samples were tested in supercritical water (SCW) to evaluate their corrosion behavior. The doped samples were produced by mechanically alloying standard 7 wt.% Y2O3-ZrO2 with 5, 10, and 15 wt.% of TiO2 first. The bulk sample pieces were then obtained using plasma spraying of the alloyed powder materials followed by sintering. The results showed that the weight changes for 5TiYSZ and 10TiYSZ after 1000 h of exposure in SCW were negligible and the sample surfaces did not exhibit any indication of corrosion. In comparison to the reference materials (Al2O3 and 7YSZ) processed using the same method, the rate of weight change followed the order of Al2O3 > 7YSZ, 15TiYSZ > 10TiYSZ > 5TiYSZ. As several TiO2-doped 7SYZ compositions also display increased fracture toughness and reduced thermal conductivity, they may be considered as potential candidates for thermal insulation in a SCW-cooled nuclear reactor.

  9. Catalytic supercritical water gasification of primary paper sludge using a homogeneous and heterogeneous catalyst: Experimental vs thermodynamic equilibrium results.

    PubMed

    Louw, Jeanne; Schwarz, Cara E; Burger, Andries J

    2016-02-01

    H2, CH4, CO and CO2 yields were measured during supercritical water gasification (SCWG) of primary paper waste sludge (PWS) at 450°C. Comparing these yields with calculated thermodynamic equilibrium values offer an improved understanding of conditions required to produce near-equilibrium yields. Experiments were conducted at different catalyst loads (0-1g/gPWS) and different reaction times (15-120min) in a batch reactor, using either K2CO3 or Ni/Al2O3-SiO2 as catalyst. K2CO3 up to 1g/gPWS increased the H2 yield significantly to 7.5mol/kgPWS. However, these yields and composition were far from equilibrium values, with carbon efficiency (CE) and energy recovery (ER) of only 29% and 20%, respectively. Addition of 0.5-1g/gPWS Ni/Al2O3-SiO2 resulted in high H2 and CH4 yields (6.8 and 14.8mol/kgPWS), CE of 84-90%, ER of 83% and a gas composition relatively close to the equilibrium values (at hold times of 60-120min).

  10. Quantitative evaluation of heavy metals in solid residues from sub- and super-critical water gasification of sewage sludge.

    PubMed

    Li, Lei; Xu, Z R; Zhang, Chunlei; Bao, Jianping; Dai, Xiaoxuan

    2012-10-01

    Solid residues (SRs) are important byproducts of sub- and super-critical water gasification of sewage sludge (SS). In this study, the quantitative evaluation of heavy metals (HMs) in SRs, compared with SS, is applied in terms of potential ecological risks, pollution levels, and both bioavailability and eco-toxicity. The results show the bioavailability and eco-toxicity of HMs in SRs decrease, although the total concentration of HMs increased, particularly in the bioavailable fraction of Cu, which decreased nearly 97%. The geo-accumulation and potential ecological risk index indicated that the gasification process increased contamination by two levels (to the maximum), while the overall risk was in keeping with SS. However, based on the risk assessment code, each tested HM exhibited lower environmental risk after gasification, especially for Cd, which drastically dropped from 66.67 (very high risk) in SS to 0.71 (no risk) in SRs, with a reaction temperature of 375°C for 60 min.

  11. Catalytic supercritical water gasification of primary paper sludge using a homogeneous and heterogeneous catalyst: Experimental vs thermodynamic equilibrium results.

    PubMed

    Louw, Jeanne; Schwarz, Cara E; Burger, Andries J

    2016-02-01

    H2, CH4, CO and CO2 yields were measured during supercritical water gasification (SCWG) of primary paper waste sludge (PWS) at 450°C. Comparing these yields with calculated thermodynamic equilibrium values offer an improved understanding of conditions required to produce near-equilibrium yields. Experiments were conducted at different catalyst loads (0-1g/gPWS) and different reaction times (15-120min) in a batch reactor, using either K2CO3 or Ni/Al2O3-SiO2 as catalyst. K2CO3 up to 1g/gPWS increased the H2 yield significantly to 7.5mol/kgPWS. However, these yields and composition were far from equilibrium values, with carbon efficiency (CE) and energy recovery (ER) of only 29% and 20%, respectively. Addition of 0.5-1g/gPWS Ni/Al2O3-SiO2 resulted in high H2 and CH4 yields (6.8 and 14.8mol/kgPWS), CE of 84-90%, ER of 83% and a gas composition relatively close to the equilibrium values (at hold times of 60-120min). PMID:26638140

  12. Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CO2: Implications for Caprock Integrity

    NASA Astrophysics Data System (ADS)

    Loring, J. S.; Chen, J.; Thompson, C.; Schaef, T.; Miller, Q. R.; Martin, P. F.; Ilton, E. S.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

    2012-12-01

    The effectiveness of geologic sequestration as an enterprise for CO2 storage depends partly on the reactivity of supercritical CO2 (scCO2) with caprock minerals. Injection of scCO2 will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Caprock formations have high concentrations of clay minerals, including expandable montmorillonites. Water-bearing scCO2 is highly reactive and capable of hydrating or dehydrating clays, possibly leading to porosity and permeability changes that directly impact caprock performance. Dehydration will cause montmorillonite clay minerals in caprocks to contract, thereby decreasing solid volume and possibly increasing caprock permeability and porosity. On the other hand, water intercalation will cause these clays to expand, thereby increasing solid volume and possibly leading to self-sealing of caprock fractures. Pacific Northwest National Laboratory's Carbon Sequestration Initiative is developing capabilities for studying wet scCO2-mineral reactions in situ. Here, we introduce novel in situ infrared (IR) spectroscopic instrumentation that enables quantitative titrations of reactant minerals with water in scCO2. Results are presented for the infrared spectroscopic titrations of Na-, Ca-, and Mg-saturated Wyoming betonites with water over concentrations ranging from zero to scCO2 saturated. These experiments were carried out at 50°C and 90 bar. Transmission IR spectroscopy was used to measure concentrations of water dissolved in the scCO2 or intercalated into the clays. The titration curves evaluated from the transmission-IR data are compared between the three types of clays to assess the effects of the cation on water partitioning. Single-reflection attenuated total reflection (ATR) IR spectroscopy was used to collect the spectrum of the clays as they hydrate at every total water concentration during the titration. Clay hydration is evidenced by

  13. Comparison of large scale purification processes of naproxen enantiomers by chromatography using methanol-water and methanol-supercritical carbon dioxide mobile phases.

    PubMed

    Kamarei, Fahimeh; Vajda, Péter; Guiochon, Georges

    2013-09-20

    This paper compares two methods used for the preparative purification of a mixture of (S)-, and (R)-naproxen on a Whelk-O1 column, using either high performance liquid chromatography or supercritical fluid chromatography. The adsorption properties of both enantiomers were measured by frontal analysis, using methanol-water and methanol-supercritical carbon dioxide mixtures as the mobile phases. The measured adsorption data were modeled, providing the adsorption isotherms and their parameters, which were derived from the nonlinear fit of the isotherm models to the experimental data points. The model used was a Bi-Langmuir isotherm, similar to the model used in many enantiomeric separations. These isotherms were used to calculate the elution profiles of overloaded elution bands, assuming competitive Bi-Langmuir behavior of the two enantiomers. The analysis of these profiles provides the basis for a comparison between supercritical fluid chromatographic and high performance liquid chromatographic preparative scale separations. It permits an illustration of the advantages and disadvantages of these methods and a discussion of their potential performance.

  14. Simultaneous analysis for water- and fat-soluble vitamins by a novel single chromatography technique unifying supercritical fluid chromatography and liquid chromatography.

    PubMed

    Taguchi, Kaori; Fukusaki, Eiichiro; Bamba, Takeshi

    2014-10-01

    Chromatography techniques usually use a single state in the mobile phase, such as liquid, gas, or supercritical fluid. Chromatographers manage one of these techniques for their purpose but are sometimes required to use multiple methods, or even worse, multiple techniques when the target compounds have a wide range of chemical properties. To overcome this challenge, we developed a single method covering a diverse compound range by means of a "unified" chromatography which completely bridges supercritical fluid chromatography and liquid chromatography. In our method, the phase state was continuously changed in the following order; supercritical, subcritical and liquid. Moreover, the gradient of the mobile phase starting at almost 100% CO2 was replaced with 100% methanol at the end completely. As a result, this approach achieved further extension of the polarity range of the mobile phase in a single run, and successfully enabled the simultaneous analysis of fat- and water-soluble vitamins with a wide logP range of -2.11 to 10.12. Furthermore, the 17 vitamins were exceptionally separated in 4min. Our results indicated that the use of dense CO2 and the replacement of CO2 by methanol are practical approaches in unified chromatography covering diverse compounds. Additionally, this is a first report to apply the novel approach to unified chromatography, and can open another door for diverse compound analysis in a single chromatographic technique with single injection, single column and single system.

  15. Water Conservation Education with a Rainfall Simulator.

    ERIC Educational Resources Information Center

    Kok, Hans; Kessen, Shelly

    1997-01-01

    Describes a program in which a rainfall simulator was used to promote water conservation by showing water infiltration, water runoff, and soil erosion. The demonstrations provided a good background for the discussion of issues such as water conservation, crop rotation, and conservation tillage practices. The program raised awareness of…

  16. Subcritical and supercritical water oxidation of organic, wet wastes for carbon cycling in regenerative life support systems

    NASA Astrophysics Data System (ADS)

    Ronsse, Frederik; Lasseur, Christophe; Rebeyre, Pierre; Clauwaert, Peter; Luther, Amanda; Rabaey, Korneel; Zhang, Dong Dong; López Barreiro, Diego; Prins, Wolter; Brilman, Wim

    2016-07-01

    For long-term human spaceflight missions, one of the major requirements is the regenerative life support system which has to be capable of recycling carbon, nutrients and water from both solid and liquid wastes generated by the crew and by the local production of food through living organisms (higher plants, fungi, algae, bacteria, …). The European Space Agency's Life Support System, envisioned by the MELiSSA project, consists of a 5 compartment artificial ecosystem, in which the waste receiving compartment (so-called compartment I or briefly 'CI') is based on thermophilic fermentation. However, as the waste generated by the crew compartment and food production compartment contain typical plant fibres (lignin, cellulose and hemicellulose), these recalcitrant fibres end up largely unaffected in the digestate (sludge) generated in the C-I compartment. Therefore, the C-I compartment has to be supplemented with a so-called fibre degradation unit (in short, FDU) for further oxidation or degradation of said plant fibres. A potential solution to degrading these plant fibres and other recalcitrant organics is their oxidation, by means of subcritical or supercritical water, into reusable CO2 while retaining the nutrients in an organic-free liquid effluent. By taking advantage of the altered physicochemical properties of water above or near its critical point (647 K, 22.1 MPa) - including increased solubility of non-polar compounds and oxygen, ion product and diffusivity - process conditions can be created for rapid oxidation of C into CO2. In this research, the oxidizer is provided as a hydrogen peroxide solution which, at elevated temperature, will dissociated into O2. The purpose of this study is to identify ideal process conditions which (a) ensure complete oxidation of carbon, (b) retaining the nutrients other than C in the liquid effluent and (c) require as little oxidizer as possible. Experiments were conducted on a continuous, tubular heated reactor and on batch

  17. NMR study comparing capillary trapping in Berea sandstone of air, carbon dioxide, and supercritical carbon dioxide after imbibition of water

    NASA Astrophysics Data System (ADS)

    Prather, Cody A.; Bray, Joshua M.; Seymour, Joseph D.; Codd, Sarah L.

    2016-02-01

    Nuclear magnetic resonance (NMR) techniques were used to study the capillary trapping mechanisms relevant to carbon sequestration. Capillary trapping is an important mechanism in the initial trapping of supercritical CO2 in the pore structures of deep underground rock formations during the sequestration process. Capillary trapping is considered the most promising trapping option for carbon sequestration. NMR techniques noninvasively monitor the drainage and imbibition of air, CO2, and supercritical CO2 with DI H2O at low capillary numbers in a Berea sandstone rock core under conditions representative of a deep underground saline aquifer. Supercritical CO2 was found to have a lower residual nonwetting (NW) phase saturation than that of air and CO2. Supercritical CO2 behaves differently than gas phase air or CO2 and leads to a reduction in capillary trapping. NMR relaxometry data suggest that the NW phase, i.e., air, CO2, or supercritical CO2, is preferentially trapped in larger pores. This is consistent with snap-off conditions being more favorable in macroscale pores, as NW fluids minimize their contact area with the solid and hence prefer larger pores.

  18. Microemulsions in supercritical hydrochlorofluorocarbons

    SciTech Connect

    Jackson, K.; Fulton, J.L.

    1996-10-30

    We report the properties of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) microemulsions formed in supercritical hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons, and flourocarbons. The fluids used in this study include compounds that are of low toxicity and flammability and that are expected to remain environmentally acceptable well into the next century (e.g., 1,1,1, 2-tetrafluoroethane (R134a) and chlorodifluoromethane (R22)). We show that it is possible to form a water-in-oil type of microemulsion in a low molecular weight HCFC (R22). In addition to these HCFCs, We also review the ability to form microemulsions in 14 other fluids (ethane, propene, propane, n-butane, n-pentane, n-haxane, isobutane, isooctane, difluoromethane, trifluoromethane, hexafluoroethane, sulfur haxafluoride, xenon, and carbon dioxide) at conditions just above or below the critical point (0.75 < T/T{sub c} <1.1) of the solvent. We report extensively the phase behavior of AOT and didodecyldimethylammonium bromide microemulsions formed in a supercritical HCFC, R22. We show that microemulsions in HCFCs are practical alternatives to other fluids, such as supercritical carbon dioxide. 56 refs., 7 figs., 1 tab.

  19. WQM: A Water Quality Management Simulation Game.

    ERIC Educational Resources Information Center

    Sharda, Ramesh; And Others

    1988-01-01

    Description of WQM, a simulation game designed to introduce students to the water quality management function, emphasizes the decision-making process involved in various facets of business. The simulation model is described, computer support is explained, and issues in water resource management are discussed. (13 references) (LRW)

  20. Reaction of Water-Saturated Supercritical CO2 with Forsterite: Evidence for Magnesite Formation at Low Temperatures

    SciTech Connect

    Felmy, Andrew R.; Qafoku, Odeta; Arey, Bruce W.; Hu, Jian Z.; Hu, Mary Y.; Schaef, Herbert T.; Ilton, Eugene S.; Hess, Nancy J.; Pearce, Carolyn I.; Feng, Ju; Rosso, Kevin M.

    2012-08-01

    The nature of the reaction products that form on the surfaces of nanometer-sized forsterite particles during reaction with H2O saturated supercritical CO2 (scCO2) at 35 C and 50 C were examined under in situ conditions and ex situ following reaction. The in situ analysis was conducted by X-ray diffraction (XRD). Ex situ analysis consisted of scanning electron microscopy (SEM) examination of the surface phases and chemical characterization of precipitates using a combination of confocal Raman spectroscopy, 13C and 29Si NMR spectroscopy, and energy-dispersive X-ray Spectroscopy (EDS). The results show that the forsterite surface is highly reactive with the primary reaction products being a mixture of nesquehonite (MgCO3.3H2O) and magnesite (MgCO3) at short reaction times ({approx}3-4 days) and then magnesite (MgCO3) and a highly porous amorphous silica phase at longer reaction times (14 days). After 14 days of reaction most of the original forsterite transformed to reaction products. Importantly, the formation of magnesite was observed at temperatures much lower (35 C) than previously thought needed to overcome its well known sluggish precipitation kinetics. The conversion of nesquehonite to magnesite liberates H2O which can potentially facilitate further metal carbonation, as postulated by previous investigators, based upon studies at higher temperature (80 C). The observation that magnesite can form at lower temperatures implies that water recycling may also be important in determining the rate and extent of mineral carbonation in a wide range of potential CO2 storage reservoirs.

  1. Hydrogen production via supercritical water gasification of bagasse using Ni-Cu/γ-Al2O3 nano-catalysts.

    PubMed

    Mehrani, Reza; Barati, Mohammad; Tavasoli, Ahmad; Karimi, Ali

    2015-01-01

    Biomass gasification in supercritical water media is a promising method for the production of hydrogen. In this research, Cu-promoted Ni/γ-Al2O3 nano-catalysts were prepared with 2.5-30 wt% Ni and 0.6-7.5 wt% Cu loadings via the microemulsion method. Nano-catalysts were characterized by inductively coupled plasma (ICP), Brunauer Emmett Teller (BET) technique, X-Ray Diffraction (XRD), H2 chemisorption and Transmission Electron Microscopy (TEM) technique, as well as Carbon-Hydrogen-Nitrogen-Sulfur (CHNS) analysis was carried out for elemental analysis of bagasse. Nano-catalysts were assessed in a batch micro-reactor under 400°C and 240 bar. The microemulsion method decreased the catalyst average particle size and increased the percentage dispersion and reduction of the catalysts. The total gas yield increased with an increase in Ni and Cu loadings up to 20 wt% Ni and 5 wt% Cu and then started to decrease. Using the microemulsion technique for the preparation of Ni-Cu/γ-Al2O3 nano-catalyst, increased the hydrogen yield to 11.76 (mmol of H2/g of bagasse), CO yield to 2.67 (mmol of CO/g of bagasse) and light gaseous hydrocarbons to 0.6 (mmol of light gaseous hydrocarbons/g of bagasse). Promotion of Ni/γ-Al2O3 with copper increased the mole fraction of hydrogen in the final gasification products to 58.1 mol%.

  2. Hydrogen production via supercritical water gasification of bagasse using Ni-Cu/γ-Al2O3 nano-catalysts.

    PubMed

    Mehrani, Reza; Barati, Mohammad; Tavasoli, Ahmad; Karimi, Ali

    2015-01-01

    Biomass gasification in supercritical water media is a promising method for the production of hydrogen. In this research, Cu-promoted Ni/γ-Al2O3 nano-catalysts were prepared with 2.5-30 wt% Ni and 0.6-7.5 wt% Cu loadings via the microemulsion method. Nano-catalysts were characterized by inductively coupled plasma (ICP), Brunauer Emmett Teller (BET) technique, X-Ray Diffraction (XRD), H2 chemisorption and Transmission Electron Microscopy (TEM) technique, as well as Carbon-Hydrogen-Nitrogen-Sulfur (CHNS) analysis was carried out for elemental analysis of bagasse. Nano-catalysts were assessed in a batch micro-reactor under 400°C and 240 bar. The microemulsion method decreased the catalyst average particle size and increased the percentage dispersion and reduction of the catalysts. The total gas yield increased with an increase in Ni and Cu loadings up to 20 wt% Ni and 5 wt% Cu and then started to decrease. Using the microemulsion technique for the preparation of Ni-Cu/γ-Al2O3 nano-catalyst, increased the hydrogen yield to 11.76 (mmol of H2/g of bagasse), CO yield to 2.67 (mmol of CO/g of bagasse) and light gaseous hydrocarbons to 0.6 (mmol of light gaseous hydrocarbons/g of bagasse). Promotion of Ni/γ-Al2O3 with copper increased the mole fraction of hydrogen in the final gasification products to 58.1 mol%. PMID:25387488

  3. Solvation structure and dynamics of cis- and trans-1,2 dichloroethene isomers in supercritical carbon dioxide. A molecular dynamics simulation study.

    PubMed

    Dellis, Dimitris; Skarmoutsos, Ioannis; Samios, Jannis

    2011-10-27

    Molecular dynamics simulation techniques have been employed to investigate the solvation structure and dynamics in dilute mixtures of cis- and trans-1,2-dichloroethene in supercritical carbon dioxide. The calculations were performed for state points along a near-critical isotherm (1.02 T(c)) over a wide range of densities, using new developed optimized potential models for both isomers. The similarities and differences in the solvation structures around each isomer have been presented and discussed. The local density augmentation and enhancement factors of CO(2) around the isomers have been found significantly larger than the corresponding values for pure supercritical CO(2). The dynamic local density reorganization has been investigated and related to previously proposed relaxation mechanisms. The density dependence of the calculated self-diffusion coefficients has revealed the existence of a plateau in the region of 0.7-1.1 ρ(c), where the local density augmentation exhibits the maximum value. The reorientational dynamics of the C═C bond vector have been also studied, exhibiting significant differences between the two isomers in the case of the second-order Legendre time correlation functions.

  4. Computer simulation of argon adsorption on graphite surface from subcritical to supercritical conditions: the behavior of differential and integral molar enthalpies of adsorption.

    PubMed

    Fan, Chunyan; Do, D D; Li, Zili; Nicholson, D

    2010-10-19

    We investigate in detail the computer simulation of argon adsorption on a graphite surface over a very wide range of temperature, from below the triple point to well above the critical point. Adsorption over such a wide temperature range has not been reported previously in the form of adsorption isotherms and enthalpy change during adsorption. The adsorption isotherms can be classified broadly into four categories: below the triple point, the isotherms show stepwise character (a strict layering mechanism) with 2D condensation; type II (according to the IUPAC classification) is followed by isotherms at temperatures above the triple point and below the critical point and a sharp spike is seen for isotherms in the neighborhood of the critical point; and finally the typical behavior of a maximum is observed for isotherms above the critical point. For the isosteric heat, the heat curve (plotted against loading) remains finite for subcritical conditions but is infinite (singularity) at the maximum in excess loading for supercritical adsorption. For the latter case, a better representation of the energy change is the use of the integral molecular enthalpy because this does not exhibit a singularity as in the case of isosteric heat. We compare the differential and integral molecular enthalpies for the subcritical and supercritical adsorptions.

  5. Characteristics of supercritical turbulence from Direct Numerical Simulations of C(sub 7)H(sub 16)/N(sub 2) and O(sub 2)/H(sub 2)

    NASA Technical Reports Server (NTRS)

    Okong'o, N. A.; Bellan, J.

    2003-01-01

    Analysis of Direct Numerical Simulations (DNS) transitional states of temporal, supercritical mixing layers for C7H16/N2 and O2/H2 shows that the evolution of all layers is characterized by the formation of high-density-gradient magnitude (HDGM) regions.

  6. Quantifying the flow dynamics of supercritical CO2-water displacement in a 2D porous micromodel using fluorescent microscopy and microscopic PIV

    NASA Astrophysics Data System (ADS)

    Kazemifar, Farzan; Blois, Gianluca; Kyritsis, Dimitrios C.; Christensen, Kenneth T.

    2016-09-01

    The multi-phase flow of liquid/supercritical CO2 and water (non-wetting and wetting phases, respectively) in a two-dimensional silicon micromodel was investigated at reservoir conditions (80 bar, 24 °C and 40 °C). The fluorescent microscopy and microscopic particle image velocimetry (micro-PIV) techniques were combined to quantify the flow dynamics associated with displacement of water by CO2 (drainage) in the porous matrix. To this end, water was seeded with fluorescent tracer particles, CO2 was tagged with a fluorescent dye and each phase was imaged independently using spectral separation in conjunction with microscopic imaging. This approach allowed simultaneous measurement of the spatially-resolved instantaneous velocity field in the water and quantification of the spatial configuration of the two fluid phases. The results, acquired with sufficient time resolution to follow the dynamic progression of both phases, provide a comprehensive picture of the flow physics during the migration of the CO2 front, the temporal evolution of individual menisci, and the growth of fingers within the porous microstructure. During that growth process, velocity jumps 20-25 times larger in magnitude than the bulk velocity were measured in the water phase and these bursts of water flow occurred both in-line with and against the bulk flow direction. These unsteady velocity events support the notion of pressure bursts and Haines jumps during pore drainage events as previously reported in the literature [1-3]. After passage of the CO2 front, shear-induced flow was detected in the trapped water ganglia in the form of circulation zones near the CO2-water interfaces as well as in the thin water films wetting the surfaces of the silicon micromodel. To our knowledge, the results presented herein represent the first quantitative spatially and temporally resolved velocity-field measurements at high pressure for water displacement by liquid/supercritical CO2 injection in a porous micromodel.

  7. Dynamic transition in supercritical iron

    PubMed Central

    Fomin, Yu. D.; Ryzhov, V. N.; Tsiok, E. N.; Brazhkin, V. V.; Trachenko, K.

    2014-01-01

    Recent advance in understanding the supercritical state posits the existence of a new line above the critical point separating two physically distinct states of matter: rigid liquid and non-rigid gas-like fluid. The location of this line, the Frenkel line, remains unknown for important real systems. Here, we map the Frenkel line on the phase diagram of supercritical iron using molecular dynamics simulations. On the basis of our data, we propose a general recipe to locate the Frenkel line for any system, the recipe that importantly does not involve system-specific detailed calculations and relies on the knowledge of the melting line only. We further discuss the relationship between the Frenkel line and the metal-insulator transition in supercritical liquid metals. Our results enable predicting the state of supercritical iron in several conditions of interest. In particular, we predict that liquid iron in the Jupiter core is in the “rigid liquid” state and is highly conducting. We finally analyse the evolution of iron conductivity in the core of smaller planets such as Earth and Venus as well as exoplanets: as planets cool off, the supercritical core undergoes the transition to the rigid-liquid conducting state at the Frenkel line. PMID:25424664

  8. Corrosion and microstructural analysis data for AISI 316L and AISI 347H stainless steels after exposure to a supercritical water environment

    PubMed Central

    Ruiz, A.; Timke, T.; van de Sande, A.; Heftrich, T.; Novotny, R.; Austin, T.

    2016-01-01

    This article presents corrosion data and microstructural analysis data of austenitic stainless steels AISI 316L and AISI 347H exposed to supercritical water (25 MPa, 550 °C) with 2000 ppb of dissolved oxygen. The corrosion tests lasted a total of 1200 h but were interrupted at 600 h to allow measurements to be made. The microstructural data have been collected in the grain interior and at grain boundaries of the bulk of the materials and at the superficial oxide layer developed during the corrosion exposure. PMID:27158647

  9. Corrosion behavior of alloy 800H (Fe-21Cr-32Ni) in supercritical water

    SciTech Connect

    Tan, Lizhen; Allen, Todd R.; Yang, Ying

    2011-01-01

    The effect of testing conditions (temperature, time, and oxygen content) and material's microstructure (the as-received and the grain boundary engineered conditions) on the corrosion behavior of alloy 800H in high-temperature pressurized water was studied using a variety of characterization techniques. Oxidation was observed as the primary corrosion behavior on the samples. Oxide exfoliation was significantly mitigated on the grain boundary engineered samples compared to the as-received ones. The oxide formation, including some 'mushroom-shaped oxidation', is predicted via a combination of thermodynamics and kinetics influenced by the preferential diffusion of specific species using short-cut diffusion paths.

  10. Semi-analytical prediction of hydraulic resistance and heat transfer for pipe and channel flows of water at supercritical pressure

    SciTech Connect

    Laurien, E.

    2012-07-01

    Within the Generation IV International Forum the Supercritical Water Reactor is investigated. For its core design and safety analysis the efficient prediction of flow and heat transfer parameters such as the wall-shear stress and the heat-transfer coefficient for pipe and channel flows is needed. For circular pipe flows a numerical model based on the one-dimensional conservation equations of mass, momentum end energy in the radial direction is presented, referred to as a 'semi-analytical' method. An accurate, high-order numerical method is employed to evaluate previously derived analytical solutions of the governing equations. Flow turbulence is modeled using the algebraic approach of Prandtl/van-Karman, including a model for the buffer layer. The influence of wall roughness is taken into account by a new modified numerical damping function of the turbulence model. The thermo-hydraulic properties of water are implemented according to the international standard of 1997. This method has the potential to be used within a sub-channel analysis code and as wall-functions for CFD codes to predict the wall shear stress and the wall temperature. The present study presents a validation of the method with comparison of model results with experiments and multi-dimensional computational (CFD) studies in a wide range of flow parameters. The focus is laid on forced convection flows related to reactor design and near-design conditions. It is found, that the method can accurately predict the wall temperature even under deterioration conditions as they occur in the selected experiments (Yamagata el al. 1972 at 24.5 MPa, Ornatski et al. 1971 at 25.5 and Swenson et al. 1963 at 22.75 MPa). Comparison of the friction coefficient under high heat flux conditions including significant viscosity and density reductions near the wall with various correlations for the hydraulic resistance will be presented; the best agreement is achieve with the correlation of Pioro et al. 2004. It is

  11. Determination of Organic Partitioning Coefficients in Water-Supercritical CO2 Systems by Simultaneous in Situ UV and Near-Infrared Spectroscopies.

    PubMed

    Bryce, David A; Shao, Hongbo; Cantrell, Kirk J; Thompson, Christopher J

    2016-06-01

    CO2 injected into depleted oil or gas reservoirs for long-term storage has the potential to mobilize organic compounds and distribute them between sediments and reservoir brines. Understanding this process is important when considering health and environmental risks, but little quantitative data currently exists on the partitioning of organics between supercritical CO2 and water. In this work, a high-pressure, in situ measurement capability was developed to assess the distribution of organics between CO2 and water at conditions relevant to deep underground storage of CO2. The apparatus consists of a titanium reactor with quartz windows, near-infrared and UV spectroscopic detectors, and switching valves that facilitate quantitative injection of organic reagents into the pressurized reactor. To demonstrate the utility of the system, partitioning coefficients were determined for benzene in water/supercritical CO2 over the range 35-65 °C and approximately 25-150 bar. Density changes in the CO2 phase with increasing pressure were shown to have dramatic impacts on benzene's partitioning behavior. Our partitioning coefficients were approximately 5-15 times lower than values previously determined by ex situ techniques that are prone to sampling losses. The in situ methodology reported here could be applied to quantify the distribution behavior of a wide range of organic compounds that may be present in geologic CO2 storage scenarios.

  12. Simulated water productivity in Gansu Province, China

    NASA Astrophysics Data System (ADS)

    Zhan, Jinyan; Sun, Zhongxiao; Wang, Zhan; Chen, Jiancheng; Li, Zhaohua

    Economic value of water and economic analysis of water use management in Gansu Province of China have attracted widespread public attention. With the socioeconomic development, research on water resources has become more important than before. In this study, we define "water productivity" as the changes of economic production outputs of sectoral activities in every cubic meter of water input, which is also the technical coefficient of water resource use in each sector. According to Computable General Equilibrium (CGE) framework, based on the Input-Output Table 2007 and water resources bulletin of Gansu Province, we introduced the water into the ORANI-G (A Generic Single-Country Computable General Equilibrium model) model through the nested constant elasticity of substitution (CES) production function to analyze the changes of economic productions caused by water supply changes. We then examined water productivity in different sectors. Empirical results showed that current water productivity is underestimated. Agricultural water productivity is lower than that of the secondary and tertiary industries, even although agricultural water use is the largest part of water use in Gansu Province, and therefore improving agricultural water productivity can greatly mitigate the water shortage. Simulation results indicate that industrial transformation and development of water-saving industries will also mitigate water scarcity. Moreover, sensitivity analysis shows that the empirical results are robust under different scenarios. The results also show that higher constant elasticity of substitution rate (CES) between water and other production factors will contribute to sustainable development.

  13. Thermodynamic Analysis of the Use a Chemical Heat Pump to Link a Supercritical Water-Cooled Nuclear Reactor and a Thermochemical Water-Splitting Cycle for Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Granovskii, Mikhail; Dincer, Ibrahim; Rosen, Marc A.; Pioro, Igor

    Increases in the power generation efficiency of nuclear power plants (NPPs) are mainly limited by the permissible temperatures in nuclear reactors and the corresponding temperatures and pressures of the coolants in reactors. Coolant parameters are limited by the corrosion rates of materials and nuclear-reactor safety constraints. The advanced construction materials for the next generation of CANDU reactors, which employ supercritical water (SCW) as a coolant and heat carrier, permit improved “steam” parameters (outlet temperatures up to 625°C and pressures of about 25 MPa). An increase in the temperature of steam allows it to be utilized in thermochemical water splitting cycles to produce hydrogen. These methods are considered by many to be among the most efficient ways to produce hydrogen from water and to have advantages over traditional low-temperature water electrolysis. However, even lower temperature water splitting cycles (Cu-Cl, UT-3, etc.) require an intensive heat supply at temperatures higher than 550-600°C. A sufficient increase in the heat transfer from the nuclear reactor to a thermochemical water splitting cycle, without jeopardizing nuclear reactor safety, might be effectively achieved by application of a heat pump, which increases the temperature of the heat supplied by virtue of a cyclic process driven by mechanical or electrical work. Here, a high-temperature chemical heat pump, which employs the reversible catalytic methane conversion reaction, is proposed. The reaction shift from exothermic to endothermic and back is achieved by a change of the steam concentration in the reaction mixture. This heat pump, coupled with the second steam cycle of a SCW nuclear power generation plant on one side and a thermochemical water splitting cycle on the other, increases the temperature of the “nuclear” heat and, consequently, the intensity of heat transfer into the water splitting cycle. A comparative preliminary thermodynamic analysis is conducted

  14. Reaction enthalpies along the two channels of geminate electron recombination in liquid-to-supercritical water

    NASA Astrophysics Data System (ADS)

    Schiller, Robert; Horváth, Ákos

    2013-11-01

    Ionizing radiation or UV light produces electrons and H2O+ ions in water. These species transform into hydrated electron, e-aq, hydrated H3O+ ion, and ·OH radical in each other's neighborhood much faster than any forthcoming chemical transformation. Part of the electrons escapes their geminate partners. There exists two possible paths for the remaining fraction to react: H3O++e-aq=H3O· [channel (A)] and ·OH+e-aq=OH- [channel (B)]. We devised two thermodynamic cycles for the computation of the reaction enthalpies of both channels. Channel (A) was found to be endothermic with an enthalpy of 3.61 eV at room temperature. The enthalpy is seen to be almost constant up to 500 K, to increase at 600 K and to drop abruptly around 650 K, i.e. in the region where the dielectric constant is below 20. Channel (B) was found to be exothermic with an enthalpy of -2.33 eV at room temperature. It is becoming gradually less exothermic with increasing temperature the variation becoming fast around 650 K. The tendency of these thermochemical results parallel with recent kinetic calculations by Torres-Alacan et al. (J. Torres-Alacan, S. Kratz, P. Vöhringer, 2011. Phys. Chem. Chem. Phys. 13, 20806-20819)

  15. Corrosion in supercritical fluids

    SciTech Connect

    Propp, W.A.; Carleson, T.E.; Wai, Chen M.; Taylor, P.R.; Daehling, K.W.; Huang, Shaoping; Abdel-Latif, M.

    1996-05-01

    Integrated studies were carried out in the areas of corrosion, thermodynamic modeling, and electrochemistry under pressure and temperature conditions appropriate for potential applications of supercritical fluid (SCF) extractive metallurgy. Carbon dioxide and water were the primary fluids studied. Modifiers were used in some tests; these consisted of 1 wt% water and 10 wt% methanol for carbon dioxide and of sulfuric acid, sodium sulfate, ammonium sulfate, and ammonium nitrate at concentrations ranging from 0.00517 to 0.010 M for the aqueous fluids. The materials studied were Types 304 and 316 (UNS S30400 and S31600) stainless steel, iron, and AISI-SAE 1080 (UNS G10800) carbon steel. The thermodynamic modeling consisted of development of a personal computer-based program for generating Pourbaix diagrams at supercritical conditions in aqueous systems. As part of the model, a general method for extrapolating entropies and related thermodynamic properties from ambient to SCF conditions was developed. The experimental work was used as a tool to evaluate the predictions of the model for these systems. The model predicted a general loss of passivation in iron-based alloys at SCF conditions that was consistent with experimentally measured corrosion rates and open circuit potentials. For carbon-dioxide-based SCFs, measured corrosion rates were low, indicating that carbon steel would be suitable for use with unmodified carbon dioxide, while Type 304 stainless steel would be suitable for use with water or methanol as modifiers.

  16. Influence of the reactant carbon-hydrogen-oxygen composition on the key products of the direct gasification of dewatered sewage sludge in supercritical water.

    PubMed

    Gong, Miao; Zhu, Wei; Fan, Yujie; Zhang, Huiwen; Su, Ying

    2016-05-01

    The supercritical water gasification of ten different types of dewatered sewage sludges was investigated to understand the relationship between sludge properties and gasification products. Experiments were performed in a high-pressure autoclave at 400°C for 60 min. Results showed that gasification of sewage sludge in supercritical water consists mainly of a gasification reaction, a carbonization reaction and a persistent organic pollutants synthesis reaction. Changes in the reactant C/H/O composition have significant effects on the key gasification products. Total gas production increased with increasing C/H2O of the reactant. The char/coke content increased with increasing C/H ratio of the reactant. A decrease in the C/O ratio of the reactant led to a reduction in polycyclic aromatic hydrocarbon formation. This means that we can adjust the reactant C/H/O composition by adding carbon-, hydrogen-, and oxygen-containing substances such as coal, algae and H2O2 to optimize hydrogen production and to inhibit an undesired by-product formation. PMID:26922316

  17. A comparison of chilled DI water/ozone and CO{sub 2}-based supercritical fluids as replacements for photoresist-stripping solvents

    SciTech Connect

    Rubin, J.B.; Davenhall, L.B.; Barton, J.; Taylor, C.M.V.; Tiefert, K.

    1998-12-31

    Part of the Hewlett Packard Components Group`s Product Stewardship program is the ongoing effort to investigate ways to eliminate or reduce as much as possible the use of chemical substances from manufacturing processes. Currently used techniques to remove hard-baked photoresists from semiconductor wafers require the use of inorganic chemicals or organic strippers and associated organic solvents. Environmental, health and safety, as well as cost considerations prompted the search for alternative, more environmentally-benign, and cost-effective solutions. Two promising, emerging technologies were selected for evaluation: the chilled DI water/ozone technique and supercritical fluids based on carbon dioxide (CO{sub 2}). Evaluating chilled DI water/ozone shows this process to be effective for positive photoresist removal, but may not be compatible with all metallization systems. Testing of a closed-loop CO{sub 2}-based supercritical CO{sub 2} Resist Remover, or SCORR, at Los Alamos, on behalf of Hewlett-packard, shows that this treatment process is effective in removing photoresists, and is fully compatible with commonly used metallization systems. In this paper, the authors present details on the testing programs conducted with both the chilled DI H{sub 2}O/ozone and SCORR treatment processes.

  18. Influence of the reactant carbon-hydrogen-oxygen composition on the key products of the direct gasification of dewatered sewage sludge in supercritical water.

    PubMed

    Gong, Miao; Zhu, Wei; Fan, Yujie; Zhang, Huiwen; Su, Ying

    2016-05-01

    The supercritical water gasification of ten different types of dewatered sewage sludges was investigated to understand the relationship between sludge properties and gasification products. Experiments were performed in a high-pressure autoclave at 400°C for 60 min. Results showed that gasification of sewage sludge in supercritical water consists mainly of a gasification reaction, a carbonization reaction and a persistent organic pollutants synthesis reaction. Changes in the reactant C/H/O composition have significant effects on the key gasification products. Total gas production increased with increasing C/H2O of the reactant. The char/coke content increased with increasing C/H ratio of the reactant. A decrease in the C/O ratio of the reactant led to a reduction in polycyclic aromatic hydrocarbon formation. This means that we can adjust the reactant C/H/O composition by adding carbon-, hydrogen-, and oxygen-containing substances such as coal, algae and H2O2 to optimize hydrogen production and to inhibit an undesired by-product formation.

  19. Feasibility Study of Supercritical Light Water Cooled Fast Reactors for Actinide Burning and Electric Power Production Progress Report for Year 1, Quarter 2 (January - March 2002)

    SciTech Connect

    Mac Donald, Philip Elsworth; Buongiorno, Jacopo; Davis, Cliff Bybee; Weaver, Kevan Dean

    2002-03-01

    The use of light water at supercritical pressures as the coolant in a nuclear reactor offers the potential for considerable plant simplification and consequent capital and O&M cost reduction compared with current light water reactor (LWR) designs. Also, given the thermodynamic conditions of the coolant at the core outlet (i.e. temperature and pressure beyond the water critical point), very high thermal efficiencies of the power conversion cycle are possible (i.e. up to about 45%). Because no change of phase occurs in the core, the need for steam separators and dryers as well as for BWR-type re-circulation pumps is eliminated, which, for a given reactor power, results in a substantially shorter reactor vessel and smaller containment building than the current BWRs. Furthermore, in a direct cycle the steam generators are not needed.

  20. Kinetic investigation of the oxidation of naval excess hazardous materials in supercritical water for the design of a transpiration-wall reactor

    SciTech Connect

    Rice, S.F.; Hanush, R.G.; Hunter, T.B.

    1997-01-01

    Experiments were conducted in Sandia`s supercritical fluids reactor (SFR) to generate data for the design of a transpiration-wall supercritical water oxidation (SCWO) reactor. The reactor is intended for the disposal of hazardous material generated on naval vessels. The design parameters for the system require an accurate knowledge of destruction efficiency vs. time and temperature. Three candidate materials were selected for testing. The experiments consisted of oxidizing these materials in the SFR at isothermal conditions over the temperature range of 400-550C at 24.1 MPa. A small extrapolation of the results shows that these materials can be adequately destroyed (to 99.9% destruction removal efficiency, DRE, based on total organic carbon (TOC) in the effluent) in approximately 5 seconds at 600C. The results vary smoothly and predictably with temperature such that extrapolation to higher temperatures beyond the experimental capabilities of the SFR can be made with reasonable confidence. The preliminary design of the transpiration-wall reactor has a rapid heat-up section within the reactor vessel that requires the addition of a fuel capable of quickly reacting with oxygen at temperatures below 500C. Candidate alcohols and JP-5 jet fuel were evaluated in this context. Oxidation rates for the alcohols were examined using in situ Raman spectroscopy. In addition, the potential utility of supplying the oxidizer line with hydrogen peroxide as an additive to enhance rapid initiation of the feed at unusually low temperatures was investigated. Experiments were conducted in the Supercritical Constant Volume Reactor (SCVR) using hydrogen peroxide as the initial oxidizing species. The results show that this concept as a method of enhancing low temperature reactivity appears to fail because thermal decomposition of the hydrogen peroxide is more rapid than the fuel oxidation rate at low temperatures. 8 refs., 16 figs., 5 tabs.

  1. Simulation of Liquid and Supercritical Hydrogen Sulfide and of Alkali Ions in the Pure and Aqueous Liquid.

    PubMed

    Orabi, Esam A; Lamoureux, Guillaume

    2014-08-12

    A polarizable model for hydrogen sulfide (H2S) is optimized based on the experimental properties of the monomer and of the bulk liquid. The model is characterized by rigid SH bonds but flexible HSH angle and the polarizability is based on the Drude oscillator model. Bonded parameters and atomic charges are based on the experimental properties of the gaseous monomer. Atomic Lennard-Jones (LJ) parameters are adjusted based on the density of H2S around the critical point (in the temperature range 363-393 K and pressure range 8.023-10.013 MPa). The model gives binding energies for H2S dimers, trimers, and tetramers in good agreement with ab initio MP2(full)/6-311++G(d,p) results. It shows a liquid structure in very good agreement with neutron diffraction data. The model also gives density, self-diffusion coefficient, heat of vaporization, and dielectric constant of liquid hydrogen sulfide at the normal boiling point in good agreement with experimental data. In addition, the model is transferable to high temperature and pressure conditions, as evidenced from simulations up to 542.2 K and 40 MPa. The model is used in combination with the SWM4-NDP water model, with LJ parameters between the S and O atoms adjusted to reproduce the experimental hydration free energy of H2S. Simulations suggest that, in its first solvation shell, a single H2O molecule is solvated by 10 H2S molecules while a single H2S molecule is solvated by 20.5 H2O molecules. Pair-specific LJ parameters between alkali ions (Li(+), Na(+), K(+), Rb(+), Cs(+)) and the S atom are adjusted to reproduce ab initio binding energies of the ion-H2S pairs at the CCSD(T) level. Simulations based on these parameters show that alkali ions have higher coordination numbers and lower solvation free energies in liquid H2S than in liquid water or liquid ammonia. The model is also used to investigate the preferential solvation of the ions in aqueous solutions with a 10% H2S mole fraction. Results show that the ions are

  2. Advanced degradation of brominated epoxy resin and simultaneous transformation of glass fiber from waste printed circuit boards by improved supercritical water oxidation processes.

    PubMed

    Liu, Kang; Zhang, Zhiyuan; Zhang, Fu-Shen

    2016-10-01

    This work investigated various supercritical water oxidation (SCWO) systems, i.e. SCWO1 (only water), SCWO2 (water+H2O2) and SCWO3 (water+H2O2/NaOH), for waste printed circuit boards (PCBs) detoxification and recycling. Response surface methodology (RSM) was applied to optimize the operating conditions of the optimal SCWO3 systems. The optimal reaction conditions for debromination were found to be the NaOH of 0.21g, the H2O2 volume of 9.04mL, the time of 39.7min, maximum debromination efficiency of 95.14%. Variance analysis indicated that the factors influencing debromination efficiency was in the sequence of NaOH>H2O2>time. Mechanism studies indicated that the dissociated ions from NaOH in supercritical water promoted the debromination of brominated epoxy resins (BERs) through an elimination reaction and nucleophilic substitution. HO2, produced by H2O2 could induce the oxidation of phenol ring to open (intermediates of BERs), which were thoroughly degraded to form hydrocarbons, CO2, H2O and NaBr. In addition, the alkali-silica reaction between OH(-) and SiO2 induced the phase transformation of glass fibers, which were simultaneously converted into anorthite and albite. Waste PCBs in H2O2/NaOH improved SCWO system were fully degraded into useful products and simultaneously transformed into functional materials. These findings are helpful for efficient recycling of waste PCBs.

  3. Simulating farmer behaviour under water markets

    NASA Astrophysics Data System (ADS)

    Padula, SIlvia; Erfani, Tohid; Henriques, Catarina; Maziotis, Alexandros; Garbe, Jennifer; Swinscoe, Thomas; Harou, Julien; Weatherhead, Keith; Beevers, Lindsay; Fleskens, Luuk

    2015-04-01

    Increasing water scarcity may lead water managers to consider alternative approaches to water allocation including water markets. One concern with markets is how will specific sectors interact with a potential water market, when will they gain or loose water and will they benefit economically - why, when and how? The behaviours of different individual abstractors or institutional actors under water markets is of interest to regulators who seek to design effective market policies which satisfy multiple stakeholder groups. In this study we consider two dozen agricultural water users in eastern England (Nar basin). Using partially synthetic but regionally representative cropping and irrigation data we simulate the buying and selling behaviour of farmers on a weekly basis over multiple years. The impact of on-farm water storage is assessed for farmers who own a reservoir. A river-basin-scale hydro-economic multi-agent model is used that represents individual abstractors and can simulate a spot market under various licensing regimes. Weekly varying economic demand curves for water are calibrated based on historical climate and water use data. The model represents the trade-off between current use value and expected gains from trade to reach weekly decisions. Early results are discussed and model limitations and possible extensions are presented.

  4. Simulating water markets with transaction costs

    PubMed Central

    Erfani, Tohid; Binions, Olga; Harou, Julien J

    2014-01-01

    This paper presents an optimization model to simulate short-term pair-wise spot-market trading of surface water abstraction licenses (water rights). The approach uses a node-arc multicommodity formulation that tracks individual supplier-receiver transactions in a water resource network. This enables accounting for transaction costs between individual buyer-seller pairs and abstractor-specific rules and behaviors using constraints. Trades are driven by economic demand curves that represent each abstractor's time-varying water demand. The purpose of the proposed model is to assess potential hydrologic and economic outcomes of water markets and aid policy makers in designing water market regulations. The model is applied to the Great Ouse River basin in Eastern England. The model assesses the potential weekly water trades and abstractions that could occur in a normal and a dry year. Four sectors (public water supply, energy, agriculture, and industrial) are included in the 94 active licensed water diversions. Each license's unique environmental restrictions are represented and weekly economic water demand curves are estimated. Rules encoded as constraints represent current water management realities and plausible stakeholder-informed water market behaviors. Results show buyers favor sellers who can supply large volumes to minimize transactions. The energy plant cooling and agricultural licenses, often restricted from obtaining water at times when it generates benefits, benefit most from trades. Assumptions and model limitations are discussed. Key Points Transaction tracking hydro-economic optimization models simulate water markets Proposed model formulation incorporates transaction costs and trading behavior Water markets benefit users with the most restricted water access PMID:25598558

  5. Detoxification of military wastes by near critical and supercritical water and QSPR investigations. Final report, 17 July 1995--16 July 1998

    SciTech Connect

    Katritzky, A.R.

    1998-09-10

    The work on the behavior of a series of organophosphorus and organoarsenic compounds in superheated water was completed. Additional work was carried out in the area of aquathermolysis of aliphatic, aromatic, and heterocyclic amino compounds and heteroaromatic nitrogen-containing compounds. The results obtained show potential for the detoxification of military wastes by high-temperature supercritical hydrolysis. The work on the property and activity relationships with structures (QSPR/QSAR) was carried out using the recently developed CODESSA (Comprehensive Descriptors for Statistical and Structural Analysis) program containing around 1000 descriptors all of which are calculated only from the molecular structure without requiring any experimental data. The authors applied this approach for developing models for toxicities, vapor pressures, aqueous solubilities, water-air partition coefficients, critical temperatures, organic solvent scales, glass transition temperatures of polymers, refractive index values for polymers and organic compounds, and other properties. The correlation equations obtained can be successfully used to predict all these physicochemical properties.

  6. Feasibility Study of Supercritical Light Water Cooled Fast Reactors for Actinide Burning and Electric Power Production, Progress Report for Work Through September 2002, 4th Quarterly Report

    SciTech Connect

    Mac Donald, Philip Elsworth

    2002-09-01

    The use of light water at supercritical pressures as the coolant in a nuclear reactor offers the potential for considerable plant simplification and consequent capital and O&M cost reduction compared with current light water reactor (LWR) designs. Also, given the thermodynamic conditions of the coolant at the core outlet (i.e. temperature and pressure beyond the water critical point), very high thermal efficiencies of the power conversion cycle are possible (i.e. up to about 45%). Because no change of phase occurs in the core, the need for steam separators and dryers as well as for BWR-type re-circulation pumps is eliminated, which, for a given reactor power, results in a substantially shorter reactor vessel and smaller containment building than the current BWRs. Furthermore, in a direct cycle the steam generators are not needed. If no additional moderator is added to the fuel rod lattice, it is possible to attain fast neutron energy spectrum conditions in a supercritical water-cooled reactor (SCWR). This type of core can make use of either fertile or fertile-free fuel and retain a hard spectrum to effectively burn plutonium and minor actinides from LWR spent fuel while efficiently generating electricity. One can also add moderation and design a thermal spectrum SCWR. The Generation IV Roadmap effort has identified the thermal spectrum SCWR (followed by the fast spectrum SCWR) as one of the advanced concepts that should be developed for future use. Therefore, the work in this NERI project is addressing both types of SCWRs.

  7. Simulating water markets with transaction costs

    NASA Astrophysics Data System (ADS)

    Erfani, Tohid; Binions, Olga; Harou, Julien J.

    2014-06-01

    This paper presents an optimization model to simulate short-term pair-wise spot-market trading of surface water abstraction licenses (water rights). The approach uses a node-arc multicommodity formulation that tracks individual supplier-receiver transactions in a water resource network. This enables accounting for transaction costs between individual buyer-seller pairs and abstractor-specific rules and behaviors using constraints. Trades are driven by economic demand curves that represent each abstractor's time-varying water demand. The purpose of the proposed model is to assess potential hydrologic and economic outcomes of water markets and aid policy makers in designing water market regulations. The model is applied to the Great Ouse River basin in Eastern England. The model assesses the potential weekly water trades and abstractions that could occur in a normal and a dry year. Four sectors (public water supply, energy, agriculture, and industrial) are included in the 94 active licensed water diversions. Each license's unique environmental restrictions are represented and weekly economic water demand curves are estimated. Rules encoded as constraints represent current water management realities and plausible stakeholder-informed water market behaviors. Results show buyers favor sellers who can supply large volumes to minimize transactions. The energy plant cooling and agricultural licenses, often restricted from obtaining water at times when it generates benefits, benefit most from trades. Assumptions and model limitations are discussed. This article was corrected on 13 JUN 2014. See the end of the full text for details.

  8. Recovery of Minerals in Martian Soils Via Supercritical Fluid Extraction

    NASA Astrophysics Data System (ADS)

    Debelak, Kenneth A.; Roth, John A.

    2001-03-01

    We are investigating the use of supercritical fluids to extract mineral and/or carbonaceous material from Martian surface soils and its igneous crust. Two candidate supercritical fluids are carbon dioxide and water. The Martian atmosphere is composed mostly of carbon dioxide (approx. 95.3%) and could therefore provide an in-situ source of carbon dioxide. Water, although present in the Martian atmosphere at only approx. 0.03%, is also a candidate supercritical solvent. Previous work done with supercritical fluids has focused primarily on their solvating properties with organic compounds. Interestingly, the first work reported by Hannay and Hogarth at a meeting of the Royal Society of London in 1879 observed that increasing or decreasing the pressure caused several inorganic salts e.g., cobalt chloride, potassium iodide, and potassium bromide, to dissolve or precipitate in supercritical ethanol. In high-pressure boilers, silica, present in most boiler feed waters, is dissolved in supercritical steam and transported as dissolved silica to the turbine blades. As the pressure is reduced the silica precipitates onto the turbine blades eventually requiring the shutdown of the generator. In supercritical water oxidation processes for waste treatment, dissolved salts present a similar problem. The solubility of silicon dioxide (SiO2) in supercritical water is shown. The solubility curve has a shape characteristic of supercritical systems. At a high pressure (greater than 1750 atmospheres) increasing the temperature results in an increase in solubility of silica, while at low pressures, less than 400 atm., the solubility decreases as temperature increases. There are only a few studies in the literature where supercritical fluids are used in extractive metallurgy. Bolt modified the Mond process in which supercritical carbon monoxide was used to produce nickel carbonyl (Ni(CO)4). Tolley and Tester studied the solubility of titanium tetrachloride (TiCl4) in supercritical CO2

  9. Thermodynamic modelling of supercritical water gasification: investigating the effect of biomass composition to aid in the selection of appropriate feedstock material.

    PubMed

    Louw, Jeanne; Schwarz, Cara E; Knoetze, Johannes H; Burger, Andries J

    2014-12-01

    A process model developed in Aspen Plus®, was used for the thermodynamic modelling of supercritical water gasification (SCWG) using a wide variety of biomass materials as feedstock. The influence of the composition of the biomass material (in terms of carbon, hydrogen and oxygen content) on various performance indicators (such as gas yields, cold gas efficiency, calorific value of product gas and heat of reaction), were determined at various temperatures (600, 700 and 800°C) and biomass feed concentrations (5, 15 and 25wt.%). Generalised contour plots, based on the biomass composition, were developed for these performance indicators to provide the thermodynamic limits at various operating conditions. These plots can aid in the selection or screening of potential biomass materials and appropriate operating conditions for SCWG prior to conducting experimental work.

  10. Pulsed supercritical synthesis of anatase TiO2 nanoparticles in a water-isopropanol mixture studied by in situ powder X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Eltzholtz, Jakob Rostgaard; Tyrsted, Christoffer; Jensen, Kirsten Marie Ørnsbjerg; Bremholm, Martin; Christensen, Mogens; Becker-Christensen, Jacob; Iversen, Bo Brummerstedt

    2013-02-01

    A new step in supercritical nanoparticle synthesis, the pulsed supercritical synthesis reactor, is investigated in situ using synchrotron powder X-ray diffraction (PXRD) to understand the formation of nanoparticles in real time. This eliminates the common problem of transferring information gained during in situ studies to subsequent laboratory reactor conditions. As a proof of principle, anatase titania nanoparticles were synthesized in a 50/50 mixture of water and isopropanol near and above the critical point of water (P = 250 bar, T = 300, 350, 400, 450, 500 and 550 °C). The evolution of the reaction product was followed by sequentially recording PXRD patterns with a time resolution of less than two seconds. The crystallite size of titania is found to depend on both temperature and residence time, and increasing either parameter leads to larger crystallites. A simple adjustment of either temperature or residence time provides a direct method for gram scale production of anatase nanoparticles of average crystallite sizes between 7 and 35 nm, thus giving the option of synthesizing tailor-made nanoparticles. Modeling of the in situ growth curves using an Avrami growth model gave an activation energy of 66(19) kJ mol-1 for the initial crystallization. The in situ PXRD data also provide direct information about the size dependent macrostrain in the nanoparticles and with decreasing crystallite size the unit cell contracts, especially along the c-direction. This agrees well with previous ex situ results obtained for hydrothermal synthesis of titania nanoparticles.A new step in supercritical nanoparticle synthesis, the pulsed supercritical synthesis reactor, is investigated in situ using synchrotron powder X-ray diffraction (PXRD) to understand the formation of nanoparticles in real time. This eliminates the common problem of transferring information gained during in situ studies to subsequent laboratory reactor conditions. As a proof of principle, anatase titania

  11. Thermodynamic modelling of supercritical water gasification: investigating the effect of biomass composition to aid in the selection of appropriate feedstock material.

    PubMed

    Louw, Jeanne; Schwarz, Cara E; Knoetze, Johannes H; Burger, Andries J

    2014-12-01

    A process model developed in Aspen Plus®, was used for the thermodynamic modelling of supercritical water gasification (SCWG) using a wide variety of biomass materials as feedstock. The influence of the composition of the biomass material (in terms of carbon, hydrogen and oxygen content) on various performance indicators (such as gas yields, cold gas efficiency, calorific value of product gas and heat of reaction), were determined at various temperatures (600, 700 and 800°C) and biomass feed concentrations (5, 15 and 25wt.%). Generalised contour plots, based on the biomass composition, were developed for these performance indicators to provide the thermodynamic limits at various operating conditions. These plots can aid in the selection or screening of potential biomass materials and appropriate operating conditions for SCWG prior to conducting experimental work. PMID:25463777

  12. Leaching of Au, Ag, and Pd from waste printed circuit boards of mobile phone by iodide lixiviant after supercritical water pre-treatment.

    PubMed

    Xiu, Fu-Rong; Qi, Yingying; Zhang, Fu-Shen

    2015-07-01

    Precious metals are the most attractive resources in waste printed circuit boards (PCBs) of mobile phones. In this work, an alternative process for recovering Au, Ag, and Pd from waste PCBs of mobile phones by supercritical water oxidation (SCWO) pre-treatment combined with iodine-iodide leaching process was developed. In the process, the waste PCBs of mobile phones were pre-treated in supercritical water, then a diluted hydrochloric acid leaching (HL) process was used to recovery the Cu, whose leaching efficiency was approximately 100%, finally the resulting residue was subjected to the iodine-iodide leaching process for recovering the Au, Ag, and Pd. Experimental results indicated that SCWO pre-treatment temperature, time, and pressure had significant influence on the Au, Ag, and Pd leaching from (SCWO+HL)-treated waste PCBs. The optimal SCWO pre-treatment conditions were 420°C and 60min for Au and Pd, and 410°C and 30min for Ag. The optimum dissolution parameters for Au, Pd, and Ag in (SCWO+HL)-treated PCBs with iodine-iodide system were leaching time of 120min (90min for Ag), iodine/iodide mole ratio of 1:5 (1:6 for Ag), solid-to-liquid ratio (S/L) of 1:10g/mL (1:8g/mL for Ag), and pH of 9, respectively. It is believed that the process developed in this study is environment friendly for the recovery of Au, Ag, and Pd from waste PCBs of mobile phones by SCWO pre-treatment combined with iodine-iodide leaching process.

  13. Supercritical fluid extraction

    DOEpatents

    Wai, Chien M.; Laintz, Kenneth

    1994-01-01

    A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated or lipophilic crown ether or fluorinated dithiocarbamate. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

  14. Electrodeposition from supercritical fluids.

    PubMed

    Bartlett, P N; Cook, D A; George, M W; Hector, A L; Ke, J; Levason, W; Reid, G; Smith, D C; Zhang, W

    2014-05-28

    Recent studies have shown that it is possible to electrodeposit a range of materials, such as Cu, Ag and Ge, from various supercritical fluids, including hydrofluorocarbons and mixtures of CO2 with suitable co-solvents. In this perspective we discuss the relatively new field of electrodeposition from supercritical fluids. The perspective focuses on some of the underlying physical chemistry and covers both practical and scientific aspects of electrodeposition from supercritical fluids. We also discuss possible applications for supercritical fluid electrodeposition and suggest some key developments that are required to take the field to the next stage.

  15. Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

    NASA Astrophysics Data System (ADS)

    Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

    2014-12-01

    Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the

  16. Robust three-body water simulation model

    NASA Astrophysics Data System (ADS)

    Tainter, C. J.; Pieniazek, P. A.; Lin, Y.-S.; Skinner, J. L.

    2011-05-01

    The most common potentials used in classical simulations of liquid water assume a pairwise additive form. Although these models have been very successful in reproducing many properties of liquid water at ambient conditions, none is able to describe accurately water throughout its complicated phase diagram. The primary reason for this is the neglect of many-body interactions. To this end, a simulation model with explicit three-body interactions was introduced recently [R. Kumar and J. L. Skinner, J. Phys. Chem. B 112, 8311 (2008), 10.1021/jp8009468]. This model was parameterized to fit the experimental O-O radial distribution function and diffusion constant. Herein we reparameterize the model, fitting to a wider range of experimental properties (diffusion constant, rotational correlation time, density for the liquid, liquid/vapor surface tension, melting point, and the ice Ih density). The robustness of the model is then verified by comparing simulation to experiment for a number of other quantities (enthalpy of vaporization, dielectric constant, Debye relaxation time, temperature of maximum density, and the temperature-dependent second and third virial coefficients), with good agreement.

  17. An open source simulator for water management

    NASA Astrophysics Data System (ADS)

    Knox, Stephen; Meier, Philipp; Selby, Philip; Mohammed, Khaled; Khadem, Majed; Padula, Silvia; Harou, Julien; Rosenberg, David; Rheinheimer, David

    2015-04-01

    Descriptive modelling of water resource systems requires the representation of different aspects in one model: the physical system including hydrological inputs and engineered infrastructure, and human management, including social, economic and institutional behaviours and constraints. Although most water resource systems share some characteristics such as the ability to represent them as a network of nodes and links, geographical, institutional and other differences mean that invariably each water system functions in a unique way. A diverse group is developing an open source simulation framework which will allow model developers to build generalised water management models that are customised to the institutional, physical and economical components they are seeking to model. The framework will allow the simulation of complex individual and institutional behaviour required for the assessment of real-world resource systems. It supports the spatial and hierarchical structures commonly found in water resource systems. The individual infrastructures can be operated by different actors while policies are defined at a regional level by one or more institutional actors. The framework enables building multi-agent system simulators in which developers can define their own agent types and add their own decision making code. Developers using the framework have two main tasks: (i) Extend the core classes to represent the aspects of their particular system, and (ii) write model structure files. Both are done in Python. For task one, users must either write new decision making code for each class or link to an existing code base to provide functionality to each of these extension classes. The model structure file links these extension classes in a standardised way to the network topology. The framework will be open-source and written in Python and is to be available directly for download through standard installer packages. Many water management model developers are unfamiliar

  18. Supercritical fluid chromatography

    SciTech Connect

    Gere, D.R.

    1983-10-21

    Chromatographic separations with a supercritical fluid as the mobile phase were suggested more than 20 years ago. Availability of commercial hardware makes this technique more widely usable today. Many separations by this method are now carried out with supercritical carbon dioxide as the mobile phase and packed liquid-chromatography columns as the stationary phase. Although carbon dioxide has many practical advantages, including its near-ambient critical temperature and minimal interference with spectrometric detection, the use of other supercritical fluids or addition of modifiers to carbon dioxide may extend the applications of this technique. Some mixtures that are difficult to analyze by other chromatographic methods may be susceptible to separation by supercritical fluid chromatography. Mixtures that have been separated with supercritical carbon dioxide include resin acids with the empirical formula C/sub 20/H/sub 30/O/sub 2/ and ubiquinones from bacterial cell wall extracts of Legionella pneumophila. 60 refs., 8 figs.

  19. Calculation of liquid water-hydrate-methane vapor phase equilibria from molecular simulations.

    PubMed

    Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas; Wierzchowski, Scott; Walsh, Matthew R; Koh, Carolyn A; Sloan, E Dendy; Wu, David T; Sum, Amadeu K

    2010-05-01

    Monte Carlo simulation methods for determining fluid- and crystal-phase chemical potentials are used for the first time to calculate liquid water-methane hydrate-methane vapor phase equilibria from knowledge of atomistic interaction potentials alone. The water and methane molecules are modeled using the TIP4P/ice potential and a united-atom Lennard-Jones potential, respectively. The equilibrium calculation method for this system has three components, (i) thermodynamic integration from a supercritical ideal gas to obtain the fluid-phase chemical potentials, (ii) calculation of the chemical potential of the zero-occupancy hydrate system using thermodynamic integration from an Einstein crystal reference state, and (iii) thermodynamic integration to obtain the water and guest molecules' chemical potentials as a function of the hydrate occupancy. The three-phase equilibrium curve is calculated for pressures ranging from 20 to 500 bar and is shown to follow the Clapeyron behavior, in agreement with experiment; coexistence temperatures differ from the latter by 4-16 K in the pressure range studied. The enthalpy of dissociation extracted from the calculated P-T curve is within 2% of the experimental value at corresponding conditions. While computationally intensive, simulations such as these are essential to map the thermodynamically stable conditions for hydrate systems.

  20. The interplay between the paracetamol polymorphism and its molecular structures dissolved in supercritical CO2 in contact with the solid phase: In situ vibration spectroscopy and molecular dynamics simulation analysis.

    PubMed

    Oparin, Roman D; Moreau, Myriam; De Walle, Isabelle; Paolantoni, Marco; Idrissi, Abdenacer; Kiselev, Michael G

    2015-09-18

    The aim of this paper is to characterize the distribution of paracetamol conformers which are dissolved in a supercritical CO2 phase being in equilibrium with their corresponding crystalline form. The quantum calculations and molecular dynamics simulations were used in order to characterize the structure and analyze the vibration spectra of the paracetamol conformers in vacuum and in a mixture with CO2 at various thermodynamic state parameters (p,T). The metadynamics approach was applied to efficiently sample the various conformers of paracetamol. Furthermore, using in situ IR spectroscopy, the conformers that are dissolved in supercritical CO2 were identified and the evolution of the probability of their presence as a functions of thermodynamic condition was quantified while the change in the crystalline form of paracetamol have been monitored by DSC, micro IR and Raman techniques. The DSC analysis as well as micro IR and Raman spectroscopic studies of the crystalline paracetamol show that the subsequent heating up above the melting temperature of the polymorph I of paracetamol and the cooling down to room temperature in the presence of supercritical CO2 induces the formation of polymorph II. The in situ IR investigation shows that two conformers (Conf. 1 and Conf. 2) are present in the phase of CO2 while conformer 3 (Conf. 3) has a high probability to be present after re-crystallization.

  1. Thermal-hydraulic instabilities in natural circulation flow loops under supercritical conditions

    NASA Astrophysics Data System (ADS)

    Jain, Rachna

    In recent years, a growing interest has been generated in investigating the thermal hydraulics and flow stability phenomenon in supercritical natural circulation loops. These flow conditions are relevant to some of the innovative passive safety designs proposed for the Gen-IV Supercritical Water Reactor (SCWR) concepts. A computational model has been developed at UW Madison which provides a good basic simulation tool for the steady state and transient analysis of one dimensional natural circulation flow, and can be applied to conduct stability analysis. Several modifications and improvements were incorporated in an earlier numerical scheme before applying it to investigate the transient behavior of two experimental loops, namely, the supercritical water loop at UW-Madison and the supercritical carbon-dioxide (SCCO2) loop at Argonne National Laboratories. Although the model predicted development of instabilities for both SCW and SCCO2 loop which agrees with some previous work, the experiments conducted at SCCO2 loop exhibited stable behavior under similar conditions. To distinguish between numerical effects and physical processes, a linear stability approach has also been developed to investigate the stability characteristics associated with the natural circulation loop systems for various inlet conditions, input powers and geometries. The linear stability results for the SCW and SCCO2 loops exhibited differences with the corresponding transient simulations. This linear model also predicted the presence of instability in the SCCO 2 loop for certain high input powers contradictory to the experimental findings. Dimensionless parameters were proposed which would generalize the stability characteristics of the natural circulation flow loops under supercritical conditions.

  2. Resilience Simulation for Water, Power & Road Networks

    NASA Astrophysics Data System (ADS)

    Clark, S. S.; Seager, T. P.; Chester, M.; Eisenberg, D. A.; Sweet, D.; Linkov, I.

    2014-12-01

    The increasing frequency, scale, and damages associated with recent catastrophic events has called for a shift in focus from evading losses through risk analysis to improving threat preparation, planning, absorption, recovery, and adaptation through resilience. However, neither underlying theory nor analytic tools have kept pace with resilience rhetoric. As a consequence, current approaches to engineering resilience analysis often conflate resilience and robustness or collapse into a deeper commitment to the risk analytic paradigm proven problematic in the first place. This research seeks a generalizable understanding of resilience that is applicable in multiple disciplinary contexts. We adopt a unique investigative perspective by coupling social and technical analysis with human subjects research to discover the adaptive actions, ideas and decisions that contribute to resilience in three socio-technical infrastructure systems: electric power, water, and roadways. Our research integrates physical models representing network objects with examination of the knowledge systems and social interactions revealed by human subjects making decisions in a simulated crisis environment. To ensure a diversity of contexts, we model electric power, water, roadway and knowledge networks for Phoenix AZ and Indianapolis IN. We synthesize this in a new computer-based Resilient Infrastructure Simulation Environment (RISE) to allow individuals, groups (including students) and experts to test different network design configurations and crisis response approaches. By observing simulated failures and best performances, we expect a generalizable understanding of resilience may emerge that yields a measureable understanding of the sensing, anticipating, adapting, and learning processes that are essential to resilient organizations.

  3. Analysis of the aggregation of an anionic porphyrin with a cationic surfactant at the supercritical carbon dioxide-water interface using UV-visible external reflection spectrometry.

    PubMed

    Ohashi, Akira; Yamagata, Akihiro; Kim, Haeng-Boo

    2014-10-01

    An external reflection (ER) spectrometric device was developed to directly measure adsorbates at the supercritical carbon dioxide (SC-CO2)-water interface. The aggregation of diprotonated species of 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid (H4tpps(2-)) at the positively charged SC-CO2-water interface, prepared by adsorption by the cetyltrimethylammonium ion (CTA(+)), was studied using this device. Orientations of the H4tpps(2-) monomers and J-aggregates at the SC-CO2-water interface were assessed using s- and p-polarized external reflection (ER) spectra. It appeared that the porphyrin plane of the H4tpps(2-) monomer was nearly parallel to the SC-CO2-water interface, and that the long axis of the rod-like H4tpps(2-) J-aggregate was also nearly parallel to the interface. Dependence of the ER spectra on CTA(+) concentration and CO2 pressure were investigated, and the interfacial CTA(+) concentration was found to cause changes in the interfacial H4tpps(2-) species present. Increasing the CO2 pressure changed the interfacial species from the H4tpps(2-) monomer to the H4tpps(2-) J-aggregate because the interfacial CTA(+) concentration increased as the pressure increased. This suggests that the interfacial chemical species can be changed by controlling the pressure and temperature of the SC-CO2. This is the first report of direct measurements of the chemical species at the SC-CO2-water interface, as far as we know.

  4. Leaching of Au, Ag, and Pd from waste printed circuit boards of mobile phone by iodide lixiviant after supercritical water pre-treatment

    SciTech Connect

    Xiu, Fu-Rong; Qi, Yingying; Zhang, Fu-Shen

    2015-07-15

    Highlights: • We report a novel process for recovering Au, Ag, and Pd from waste PCBs. • The effect of SCWO on the leaching of Au, Ag, and Pd in waste PCBs was studied. • SCWO was highly efficient for enhancing the leaching of Au, Ag, and Pd. • The optimum leaching parameters for Au, Ag, and Pd in iodine–iodide were studied. - Abstract: Precious metals are the most attractive resources in waste printed circuit boards (PCBs) of mobile phones. In this work, an alternative process for recovering Au, Ag, and Pd from waste PCBs of mobile phones by supercritical water oxidation (SCWO) pre-treatment combined with iodine–iodide leaching process was developed. In the process, the waste PCBs of mobile phones were pre-treated in supercritical water, then a diluted hydrochloric acid leaching (HL) process was used to recovery the Cu, whose leaching efficiency was approximately 100%, finally the resulting residue was subjected to the iodine–iodide leaching process for recovering the Au, Ag, and Pd. Experimental results indicated that SCWO pre-treatment temperature, time, and pressure had significant influence on the Au, Ag, and Pd leaching from (SCWO + HL)-treated waste PCBs. The optimal SCWO pre-treatment conditions were 420 °C and 60 min for Au and Pd, and 410 °C and 30 min for Ag. The optimum dissolution parameters for Au, Pd, and Ag in (SCWO + HL)-treated PCBs with iodine–iodide system were leaching time of 120 min (90 min for Ag), iodine/iodide mole ratio of 1:5 (1:6 for Ag), solid-to-liquid ratio (S/L) of 1:10 g/mL (1:8 g/mL for Ag), and pH of 9, respectively. It is believed that the process developed in this study is environment friendly for the recovery of Au, Ag, and Pd from waste PCBs of mobile phones by SCWO pre-treatment combined with iodine–iodide leaching process.

  5. Modeling of flow and heat transfer for fluids at supercritical conditions

    NASA Astrophysics Data System (ADS)

    Gallaway, Tara

    2011-12-01

    The Supercritical Water Reactor (SCWR) has been proposed as one of the six Generation IV reactor design concepts under consideration. The key feature of the SCWR is that water at supercritical pressures is used as the reactor coolant. At supercritical pressures, the working fluid does not undergo phase change as it is heated, but rather the fluid properties experience dramatic variations throughout what is known as the pseudo-critical region. Highly nonuniform temperature and uid property distributions are expected in the reactor core, which will have a significant impact on turbulence and heat transfer as well as stability limits for future SCWRs. The goal of this work is to understand and predict the effects of these fluid property variations on turbulence and heat transfer throughout the reactor core and to predict the potential onset of dynamic instabilities. CO2 at supercritical conditions is included in the current study due in some part to its use as a viable simulant fluid in place of water for experimental studies. The use of CO2 at supercritical conditions as a reactor coolant has also gained popularity in recent years. Spline-type property models have been developed for both water and CO2 at supercritical pressures in order to include the property variations into a numerical solver. Turbulence and heat transfer models for fluids at supercritical conditions have been developed and implemented into the NPHASE-CMFD computer code. The results of predictions using the proposed models have been compared to experimental data from the Korea Atomic Energy Research Institute (KAERI) for various heat transfer regimes. While no model is without some deficiency, the Chien Low-Reynolds k -- epsilon model performs best at predicting the experimental data. A stability model has been developed and is presented in this dissertation as well. This model utilizes three different solution methods and tests the effects of inlet temperature, mass flow rate, local loss

  6. Electrochemistry in supercritical fluids

    PubMed Central

    Branch, Jack A.; Bartlett, Philip N.

    2015-01-01

    A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide–acetonitrile and supercritical HFCs. PMID:26574527

  7. Electrochemistry in supercritical fluids.

    PubMed

    Branch, Jack A; Bartlett, Philip N

    2015-12-28

    A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide-acetonitrile and supercritical HFCs.

  8. Supercritical Fluid Chromatography, Pressurized Liquid Extraction and Supercritical Fluid Extraction

    SciTech Connect

    Henry, Matthew C.; Yonker, Clement R.

    2006-06-15

    are regulated as food supplements but are intended to treat disease or maintain health. Antioxidants and beneficial lipid products are major examples in this category. The final major category consists of environmental applications, both as an extraction technique for environmental analysis, and as a possible remediation strategy for removing contaminants that would otherwise be too expensive to recover. Most of the work in this area has focused on non-polar compounds, such as polyaromatic hydrocarbons (PAHs) and poly-chlorinated biphenyls (PCB’s), where non-polar supercritical (SC) CO2 offers high extraction efficiencies. Co-solvent systems combining CO2 with one or more modifiers extend the utility of SC CO2 to polar and even ionic compounds. Supercritical water can extract polar compounds, and it has the additional advantage of combining extraction and destruction of contaminants via the supercritical water oxidation (SUWOX) process. Supercritical fluids are also useful in various niche applications. Fuel extraction, conversion, and analysis is one such application. Extraction of metals from various matrixes is also an area of continuing interest. The application of supercritical fluid (SCF) technology to production of nano-structured materials is a new area likely to see rapid growth in the next few years.

  9. Evidence for very tight sequestration of BTEX compounds in manufactured gas plant soils based on selective supercritical fluid extraction and soil/water partitioning.

    PubMed

    Hawthorne, Steven B; Miller, David J

    2003-08-15

    Benzene, toluene, ethylbenzene, o-, m-, and p-xylenes (BTEX), and polycyclic aromatic hydrocarbons (PAHs) were extracted from eight manufactured gas plant (MGP) soils from sites that had been abandoned for several decades. Supercritical fluid extraction (SFE) with pure carbon dioxide demonstrated the presence of BTEX compounds that were highly sequestered in both coal gas and oil gas MGP soils and soots. Benzene was generally the slowest compound to extract from all samples and was even more difficult to extract than most two- to five-ring PAHs found on the same samples. Since the solubility of benzene in carbon dioxide is 2-5 orders of magnitude higher than the solubilities of PAHs, these results demonstrate that benzene was more tightly sequestered than toluene, ethylbenzene, xylenes, or the multi-ring PAHs. Additional evidence for very tight binding was based on the fact that BTEX concentrations determined using either SFE or with methylene chloride sonication were much higher than those obtained by the U.S. EPA purge-and-trap method, especially for benzene (whose concentration was underestimated by as much as 1000-fold by the EPA method). However, soil/water desorption showed little benzene mobility, and Kd values for benzene were 1-2 orders of magnitude higher than those calculated based on literature sorption K(OC) values. These results indicate that environmentally relevant concentrations of benzene may be better represented by mild extraction methods than by methods capable of extracting tightly bound benzene. PMID:12953870

  10. A supercritical airfoil experiment

    NASA Technical Reports Server (NTRS)

    Mateer, G. G.; Seegmiller, H. L.; Hand, L. A.; Szodruck, J.

    1994-01-01

    The purpose of this investigation is to provide a comprehensive data base for the validation of numerical simulations. The objective of the present paper is to provide a tabulation of the experimental data. The data were obtained in the two-dimensional, transonic flowfield surrounding a supercritical airfoil. A variety of flows were studied in which the boundary layer at the trailing edge of the model was either attached or separated. Unsteady flows were avoided by controlling the Mach number and angle of attack. Surface pressures were measured on both the model and wind tunnel walls, and the flowfield surrounding the model was documented using a laser Doppler velocimeter (LDV). Although wall interference could not be completely eliminated, its effect was minimized by employing the following techniques. Sidewall boundary layers were reduced by aspiration, and upper and lower walls were contoured to accommodate the flow around the model and the boundary-layer growth on the tunnel walls. A data base with minimal interference from a tunnel with solid walls provides an ideal basis for evaluating the development of codes for the transonic speed range because the codes can include the wall boundary conditions more precisely than interference connections can be made to the data sets.

  11. Pore-scale Simulations of Capillary Trapping of Supercritical CO2 after Multiple Drainage and Imbibition Cycles

    NASA Astrophysics Data System (ADS)

    Schaap, M. G.

    2015-12-01

    Carbon capture and storage (CCS) of carbon dioxide emissions generated by production or combustion of fossil fuels is a technologically viable means to reduce the build-up of CO2 in the atmosphere and oceans. On a fundamental level, capillary trapping of scCO2 is a pore-scale process that shares mechanisms that are relevant, for example in oil recovery and remediation of NAPL-contaminated aquifers. Capillary trapping of scCO2 differs rather significantly from trapping of oil recovery and NAPL remediation in that the goal is to maximize the amount of NWP storage, whereas the objective of the other applications is to minimize the amount of residual NWP. This difference makes research into capillary trapping of scCO2 unique, but also complex because scCO2 phase properties (e.g. viscosity, density, and interfacial tension) exhibit large shifts with pressure and temperature which can strongly alter the trapping potential and efficiency. In this presentation we compare direct pore-scale observations of the Brine-CO2 drainage and imbibition process with lattice Boltzmann model simulations. The observations were conducted with the synchrotron-based x-ray microtomography facility at the Advanced Photon Source (APS) at Argonne National Laboratory using a novel x-ray compatible, high-pressure, elevated temperature setup. The "large" volumes (~1200 mm3; 6.3 mm diameter and 40 mm in length) were segmented into solid phase (Bentheimer Sandstone), Brine (KI, 1140 kg/m3) and scCO2. We will present LB simulations of small (64^3 voxels) and large sections of the scanned cores with a simple Shan-Chen-type model and a more advanced Equation of State-type model and compare model results to pressure and CO2 saturation levels that were observed for the CO2 invasion and Brine re-imbibition process. We will present results for the smaller sections under multiple drainage and imbibition cycles to investigate whether this will lead to enhanced trapping of scCO2 as found in earlier research.

  12. Direct numerical simulation of supercritical gas flow in complex nanoporous media: Elucidating the relationship between permeability and pore space geometry

    NASA Astrophysics Data System (ADS)

    Landry, C. J.; Prodanovic, M.; Eichhubl, P.

    2015-12-01

    Mudrocks and shales are currently a significant source of natural gas and understanding the basic transport properties of these formations is critical to predicting long-term production, however, the nanoporous nature of mudrocks presents a unique challenge. Mudrock pores are predominantly in the range of 1-100 nm, and within this size range the flow of gas at reservoir conditions will fall within the slip-flow and early transition-flow regime (0.001 < Kn < 1.0). Therefore, flow-rates will significantly deviate from Navier-Stokes predictions. Currently, the study of slip-flows is mostly limited to simple tube and channel geometries, but the geometry of mudrock pores is often sponge-like (organic matter) and/or platy (clays). Here we present a local effective viscosity lattice Boltzmann model (LEV-LBM) constructed for flow simulation in the slip- and early-transition flow regimes, adapted here for complex geometries. At the macroscopic scale the LEV-LBM is parameterized with local effective viscosities at each node to capture the variance of the mean free path of gas molecules in a bounded system. The LEV-LBM is first validated in simple tube geometries, where excellent agreement with linearized Boltzmann solutions is found for Knudsen numbers up to 1.0. The LEV-LBM is then employed to quantify the length effect on the apparent permeability of tubes, which suggests pore network modeling of flow in the slip and early-transition regime will result in overestimation unless the length effect is considered. Furthermore, the LEV-LBM is used to evaluate the predictive value of commonly measured pore geometry characteristics such as porosity, pore size distribution, and specific solid surface area for the calculation of permeability. We show that bundle of tubes models grossly overestimate apparent permeability, as well as underestimate the increase in apparent permeability with decreasing pressure as a result of excluding topology and pore shape from calculations.

  13. Simulating Water Markets to Help Design Water Rights Regimes

    NASA Astrophysics Data System (ADS)

    Harou, J. J.; Erfani, T.; Huskova, I.; Binions, O.

    2012-12-01

    In many catchments in England no further licenses are available from the Environmental regulator that provides them. The possibility of trading water between license holders has been recognized as a potentially effective and economically efficient strategy to mitigate increasing scarcity. Although trading licenses has been possible since several years, it very rarely happens (roughly 50 trades in 8 years). Several barriers to trade exist including lack of sufficient and prolonged scarcity, license-holder unwillingness to risk future renewal, likelihood license will be downgraded during a trade, duration of time required for approving a trade, etc. Regulators seek to make policy changes so that their inability to grant new licenses will not harm the local and national economy. What policy changes will most cost-effectively increase trading and allow it to effectively reduce the economic cost of scarcity events? A screening tool that could help evaluate problems and advantages of different regulatory solutions, and that could serve to test, assuming transaction costs can be quantified, their effect on trading under specific conditions would be useful. We propose such a water market simulator that predicts economically efficient pair-wise trade (between willing buyers and sellers) and represents the interaction of trades with natural hydrological flows, engineered infrastructure and a particular regulatory regime. The model emulates license-holders' willingness to engage in short-term trade transactions. In their initial form different 'agents' (license holders) are represented using an economic benefit function of water use which is supplemented by rules to represent behavioral or other characteristics of realistic system behavior. A case study based on the river Ouse basin (UK) is made to test the model. The model simulates the catchment weekly over several years considering reservoirs and pair-wise specific transaction costs. Several regulatory policies are tested

  14. The Water Budget of a Simulated Hurricane

    NASA Technical Reports Server (NTRS)

    Braun, S.

    2005-01-01

    The Pennsylvania State University-National Center for Atmospheric Research mesoscale model MM5 is used to simulate Hurricane Bonnie at high resolution (2-km spacing) in order to examine budgets of water vapor, cloud condensate, and precipitation. Virtually all budget terms are derived directly from the model (except for the effects of storm motion). The water vapor budget reveals that a majority of the condensation in the eyewall occurs in convective hot towers, while outside of the eyewall most of the condensation occurs in weaker updrafts, indicative of a larger role of stratiform precipitation processes. The ocean source of water vapor in the eyewall region is only a very small fraction of that transported inward in the boundary layer inflow or that condensed in the updrafts. In contrast, in the outer regions, the ocean vapor source is larger owing to the larger area, counters the drying effect of low-level subsidence, and enhances the moisture transported in toward the eyewall. In this mature storm, cloud condensate is consumed as rapidly as it is produced. Cloud water peaks at the top of the boundary layer and within the melting layer, where cooling from melting enhances condensation. Unlike in squall lines, in the hurricane, very little condensate produced in the eyewall convection is transported outward into the surrounding precipitation area. Most of the mass ejected outward is likely in the form of small snow particles that seed the outer regions and enhance in situ stratiform precipitation development through additional growth by vapor deposition and aggregation. We examine artificial source terms for cloud and precipitation mass associated with setting to zero negative mixing ratios that arise from numerical advection errors. Although small at any given point and time, the cumulative effect of these terms contributes an amount of mass equivalent to 13% of the total condensation and 15-20% of the precipitation. Thus, these terms must be accounted for to

  15. Establishment of Compact Chemical Process by Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Kawasaki, Shin-Ichiro; Suzuki, Akira

    The organic reaction using supercritical water is not only harmonization with earth environment, it was also expected the compatible possibility of high reaction rate and high reaction controllability that was not obtained by the liquid phase reaction or gas phase reaction. However, the conventional supercritical water reaction system was not enough to elicit performance of supercritical water due to side reaction or excessive decomposition during heating process or cooling process. The micro reactor which was characterized by the high heat exchange rate and high mixing performance was applied to the supercritical water reaction system. The micro mixer for the quick heating and quenching was developed. As a result, the innovative organic reaction and inorganic reaction were developed.

  16. Multidimensional Simulation Applied to Water Resources Management

    NASA Astrophysics Data System (ADS)

    Camara, A. S.; Ferreira, F. C.; Loucks, D. P.; Seixas, M. J.

    1990-09-01

    A framework for an integrated decision aiding simulation (IDEAS) methodology using numerical, linguistic, and pictorial entities and operations is introduced. IDEAS relies upon traditional numerical formulations, logical rules to handle linguistic entities with linguistic values, and a set of pictorial operations. Pictorial entities are defined by their shape, size, color, and position. Pictorial operators include reproduction (copy of a pictorial entity), mutation (expansion, rotation, translation, change in color), fertile encounters (intersection, reunion), and sterile encounters (absorption). Interaction between numerical, linguistic, and pictorial entities is handled through logical rules or a simplified vector calculus operation. This approach is shown to be applicable to various environmental and water resources management analyses using a model to assess the impacts of an oil spill. Future developments, including IDEAS implementation on parallel processing machines, are also discussed.

  17. Influence of particle design on oral absorption of poorly water-soluble drug in a silica particle-supercritical fluid system.

    PubMed

    Miura, Hiroshi; Kanebako, Makoto; Shirai, Hiroyuki; Nakao, Hiroshi; Inagi, Toshio; Terada, Katsuhide

    2011-01-01

    The physicochemical characteristics and oral absorption of a poorly water-soluble drug, K-832, adsorbed onto porous silica (Sylysia 350), were compared with those of K-832 adsorbed onto non-porous silica (Aerosil 200). K-832 and silica were treated with supercritical CO(2) (scCO(2)) to produce K-832-Sylysia 350 and K-832-Aerosil 200 formulations. Scanning electron microscopy, polarizing microscopy, powder X-ray diffraction, and differential scanning calorimetry results suggested that K-832 mainly existed in an amorphous state in both formulations. The specific surface area of both formulations was much larger than that of pure K-832 crystals. The dissolution rate of K-832 from both formulations was considerably greater than that from corresponding physical mixtures due to rapid wetting of the hydrophilic carrier surfaces and amorphous state, the dissolution from the K-832-Sylysia 350 formulation being the fastest. In vivo absorption tests on the two formulations indicated no significant differences in their peak concentration (C(max)) and the area under their plasma concentration-time curve (AUC), while the concentrations of K-832 in the K-832-Sylysia 350 formulation were significantly higher than those in the K-832-Aerosil 200 formulation 1 h and 1.5 h after administration of these formulations (p<0.05). This could be attributed to the different dispersion states of K-832 in the formulations due to their different three-dimensional structures (porous and non-porous). In physical stability tests, the amorphous drugs in both formulations were stable at room temperature for at least 14 months. Thus, the absorption of poorly water-soluble drugs could be greatly improved by adsorption onto porous silica using scCO(2).

  18. Simulations of asteroid impacts on water

    NASA Astrophysics Data System (ADS)

    Gisler, G. R.; Weaver, R. P.; Gittings, M. L.

    2002-05-01

    We have performed a series of two-dimensional and three-dimensional simulations of asteroid impacts into an ocean using the SAGE code from Los Alamos National Laboratory and Science Applications International Corporation. The SAGE code is a compressible Eulerian hydrodynamics code using continuous adaptive mesh refinement for following discontinuities with a fine grid while treating the bulk of the simulation more coarsely. We have used realistic equations of state for the atmosphere, sea water, the oceanic crust and mantle. In two dimensions, we threw asteroid impactors at 20 km/s vertically through an exponential atmosphere into a 5 km deep ocean. The impactors were composed of mantle material (3.32 g/cc) with diameters of 250m, 500m, and 1000m, chosen to compare with the previous work of Crawford and Mader. We also performed some runs with asteroids composed of iron (7.8 g/cc). Because some of the iron asteroids produced craters that penetrated the basalt crust, we included a layer of mantle material in all simulations. A vertical impact produces a large underwater cavity with nearly vertical walls followed by a collapse starting from the bottom and subsequent vertical jetting. Tsunamis up to a kilometer in initial height were generated and followed out to 100 km from the point of impact. In the three-dimensional run, an impactor of iron was thrown at 20 km/s at an angle of 45 degrees. Differences between this run and the vertical two-dimensional runs will be discussed.

  19. Novel Supercritical Carbon Dioxide Power Cycle Utilizing Pressured Oxy-combustion in Conjunction with Cryogenic Compression

    SciTech Connect

    Brun, Klaus; McClung, Aaron; Davis, John

    2014-03-31

    such as blade cooling. The overall technical readiness of the supercritical oxy-combustion cycle is TRL 2, Technology Concept, due to the maturity level of the supercritical oxy-combustor for solid fuels, and several critical supporting components, as identified in the Technical Gap Analysis. The supercritical oxycombustor for solid fuels operating at pressures near 100 atm is a unique component of the supercritical oxy-combustion cycle. In addition to the low TRL supercritical oxy-combustor, secondary systems were identified that would require adaptation for use with the supercritical oxycombustion cycle. These secondary systems include the high pressure pulverized coal feed, high temperature cyclone, removal of post-combustion particulates from the high pressure cyclone underflow stream, and micro-channel heat exchangers tolerant of particulate loading. Bench scale testing was utilized to measure coal combustion properties at elevated pressures in a CO{sub 2} environment. This testing included coal slurry preparation, visualization of coal injection into a high pressure fluid, and modification of existing test equipment to facilitate the combustion properties testing. Additional bench scale testing evaluated the effectiveness of a rotary atomizer for injecting a coal-water slurry into a fluid with similar densities, as opposed to the typical application where the high density fluid is injected into a low density fluid. The swirl type supercritical oxy-combustor was developed from initial concept to an advanced design stage through numerical simulation using FLUENT and Chemkin to model the flow through the combustor and provide initial assessment of the coal combustion reactions in the flow path. This effort enabled the initial combustor mechanical layout, initial pressure vessel design, and the conceptual layout of a pilot scale test loop. A pilot scale demonstration of the supercritical oxy-combustion cycle is proposed as the next step in the technology development

  20. In Situ Infrared Spectroscopic Study of Brucite Carbonation in Dry to Water-Saturated Supercritical Carbon Dioxide

    SciTech Connect

    Loring, John S.; Thompson, Christopher J.; Zhang, Changyong; Wang, Zheming; Schaef, Herbert T.; Rosso, Kevin M.

    2012-04-25

    In geologic carbon sequestration, while part of the injected carbon dioxide will dissolve into host brine, some will remain as neat to water saturated super critical CO2 (scCO2) near the well bore and at the caprock, especially in the short-term life cycle of the sequestration site. Little is known about the reactivity of minerals with scCO2 containing variable concentrations of water. In this study, we used high-pressure infrared spectroscopy to examine the carbonation of brucite (Mg(OH)2) in situ over a 24 hr reaction period with scCO2 containing water concentrations between 0% and 100% saturation, at temperatures of 35, 50, and 70 °C, and at a pressure of 100 bar. Little or no detectable carbonation was observed when brucite was reacted with neat scCO2. Higher water concentrations and higher temperatures led to greater brucite carbonation rates and larger extents of conversion to magnesium carbonate products. The only observed carbonation product at 35 °C was nesquehonite (MgCO3 • 3H2O). Mixtures of nesquehonite and magnesite (MgCO3) were detected at 50 °C, but magnesite was more prevalent with increasing water concentration. Both an amorphous hydrated magnesium carbonate solid and magnesite were detected at 70 °C, but magnesite predominated with increasing water concentration. The identity of the magnesium carbonate products appears strongly linked to magnesium water exchange kinetics through temperature and water availability effects.

  1. Supercritical waste oxidation of aqueous wastes

    NASA Technical Reports Server (NTRS)

    Modell, M.

    1986-01-01

    For aqueous wastes containing 1 to 20 wt% organics, supercritical water oxidation is less costly than controlled incineration or activated carbon treatment and far more efficient than wet oxidation. Above the critical temperature (374 C) and pressure (218 atm) of water, organic materials and gases are completely miscible with water. In supercritical water oxidation, organics, air and water are brought together in a mixture at 250 atm and temperatures above 400 C. Organic oxidation is initiated spontaneously at these conditions. The heat of combustion is released within the fluid and results in a rise in temperature 600 to 650 C. Under these conditions, organics are destroyed rapidly with efficiencies in excess of 99.999%. Heteroatoms are oxidized to acids, which can be precipitated out as salts by adding a base to the feed. Examples are given for process configurations to treat aqueous wastes with 10 and 2 wt% organics.

  2. Integrated Water Resources Simulation Model for Rural Community

    NASA Astrophysics Data System (ADS)

    Li, Y.-H.; Liao, W.-T.; Tung, C.-P.

    2012-04-01

    The purpose of this study is to develop several water resources simulation models for residence houses, constructed wetlands and farms and then integrate these models for a rural community. Domestic and irrigation water uses are the major water demand in rural community. To build up a model estimating domestic water demand for residence houses, the average water use per person per day should be accounted first, including water uses of kitchen, bathroom, toilet and laundry. On the other hand, rice is the major crop in the study region, and its productive efficiency sometimes depends on the quantity of irrigation water. The water demand can be estimated by crop water use, field leakage and water distribution loss. Irrigation water comes from rainfall, water supply system and reclaimed water which treated by constructed wetland. In recent years, constructed wetlands play an important role in water resources recycle. They can purify domestic wastewater for water recycling and reuse. After treating from constructed wetlands, the reclaimed water can be reused in washing toilets, watering gardens and irrigating farms. Constructed wetland is one of highly economic benefits for treating wastewater through imitating the processing mechanism of natural wetlands. In general, the treatment efficiency of constructed wetlands is determined by evapotranspiration, inflow, and water temperature. This study uses system dynamics modeling to develop models for different water resource components in a rural community. Furthermore, these models are integrated into a whole system. The model not only is utilized to simulate how water moves through different components, including residence houses, constructed wetlands and farms, but also evaluates the efficiency of water use. By analyzing the flow of water, the water resource simulation model can optimizes water resource distribution under different scenarios, and the result can provide suggestions for designing water resource system of a

  3. Prediction of cosolvent effect on solvation free energies and solubilities of organic compounds in supercritical carbon dioxide based on fully atomistic molecular simulations.

    PubMed

    Frolov, Andrey I; Kiselev, Michael G

    2014-10-01

    The solubility of organic compounds in supercritical fluids can be dramatically affected by addition of a suitable cosolvent (entrainer) at small concentrations. This makes the screening of the best-suited cosolvent an important task for the supercritical technology. The present study aims to improve our fundamental understanding of solvation in supercritical CO2 with cosolvents. We address the following questions: (1) How does the solvation free energy depend on the chemical class of an organic solute and the chemical nature of co-solvents? (2) Which intermolecular interactions determine the effect of a cosolvent on the solubility of organic compounds? We performed extensive calculations of solvation free energies of monofunctional organic molecules at infinite dilution in supercritical media by the Bennett's acceptance ratio method based on fully atomistic molecular dynamics sampling. Sixteen monofunctional organic molecules were solvated in pure sc-CO2 and sc-CO2 with addition of 6 molar % of cosolvents of different chemical nature: ethanol, acetone, and n-hexane. Cosolvent-induced solubility enhancement (CISE) factors were also calculated. It was found that formation of significant number of hydrogen bonds between a solute and cosolvent molecules leads to a profound solubility enhancement. The cosolvent effect is proportional to the number of hydrogen bonds. When polar cosolvents do not form hydrogen bonds with solutes, the CISE correlates with the dipole moment of solute molecules. However, the electrostatic interactions have a small impact on the solubility enhancement compared to hydrogen bonding. Addition of a nonpolar cosolvent, n-hexane, has a very little effect on the solvation Gibbs free energy of studied small organic molecules. The observed trends were discussed in line with available experimental data.

  4. Evaluation of the pressure-volume-temperature (PVT) data of water from experiments and molecular simulations since 1990

    NASA Astrophysics Data System (ADS)

    Guo, Tao; Hu, Jiawen; Mao, Shide; Zhang, Zhigang

    2015-08-01

    Since 1990, many groups of pressure-volume-temperature (PVT) data from experiments and molecular dynamics (MD) or Monte Carlo (MC) simulations have been reported for supercritical and subcritical water. In this work, fifteen groups of PVT data (253.15-4356 K and 0-90.5 GPa) are evaluated in detail with the aid of the highly accurate IAPWS-95 formulation. The evaluation gives the following results: (1) Six datasets are found to be of good accuracy. They include the simulated results based on SPCE potential above 100 MPa and those derived from sound velocity measurements, but the simulated results below 100 MPa have large uncertainties. (2) The data from measurements with a piston cylinder apparatus and simulations with an exp-6 potential contain large uncertainties and systematic deviations. (3) The other seven datasets show obvious systematic deviations. They include those from experiments with synthesized fluid inclusion techniques (three groups), measured velocities of sound (one group), and automated high-pressure dilatometer (one group) and simulations with TIP4P potential (two groups), where the simulated data based on TIP4P potential below 200 MPa have large uncertainties. (4) The simulated data but those below 1 GPa agree with each other within 2-3%, and mostly within 2%. The data from fluid inclusions show similar systematic deviations, which are less than 2-5%. The data obtained with automated high-pressure dilatometer and those derived from sound velocity measurements agree with each other within 0.3-0.6% in most cases, except for those above 10 GPa. In principle, the systematic deviations mentioned above, except for those of the simulated data below 1 GPa, can be largely eliminated or significantly reduced by appropriate corrections, and then the accuracy of the relevant data can be improved significantly. These are very important for the improvement of experiments or simulations and the refinement and correct use of the PVT data in developing

  5. High Density Thermal Energy Storage with Supercritical Fluids

    NASA Technical Reports Server (NTRS)

    Ganapathi, Gani B.; Wirz, Richard

    2012-01-01

    A novel approach to storing thermal energy with supercritical fluids is being investigated, which if successful, promises to transform the way thermal energy is captured and utilized. The use of supercritical fluids allows cost-affordable high-density storage with a combination of latent heat and sensible heat in the two-phase as well as the supercritical state. This technology will enhance penetration of several thermal power generation applications and high temperature water for commercial use if the overall cost of the technology can be demonstrated to be lower than the current state-of-the-art molten salt using sodium nitrate and potassium nitrate eutectic mixtures.

  6. DSMC simulation of Europa water vapor plumes

    NASA Astrophysics Data System (ADS)

    Berg, J. J.; Goldstein, D. B.; Varghese, P. L.; Trafton, L. M.

    2016-10-01

    A computational investigation of the physics of water vapor plumes on Europa was performed with a focus on characteristics relevant to observation and spacecraft mission operations. The direct simulation Monte Carlo (DSMC) method was used to model the plume expansion assuming a supersonic vent source. The structure of the plume was determined, including the number density, temperature, and velocity fields. The possibility of ice grain growth above the vent was considered and deemed probable for large (diameter > ∼20 m) vents at certain Mach numbers. Additionally, preexisting grains of three diameters (0.1, 1, 50 μm) were included and their trajectories examined. A preliminary study of photodissociation of H2O into OH and H was performed to demonstrate the behavior of daughter species. A set of vent parameters was evaluated including Mach number (Mach 2, 3, 5), reduced temperature as a proxy for flow energy loss to the region surrounding the vent, and mass flow rate. Plume behavior was relatively insensitive to these factors, with the notable exception of mass flow rate. With an assumed mass flow rate of ∼1000 kg/s, a canopy shock occurred and a maximum integrated line of sight column density of ∼1020 H2O molecules/m2 was calculated, comparing favorably with observation (Roth et al., 2014a).

  7. Supercritical synthesis of biodiesel.

    PubMed

    Bernal, Juana M; Lozano, Pedro; García-Verdugo, Eduardo; Burguete, M Isabel; Sánchez-Gómez, Gregorio; López-López, Gregorio; Pucheault, Mathieu; Vaultier, Michel; Luis, Santiago V

    2012-07-23

    The synthesis of biodiesel fuel from lipids (vegetable oils and animal fats) has gained in importance as a possible source of renewable non-fossil energy in an attempt to reduce our dependence on petroleum-based fuels. The catalytic processes commonly used for the production of biodiesel fuel present a series of limitations and drawbacks, among them the high energy consumption required for complex purification operations and undesirable side reactions. Supercritical fluid (SCF) technologies offer an interesting alternative to conventional processes for preparing biodiesel. This review highlights the advances, advantages, drawbacks and new tendencies involved in the use of supercritical fluids (SCFs) for biodiesel synthesis.

  8. Ultra supercritical steamside oxidation

    SciTech Connect

    Holcomb, Gordon R.; Covino, Bernard S., Jr.; Bullard, Sophie J.; Cramer, Stephen D.; Ziomek-Moroz, M.; Alman, David A.; Ochs, Thomas L.

    2004-01-01

    Ultra supercritical (USC) power plants offer the promise of higher efficiencies and lower emissions, which are part of the U.S. Department of Energy's Vision 21 goals. Most current coal power plants in the U.S. operate at a maximum steam temperature of 538 C. However, new supercritical plants worldwide are being brought into service with steam temperatures of up to 620 C. Vision 21 goals include steam temperatures of up to 760 C. This research examines the steamside oxidation of advanced alloys for use in USC systems. Emphasis is placed on alloys for high- and intermediate-pressure turbine sections. Initial results of this research are presented.

  9. Numerical Modeling of a Thermal-Hydraulic Loop and Test Section Design for Heat Transfer Studies in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    McGuire, Daniel

    A numerical tool for the simulation of the thermal dynamics of pipe networks with heat transfer has been developed with the novel capability of modeling supercritical fluids. The tool was developed to support the design and deployment of two thermal-hydraulic loops at Carleton University for the purpose of heat transfer studies in supercritical and near-critical fluids. First, the system was characterized based on its defining features; the characteristic length of the flow path is orders of magnitude larger than the other characteristic lengths that define the system's geometry; the behaviour of the working fluid in the supercritical thermodynamic state. An analysis of the transient thermal behaviour of the model's domains is then performed to determine the accuracy and range of validity of the modeling approach for simulating the transient thermal behaviour of a thermal-hydraulic loop. Preliminary designs of three test section geometries, for the purpose of heat transfer studies, are presented in support of the overall design of the Carleton supercritical thermal-hydraulic loops. A 7-rod-bundle, annular and tubular geometries are developed with support from the new numerical tool. Materials capable of meeting the experimental requirements while operating in supercritical water are determined. The necessary geometries to satisfy the experimental goals are then developed based on the material characteristics and predicted heat transfer behaviour from previous simulation results. An initial safety analysis is performed on the test section designs, where they are evaluated against the ASME Boiler, Pressure Vessel, and Pressure Piping Code standard, required for safe operation and certification.

  10. COMPARISONS OF SOXHLET EXTRACTION, PRESSURIZED LIQUID EXTRACTION, SUPERCRITICAL FLUID EXTRACTION, AND SUBCRITICAL WATER EXTRACTION FOR ENVIRONMENTAL SOLIDS: RECOVERY, SELECTIVITY, AND EFFECTS ON SAMPLE MATRIX. (R825394)

    EPA Science Inventory

    Extractions of a polycyclic aromatic hydrocarbon (PAH)-contaminated soil from a former manufactured gas plant site were performed with a Soxhlet apparatus (18 h), by pressurized liquid extraction (PLE) (50 min at 100°C), supercritical fluid extraction (SFE) (1 h at 150°...

  11. Formulation and make-up of simulated cement modified water

    SciTech Connect

    Gdowski, G.

    1997-09-12

    This procedure describes the formulation and make-up of Simulated Cement-Modified Waters (SCMW), which are aqueous solutions to be used for Activity E-20-50 Long-Term Corrosion Studies. These solutions simulate the changes to representative Yucca Mountain water chemistry because of prolonged contact with aged cement. The representative water was chosen as J-13 well water [Harrar, 1990]. J-13 well water is obtained from ground water that is in contact with the Topopah Spring tuff, which is the repository horizon rock.

  12. Hydraulic studies of drilling microbores with supercritical steam, nitrogen and carbon dioxide

    DOE Data Explorer

    Ken Oglesby

    2010-01-01

    Hydraulic studies of drilling microbores at various depths and with various hole sizes, tubing, fluids and rates showed theoretical feasibility. WELLFLO SIMULATIONS REPORT STEP 4: DRILLING 10,000 FT WELLS WITH SUPERCRITICAL STEAM, NITROGEN AND CARBON DIOXIDE STEP 5: DRILLING 20,000 FT WELLS WITH SUPERCRITICAL STEAM, NITROGEN AND CARBON DIOXIDE STEP 6: DRILLING 30,000 FT WELLS WITH SUPERCRITICAL STEAM, NITROGEN AND CARBON DIOXIDE Mehmet Karaaslan, MSI

  13. Launch Environment Water Flow Simulations Using Smoothed Particle Hydrodynamics

    NASA Technical Reports Server (NTRS)

    Vu, Bruce T.; Berg, Jared J.; Harris, Michael F.; Crespo, Alejandro C.

    2015-01-01

    This paper describes the use of Smoothed Particle Hydrodynamics (SPH) to simulate the water flow from the rainbird nozzle system used in the sound suppression system during pad abort and nominal launch. The simulations help determine if water from rainbird nozzles will impinge on the rocket nozzles and other sensitive ground support elements.

  14. Petrophysical core characterization at supercritical geothermal conditions

    NASA Astrophysics Data System (ADS)

    Kummerow, Juliane; Raab, Siegfried

    2015-04-01

    There is a growing scientific interest in the exploitation of supercritical geothermal reservoirs to increase the efficiency of geothermal power plants. The utilisation of geothermal energy requires in any case the detailed knowledge of the reservoir. In reservoir engineering, the characterisation of the geothermal system by electrical resistivity tomography (ERT) is a common geophysical exploration and monitoring strategy. For a realistic interpretation of the field measurements it is necessary to know both, the physical properties of the rock and those of the interacting fluid at defined temperature and pressure conditions. While there have been made great effort in determine the physical and chemical properties of water above its critical point (Tcritical = 374.21° C and pcritical = 221.2 bar), the influence of fluid-rock interactions on petrophysical properties in supercritical aqueous systems is nearly unknown. At supercritical conditions the viscosity of the fluid is low, which enhances the mass transfer and diffusion-controlled chemical reactions. This may have considerable effects on the porosity and hydraulic properties of a rock. To investigate high-enthalpy fluid-rock systems, in the framework of the EU-funded project IMAGE we have built a new percolation set-up, which allows for the measurement of electrical resistivity and permeability of rock samples at controlled supercritical conditions of aqueous fluids (pore pressure = 400 bar and a temperature = 400° C). First results will be presented.

  15. Thermally and Acoustically Driven Transport in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Hasan, Nusair Mohammed Ibn

    Supercritical fluids are fluids at temperature and pressure above their respective critical values. Such fluids are increasingly being used in power generation, refrigeration and chemical process industry. The objectives of the current research were to develop a fundamental understanding of the transport phenomena in near-critical supercritical fluids via high-resolution numerical simulations and careful experiments for improved design of industrial processes and applications that employ supercritical fluids. A set of synergistic experimental and numerical studies were proposed in this research. Four main focus areas under the broad spectrum of supercritical fluid transport were chosen -- (a) characterization of thermoacoustic transport, (b) interaction of thermoacoustic transport with natural convection, (c) characterization of acoustically augmented transport and (d) enhancement of mass transport using acoustic waves. A numerical model to simulate thermoacoustic convection in near-critical fluids was developed. In the computational model, the conservation equations were solved along with a real-fluid equation of state for supercritical fluid and variable thermo-physical properties. Thermoacoustic waves in near-critical carbon dioxide were also investigated experimentally on acoustic time scales using a fast response measurement system. The predicted results from the calculation and the measurements provide interesting details regarding the thermal transport mechanisms at near-critical states. The numerical model was applied to investigate the interaction of buoyancy driven flows with thermoacoustic convection in near-critical supercritical fluids. This model can be extensively used for studying the steady-state thermal transport and stability behavior of near-critical fluids. Mechanically driven acoustic waves in supercritical fluid generated by a vibrating wall in a cylindrical resonator were studied both numerically and experimentally. The simulations revealed

  16. Optimization of Polycyclic Aromatic Hydrocarbon (PAH) Extraction Efficiency Parameters for Sub- and Supercritical Water Extraction (SCWE) Instrument

    NASA Technical Reports Server (NTRS)

    Okada, Asahi A.

    2005-01-01

    Polycyclic aromatic hydrocarbons are a class of molecules composed of multiple, bonded benzene rings. As PAHS are believed to be present on Mars, positive confirmation of their presence on Mars is highly desirable. To extract PAHS, which have low volatility, a fluid extraction method is ideal, and one that does not utilize organic solvents is especially ideal for in situ instrumental analysis. The use of water as a solvent, which at subcritical pressures and temperatures is relatively non-Polar, has significant potential. As SCWE instruments have not yet been commercialized, all instruments are individually-built research prototypes: thus, initial efforts were intended to determine if extraction efficiencies on the JPL-built laboratory-scale SCWE instrument are comparable to differing designs built elsewhere. Samples of soil with certified reference concentrations of PAHs were extracted using SCWE as well as conventional Soxhlet extraction. Continuation of the work would involve extractions on JPL'S newer, portable SCWE instrument prototype to determine its efficiency in extracting PAHs.

  17. Study of the sequential conversion of citric to itaconic to methacrylic acid in near-critical and supercritical water

    SciTech Connect

    Carlsson, M.; Habenicht, C.; Kam, L.C.; Antal, M.J. Jr. ); Bian, N.; Cunningham, R.J.; Jones, M. Jr. . Dept. of Chemistry)

    1994-08-01

    Between 200 and 400 million lb of citric acid are produced annually in the USA by fermentation of molasses and other sugars using the microorganism Aspergillus niger. A lesser quantity of itaconic acid is manufactured by a similar technology using Aspergillus terreus. The recovery of citric acid from its fermentation broth via calcium salt precipitation is a costly, highly complex, sophisticated operation. USDOE estimates the cost of dry citric acid produced from a new plant to be about $0.59/lb, whereas the estimated cost of wet citric acid (in its fermentation broth) from a new plant is about $0.19/lb and from an old plant is about $0.15/lb. Citric acid rapidly reacts in hot (250 C), compressed (34.5 MPa) liquid water to form itaconic and citraconic acids with a combined selectivity that exceeds 90%. At higher temperatures (360 C), in the absence and presence of NaOH, itaconic acid decarboxylates to form methacrylic acid. The yield of methacrylic acid depends on the temperature, pH, and buffer strength of the medium, reaching a maximum of about 70% (by mole) of the itaconic acid feed. Conditions which favor the production of methacrylic acid also lead to the formation of its hydration product: hydroxyisobutyric acid. Under optimum conditions the combined yield of methacrylic acid and hydroxyisobutyric acid from itaconic acid exceeds 80%. Results are consistent with well-established dehydration and decarboxylation mechanisms.

  18. Does consideration of water routing affect simulated water and carbon dynamics in terrestrial ecosystems?

    NASA Astrophysics Data System (ADS)

    Tang, G.; Schneiderman, E. M.; Band, L. E.; Hwang, T.; Pierson, D. C.; Pradhanang, S. M.; Zion, M. S.

    2013-10-01

    The cycling of carbon in terrestrial ecosystems is closely coupled with the cycling of water. An important mechanism connecting ecological and hydrological processes in terrestrial ecosystems is lateral flow of water along landscapes. Few studies, however, have examined explicitly how consideration of water routing affects simulated water and carbon dynamics in terrestrial ecosystems. The objective of this study is to explore how consideration of water routing in a process-based hydroecological model affects simulated water and carbon dynamics. To achieve that end, we rasterized the regional hydroecological simulation systems (RHESSys) and employed the rasterized RHESSys (R-RHESSys) in a forested watershed. We performed and compared two contrasting simulations, one with and another without water routing. We found that R-RHESSys is able to correctly simulate major hydrological and ecological variables regardless of whether water routing is considered. When water routing was neglected, however, soil water table depth and saturation deficit were simulated to be smaller and spatially more homogeneous. As a result, evaporation, forest productivity and soil heterotrophic respiration also were simulated to be spatially more homogeneous compared to simulation with water routing. When averaged for the entire watershed, however, differences in simulated water and carbon fluxes are not significant between the two simulations. Overall, the study demonstrated that consideration of water routing enabled R-RHESSys to better capture our preconception of the spatial patterns of water table depth and saturation deficit across the watershed. Because the spatial pattern of soil moisture is fundamental to water efflux from land to the atmosphere, forest productivity and soil microbial activity, ecosystem and carbon cycle models, therefore, need to explicitly represent water routing in order to accurately quantify the magnitudes and patterns of water and carbon fluxes in terrestrial

  19. Water Clarity Simulant for K East Basin Filtration Testing

    SciTech Connect

    Schmidt, Andrew J.

    2006-01-20

    This document provides a simulant formulation intended to mimic the behavior of the suspended solids in the K East (KE) Basin fuel storage pool. The simulant will be used to evaluate alternative filtration apparatus to improve Basin water clarity and to possibly replace the existing sandfilter. The simulant was formulated based on the simulant objectives, the key identified parameters important to filtration, the composition and character of the KE Basin suspended sludge particles, and consideration of properties of surrogate materials.

  20. Simulation of water flow in terrestrial systems

    2008-12-18

    ParFlow is a parallel, variabley saturated groundwater flow code that is especially suitable for large scale problem. ParFlow simulates the three-dimensional saturated and variably saturated subsurface flow in heterogeneous porous media in three spatial dimensions. ParFlow's developemt and appkication has been on-ging for more than 10 uear. ParFlow has recently been extended to coupled surface-subsurface flow to enabel the simulation of hillslope runoff and channel routing in a truly integrated fashion. ParFlow simulates the three-dimensionalmore » varably saturated subsurface flow in strongly heterogeneous porous media in three spatial dimension.« less

  1. Supercritical fluid extraction of mercury species.

    PubMed

    Foy, G P; Pacey, G E

    2003-12-23

    Supercritical fluid extraction was used to recover organic and inorganic mercury species. Variations in pressure, water, methanol, and chelator create methods that allowed separation of inorganic from organic mercury species. When extracted using a compromised set of extraction conditions, the order of extraction was methyl, phenyl and inorganic mercury. For the individually optimized conditions, quantitative recoveries were observed. Level as low as 20 ppb were extracted and then determined using ICP.

  2. Extraction of iron and calcium from low rank coal by supercritical carbon dioxide with entrainers

    SciTech Connect

    Iwai, Y.; Okamoto, N.; Ohta, S.; Arai, Y.; Sakanishi, K.

    2007-03-15

    Iron and calcium were extracted from low rank coal with supercritical carbon dioxide and methanol, ethanol, acetic acid, acetyl acetone, ethanol and acetic acid, or acetyl acetone and water entrainers at 313.2 K and 15.0 MPa. The low rank coal used in this study was Berau coal from Indonesia. The addition of methanol, ethanol, or acetic acid entrainers in supercritical carbon dioxide showed very limited effect on enhancement of the recovery rates of Fe. The recovery rates of Fe from dried coal by supercritical carbon dioxide with acetyl acetone were low however, the addition of acetyl acetone with water in supercritical carbon dioxide remarkably enhanced the recovery rates of Fe. Water seems to play an important role in extracting Fe from coal with supercritical carbon dioxide and acetyl acetone. On the other hand, the extraction rates of Ca with supercritical carbon dioxide and water, methanol, ethanol, and acetyl acetone entrainers were very low. The addition of acetic acid with or without water in supercritical carbon dioxide slightly enhanced the recovery rates of Ca. The addition of acetic acid with ethanol in supercritical carbon dioxide remarkably enhanced the recovery rates of Ca. The effect of carbon dioxide flow rate and coal particle size on the recovery rates of Fe were examined. The recovery rate of Fe increased with increasing carbon dioxide flow rate and with decreasing particle size of the low rank coal.

  3. MICROBIOLOGICAL CHARACTERIZATION OF BACTERIA INHABITING A WATER DISTRIBUTION SYSTEM SIMULATOR

    EPA Science Inventory

    The impact of chlorination and chloramination treatments on heterotrophic bacteria (HB) and ammonia oxidizing bacteria (AOB) inhabiting a water distribution system simulator was investigated. Notable changes in bacterial densities were observed during this monitoring study. For e...

  4. Molecular Dynamics Simulations of Carbon Nanotubes in Water

    NASA Technical Reports Server (NTRS)

    Walther, J. H.; Jaffe, R.; Halicioglu, T.; Koumoutsakos, P.

    2000-01-01

    We study the hydrophobic/hydrophilic behavior of carbon nanotubes using molecular dynamics simulations. The energetics of the carbon-water interface are mainly dispersive but in the present study augmented with a carbon quadrupole term acting on the charge sites of the water. The simulations indicate that this contribution is negligible in terms of modifying the structural properties of water at the interface. Simulations of two carbon nanotubes in water display a wetting and drying of the interface between the nanotubes depending on their initial spacing. Thus, initial tube spacings of 7 and 8 A resulted in a drying of the interface whereas spacing of > 9 A remain wet during the course of the simulation. Finally, we present a novel particle-particle-particle-mesh algorithm for long range potentials which allows for general (curvilinear) meshes and "black-box" fast solvers by adopting an influence matrix technique.

  5. Cosmonaut Yuriy Onufriyenko simulates parachute drop into water

    NASA Technical Reports Server (NTRS)

    1994-01-01

    Cosmonaut Yuriy I. Onufriyenko (right), in the United States to participate in training for joint Russia - United States space missions, simulates a parachute drop into the water. The training took place in the JSC Weightless Environment Training Facility

  6. Supercritical solvent coal extraction

    NASA Technical Reports Server (NTRS)

    Compton, L. E. (Inventor)

    1984-01-01

    Yields of soluble organic extract are increased up to about 50% by the supercritical extraction of particulate coal at a temperature below the polymerization temperature for coal extract fragments (450 C.) and a pressure from 500 psig to 5,000 psig by the conjoint use of a solvent mixture containing a low volatility, high critical temperature coal dissolution catalyst such as phenanthrene and a high volatility, low critical temperature solvent such as toluene.

  7. Supercritical fluids cleaning

    SciTech Connect

    Butner, S.; Hjeresen, D.; Silva, L.; Spall, D.; Stephenson, R.

    1991-01-01

    This paper discusses a proposed multi-party research and development program which seeks to develop supercritical fluid cleaning technology as an alternative to existing solvent cleaning applications. While SCF extraction technology has been in commercial use for several years, the use of these fluids as cleaning agents poses several new technical challenges. Problems inherent in the commercialization of SCF technology include: the cleaning efficacy and compatibility of supercritical working fluids with the parts to be cleaned must be assessed for a variety of materials and components; process parameters and equipment design Have been optimized for extractive applications and must be reconsidered for application to cleaning; and co-solvents and entrainers must be identified to facilitate the removal of polar inorganic and organic contaminants, which are often not well solvated in supercritical systems. The proposed research and development program would address these issues and lead to the development and commercialization of viable SCF-based technology for precision cleaning applications. This paper provides the technical background, program scope, and delineates the responsibilities of each principal participant in the program.

  8. Experimental study of heat transfer in a 7-element bundle cooled with supercritical Freon-12

    SciTech Connect

    Richards, G.; Shelegov, A. S.; Kirillov, P. L.; Pioro, I. L.; Harvel, G.

    2012-07-01

    Experimental data on Supercritical-Water (SCW) cooled bundles are very limited. Major problems with performing such experiments are technical difficulties in testing and experimental costs at high pressures, temperatures and heat fluxes. Also, there are only a few SCW experimental setups currently in the world capable of providing data. Supercritical Water-cooled nuclear Reactors (SCWRs), as one of the six concepts of Generation IV reactors, cannot be designed without such data. Therefore, a preliminary approach uses modeling fluids such as carbon dioxide and refrigerants instead of water is practical. In particularly, experiments in supercritical refrigerant-cooled bundles can be used. One of the SC modeling fluids typically used is Freon-12 (R-12) with the critical pressure of 4.136 MPa and the critical temperature of 111.97 deg. C. These conditions correspond to the critical pressure of 22.064 MPa and critical temperature of 373.95 deg. C in water. A set of experimental data obtained at the Inst. of Physics and Power Engineering (IPPE, Obninsk, Russia) in a vertically-oriented bundle cooled with supercritical R-12 was analyzed. This dataset consisted of 20 runs. The test section was 7-element bundle installed in a hexagonal flow channel with 3 grid spacers. Data was collected at pressures of approximately 4.65 MPa for several different combinations of wall and bulk-fluid temperatures that were below, at, or above the pseudo-critical temperature. The values of mass flux were ranged from 400 to 1320 kg/m{sup 2}s and inlet temperatures ranged from 72 to 120 deg. C. The test section consisted of fuel-element simulators that were 9.5 mm in OD with the total heated length of about 1 m. Bulk-fluid and wall temperature profiles were recorded using a combination of 8 different thermocouples. Analysis of the data has confirmed that there are three distinct heat-transfer regimes for forced convention in supercritical fluids: 1) Normal heat transfer; 2) Deteriorated heat

  9. Coarse grained molecular dynamics simulation of nanoconfined water.

    PubMed

    Eslami, Hossein; Jaafari, Bahram; Mehdipour, Nargess

    2013-04-01

    A coarse-grained (CG) model for the simulation of nanoconfined water between graphene surfaces is developed. For this purpose, mixed-grained simulations are done, in which the two-site water model of Riniker and van Gunsteren [S. Riniker, W. F. van Gunsteren, J. Chem. Phys. 2011, 134, 084110] is simulated between atomistically resolved graphene surfaces. In the developed pure CG model, the two interaction sites of water and a combination of eight carbon atoms in the graphene surface are grouped together to construct water and surface CG beads. The pure CG potentials are constructed by iteratively matching the radial distribution functions and the density profiles of water beads in the pore with the corresponding mixed-grained distributions. The constructed potentials are shown to be pore-size transferable, capable of predicting structural properties of confined water over the whole range of pore sizes, ranging from extremely narrow pores to bulk water. The model is used to simulate a number of nanoconfined systems of a variety of pore sizes at constant temperature, constant parallel component of pressure, and constant surface area of the confining surfaces. The model is shown to predict the layering of water in contact with the surfaces, and the solvation force is in complete agreement with the mixed-grained model. It is shown that water molecules in the pore have smaller parallel diffusion coefficients compared to bulk water. Well-organized layers beside the surfaces are shown to have lower diffusion coefficients than diffuse layers. More information on the dynamics of water in the pore is obtained by calculating the rate of water exchange between slabs parallel to the surfaces. The time scale to achieve equilibrium for this process, depending on the pore width and on the degree of layering of water beside the surfaces, is a few nanoseconds in nanometric pores.

  10. SUPERCRITICAL FLUID EXTRACTION OF POLYCYCLIC AROMATIC HYDROCARBON MIXTURES FROM CONTAMINATED SOILS

    EPA Science Inventory

    Highly contaminated (with PAHs) topsoils were extracted with supercritical CO2 to determine the feasibility and mechanism of supercritical fluid extraction (SFE). Effect of SCF density, temperature, cosolvent type and amount, and of slurrying the soil with water were ...

  11. GROWTH OF HETROTROPHIC BIOFILMS IN A WATER DISTRIBUTION SYSTEM SIMULATOR

    EPA Science Inventory

    The U.S. EPA has designed and constructed a distribution system simulator (DSS) to evaluate factors which influence water quality within water distribution systems. Six individual 25 meter lengths of 15 cm diameter ductile iron pipe are arranged into loop configurations. Each lo...

  12. Simulation study of water/silicon oxide interface

    NASA Astrophysics Data System (ADS)

    Lorenz, Christian; Rempe, Susan; Stevens, Mark; Grest, Gary; Tsige, Mesfin

    2006-03-01

    The interaction of water with solid surfaces plays a crucial role in many phenomena. The water-silica interface is one of the typical systems encountered in technological and natural materials. Numerous technological applications of silica were found to rely on its specific surface properties. Large scale quantum mechanics (QM) and classical molecular dynamics (MD) simulations are used to study the molecular configurations and wetting properties of water at the interface of different silicon oxide surfaces. In order to understand how the surface coverage of silanols (-SiOH) affects the wetting behavior of the silica surfaces, both crystalline ((001) α-quartz (coverage 9.6 nm-2) and (100) β-cristobalite (7.8 nm-2)) and amorphous silica (5.0 nm-2) substrates have been studied. The binding energy of the water, the number of water molecules hydrogen-bonded to the surface and the configuration of the hydrogen-bonded water molecules are determined as a function of silanol coverage from QM simulations. The number of water molecules within a monolayer and the orientation of the water molecules within the monolayer and in the bulk are determined from MD simulations. Results from two classical force fields are compared to one another and to the relevant quantities from the QM simulations. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  13. Coiled tubing drilling with supercritical carbon dioxide

    DOEpatents

    Kolle , Jack J.

    2002-01-01

    A method for increasing the efficiency of drilling operations by using a drilling fluid material that exists as supercritical fluid or a dense gas at temperature and pressure conditions existing at a drill site. The material can be used to reduce mechanical drilling forces, to remove cuttings, or to jet erode a substrate. In one embodiment, carbon dioxide (CO.sub.2) is used as the material for drilling within wells in the earth, where the normal temperature and pressure conditions cause CO.sub.2 to exist as a supercritical fluid. Supercritical carbon dioxide (SC--CO.sub.2) is preferably used with coiled tube (CT) drilling equipment. The very low viscosity SC--CO.sub.2 provides efficient cooling of the drill head, and efficient cuttings removal. Further, the diffusivity of SC--CO.sub.2 within the pores of petroleum formations is significantly higher than that of water, making jet erosion using SC--CO.sub.2 much more effective than water jet erosion. SC--CO.sub.2 jets can be used to assist mechanical drilling, for erosion drilling, or for scale removal. A choke manifold at the well head or mud cap drilling equipment can be used to control the pressure within the borehole, to ensure that the temperature and pressure conditions necessary for CO.sub.2 to exist as either a supercritical fluid or a dense gas occur at the drill site. Spent CO.sub.2 can be vented to the atmosphere, collected for reuse, or directed into the formation to aid in the recovery of petroleum.

  14. Molecular dynamic simulations of the water absorbency of hydrogels.

    PubMed

    Ou, Xiang; Han, Qiang; Dai, Hui-Hui; Wang, Jiong

    2015-09-01

    A polymer gel can imbibe solvent molecules through surface tension effect. When the solvent happens to be water, the gel can swell to a large extent and forms an aggregate called hydrogel. The large deformation caused by such swelling makes it difficult to study the behaviors of hydrogels. Currently, few molecular dynamic simulation works have been reported on the water absorbing mechanism of hydrogels. In this paper, we first use molecular dynamic simulation to study the water absorbing mechanism of hydrogels and propose a hydrogel-water interface model to study the water absorbency of the hydrogel surface. Also, the saturated water content and volume expansion rate of the hydrogel are investigated by building a hydrogel model with different cross-linking degree and by comparing the water absorption curves under different temperatures. The sample hydrogel model used consists of Polyethylene glycol diglycidyl ether (PEGDGE) as epoxy and the Jeffamine, poly-oxy-alkylene-amines, as curing agent. The conclusions obtained are useful for further investigation on PEGDGE/Jeffamine hydrogel. Moreover, the simulation methods, including hydrogel-water interface modeling, we first propose are also suitable to study the water absorbing mechanism of other hydrogels. PMID:26271733

  15. Water management simulation games and the construction of knowledge

    NASA Astrophysics Data System (ADS)

    Rusca, M.; Heun, J.; Schwartz, K.

    2012-03-01

    In recent years simulations have become an important part of teaching activities. The reasons behind the popularity of simulation games are twofold. On the one hand, emerging theories on how people learn have called for an experienced-based learning approach. On the other hand, the demand for water management professionals has changed. Three important developments are having considerable consequences for water management programmes, which educate and train these professionals. These developments are the increasing emphasis on integration in water management, the characteristics and speed of reforms in the public sector and the shifting state-society relations in many countries. In response to these developments, demand from the labour market is oriented toward water professionals who need to have both a specialist in-depth knowledge in their own field, as well as the ability to understand and interact with other disciplines and interests. In this context, skills in negotiating, consensus building and working in teams are considered essential for all professionals. In this paper we argue that simulation games have an important role to play in (actively) educating students and training the new generation of water professionals to respond to the above-mentioned challenges. At the same time, simulations are not a panacea for learners and teachers. Challenges of using simulations games include the demands it places on the teacher. Setting up the simulation game, facilitating the delivery and ensuring that learning objectives are achieved requires considerable knowledge and experience as well as considerable time-inputs of the teacher. Moreover, simulation games usually incorporate a case-based learning model, which may neglect or underemphasize theories and conceptualization. For simulations to be effective they have to be embedded in this larger theoretical and conceptual framework. Simulations, therefore, complement rather than substitute traditional teaching methods.

  16. Water management simulation games and the construction of knowledge

    NASA Astrophysics Data System (ADS)

    Rusca, M.; Heun, J.; Schwartz, K.

    2012-08-01

    In recent years, simulations have become an important part of teaching activities. The reasons behind the popularity of simulation games are twofold. On the one hand, emerging theories on how people learn have called for an experienced-based learning approach. On the other hand, the demand for water management professionals has changed. Three important developments are having considerable consequences for water management programmes, which educate and train these professionals. These developments are the increasing emphasis on integration in water management, the characteristics and speed of reforms in the public sector and the shifting state-society relations in many countries. In response to these developments, demand from the labour market is oriented toward water professionals who need to have both a specialist in-depth knowledge in their own field, as well as the ability to understand and interact with other disciplines and interests. In this context, skills in negotiating, consensus building and working in teams are considered essential for all professionals. In this paper, we argue that simulation games have an important role to play in (actively) educating students and training the new generation of water professionals to respond to the above-mentioned challenges. At the same time, simulations are not a panacea for learners and teachers. Challenges of using simulation games include the demands it places on the teacher. Setting up the simulation game, facilitating the delivery and ensuring that learning objectives are achieved require considerable knowledge and experience as well as considerable time-inputs of the teacher. Moreover, simulation games usually incorporate a case-based learning model, which may neglect or underemphasize theories and conceptualizations. For simulations to be effective, they have to be embedded in this larger theoretical and conceptual framework. Simulations, therefore, complement rather than substitute traditional teaching

  17. Water as a lubricant for graphite: a computer simulation study.

    PubMed

    Pertsin, Alexander; Grunze, Michael

    2006-09-21

    The phase state and shear behavior of water confined between parallel graphite sheets are studied using the grand canonical Monte Carlo technique and TIP4P model for water. In describing the water-graphite interaction, two orientation-dependent potentials are tried. Both potentials are fitted to many-body polarizable model predictions for the binding energy and the equilibrium conformation of the water-graphite complex [K. Karapetian and K. D. Jordan in Water in Confining Geometries, edited by V. Buch and J. P. Devlin (Springer, Berlin, 2003), pp. 139-150]. Based on the simulation results, the property of water to serve as a lubricant between the rubbing surfaces of graphitic particles is associated, first, with the capillary condensation of water occurring in graphitic pores of monolayer width and, second, with the fact that the water monolayer compressed between graphite particles retains a liquidlike structure and offers only slight resistance to shear.

  18. Water balance measurements and simulations of maize plants on lysimeters

    NASA Astrophysics Data System (ADS)

    Heinlein, Florian; Biernath, Christian; Klein, Christian; Thieme, Christoph; Priesack, Eckart

    2016-04-01

    In Central Europe expected major aspects of climate change are a shift of precipitation events and amounts towards winter months, and the general increase of extreme weather events like heat waves or summer droughts. This will lead to strongly changing regional water availability and will have an impact on future crop growth, water use efficiency and yields. Therefore, to estimate future crop yields by growth models accurate descriptions of transpiration as part of the water balance is important. In this study, maize was grown on weighing lysimeters (sowdate: 24 April 2013). Transpiration was determined by sap flow measurement devices (ICT International Pty Ltd, Australia) using the Heat-Ratio-Method: two temperature probes, 0.5 cm above and below a heater, detect a heat pulse and its speed which allows the calculation of sap flow. Water balance simulations were executed with different applications of the model framework Expert-N. The same pedotransfer and hydraulic functions and the same modules to simulate soil water flow, soil heat and nitrogen transport, nitrification, denitrification and mineralization were used. Differences occur in the chosen potential evapotranspiration ETpot (Penman-Monteith ASCE, Penman-Monteith FAO, Haude) and plant modules (SPASS, CERES). In all simulations ETpot is separated into a soil and a plant part using the leaf are index (LAI). In a next step, these parts are reduced by soil water availability. The sum of these parts is the actual evapotranspiration ETact which is compared to the lysimeter measurements. The results were analyzed from Mid-August to Mid-September 2013. The measured sap flow rates show clear diurnal cycles except on rainy days. The SPASS model is able to simulate these diurnal cycles, overestimates the measurements on rainy days and at the beginning of the analyzed period, and underestimates transpiration on the other days. The main reason is an overestimation of potential transpiration Tpot due to too high

  19. Basic Engineering Research for D and D of R Reactor Storage Pond Sludge: Electrokinetics, Carbon Dioxide Extraction, and Supercritical Water Oxidation

    SciTech Connect

    Michael A. Matthews; David A. Bruce,; Thomas A. Davis; Mark C. Thies; John W. Weidner; Ralph E. White

    2002-04-01

    Large quantities of mixed low level waste (MLLW) that fall under the Toxic Substances Control Act (TSCA) exist and will continue to be generated during D and D operations at DOE sites across the country. The standard process for destruction of MLLW is incineration, which has an uncertain future. The extraction and destruction of PCBs from MLLW was the subject of this research Supercritical Fluid Extraction (SFE) with carbon dioxide with 5% ethanol as cosolvent and Supercritical Waster Oxidation (SCWO) were the processes studied in depth. The solid matrix for experimental extraction studies was Toxi-dry, a commonly used absorbent made from plant material. PCB surrogates were 1.2,4-trichlorobenzene (TCB) and 2-chlorobiphenyl (2CBP). Extraction pressures of 2,000 and 4,000 psi and temperatures of 40 and 80 C were studied. Higher extraction efficiencies were observed with cosolvent and at high temperature, but pressure little effect. SCWO treatment of the treatment of the PCB surrogates resulted in their destruction below detection limits.

  20. Simulated Water Adsorption Isotherms in Hydrophilic and Hydrophobic Cylinderical Nanopores

    SciTech Connect

    StrioloDr., A; Naicker, P. K.; Chialvo, Ariel A; Cummings, Peter T; Gubbins, Dr. K. E.

    2005-01-01

    Grand canonical Monte Carlo simulations are performed to study the adsorption of water in single-walled carbon nanotubes (SWCNs). At room temperature the resulting adsorption isotherms in (10:10) and wider SWCNs are characterized by negligible amount of water uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption/desorption hysteresis loops. The width of these loops decreases as pore diameter narrows. Adsorption/desorption hysteresis loops are not observed for water adsorption in (6:6) SWCNs. When the nanotubes are doped with small amounts of oxygenated sites it is possible to obtain adsorption isotherms in which the water uptake increases gradually as the pressure increases. Simulated X-ray diffraction patterns for confined water are also reported.

  1. Ecologic simulation of warm water aquaculture ponds

    SciTech Connect

    Piedrahitu, R.H.; Brune, D.E.; Orlob, G.T.; Tchobanoglous, G.

    1983-06-01

    A generalized ecologic model of a fertilized warm-water aquaculture pond is under development. The model is intended to represent the pond ecosystem and its response to external stimuli. The major physical, chemical and biological processes and parameters are included in the model. A total of 19 state variables are included in the model (dissolved oxygen, alkalinity, pH, ammonia, phytoplankton, etc.). The model is formulated as a system of mass balance equations. The equations include stimulatory and inhibitory effects of environmental parameters on processes taking place in the pond. The equations may be solved for the entire growth period and diurnal as well as seasonal fluctuations may be identified. The ultimate objective of the model is to predict the fish biomass that can be produced in a pond under a given set of environmental conditions.

  2. Molecular dynamics simulations of water droplets on polymer surfaces.

    PubMed

    Hirvi, Janne T; Pakkanen, Tapani A

    2006-10-14

    Molecular dynamics simulations were used to study the wetting of polymer surfaces with water. Contact angles of water droplets on crystalline and two amorphous polyethylene (PE) and poly(vinyl chloride) (PVC) surfaces were extracted from atomistic simulations. Crystalline surfaces were produced by duplicating the unit cell of an experimental crystal structure, and amorphous surfaces by pressing the bulk polymer step by step at elevated temperature between two repulsive grid surfaces to a target density. Different-sized water droplets on the crystalline PE surface revealed a slightly positive line tension on the order of 10(-12)-10(-11) N, whereas droplets on crystalline PVC did not yield a definite line tension. Microscopic contact angles produced by the simple point charge (SPC) water model were mostly a few degrees smaller than those produced by the extended SPC model, which, as the model with lowest bulk energy, presents an upper boundary for contact angles. The macroscopic contact angle for the SPC model was 94 degrees on crystalline PVC and 113 degrees on crystalline PE. Amorphicity of the surface increased the water contact angle on PE but decreased it on PVC, for both water models. If the simulated contact angles on crystalline and amorphous surfaces are combined in proportion to the crystallinity of the polymer in question, simulated values in relatively good agreement with measured values are obtained.

  3. Chemical durability of simulated nuclear glasses containing water

    SciTech Connect

    Li, H.; Tomozawa, M.

    1995-04-01

    The chemical durability of simulated nuclear waste glasses having different water contents was studied. Results from the product consistency test (PCT) showed that glass dissolution increased with water content in the glass. This trend was not observed during MCC-1 testing. This difference was attributed to the differences in reactions between glass and water. In the PCT, the glass network dissolution controlled the elemental releases, and water in the glass accelerated the reaction rate. On the other hand, alkali ion exchange with hydronium played an important role in the MCC-1. For the latter, the amount of water introduced into a leached layer from ion-exchange was found to be much greater than that of initially incorporated water in the glass. Hence, the initial water content has no effect on glass dissolution as measured by the MCC-1 test.

  4. Spatial and dynamic simulation for Miyun Reservoir waters in Beijing.

    PubMed

    Jia, H; Cheng, S

    2002-01-01

    In order to assist the water quality management in Miyun Reservoir, a spatial and dynamic simulation model system was built. In the model system, GIS was integrated with the WASP5 model. The integrated model system was then calibrated and verified in different sets of field data. The result showed that the integrated model system could characterize the Miyun Reservoir waters. Two scenarios were then designed and analyzed with the integrated model system. It was indicated that the water quality would improve if the cage fishery was banned, the algae blooms might occur in Miyun Reservoir if the low water stage ocurred but loads remained unchanged.

  5. Thermodynamics and kinetics of ion speciation in supercritical aqueous solutions: A molecular based study

    SciTech Connect

    Chialvo, A.A.; Cummings, P.T. |; Simonson, J.M.; Mesmer, R.E.

    1997-05-01

    Molecular simulation of infinitely dilute NaCl aqueous solutions are performed to study the Na{sup +}/Cl{sup -} ion pairing in a polarizable and a nonpolarizable solvent at supercritical conditions. The Simple Point Charge, Pettitt-Rossky, and Fumi-Tosi models for the water-water, ion-water, and ion-ion interactions are used in determining the degree of dissociation, its temperature and density dependence, and the kinetics of the interconversion between ion-pair configurations in a nonpolarizable medium. To assess the effect of the solvent polarizability on the stability of the ion-pair configurations, we replace the Simple Point Charge by the Polarizable Point Charge water model and determine the anion-cation potential of mean force at T{sub r}=1.20 and {rho}{sub r}=1.5.

  6. Understanding water: Molecular dynamics simulations of solubilized and crystallized myoglobin

    SciTech Connect

    Wei Gu; Garcia, A.E.; Schoenborn, B.P.

    1994-12-31

    Molecular dynamics simulations were performed on CO myoglobin to evaluate the stability of the bound water molecules as determined in a neutron diffraction analysis. The myoglobin structure derived from the neutron analysis provided the starting coordinate set used in the simulations. The simulations show that only a few water molecules are tightly bound to protein atoms, while most solvent molecules are labile, breaking and reforming hydrogen bonds. Comparison between myoglobin in solution and in a single crystal highlighted some of the packing effects on the solvent structure and shows that water solvent plays an indispensable role in protein dynamics and structural stability. The described observations explain some of the differences in the experimental results of protein hydration as observed in NMR, neutron and X-ray diffraction studies.

  7. Simulations of ion channels--watching ions and water move.

    PubMed

    Sansom, M S; Shrivastava, I H; Ranatunga, K M; Smith, G R

    2000-08-01

    Ion channels mediate electrical excitability in neurons and muscle. Three-dimensional structures for model peptide channels and for a potassium (K+) channel have been combined with computer simulations to permit rigorous exploration of structure-function relations of channels. Water molecules and ions within transbilayer pores tend to diffuse more slowly than in bulk solutions. In the narrow selectivity filter of the bacterial K+ channel (i.e. the region of the channel that discriminates between different species of ions) a column of water molecules and K+ ions moves in a concerted fashion. By combining atomistic simulations (in which all atoms of the channel molecule, water and ions are treated explicitly) with continuum methods (in which the description of the channel system is considerably simplified) it is possible to simulate some of the physiological properties of channels.

  8. Structure and dynamics of complex liquid water: Molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    S, Indrajith V.; Natesan, Baskaran

    2015-06-01

    We have carried out detailed structure and dynamical studies of complex liquid water using molecular dynamics simulations. Three different model potentials, namely, TIP3P, TIP4P and SPC-E have been used in the simulations, in order to arrive at the best possible potential function that could reproduce the structure of experimental bulk water. All the simulations were performed in the NVE micro canonical ensemble using LAMMPS. The radial distribution functions, gOO, gOH and gHH and the self diffusion coefficient, Ds, were calculated for all three models. We conclude from our results that the structure and dynamical parameters obtained for SPC-E model matched well with the experimental values, suggesting that among the models studied here, the SPC-E model gives the best structure and dynamics of bulk water.

  9. How processing digital elevation models can affect simulated water budgets

    USGS Publications Warehouse

    Kuniansky, E.L.; Lowery, M.A.; Campbell, B.G.

    2009-01-01

    For regional models, the shallow water table surface is often used as a source/sink boundary condition, as model grid scale precludes simulation of the water table aquifer. This approach is appropriate when the water table surface is relatively stationary. Since water table surface maps are not readily available, the elevation of the water table used in model cells is estimated via a two-step process. First, a regression equation is developed using existing land and water table elevations from wells in the area. This equation is then used to predict the water table surface for each model cell using land surface elevation available from digital elevation models (DEM). Two methods of processing DEM for estimating the land surface for each cell are commonly used (value nearest the cell centroid or mean value in the cell). This article demonstrates how these two methods of DEM processing can affect the simulated water budget. For the example presented, approximately 20% more total flow through the aquifer system is simulated if the centroid value rather than the mean value is used. This is due to the one-third greater average ground water gradients associated with the centroid value than the mean value. The results will vary depending on the particular model area topography and cell size. The use of the mean DEM value in each model cell will result in a more conservative water budget and is more appropriate because the model cell water table value should be representative of the entire cell area, not the centroid of the model cell.

  10. Adaptive resolution simulation of an atomistic protein in MARTINI water

    SciTech Connect

    Zavadlav, Julija; Melo, Manuel Nuno; Marrink, Siewert J.; Praprotnik, Matej

    2014-02-07

    We present an adaptive resolution simulation of protein G in multiscale water. We couple atomistic water around the protein with mesoscopic water, where four water molecules are represented with one coarse-grained bead, farther away. We circumvent the difficulties that arise from coupling to the coarse-grained model via a 4-to-1 molecule coarse-grain mapping by using bundled water models, i.e., we restrict the relative movement of water molecules that are mapped to the same coarse-grained bead employing harmonic springs. The water molecules change their resolution from four molecules to one coarse-grained particle and vice versa adaptively on-the-fly. Having performed 15 ns long molecular dynamics simulations, we observe within our error bars no differences between structural (e.g., root-mean-squared deviation and fluctuations of backbone atoms, radius of gyration, the stability of native contacts and secondary structure, and the solvent accessible surface area) and dynamical properties of the protein in the adaptive resolution approach compared to the fully atomistically solvated model. Our multiscale model is compatible with the widely used MARTINI force field and will therefore significantly enhance the scope of biomolecular simulations.

  11. Pump-stopping water hammer simulation based on RELAP5

    NASA Astrophysics Data System (ADS)

    Yi, W. S.; Jiang, J.; Li, D. D.; Lan, G.; Zhao, Z.

    2013-12-01

    RELAP5 was originally designed to analyze complex thermal-hydraulic interactions that occur during either postulated large or small loss-of-coolant accidents in PWRs. However, as development continued, the code was expanded to include many of the transient scenarios that might occur in thermal-hydraulic systems. The fast deceleration of the liquid results in high pressure surges, thus the kinetic energy is transformed into the potential energy, which leads to the temporary pressure increase. This phenomenon is called water hammer. Generally water hammer can occur in any thermal-hydraulic systems and it is extremely dangerous for the system when the pressure surges become considerably high. If this happens and when the pressure exceeds the critical pressure that the pipe or the fittings along the pipeline can burden, it will result in the failure of the whole pipeline integrity. The purpose of this article is to introduce the RELAP5 to the simulation and analysis of water hammer situations. Based on the knowledge of the RELAP5 code manuals and some relative documents, the authors utilize RELAP5 to set up an example of water-supply system via an impeller pump to simulate the phenomena of the pump-stopping water hammer. By the simulation of the sample case and the subsequent analysis of the results that the code has provided, we can have a better understand of the knowledge of water hammer as well as the quality of the RELAP5 code when it's used in the water-hammer fields. In the meantime, By comparing the results of the RELAP5 based model with that of other fluid-transient analysis software say, PIPENET. The authors make some conclusions about the peculiarity of RELAP5 when transplanted into water-hammer research and offer several modelling tips when use the code to simulate a water-hammer related case.

  12. Systematic evaluation of bundled SPC water for biomolecular simulations.

    PubMed

    Gopal, Srinivasa M; Kuhn, Alexander B; Schäfer, Lars V

    2015-04-01

    In bundled SPC water models, the relative motion of groups of four water molecules is restrained by distance-dependent potentials. Bundled SPC models have been used in hybrid all-atom/coarse-grained (AA/CG) multiscale simulations, since they enable to couple atomistic SPC water with supra-molecular CG water models that effectively represent more than a single water molecule. In the present work, we systematically validated and critically tested bundled SPC water models as solvent for biomolecular simulations. To that aim, we investigated both thermodynamic and structural properties of various biomolecular systems through molecular dynamics (MD) simulations. Potentials of mean force of dimerization of pairs of amino acid side chains as well as hydration free energies of single side chains obtained with bundled SPC and standard (unrestrained) SPC water agree closely with each other and with experimental data. Decomposition of the hydration free energies into enthalpic and entropic contributions reveals that in bundled SPC, this favorable agreement of the free energies is due to a larger degree of error compensation between hydration enthalpy and entropy. The Ramachandran maps of Ala3, Ala5, and Ala7 peptides are similar in bundled and unrestrained SPC, whereas for the (GS)2 peptide, bundled water leads to a slight overpopulation of extended conformations. Analysis of the end-to-end distance autocorrelation times of the Ala5 and (GS)2 peptides shows that sampling in more viscous bundled SPC water is about two times slower. Pronounced differences between the water models were found for the structure of a coiled-coil dimer, which is instable in bundled SPC but not in standard SPC. In addition, the hydration of the active site of the serine protease α-chymotrypsin depends on the water model. Bundled SPC leads to an increased hydration of the active site region, more hydrogen bonds between water and catalytic triad residues, and a significantly slower exchange of water

  13. Simulations of Water Migration in the Lunar Exosphere

    NASA Astrophysics Data System (ADS)

    Hurley, D.; Benna, M.; Mahaffy, P. R.; Elphic, R. C.; Goldstein, D. B.

    2014-12-01

    We perform modeling and analysis of water in the lunar exosphere. There were two controlled experiments of water interactions with the surface of the Moon observed by the Lunar Atmosphere and Dust Environment Explorer (LADEE) Neutral Mass Spectrometer (NMS). The Chang'e 3 landing on the Moon on 14 Dec 2013 putatively sprayed ~120 kg of water on the surface on the Moon at a mid-morning local time. Observations by LADEE near the noon meridian on six of the orbits in the 24 hours following the landing constrain the propagation of water vapor. Further, on 4 Apr 2014, LADEE's Orbital Maintenance Manuever (OMM) #21 sprayed the surface of the Moon with an estimated 0.73 kg of water in the pre-dawn sector. Observations of this maneuver and later in the day constrain the adsorption and release at dawn of adsorbed materials. Using the Chang'e 3 exhaust plume and LADEE's OMM-21 as control experiments, we set limits to the adsorption and thermalization of water with lunar regolith. This enables us to predict the efficiency of the migration of water as a delivery mechanism to the lunar poles. Then we simulate the migration of water through the lunar exosphere using the rate of sporadic inputs from meteoritic sources (Benna et al., this session). Simulations predict the amount of water adsorbed to the surface of the Moon and the effective delivery rate to the lunar polar cold traps.

  14. Computer simulation on the water/platinum interface

    SciTech Connect

    Spohr, E. )

    1989-08-10

    A molecular model for the water/platinum interface has been devised. It includes the surface corrugation of the metal and orientationally anisotropic water-metal interactions obtained from quantum chemical cluster calculations. Barriers for the surface diffusion and for the reorientation of a single water molecule on the quadratic (100) face of the face-centered-cubic platinum crystal are discussed. The flexible Bopp-Jancso-Heinzinger water model describes the water-water interactions, and the platinum-platinum interactions are described by a single force constant. Molecular dynamics simulations of a water lamina confined by (100) platinum surfaces have been performed using these interaction potentials. The structure is discussed on the basis of one-particle density profiles and solvent pair correlation functions. The surface-induced structural inhomogeneity ranges up to distances of 10 {angstrom}. In the center of the lamina water properties are bulklike. Hydrogen bonding in the vicinity of the interface is only slightly reduced relative to the bulk. The orientational structure of water is strongly influenced by water-water interactions and is considerably different from the preferential orientation according to the water-platinum interaction potential. It leads to a dipolar potential drop across the interface of 1.1 V.

  15. Supercritical waste oxidation pump investigation

    SciTech Connect

    Thurston, G.; Garcia, K.

    1993-02-01

    This report investigates the pumping techniques and pumping equipment that would be appropriate for a 5,000 gallon per day supercritical water oxidation waste disposal facility. The pumps must boost water, waste, and additives from atmospheric pressure to approximately 27.6 MPa (4,000 psia). The required flow ranges from 10 gpm to less than 0.1 gpm. For the higher flows, many commercial piston pumps are available. These pumps have packing and check-valves that will require periodic maintenance; probably at 2 to 6 month intervals. Several commercial diaphragm pumps were also discovered that could pump the higher flow rates. Diaphragm pumps have the advantage of not requiring dynamic seals. For the lower flows associated with the waste and additive materials, commercial diaphragm pumps. are available. Difficult to pump materials that are sticky, radioactive, or contain solids, could be injected with an accumulator using an inert gas as the driving mechanism. The information presented in this report serves as a spring board for trade studies and the development of equipment specifications.

  16. Structure of solvates of o-hydroxybenzoic acid in supercritical CO2-cosolvent media, according to molecular dynamics data

    NASA Astrophysics Data System (ADS)

    Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.

    2015-03-01

    Three-component supercritical carbon dioxide-cosolvent (methanol, ethanol, water)- o-hydroxybenzoic acid ( o-HBA) mixtures at a density of 0.7 g/cm3 and temperatures of 318 and 348 K are simulated by means of molecular dynamics. The solvate structures are investigated. It is shown that the solvation mechanism of o-HBA (particularly the o-HBA molecule forming a stable solvate complex with one molecule of a cosolvent via a hydrogen bond through the carboxyl group) does not depend on the temperature or the cosolvent. It is noted that the form of the cosolvent in a supercritical fluid varies: alcohols are distributed in the bulk in the form of monomers and hydrogen-bonded dimers, and water molecules tend to form microclusters along with chained and spatially branched structures by means of hydrogen bonds. It is established that the local molar fraction of cosolvent around the solvate complexes grows. It is concluded that the solvation of o-HBA is determined by the behavior of cosolvent in media of supercritical CO2.

  17. Numerical Simulation of Air Bubble Characteristics in Stationary Water

    NASA Astrophysics Data System (ADS)

    Zhang, C. X.; Wang, Y. X.

    The motion of air bubble in water plays a key role in such diverse aspects as air bubble curtain breakwater, air curtain drag reduction, air cushion isolation, weakening the shock wave in water by air bubble screen, etc. At present, the research on air bubble behaviors can be subdivided into several processes: air bubble formation from submerged orifices; interaction and coalescence during the ascending. The work presented in this paper focuses on numerical simulation of air bubble characteristics in stationary water, for example, air bubble formation, the ascending speed, the departing period, and so on. A series of models to simulate the characteristics of air bubble are developed by the VOF method in the two phase flow module of FLUENT. The numerical simulation results are consistent with the theoretical characteristics of air bubble in many aspects. So it is concluded that numerical simulation of air bubble characteristics in stationary water based on FLUENT is feasible. Due to the fact that the characteristics of air bubble are complicated questions, it is important that study on the air bubble behaviors in stationary water should be conducted on deeply.

  18. Impacts of simulated drought on pore water chemistry of peatlands.

    PubMed

    Juckers, Myra; Watmough, Shaun A

    2014-01-01

    Northern peatlands are increasingly threatened by climate change and industrial activities. This study examined the impact of simulated droughts on pore water chemistry at six peatlands in Sudbury, Ontario, that differ in copper (Cu), nickel (Ni) and cobalt (Co) contamination, including a site that had been previously limed. All sites responded similarly to simulated drought: pore water pH declined significantly following the 30 day drought and the decline was greater following the 60 day drought treatment. The decline in pore water pH was due to increasing sulphate concentrations, whereas nitrate increased more in the 60 day drought treatment. Decreases in pH were accompanied by large increases in Ni and Co that greatly exceeded provincial water quality guidelines. In contrast, dissolved organic carbon (DOC) concentrations decreased significantly following drought, along with concentrations of Cu and Al, which are strongly complexed by organic acids.

  19. Disintegration of fluids under supercritical conditions from mixing layer studies

    NASA Technical Reports Server (NTRS)

    Okong'o, N.; Bellan, J.

    2003-01-01

    Databases of transitional states obtained from Direct Numerical simulations (DNS) of temporal, supercritical mixing layers for two species systems, O2/H2 and C7H16/N2, are analyzed to elucidate species-specific turbulence aspects and features of fluid disintegration.

  20. Observation of laser driven supercritical radiative shock precursors.

    PubMed

    Bouquet, S; Stéhlé, C; Koenig, M; Chièze, J-P; Benuzzi-Mounaix, A; Batani, D; Leygnac, S; Fleury, X; Merdji, H; Michaut, C; Thais, F; Grandjouan, N; Hall, T; Henry, E; Malka, V; Lafon, J-P J

    2004-06-01

    We present a supercritical radiative shock experiment performed with the LULI nanosecond laser facility. Using targets filled with xenon gas at low pressure, the propagation of a strong shock with a radiative precursor is evidenced. The main measured shock quantities (electronic density and propagation velocity) are shown to be in good agreement with theory and numerical simulations. PMID:15245230

  1. Adsorption of Water on JSC-1A Lunar Simulant Samples

    NASA Technical Reports Server (NTRS)

    Goering, John; Sah, Shweta; Burghaus, Uwe; Street, Kenneth W.

    2008-01-01

    Remote sensing probes sent to the moon in the 1990s indicated that water may exist in areas such as the bottoms of deep, permanently shadowed craters at the lunar poles, buried under regolith. Water is of paramount importance for any lunar exploration and colonization project which would require self-sustainable systems. Therefore, investigating the interaction of water with lunar regolith is pertinent to future exploration. The lunar environment can be approximated in ultra-high vacuum systems such as those used in thermal desorption spectroscopy (TDS). Questions about water dissociation, surface wetting, degree of crystallization, details of water-ice transitions, and cluster formation kinetics can be addressed by TDS. Lunar regolith specimens collected during the Apollo missions are still available though precious, so testing with simulant is required before applying to use lunar regolith samples. Hence, we used for these studies JSC-1a, mostly an aluminosilicate glass and basaltic material containing substantial amounts of plagioclase, some olivine and traces of other minerals. Objectives of this project include: 1) Manufacturing samples using as little raw material as possible, allowing the use of surface chemistry and kinetics tools to determine the feasibility of parallel studies on regolith, and 2) Characterizing the adsorption kinetics of water on the regolith simulant. This has implications for the probability of finding water on the moon and, if present, for recovery techniques. For condensed water films, complex TDS data were obtained containing multiple features, which are related to subtle rearrangements of the water adlayer. Results from JSC-1a TDS studies indicate: 1) Water dissociation on JSC-1a at low exposures, with features detected at temperatures as high as 450 K and 2) The formation of 3D water clusters and a rather porous condensed water film. It appears plausible that the sub- m sized particles act as nucleation centers.

  2. Simulation of water quality for Salt Creek in northeastern Illinois

    USGS Publications Warehouse

    Melching, Charles S.; Chang, T.J.

    1996-01-01

    Water-quality processes in the Salt Creek watershed in northeastern Illinois were simulated with a computer model. Selected waste-load scenarios for 7-day, 10-year low-flow conditions were simulated in the stream system. The model development involved the calibration of the U.S. Environmental Protection Agency QUAL2E model to water-quality constituent concentration data collected by the Illinois Environmental Protection Agency (IEPA) for a diel survey on August 29-30, 1995, and the verification of this model with water-quality constituent concentration data collected by the IEPA for a diel survey on June 27-28, 1995. In-stream measurements of sediment oxygen demand rates and carbonaceous biochemical oxygen demand (CBOD) decay rates by the IEPA and traveltime and reaeration-rate coefficients by the U.S. Geological Survey facilitated the development of a model for simulation of water quality in the Salt Creek watershed. In general, the verification of the calibrated model increased confidence in the utility of the model for water-quality planning in the Salt Creek watershed. However, the model was adjusted to better simulate constituent concentrations measured during the June 27-28, 1995, diel survey. Two versions of the QUAL2E model were utilized to simulate dissolved oxygen (DO) concentrations in the Salt Creek watershed for selected effluent discharge and concentration scenarios for water-quality planning: (1) the QUAL2E model calibrated to the August 29-30, 1995, diel survey, and (2) the QUAL2E model adjusted to the June 27-28, 1995, diel survey. The results of these simulations indicated that the QUAL2E model adjusted to the June 27-28, 1995, diel survey simulates reliable information for water-quality planning. The results of these simulations also indicated that to maintain DO concentrations greater than 5 milligrams per liter (mg/L) throughout most of Salt Creek for 7-day, 10-year low-flow conditions, the sewage-treatment plants (STP's) must discharge

  3. New Spectral State of Supercritical Accretion Flow with Comptonizing Outflow

    NASA Astrophysics Data System (ADS)

    Kawashima, Tomohisa; Ohsuga, Ken; Mineshige, Shin; Heinzeller, Dominikus; Takabe, Hideaki; Matsumoto, Ryoji

    2009-08-01

    Supercritical accretion flows inevitably produce radiation-pressure driven outflows, which Compton up-scatter soft photons from the underlying accretion flow, thereby making hard emission. We performed two-dimensional radiation hydrodynamic simulations of supercritical accretion flows and outflows, while incorporating such Compton scattering effects, and demonstrated that there appears a new hard spectral state at higher photon luminosities than that of the slim-disk state. In this state, as the photon luminosity increases, the photon index decreases and the fraction of the hard emission increases. The Compton y-parameter is on the order of unity (and thus the photon index will be ˜2) when the apparent photon luminosity is ˜30LE (with LE being the Eddington luminosity) for nearly face-on sources. This explains the observed spectral hardening of the ULX NGC 1313 X-2 in its brightening phase, and thus supports the model of supercritical accretion onto stellar-mass black holes in this ULX.

  4. Surfactant/Supercritical Fluid Cleaning of Contaminated Substrates

    NASA Technical Reports Server (NTRS)

    White, Gary L.

    1997-01-01

    CFC's and halogenated hydrocarbon solvents have been the solvents of choice to degrease and otherwise clean precision metal parts to allow proper function. Recent regulations have, however, rendered most of these solvents unacceptable for these purposes. New processes which are being used or which have been proposed to replace these solvents usually either fail to remove water soluble contaminants or produce significant aqueous wastes which must then be disposed of. In this work, a new method for cleaning surfaces will be investigated. Solubility of typical contaminants such as lubricating greases and phosphatizing bath residues will be studied in several surfactant/supercritical fluid solutions. The effect of temperature, pressure, and the composition of the cleaning mixture on the solubility of oily, polar, and ionic contaminants will be investigated. A reverse micellar solution in a supercritical light hydrocarbon solvent will be used to clean samples of industrial wastes. A reverse micellar solution is one where water is dissolved into a non-polar solvent with the aid of a surfactant. The solution will be capable of dissolving both water-soluble contaminants and oil soluble contaminants. Once the contaminants have been dissolved into the solution they will be separated from the light hydrocarbon and precipitated by a relatively small pressure drop and the supercritical solvent will be available for recycle for reuse. The process will be compared to the efficacy of supercritical CO2 cleaning by attempting to clean the same types of substrates and machining wastes with the same contaminants using supercritical CO2. It is anticipated that the supercritical CO2 process will not be capable of removing ionic residues.

  5. Computational Simulation of a Water-Cooled Heat Pump

    NASA Technical Reports Server (NTRS)

    Bozarth, Duane

    2008-01-01

    A Fortran-language computer program for simulating the operation of a water-cooled vapor-compression heat pump in any orientation with respect to gravity has been developed by modifying a prior general-purpose heat-pump design code used at Oak Ridge National Laboratory (ORNL).

  6. Water Flow Simulation using Smoothed Particle Hydrodynamics (SPH)

    NASA Technical Reports Server (NTRS)

    Vu, Bruce; Berg, Jared; Harris, Michael F.

    2014-01-01

    Simulation of water flow from the rainbird nozzles has been accomplished using the Smoothed Particle Hydrodynamics (SPH). The advantage of using SPH is that no meshing is required, thus the grid quality is no longer an issue and accuracy can be improved.

  7. Simulation of an anion in water: effect of ion polarizability

    NASA Astrophysics Data System (ADS)

    Karim, Omar A.

    1991-10-01

    A polarizable-polar water model is used to study the structure of wate near a chloride ion. A semi-classical description of ion polarizability is included. Significant changes in the solute-solvent distribution functions are observed. When compared with a simulation without ion polarizability, it is found that the hydration number is further decreased when ion polarizability is present.

  8. Numerical simulations of internal wave generation by convection in water.

    PubMed

    Lecoanet, Daniel; Le Bars, Michael; Burns, Keaton J; Vasil, Geoffrey M; Brown, Benjamin P; Quataert, Eliot; Oishi, Jeffrey S

    2015-06-01

    Water's density maximum at 4°C makes it well suited to study internal gravity wave excitation by convection: an increasing temperature profile is unstable to convection below 4°C, but stably stratified above 4°C. We present numerical simulations of a waterlike fluid near its density maximum in a two-dimensional domain. We successfully model the damping of waves in the simulations using linear theory, provided we do not take the weak damping limit typically used in the literature. To isolate the physical mechanism exciting internal waves, we use the spectral code dedalus to run several simplified model simulations of our more detailed simulation. We use data from the full simulation as source terms in two simplified models of internal-wave excitation by convection: bulk excitation by convective Reynolds stresses, and interface forcing via the mechanical oscillator effect. We find excellent agreement between the waves generated in the full simulation and the simplified simulation implementing the bulk excitation mechanism. The interface forcing simulations overexcite high-frequency waves because they assume the excitation is by the "impulsive" penetration of plumes, which spreads energy to high frequencies. However, we find that the real excitation is instead by the "sweeping" motion of plumes parallel to the interface. Our results imply that the bulk excitation mechanism is a very accurate heuristic for internal-wave generation by convection. PMID:26172801

  9. Numerical simulations of internal wave generation by convection in water.

    PubMed

    Lecoanet, Daniel; Le Bars, Michael; Burns, Keaton J; Vasil, Geoffrey M; Brown, Benjamin P; Quataert, Eliot; Oishi, Jeffrey S

    2015-06-01

    Water's density maximum at 4°C makes it well suited to study internal gravity wave excitation by convection: an increasing temperature profile is unstable to convection below 4°C, but stably stratified above 4°C. We present numerical simulations of a waterlike fluid near its density maximum in a two-dimensional domain. We successfully model the damping of waves in the simulations using linear theory, provided we do not take the weak damping limit typically used in the literature. To isolate the physical mechanism exciting internal waves, we use the spectral code dedalus to run several simplified model simulations of our more detailed simulation. We use data from the full simulation as source terms in two simplified models of internal-wave excitation by convection: bulk excitation by convective Reynolds stresses, and interface forcing via the mechanical oscillator effect. We find excellent agreement between the waves generated in the full simulation and the simplified simulation implementing the bulk excitation mechanism. The interface forcing simulations overexcite high-frequency waves because they assume the excitation is by the "impulsive" penetration of plumes, which spreads energy to high frequencies. However, we find that the real excitation is instead by the "sweeping" motion of plumes parallel to the interface. Our results imply that the bulk excitation mechanism is a very accurate heuristic for internal-wave generation by convection.

  10. Supercritical fluid (SCF) technologies: Assessment of applicability to installation restoration processes

    NASA Astrophysics Data System (ADS)

    1994-03-01

    USAEC has conducted an evaluation of supercritical fluid (SCF) technologies for their applicability to treatment of explosives, chlorinated hydrocarbons, and metals in soils, water, and/or waste sludge media. Off-specification explosives and propellants that have traditionally been open burned or openly detonated were also examined. Supercritical fluids are substances which have been heated and compressed to above their critical temperatures and pressures and which possess unique transport and mass transfer properties. Supercritical fluid extraction (SFE) uses the solvating properties of supercritical fluids to extract one or more organic components from a mixture into a supercritical solvent (commonly CO2). The concentrated extract stream may then be recycled, reclaimed, or destroyed by other methods.

  11. Corrosive effects of supercritical carbon dioxide and cosolvents on metals

    SciTech Connect

    Russick, E.M.; Poulter, G.A.; Adkins, C.L.J.; Sorensen, N.R.

    1994-06-01

    With the eventual phase-out of chlorofluorocarbons, and restrictive regulations concerning the use of cleaning solvents such as hydrochlorofluorocarbons, and other volatile organic compounds, it is essential to seek new, environmentally acceptable cleaning processes. In the DOE Complex and in industry, an environmentally sound process for precision cleaning of machined metal parts is one of the issues that needs to be addressed. At Sandia, we are investigating the use of supercritical carbon dioxide (CO{sub 2}) as an alternative cleaning solvent for this application. Carbon dioxide is nontoxic, recyclable, and relatively inexpensive. Supercritical CO{sub 2} has been demonstrated as a solvent for many nonpolar organic compounds, including hydrocarbon-based machining and lubricating oils. The focus of this work is to investigate any corrosive effects of supercritical CO{sub 2} cleaning on metals. Sample coupons of several common metals were statically exposed to pure supercritical CO{sub 2}, water saturated supercritical CO{sub 2}, and 10 wt % methanol/CO{sub 2} cosolvent at 24,138 kPa (3500 psi) and 323K (50C) for 24 hours. Gravimetric analysis and magnified visual inspection of the coupons were performed before and after the exposure tests. Electron microprobe, x-ray photoelectron spectroscopy (XPS), and Auger electron surface analyses were done as needed where visual and gravimetric changes in the samples were evident. Results are reported.

  12. CASL: The Consortium for Advanced Simulation of Light Water Reactors

    NASA Astrophysics Data System (ADS)

    Kothe, Douglas B.

    2010-11-01

    Like the fusion community, the nuclear engineering community is embarking on a new computational effort to create integrated, multiphysics simulations. The Consortium for Advanced Simulation of Light Water Reactors (CASL), one of 3 newly-funded DOE Energy Innovation Hubs, brings together an exceptionally capable team that will apply existing modeling and simulation capabilities and develop advanced capabilities to create a usable environment for predictive simulation of light water reactors (LWRs). This environment, designated the Virtual Reactor (VR), will: 1) Enable the use of leadership-class computing for engineering design and analysis to improve reactor capabilities, 2) Promote an enhanced scientific basis and understanding by replacing empirically based design and analysis tools with predictive capabilities, 3) Develop a highly integrated multiphysics environment for engineering analysis through increased fidelity methods, and 4) Incorporate UQ as a basis for developing priorities and supporting, application of the VR tools for predictive simulation. In this presentation, we present the plans for CASL and comment on the similarity and differences with the proposed Fusion Simulation Project (FSP).

  13. Supercritical fluid technology

    SciTech Connect

    Penninger, J.M.L.; McHugh, M.A.; Radosz, M.; Krukonis, V.J.

    1985-01-01

    This book presents the state-of-the-art in the science and technology of supercritical fluid (scf) processing. Current research as described in the book, focuses on developments in equations of state for binary and multicomponent mixtures (including polymer solutions), solubility measurements at near-critical conditions, measurements of critical properties of binary mixtures and their correlation with equations of state. Progress in thermodynamics, coupled with advances in the design and construction of high pressure equipment, has opened up a wide avenue of commercial application (e.g. decaffeination of coffee beans, extractions of flavours and spices, purification of pharmaceutical products, separations of polymeric materials, deodorization and deacidification of vegetable oils, fractionation of fatty acids, coal liquefaction, wood delignitication, etc.)

  14. A holistic water depth simulation model for small ponds

    NASA Astrophysics Data System (ADS)

    Ali, Shakir; Ghosh, Narayan C.; Mishra, P. K.; Singh, R. K.

    2015-10-01

    Estimation of time varying water depth and time to empty of a pond is prerequisite for comprehensive and coordinated planning of water resource for its effective utilization. A holistic water depth simulation (HWDS) and time to empty (TE) model for small, shallow ephemeral ponds have been derived by employing the generalized model based on the Green-Ampt equation in the basic water balance equation. The HWDS model includes time varying rainfall, runoff, surface water evaporation, outflow and advancement of wetting front length as external inputs. The TE model includes two external inputs; surface water evaporation and advancement of wetting front length. Both the models also consider saturated hydraulic conductivity and fillable porosity of the pond's bed material as their parameters. The solution of the HWDS model involved numerical iteration in successive time intervals. The HWDS model has successfully evaluated with 3 years of field data from two small ponds located within a watershed in a semi-arid region in western India. The HWDS model simulated time varying water depth in the ponds with high accuracy as shown by correlation coefficient (R2 ⩾ 0.9765), index of agreement (d ⩾ 0.9878), root mean square errors (RMSE ⩽ 0.20 m) and percent bias (PB ⩽ 6.23%) for the pooled data sets of the measured and simulated water depth. The statistical F and t-tests also confirmed the reliability of the HWDS model at probability level, p ⩽ 0.0001. The response of the TE model showed its ability to estimate the time to empty the ponds. An additional field calibration and validation of the HWDS and TE models with observed field data in varied hydro-climatic conditions could be conducted to increase the applicability and credibility of the models.

  15. Simulation of ground-water flow and areas contributing ground water to production wells, Cadillac, Michigan

    USGS Publications Warehouse

    Hoard, Christopher J.; Westjohn, David B.

    2005-01-01

    Ground water is the primary source of water for domestic, municipal, and industrial use within the northwest section of Michigan's Lower Peninsula. Because of the importance of this resource, numerous communities including the city of Cadillac in Wexford County, Michigan, have begun local wellhead protection programs. In these programs, communities protect their ground-water resources by identifying the areas that contribute water to production wells, identifying potential sources of contamination, and developing methods to cooperatively manage and minimize threats to the water supply. The U.S. Geological Survey, in cooperation with the city of Cadillac, simulated regional ground-water flow and estimated areas contributing recharge and zones of transport to the production well field. Ground-water flow models for the Clam River watershed, in Wexford and Missaukee Counties, were developed using the U.S. Geological Survey modular three-dimensional finite-difference ground-water flow model (MODFLOW 2000). Ground-water flow models were calibrated using the observation, sensitivity, and parameter estimation packages of MODFLOW 2000. Ground-water-head solutions from calibrated flow models were used in conjunction with MODPATH, a particle-tracking program, to simulate regional ground-water flow and estimate areas contributing recharge and zones of transport to the Cadillac production-well field for a 10-year period. Model simulations match the conceptual model in that regional ground-water flow in the deep ground-water system is from southeast to northwest across the watershed. Areas contributing water were determined for the optimized parameter set and an alternate parameter set that included increased recharge and hydraulic conductivity values. Although substantially different hydrologic parameters (assumed to represent end-member ranges of realistic hydrologic parameters) were used in alternate numerical simulations, simulation results differ little in predictions of

  16. Simulations and field observations of root water uptake in plots with different soil water availability.

    NASA Astrophysics Data System (ADS)

    Cai, Gaochao; Vanderborght, Jan; Couvreur, Valentin; Javaux, Mathieu; Vereecken, Harry

    2015-04-01

    Root water uptake is a main process in the hydrological cycle and vital for water management in agronomy. In most models of root water uptake, the spatial and temporal soil water status and plant root distributions are required for water flow simulations. However, dynamic root growth and root distributions are not easy and time consuming to measure by normal approaches. Furthermore, root water uptake cannot be measured directly in the field. Therefore, it is necessary to incorporate monitoring data of soil water content and potential and root distributions within a modeling framework to explore the interaction between soil water availability and root water uptake. But, most models are lacking a physically based concept to describe water uptake from soil profiles with vertical variations in soil water availability. In this contribution, we present an experimental setup in which root development, soil water content and soil water potential are monitored non-invasively in two field plots with different soil texture and for three treatments with different soil water availability: natural rain, sheltered and irrigated treatment. Root development is monitored using 7-m long horizontally installed minirhizotubes at six depths with three replicates per treatment. The monitoring data are interpreted using a model that is a one-dimensional upscaled version of root water uptake model that describes flow in the coupled soil-root architecture considering water potential gradients in the system and hydraulic conductances of the soil and root system (Couvreur et al., 2012). This model approach links the total root water uptake to an effective soil water potential in the root zone. The local root water uptake is a function of the difference between the local soil water potential and effective root zone water potential so that compensatory uptake in heterogeneous soil water potential profiles is simulated. The root system conductance is derived from inverse modelling using

  17. Design of virtual SCADA simulation system for pressurized water reactor

    NASA Astrophysics Data System (ADS)

    Wijaksono, Umar; Abdullah, Ade Gafar; Hakim, Dadang Lukman

    2016-02-01

    The Virtual SCADA system is a software-based Human-Machine Interface that can visualize the process of a plant. This paper described the results of the virtual SCADA system design that aims to recognize the principle of the Nuclear Power Plant type Pressurized Water Reactor. This simulation uses technical data of the Nuclear Power Plant Unit Olkiluoto 3 in Finland. This device was developed using Wonderware Intouch, which is equipped with manual books for each component, animation links, alarm systems, real time and historical trending, and security system. The results showed that in general this device can demonstrate clearly the principles of energy flow and energy conversion processes in Pressurized Water Reactors. This virtual SCADA simulation system can be used as instructional media to recognize the principle of Pressurized Water Reactor.

  18. Computer simulation of water in cytochrome c oxidase.

    PubMed

    Zheng, Xuehe; Medvedev, Dmitry M; Swanson, Jessica; Stuchebrukhov, Alexei A

    2003-03-01

    Statistical mechanics and molecular dynamics simulations have been carried out to study the distribution and dynamics of internal water molecules in bovine heart cytochrome c oxidase (CcO). CcO is found to be capable of holding plenty of water, which in subunit I alone amounts to about 165 molecules. The dynamic characterization of these water molecules is carried out. The nascent water molecules produced in the redox reaction at the heme a(3)-CuB binuclear site form an intriguing chain structure. The chain begins at the position of Glu242 at the end of the D channel, and has a fork structure, one branch of which leads to the binuclear center, and the other to the propionate d of heme a(3). The branch that leads to the binuclear center has dynamic access both to the site where the formation of water occurs, and to delta-nitrogen of His291. From the binuclear center, the chain continues to run into the K channel. The stability of this hydrogen bond network is examined dynamically. The catalytic site is located at the hydrophobic region, and the nascent water molecules are produced at the top of the energy hill. The energy gradient is utilized as the mechanism of water removal from the protein. The water exit channels are explored using high-temperature dynamics simulations. Two putative channels for water exit from the catalytic site have been identified. One is leading directly toward Mg(2+) site. However, this channel is only open when His291 is dissociated from CuB. If His291 is bound to CuB, the only channel for water exit is the one that originates at E242 and leads toward the middle of the membrane. This is the same channel that is presumably used for oxygen supply. PMID:12615353

  19. Water in Biological and Chemical Processes

    NASA Astrophysics Data System (ADS)

    Bagchi, Biman

    2013-11-01

    Part I. Bulk Water: 1. Uniqueness of water; 2. Anomalies of water; 3. Dynamics of water: molecular motions and hydrogen bond breaking kinetics; 4. Inherent structures of liquid water; 5. pH of water; Part II. Water in Biology: Dynamical View and Function: 6. Biological water; 7. Explicit role of water in biological functions; 8. Hydration of proteins; 9. Can we understand protein hydration layer: lessons from computer simulations; 10. Water in and around DNA and RNA; 11. Role of water in protein-DNA interaction; 12. Water surrounding lipid bilayers; 13. Water in Darwin's world; Part III. Water in Complex Chemical Systems: 14. Hydrophilic effects; 15. Hydrophobic effects; 16. Aqueous binary mixtures: amphiphilic effect; 17. Water in and around micelles, reverse micelles and microemulsions; 18. Water in carbon nanotubes; Part IV. Bulk Water: Advanced Topics: 19. Entropy of water; 20. Freezing of water into ice; 21. Supercritical water; 22. Microscopic approaches to understand water anomalies.

  20. Simulating the fate of water in field soil crop environment

    NASA Astrophysics Data System (ADS)

    Cameira, M. R.; Fernando, R. M.; Ahuja, L.; Pereira, L.

    2005-12-01

    This paper presents an evaluation of the Root Zone Water Quality Model(RZWQM) for assessing the fate of water in the soil-crop environment at the field scale under the particular conditions of a Mediterranean region. The RZWQM model is a one-dimensional dual porosity model that allows flow in macropores. It integrates the physical, biological and chemical processes occurring in the root zone, allowing the simulation of a wide spectrum of agricultural management practices. This study involved the evaluation of the soil, hydrologic and crop development sub-models within the RZWQM for two distinct agricultural systems, one consisting of a grain corn planted in a silty loam soil, irrigated by level basins and the other a forage corn planted in a sandy soil, irrigated by sprinklers. Evaluation was performed at two distinct levels. At the first level the model capability to fit the measured data was analyzed (calibration). At the second level the model's capability to extrapolate and predict the system behavior for conditions different than those used when fitting the model was assessed (validation). In a subsequent paper the same type of evaluation is presented for the nitrogen transformation and transport model. At the first level a change in the crop evapotranspiration (ETc) formulation was introduced, based upon the definition of the effective leaf area, resulting in a 51% decrease in the root mean square error of the ETc simulations. As a result the simulation of the root water uptake was greatly improved. A new bottom boundary condition was implemented to account for the presence of a shallow water table. This improved the simulation of the water table depths and consequently the soil water evolution within the root zone. The soil hydraulic parameters and the crop variety specific parameters were calibrated in order to minimize the simulation errors of soil water and crop development. At the second level crop yield was predicted with an error of 1.1 and 2.8% for

  1. Molecular dynamics simulations of water within models of ion channels.

    PubMed Central

    Breed, J; Sankararamakrishnan, R; Kerr, I D; Sansom, M S

    1996-01-01

    The transbilayer pores formed by ion channel proteins contain extended columns of water molecules. The dynamic properties of such waters have been suggested to differ from those of water in its bulk state. Molecular dynamics simulations of ion channel models solvated within and at the mouths of their pores are used to investigate the dynamics and structure of intra-pore water. Three classes of channel model are investigated: a) parallel bundles of hydrophobic (Ala20) alpha-helices; b) eight-stranded hydrophobic (Ala10) antiparallel beta-barrels; and c) parallel bundles of amphipathic alpha-helices (namely, delta-toxin, alamethicin, and nicotinic acetylcholine receptor M2 helix). The self-diffusion coefficients of water molecules within the pores are reduced significantly relative to bulk water in all of the models. Water rotational reorientation rates are also reduced within the pores, particularly in those pores formed by alpha-helix bundles. In the narrowest pore (that of the Ala20 pentameric helix bundle) self-diffusion coefficients and reorientation rates of intra-pore waters are reduced by approximately an order of magnitude relative to bulk solvent. In Ala20 helix bundles the water dipoles orient antiparallel to the helix dipoles. Such dipole/dipole interaction between water and pore may explain how water-filled ion channels may be formed by hydrophobic helices. In the bundles of amphipathic helices the orientation of water dipoles is modulated by the presence of charged side chains. No preferential orientation of water dipoles relative to the pore axis is observed in the hydrophobic beta-barrel models. Images FIGURE 1 FIGURE 5 FIGURE 7 PMID:8785323

  2. Bedforms formed by experimental supercritical density flows

    NASA Astrophysics Data System (ADS)

    Naruse, Hajime; Izumi, Norihiro; Yokokawa, Miwa; Muto, Tetsuji

    2014-05-01

    This study reveals characteristics and formative conditions of bedforms produced by saline density flows in supercritical flow conditions, especially focusing on the mechanism of the formation of plane bed. The motion of sediment particles forming bedforms was resolved by high-speed cameras (1/1000 frame/seconds). Experimental density flows were produced by mixtures of salt water (1.01-1.04 in density) and plastic particles (1.5 in specific density, 140 or 240 mm in diameter). Salt water and plastic particles are analogue materials of muddy water and sand particles in turbidity currents respectively. Acrylic flume (4.0 m long, 2.0 cm wide and 0.5 m deep) was submerged in an experimental tank (6.0 m long, 1.8 m wide and 1.2 m deep) that was filled by clear water. Features of bedforms were observed when the bed state in the flume reached equilibrium condition. The experimental conditions range 1.5-4.2 in densimetric Froude number and 0.2-0.8 in Shields dimensionless stress. We report the two major discoveries as a result of the flume experiments: (1) Plane bed under Froude-supercritical flows and (2) Geometrical characteristics of cyclic steps formed by density flows. (1) Plane bed was formed under the condition of supercritical flow regime. In previous studies, plane bed has been known to be formed by subcritical unidirectional flows (ca. 0.8 in Froude number). However, this study implies that plane bed can also be formed by supercritical conditions with high Shields dimensionless stress (>0.4) and very high Froude number (> 4.0). This discovery may suggest that previous estimations of paleo-hydraulic conditions of parallel lamination in turbidites should be reconsidered. The previous experimental studies and data from high-speed camera suggest that the region of plane bed formation coincides with the region of the sheet flow developments. The particle transport in sheet flow (thick bedload layer) induces transform of profile of flow shear stress, which may be

  3. Dissolution of uranium dioxide in supercritical fluid carbon dioxide.

    PubMed

    Samsonov, M D; Wai, C M; Lee, S C; Kulyako, Y; Smart, N G

    2001-09-21

    Uranium dioxide can be dissolved in supercritical CO2 with a CO2-philic TBP-HNO3 complexant to form a highly soluble UO2(NO3)(2).2TBP complex; this new method of dissolving UO2 that requires no water or organic solvent may have important applications for reprocessing of spent nuclear fuels and for treatment of nuclear wastes.

  4. Microwave Extraction of Water from Lunar Regolith Simulant

    NASA Technical Reports Server (NTRS)

    Ethridge, Edwin C.; Kaukler, William

    2007-01-01

    Nearly a decade ago the DOD Clementine lunar orbital mission obtained data indicating that the permanently shaded regions at the lunar poles may have permanently frozen water in the lunar soil. Currently NASA's Robotic Lunar Exploration Program, RLEP-2, is planned to land at the lunar pole to determine if water is present. The detection and extraction of water from the permanently frozen permafrost is an important goal for NASA. Extraction of water from lunar permafrost has a high priority in the In-Situ Resource Utilization, ISRU, community for human life support and as a fuel. The use of microwave processing would permit the extraction of water without the need to dig, drill, or excavate the lunar surface. Microwave heating of regolith is potentially faster and more efficient than any other heating methods due to the very low thermal conductivity of the lunar regolith. Also, microwaves can penetrate into the soil permitting water removal from deep below the lunar surface. A cryogenic vacuum test facility was developed for evaluating the use of microwave heating and water extraction from a lunar regolith permafrost simulant. Water is obtained in a cryogenic cold trap even with soil conditions below 0 C. The results of microwave extraction of water experiments will be presented.

  5. Adaptive Resolution Simulation of Supramolecular Water: The Concurrent Making, Breaking, and Remaking of Water Bundles

    PubMed Central

    2016-01-01

    The adaptive resolution scheme (AdResS) is a multiscale molecular dynamics simulation approach that can concurrently couple atomistic (AT) and coarse-grained (CG) resolution regions, i.e., the molecules can freely adapt their resolution according to their current position in the system. Coupling to supramolecular CG models, where several molecules are represented as a single CG bead, is challenging, but it provides higher computational gains and connection to the established MARTINI CG force field. Difficulties that arise from such coupling have been so far bypassed with bundled AT water models, where additional harmonic bonds between oxygen atoms within a given supramolecular water bundle are introduced. While these models simplify the supramolecular coupling, they also cause in certain situations spurious artifacts, such as partial unfolding of biomolecules. In this work, we present a new clustering algorithm SWINGER that can concurrently make, break, and remake water bundles and in conjunction with the AdResS permits the use of original AT water models. We apply our approach to simulate a hybrid SPC/MARTINI water system and show that the essential properties of water are correctly reproduced with respect to the standard monoscale simulations. The developed hybrid water model can be used in biomolecular simulations, where a significant speed up can be obtained without compromising the accuracy of the AT water model. PMID:27409519

  6. Adaptive Resolution Simulation of Supramolecular Water: The Concurrent Making, Breaking, and Remaking of Water Bundles.

    PubMed

    Zavadlav, Julija; Marrink, Siewert J; Praprotnik, Matej

    2016-08-01

    The adaptive resolution scheme (AdResS) is a multiscale molecular dynamics simulation approach that can concurrently couple atomistic (AT) and coarse-grained (CG) resolution regions, i.e., the molecules can freely adapt their resolution according to their current position in the system. Coupling to supramolecular CG models, where several molecules are represented as a single CG bead, is challenging, but it provides higher computational gains and connection to the established MARTINI CG force field. Difficulties that arise from such coupling have been so far bypassed with bundled AT water models, where additional harmonic bonds between oxygen atoms within a given supramolecular water bundle are introduced. While these models simplify the supramolecular coupling, they also cause in certain situations spurious artifacts, such as partial unfolding of biomolecules. In this work, we present a new clustering algorithm SWINGER that can concurrently make, break, and remake water bundles and in conjunction with the AdResS permits the use of original AT water models. We apply our approach to simulate a hybrid SPC/MARTINI water system and show that the essential properties of water are correctly reproduced with respect to the standard monoscale simulations. The developed hybrid water model can be used in biomolecular simulations, where a significant speed up can be obtained without compromising the accuracy of the AT water model. PMID:27409519

  7. Adaptive Resolution Simulation of Supramolecular Water: The Concurrent Making, Breaking, and Remaking of Water Bundles.

    PubMed

    Zavadlav, Julija; Marrink, Siewert J; Praprotnik, Matej

    2016-08-01

    The adaptive resolution scheme (AdResS) is a multiscale molecular dynamics simulation approach that can concurrently couple atomistic (AT) and coarse-grained (CG) resolution regions, i.e., the molecules can freely adapt their resolution according to their current position in the system. Coupling to supramolecular CG models, where several molecules are represented as a single CG bead, is challenging, but it provides higher computational gains and connection to the established MARTINI CG force field. Difficulties that arise from such coupling have been so far bypassed with bundled AT water models, where additional harmonic bonds between oxygen atoms within a given supramolecular water bundle are introduced. While these models simplify the supramolecular coupling, they also cause in certain situations spurious artifacts, such as partial unfolding of biomolecules. In this work, we present a new clustering algorithm SWINGER that can concurrently make, break, and remake water bundles and in conjunction with the AdResS permits the use of original AT water models. We apply our approach to simulate a hybrid SPC/MARTINI water system and show that the essential properties of water are correctly reproduced with respect to the standard monoscale simulations. The developed hybrid water model can be used in biomolecular simulations, where a significant speed up can be obtained without compromising the accuracy of the AT water model.

  8. Dynamic simulation of water resources in an urban wetland based on coupled water quantity and water quality models.

    PubMed

    Zeng, Weibo; Xu, Youpeng; Deng, Xiaojun; Han, Longfei; Zhang, Qianyu

    2015-01-01

    Water quality in wetlands plays a huge role in maintaining the health of the wetland ecosystem. Water quality should be controlled by an appropriate water allocation policy for the protection of the wetlands. In this paper, models of rainfall/runoff, non-point source pollution load, water quantity/quality, and dynamic pollutant-carrying capacity were established to simulate the water quantity/quality of Xixi-wetland river network (in the Taihu basin, China). The simulation results showed a satisfactory agreement with field observations. Furthermore, a 'node-river-node' algorithm that adjusts to the 'Three Steps Method' was adopted to improve the dynamic pollutant-carrying capacity model and simulate the pollutant-carrying capacity in benchmark years. The simulation result shows that the water quality of the river network could reach class III stably all year round if the anthropogenic pollution is reduced to one-third of the current annual amount. Further investigation estimated the minimum amount of water diversion in benchmark years under the reasonable water quantity-regulating rule to keep water quality as class III. With comparison of the designed scale, the water diversion can be reduced by 184 million m3 for a dry year, 191 million m3 for a normal year, and 198 million m3 for a wet year.

  9. Dynamic simulation of water resources in an urban wetland based on coupled water quantity and water quality models.

    PubMed

    Zeng, Weibo; Xu, Youpeng; Deng, Xiaojun; Han, Longfei; Zhang, Qianyu

    2015-01-01

    Water quality in wetlands plays a huge role in maintaining the health of the wetland ecosystem. Water quality should be controlled by an appropriate water allocation policy for the protection of the wetlands. In this paper, models of rainfall/runoff, non-point source pollution load, water quantity/quality, and dynamic pollutant-carrying capacity were established to simulate the water quantity/quality of Xixi-wetland river network (in the Taihu basin, China). The simulation results showed a satisfactory agreement with field observations. Furthermore, a 'node-river-node' algorithm that adjusts to the 'Three Steps Method' was adopted to improve the dynamic pollutant-carrying capacity model and simulate the pollutant-carrying capacity in benchmark years. The simulation result shows that the water quality of the river network could reach class III stably all year round if the anthropogenic pollution is reduced to one-third of the current annual amount. Further investigation estimated the minimum amount of water diversion in benchmark years under the reasonable water quantity-regulating rule to keep water quality as class III. With comparison of the designed scale, the water diversion can be reduced by 184 million m3 for a dry year, 191 million m3 for a normal year, and 198 million m3 for a wet year. PMID:26540537

  10. Simulation of the soil water balance of an undeveloped prairie in west-central Florida

    USGS Publications Warehouse

    Bidlake, W.R.; Boetcher, P.F.

    1996-01-01

    A one-dimensional numerical model was developed to simulate the soil water balance of a densely vegetated prairie site in west-central Florida. Transient simulations of the soil water balance were performed using field-measured soil and vegetation properties. Simulated and measured soil water content generally agreed to within 0.04; however, simulated water storage and recharge were sensitive to air-entry soil-water pressure potential and depth to the water table.

  11. Feasibility Study of Supercritical Light Water Cooled Reactors for Electric Power Production, Nuclear Energy Research Initiative Project 2001-001, Westinghouse Electric Co. Grant Number: DE-FG07-02SF22533, Final Report

    SciTech Connect

    Philip E. MacDonald

    2005-01-01

    The supercritical water-cooled reactor (SCWR) is one of the six reactor technologies selected for research and development under the Generation IV program. SCWRs are promising advanced nuclear systems because of their high thermal efficiency (i.e., about 45% versus about 33% efficiency for current Light Water Reactors [LWRs]) and considerable plant simplification. SCWRs are basically LWRs operating at higher pressure and temperatures with a direct once-through cycle. Operation above the critical pressure eliminates coolant boiling, so the coolant remains single-phase throughout the system. Thus, the need for a pressurizer, steam generators, steam separators, and dryers is eliminated. The main mission of the SCWR is generation of low-cost electricity. It is built upon two proven technologies: LWRs, which are the most commonly deployed power generating reactors in the world, and supercritical fossil-fired boilers, a large number of which are also in use around the world. The reference SCWR design for the U.S. program is a direct cycle system operating at 25.0 MPa, with core inlet and outlet temperatures of 280 and 500 C, respectively. The coolant density decreases from about 760 kg/m3 at the core inlet to about 90 kg/m3 at the core outlet. The inlet flow splits with about 10% of the inlet flow going down the space between the core barrel and the reactor pressure vessel (the downcomer) and about 90% of the inlet flow going to the plenum at the top of the rector pressure vessel, to then flow down through the core in special water rods to the inlet plenum. Here it mixes with the feedwater from the downcomer and flows upward to remove the heat in the fuel channels. This strategy is employed to provide good moderation at the top of the core. The coolant is heated to about 500 C and delivered to the turbine. The purpose of this NERI project was to assess the reference U.S. Generation IV SCWR design and explore alternatives to determine feasibility. The project was

  12. Supercritical fluid extraction of Beauvericin from maize.

    PubMed

    Ambrosino, P; Galvano, F; Fogliano, V; Logrieco, A; Fresa, R; Ritieni, A

    2004-02-27

    Beauvericin (BEA), a supercritical fluid extraction with supercritical carbon dioxide from maize was investigated. Extraction efficiencies under several different extraction conditions were examined. Pressure, temperature, extraction time, organic modifier and water matrix content (10%) were investigated. The best extraction conditions were at a temperature of 60 degrees C, 3200psi, for 30min static extraction time and methanol as modifier solvent. Extraction recovery of 36% without modifier by adding water to the matrix in the extraction vessel (reproducibility relative standard deviations (R.S.D.)=3-5%) were recorded. Extraction recovery of 76.9% with methanol as co-solvent (reproducibility R.S.D.=3-5%) was obtained. Data shows that SFE gives a lower BEA recovery compared to conventional extraction protocol with organic solvents while SFE with modifier and conventional extraction yields are comparable. BEA extract contents were determined by high pressure liquid chromatography (HPLC) with a diode array detector (DAD) at 205nm and BEA peak confirmed by LC-MS. Acetonitrile-water as mobile phase and column C-18 were both tested. Instrumental and analytical parameters were optimized in the range linear interval from 1 to 500mgkg(-1) and reached a detection limit of 2ng. PMID:18969327

  13. A simulation of water pollution model parameter estimation

    NASA Technical Reports Server (NTRS)

    Kibler, J. F.

    1976-01-01

    A parameter estimation procedure for a water pollution transport model is elaborated. A two-dimensional instantaneous-release shear-diffusion model serves as representative of a simple transport process. Pollution concentration levels are arrived at via modeling of a remote-sensing system. The remote-sensed data are simulated by adding Gaussian noise to the concentration level values generated via the transport model. Model parameters are estimated from the simulated data using a least-squares batch processor. Resolution, sensor array size, and number and location of sensor readings can be found from the accuracies of the parameter estimates.

  14. Theoretical and Computational Study of Forced-Convection Heat Transfer at Supercritical Pressures

    NASA Astrophysics Data System (ADS)

    Zhong, Jianguo

    In the simulation of turbulent fluid flow and heat transfer at supercritical pressures, substantial difficulties have been encountered in the modeling of turbulence and bounda-ry layer. This is due to significant fluid property variations with respect to the local temperature and pressure, especially in the near-wall region of a heated wall, where large temperature differences occur. The classical turbulence models available in literature were typically developed for constant-property fluids, where an empirical wall function in the high-Re k-epsilon model, and a damping function in the low-Re k-epsilon model were derived based on the constant-property data to solve the boundary layer. As it can be found in the existing literature, large differences have been observed between the experimental and numerical simulation results of the heat transfer coefficient predictions in the en-hanced and deteriorated heat transfer situations for supercritical fluids. In this thesis, a novel near-wall treatment method is proposed to treat large property variations in the thermal and velocity sub-layers. In the near-wall region, the supercritical fluids can be considered thermal-conductive and viscous forces dominated. The thick-ness of the viscous sub-layer (VSL) and the conduction sub-layer (CSL) can be related to the wall shear stress and local Prandtl number information by using computational CFD models, such as that implemented in the NPHASE-CMFD code. The fluids' bulk and wall temperature information has been obtained from the literature review of experi-mental measurements. The wall temperature and heat transfer coefficient calculated from the k-epsilon model with the proposed wall treatment method have been found to be in good agreement with experimental data for both heat transfer enhancement and deterioration cases for two most widely used fluids: CO2 and water. The proposed model has been applied in the reactor-scale thermal-hydraulic analysis of different flow path

  15. Pressure-induced transformations in computer simulations of glassy water.

    PubMed

    Chiu, Janet; Starr, Francis W; Giovambattista, Nicolas

    2013-11-14

    Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water. PMID:24320281

  16. Toward Better Modeling of Supercritical Turbulent Mixing

    NASA Technical Reports Server (NTRS)

    Selle, Laurent; Okongo'o, Nora; Bellan, Josette; Harstad, Kenneth

    2008-01-01

    study was done as part of an effort to develop computational models representing turbulent mixing under thermodynamic supercritical (here, high pressure) conditions. The question was whether the large-eddy simulation (LES) approach, developed previously for atmospheric-pressure compressible-perfect-gas and incompressible flows, can be extended to real-gas non-ideal (including supercritical) fluid mixtures. [In LES, the governing equations are approximated such that the flow field is spatially filtered and subgrid-scale (SGS) phenomena are represented by models.] The study included analyses of results from direct numerical simulation (DNS) of several such mixing layers based on the Navier-Stokes, total-energy, and conservation- of-chemical-species governing equations. Comparison of LES and DNS results revealed the need to augment the atmospheric- pressure LES equations with additional SGS momentum and energy terms. These new terms are the direct result of high-density-gradient-magnitude regions found in the DNS and observed experimentally under fully turbulent flow conditions. A model has been derived for the new term in the momentum equation and was found to perform well at small filter size but to deteriorate with increasing filter size. Several alternative models were derived for the new SGS term in the energy equation that would need further investigations to determine if they are too computationally intensive in LES.

  17. Simulating Space Capsule Water Landing with Explicit Finite Element Method

    NASA Technical Reports Server (NTRS)

    Wang, John T.; Lyle, Karen H.

    2007-01-01

    A study of using an explicit nonlinear dynamic finite element code for simulating the water landing of a space capsule was performed. The finite element model contains Lagrangian shell elements for the space capsule and Eulerian solid elements for the water and air. An Arbitrary Lagrangian Eulerian (ALE) solver and a penalty coupling method were used for predicting the fluid and structure interaction forces. The space capsule was first assumed to be rigid, so the numerical results could be correlated with closed form solutions. The water and air meshes were continuously refined until the solution was converged. The converged maximum deceleration predicted is bounded by the classical von Karman and Wagner solutions and is considered to be an adequate solution. The refined water and air meshes were then used in the models for simulating the water landing of a capsule model that has a flexible bottom. For small pitch angle cases, the maximum deceleration from the flexible capsule model was found to be significantly greater than the maximum deceleration obtained from the corresponding rigid model. For large pitch angle cases, the difference between the maximum deceleration of the flexible model and that of its corresponding rigid model is smaller. Test data of Apollo space capsules with a flexible heat shield qualitatively support the findings presented in this paper.

  18. Simulation of the flow past a circular cylinder in the supercritical regime by blending RANS and variational-multiscale LES models

    NASA Astrophysics Data System (ADS)

    Moussaed, Carine; Vittoria Salvetti, Maria; Wornom, Stephen; Koobus, Bruno; Dervieux, Alain

    2014-05-01

    A strategy which blends a variational multiscale large eddy simulation (VMS-LES) model and a RANS model in a hybrid approach is investigated. A smooth blending function, which is based on the value of a blending parameter, is used for switching from VMS-LES to RANS. Different definitions of the blending parameter are investigated. The capabilities of the novel hybrid approach are appraised in the simulation of the flow around a circular cylinder at a Reynolds number 1.4×105, based on the freestream velocity and on the cylinder diameter, in the presence of turbulent boundary-layer due to turbulent inflow conditions. A second study at Reynolds numbers from Re=6.7×105 to 1.25×106 is also presented. The effect of using the VMS-LES approach in the hybrid model is evaluated. Results are compared to those of other RANS, LES and hybrid simulations in the literature and with experimental data

  19. The Consortium for Advanced Simulation of Light Water Reactors

    SciTech Connect

    Ronaldo Szilard; Hongbin Zhang; Doug Kothe; Paul Turinsky

    2011-10-01

    The Consortium for Advanced Simulation of Light Water Reactors (CASL) is a DOE Energy Innovation Hub for modeling and simulation of nuclear reactors. It brings together an exceptionally capable team from national labs, industry and academia that will apply existing modeling and simulation capabilities and develop advanced capabilities to create a usable environment for predictive simulation of light water reactors (LWRs). This environment, designated as the Virtual Environment for Reactor Applications (VERA), will incorporate science-based models, state-of-the-art numerical methods, modern computational science and engineering practices, and uncertainty quantification (UQ) and validation against data from operating pressurized water reactors (PWRs). It will couple state-of-the-art fuel performance, neutronics, thermal-hydraulics (T-H), and structural models with existing tools for systems and safety analysis and will be designed for implementation on both today's leadership-class computers and the advanced architecture platforms now under development by the DOE. CASL focuses on a set of challenge problems such as CRUD induced power shift and localized corrosion, grid-to-rod fretting fuel failures, pellet clad interaction, fuel assembly distortion, etc. that encompass the key phenomena limiting the performance of PWRs. It is expected that much of the capability developed will be applicable to other types of reactors. CASL's mission is to develop and apply modeling and simulation capabilities to address three critical areas of performance for nuclear power plants: (1) reduce capital and operating costs per unit energy by enabling power uprates and plant lifetime extension, (2) reduce nuclear waste volume generated by enabling higher fuel burnup, and (3) enhance nuclear safety by enabling high-fidelity predictive capability for component performance.

  20. Water treatment plant simulation program, version 1. 21, user's manual

    SciTech Connect

    Not Available

    1992-06-01

    The User's Manual for Version 1.21 of the Water Treatment Plant Simulation Program has been prepared to provide a basic understanding of (1) how to operate the program, and (2) the underlying assumptions and equations that are used to calculate the removal of natural organic matter and the formation of disinfection by-products. The manual represents the first public release of the program.

  1. Numerical Simulation of a Solar Domestic Hot Water System

    NASA Astrophysics Data System (ADS)

    Mongibello, L.; Bianco, N.; Di Somma, M.; Graditi, G.; Naso, V.

    2014-11-01

    An innovative transient numerical model is presented for the simulation of a solar Domestic Hot Water (DHW) system. The solar collectors have been simulated by using a zerodimensional analytical model. The temperature distributions in the heat transfer fluid and in the water inside the tank have been evaluated by one-dimensional models. The reversion elimination algorithm has been used to include the effects of natural convection among the water layers at different heights in the tank on the thermal stratification. A finite difference implicit scheme has been implemented to solve the energy conservation equation in the coil heat exchanger, and the energy conservation equation in the tank has been solved by using the finite difference Euler implicit scheme. Energy conservation equations for the solar DHW components models have been coupled by means of a home-made implicit algorithm. Results of the simulation performed using as input data the experimental values of the ambient temperature and the solar irradiance in a summer day are presented and discussed.

  2. Simulating ground water-lake interactions: Approaches and insights

    USGS Publications Warehouse

    Hunt, R.J.; Haitjema, H.M.; Krohelski, J.T.; Feinstein, D.T.

    2003-01-01

    Approaches for modeling lake-ground water interactions have evolved significantly from early simulations that used fixed lake stages specified as constant head to sophisticated LAK packages for MODFLOW. Although model input can be complex, the LAK package capabilities and output are superior to methods that rely on a fixed lake stage and compare well to other simple methods where lake stage can be calculated. Regardless of the approach, guidelines presented here for model grid size, location of three-dimensional flow, and extent of vertical capture can facilitate the construction of appropriately detailed models that simulate important lake-ground water interactions without adding unnecessary complexity. In addition to MODFLOW approaches, lake simulation has been formulated in terms of analytic elements. The analytic element lake package had acceptable agreement with a published LAK1 problem, even though there were differences in the total lake conductance and number of layers used in the two models. The grid size used in the original LAK1 problem, however, violated a grid size guideline presented in this paper. Grid sensitivity analyses demonstrated that an appreciable discrepancy in the distribution of stream and lake flux was related to the large grid size used in the original LAK1 problem. This artifact is expected regardless of MODFLOW LAK package used. When the grid size was reduced, a finite-difference formulation approached the analytic element results. These insights and guidelines can help ensure that the proper lake simulation tool is being selected and applied.

  3. I. Cognitive and instructional factors relating to students' development of personal models of chemical systems in the general chemistry laboratory II. Solvation in supercritical carbon dioxide/ethanol mixtures studied by molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Anthony, Seth

    likely to appear in students' post-laboratory refined models. These discussions during the laboratory period are primarily prompted by factors external to the students or their laboratory groups such as questions posed by the instructor or laboratory materials. Part II. Solvation of polar molecules within non-polar supercritical carbon dioxide is often facilitated by the introduction of polar cosolvents as entrainers, which are believed to preferentially surround solute molecules. Molecular dynamics simulations of supercritical carbon dioxide/ethanol mixtures reveal that ethanol molecules form hydrogen-bonded aggregates of varying sizes and structures, with cyclic tetramers and pentamers being unusually prevalent. The dynamics of ethanol molecules within these mixtures at a range of thermodynamic conditions can largely be explained by differences in size and structure in these aggregates. Simulations that include solute molecules reveal enhancement of the polar cosolvent around hydrogen-bonding sites on the solute molecules, corroborating and helping to explain previously reported experimental trends in solute mobility.

  4. Supercritical microgravity droplet vaporization

    NASA Technical Reports Server (NTRS)

    Hartfield, J.; Curtis, E.; Farrell, P.

    1990-01-01

    Supercritical droplet vaporization is an important issue in many combustion systems, such as liquid fueled rockets and compression-ignition (diesel) engines. In order to study the details of droplet behavior at these conditions, an experiment was designed to provide a gas phase environment which is above the critical pressure and critical temperature of a single liquid droplet. In general, the droplet begins as a cold droplet in the hot, high pressure environment. In order to eliminate disruptions to the droplet by convective motion in the gas, forced and natural convection gas motion are required to be small. Implementation of this requirement for forced convection is straightforward, while reduction of natural convection is achieved by reduction in the g-level for the experiment. The resulting experiment consists of a rig which can stably position a droplet without restraint in a high-pressure, high temperature gas field in microgravity. The microgravity field is currently achieved by dropping the device in the NASA Lewis 2.2 second drop tower. The performance of the experimental device and results to date are presented.

  5. Resolving Supercritical Orion Cores

    NASA Astrophysics Data System (ADS)

    Li, Di; Chapman, N.; Goldsmith, P.; Velusamy, T.

    2009-01-01

    The theoretical framework for high mass star formation (HMSF) is unclear. Observations reveal a seeming dichotomy between high- and low-mass star formation, with HMSF occurring only in Giant Molecular Clouds (GMC), mostly in clusters, and with higher star formation efficiencies than low-mass star formation. One crucial constraint to any theoretical model is the dynamical state of massive cores, in particular, whether a massive core is in supercritical collapse. Based on the mass-size relation of dust emission, we select likely unstable targets from a sample of massive cores (Li et al. 2007 ApJ 655, 351) in the nearest GMC, Orion. We have obtained N2H+ (1-0) maps using CARMA with resolution ( 2.5", 0.006 pc) significantly better than existing observations. We present observational and modeling results for ORI22. By revealing the dynamic structure down to Jeans scale, CARMA data confirms the dominance of gravity over turbulence in this cores. This work was performed by the Jet Propulsion Laboratory, California Institute of Technology, under contract with the National Aeronautics and Space Administration.

  6. D/H isotopic fractionation effects in the H2-H2O system: An in-situ experimental study at supercritical water conditions

    NASA Astrophysics Data System (ADS)

    Foustoukos, D.; Mysen, B. O.

    2011-12-01

    Understanding the effect of temperature on the relative distribution of volatiles in supercritical aqueous solutions is important to constrain elemental and isotopic partitioning/fractionation effects in systems applicable to planetary interiors where the temperature-pressure conditions are often beyond existing experimental or theoretical datasets. For example, very little exists for the fundamental equilibria between H2, D2 and HD (H2 + D2 = 2HD), which, in turn, constrains the internal D/H isotope exchange and the evolution of HD in H2-containing systems such as H2-CH4 and H2-H2O. Theoretical calculations considering the partition functions of the molecules predict that with temperature increase, the equilibrium constant of this reaction approximates values that correspond to the stochastic distribution of species. These calculations consider pure harmonic vibrational frequencies, which, however, do not apply to the diatomic molecule of hydrogen, especially because anharmonic oscillations are anticipated to become stronger at high temperatures. Published experimental data have been limited to conditions lower than 468°C with large uncertainties at elevated temperatures. To address the lack of experimental data, a series of hydrothermal diamond anvil experiments has been conducted utilizing vibrational spectroscopy as a novel quantitative method to explore the relative distribution of H- and D-bearing volatiles in the H2-D2-D2O-H2O-Ti-TiO2 system. The fundamentals of this methodology are based on the distinct Raman frequency shift resulting from deuterium substitution in the H-H and O-H bonds. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (for 3-9hrs) at 600-800°C and pressures of 0.5-1 GPa, leading to formation of H2, D2, HD and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in-situ and in the quenched gas phase, indicate a significant deviation from the theoretical estimate of the equilibrium

  7. Water properties inside nanoscopic hydrophobic pocket studied by computer simulations

    NASA Astrophysics Data System (ADS)

    Setny, Piotr; Geller, Maciej

    2006-10-01

    The structure and dynamics of water in the vicinity of the hemispherical hydrophobic pocket of 8Å radius were examined via molecular dynamics simulations in NVT ensemble. Density, hydrogen bonding properties, and residence times of water molecules were projected on two-dimensional planes providing a spatial description of water behavior. We found that the average water density is significantly depleted relative to bulk value. A detailed analysis of pocket occupancy revealed fluctuations between states of completely empty pocket and a pocket filled with a bulklike fluid, which seem to result from collective behavior of water molecules. Free energy differences accompanying these fluctuations are rather small, suggesting that the given pocket radius is close to the critical one for transition between gas and liquid phases in the considered system. We show that the situation is different in the case of a simple Lennard-Jones fluid. These results indicate that changing the surface curvature from flat to concave may lead to qualitative difference in water behavior in its vicinity. We think that our studies may also put some light on binding site desolvation process which is necessary to understand to make correct predictions of binding energies.

  8. Modeling of supercritical fluid extraction from herbaceous matrices

    SciTech Connect

    Reverchon, E.; Donsi, G.; Osseo, L.S. . Dipt. di Ingegneria Chimica e Alimentare)

    1993-11-01

    Experimental results of supercritical fluid extraction from various herbaceous matrices are presented. In optimal extraction conditions, the use of a fractional separation technique allows a nearly complete separation of the extract in cuticular waxes and essential oil. The modeling of these results is proposed starting from the description of the mass transfer from a single spherical particle. The simultaneous extraction of two pseudocompounds is assumed to simulate the two compound families obtained by fractionation. The model is then extended to simulate the whole extractor. The yields of essential oil and cuticular waxes obtained from rosemary, basil, and marjoram leaves are fairly simulated by the model. Intraparticle mass transfer resulted as the controlling stage in supercritical extraction of essential oils.

  9. Quantification of Water Erosion on Subalpine Grassland with Rain Simulators

    NASA Astrophysics Data System (ADS)

    Schindler, Y.; Alewell, Ch.; Burri, K.; Bänninger, D.

    2009-04-01

    Intensive land use and increasing storm events trigger rain erosion, thus its quantification is important. The aim of this study was to asses the influence of the vegetation on runoff and water erosion in an alpine grassland area. Further, we estimated the influence of vegetation on the soil characteristics matrix stability and C/N ratio and assessed the relationship between those parameters as well as the grain size distribution with erosion and runoff rate. To test the above hypotheses a field spray nozzles drop former hybrid simulator, consisting of a full-core Lechler nozzle and a meshed fixed below to improve the rain drop distribution, was used. Prior to the field experiment, we compared this simulator with a drop former simulator in the laboratory at the Swiss Federal Institute for Forest, Snow and Landscape Research (WSL) in terms of drop size distribution and kinetic energy. Thereby, we could estimate the accuracy of the field simulator. The rain drop size distribution and the total kinetic energy of the drops at a rain intensity of 60 mm h-1 were measured with a Joss-Waldvogel distrometer. To compare the effect of the two rain simulators as well as the influence of the soil texture on erosion and runoff rate, we used 6 silty soil monoliths and 6 clayish monoliths. To get comparable initial conditions, every soil monolith was irrigated only one time, starting at field capacity. The soil moisture was continuously recorded by TDR probes during the simulation. The comparison of the two rain simulators showed a close similarity in the drop size distributions. For both simulators, the most frequent drop size class is in the range of 1 mm in diameter. Natural rain typically shows a larger mean drop size at an intensity of 60 mm h-1. In comparison to the natural rain, the total kinetic energy of the simulated rain of both of the simulators was too small as well. These results lead to the conclusion, that the true simulation of a natural rain is hardly realizable

  10. Preparing Silica Aerogel Monoliths via a Rapid Supercritical Extraction Method

    PubMed Central

    Gorka, Caroline A.

    2014-01-01

    A procedure for the fabrication of monolithic silica aerogels in eight hours or less via a rapid supercritical extraction process is described. The procedure requires 15-20 min of preparation time, during which a liquid precursor mixture is prepared and poured into wells of a metal mold that is placed between the platens of a hydraulic hot press, followed by several hours of processing within the hot press. The precursor solution consists of a 1.0:12.0:3.6:3.5 x 10-3 molar ratio of tetramethylorthosilicate (TMOS):methanol:water:ammonia. In each well of the mold, a porous silica sol-gel matrix forms. As the temperature of the mold and its contents is increased, the pressure within the mold rises. After the temperature/pressure conditions surpass the supercritical point for the solvent within the pores of the matrix (in this case, a methanol/water mixture), the supercritical fluid is released, and monolithic aerogel remains within the wells of the mold. With the mold used in this procedure, cylindrical monoliths of 2.2 cm diameter and 1.9 cm height are produced. Aerogels formed by this rapid method have comparable properties (low bulk and skeletal density, high surface area, mesoporous morphology) to those prepared by other methods that involve either additional reaction steps or solvent extractions (lengthier processes that generate more chemical waste).The rapid supercritical extraction method can also be applied to the fabrication of aerogels based on other precursor recipes. PMID:24637334

  11. Impregnation of Fenofibrate on mesoporous silica using supercritical carbon dioxide.

    PubMed

    Bouledjouidja, Abir; Masmoudi, Yasmine; Van Speybroeck, Michiel; Schueller, Laurent; Badens, Elisabeth

    2016-02-29

    Low oral bioavailability can be circumvented by the formulation of the poorly water soluble drug in ordered mesoporous silica (OMS-L-7). Fenofibrate is an orally administered, poorly water-soluble active pharmaceutical ingredient (API), used clinically to lower lipid levels. Fenofibrate was loaded into silica using two methods: incipient wetness and supercritical impregnation. This study investigates the impact of loading and the impact of varying supercritical carbon dioxide (scCO2) processing conditions. The objective is to enhance Fenofibrate loading into silica while reducing degree of the drug crystallinity, so as to increase the drug's dissolution rate and its bioavailability. The comparison of both impregnation processes was made in terms of impregnation yields and duration as well as physical characterization of the drug. While incipient wetness method led to a Fenofibrate loading up to 300 mgdrug/gsilica in 48 h of impregnation, the supercritical impregnation method yielded loading up to 485 mgdrug/gsilica in 120 min of impregnation duration, at 16 MPa and 308 K, with a low degree of crystallinity (about 1%) comparable to the crystallinity observed via the solvent method. In addition to the enhancement of impregnation efficiency, the supercritical route provides a solvent-free alternative for impregnation.

  12. Impregnation of Fenofibrate on mesoporous silica using supercritical carbon dioxide.

    PubMed

    Bouledjouidja, Abir; Masmoudi, Yasmine; Van Speybroeck, Michiel; Schueller, Laurent; Badens, Elisabeth

    2016-02-29

    Low oral bioavailability can be circumvented by the formulation of the poorly water soluble drug in ordered mesoporous silica (OMS-L-7). Fenofibrate is an orally administered, poorly water-soluble active pharmaceutical ingredient (API), used clinically to lower lipid levels. Fenofibrate was loaded into silica using two methods: incipient wetness and supercritical impregnation. This study investigates the impact of loading and the impact of varying supercritical carbon dioxide (scCO2) processing conditions. The objective is to enhance Fenofibrate loading into silica while reducing degree of the drug crystallinity, so as to increase the drug's dissolution rate and its bioavailability. The comparison of both impregnation processes was made in terms of impregnation yields and duration as well as physical characterization of the drug. While incipient wetness method led to a Fenofibrate loading up to 300 mgdrug/gsilica in 48 h of impregnation, the supercritical impregnation method yielded loading up to 485 mgdrug/gsilica in 120 min of impregnation duration, at 16 MPa and 308 K, with a low degree of crystallinity (about 1%) comparable to the crystallinity observed via the solvent method. In addition to the enhancement of impregnation efficiency, the supercritical route provides a solvent-free alternative for impregnation. PMID:26732521

  13. Improved simulation of groundwater - surface water interaction in catchment models

    NASA Astrophysics Data System (ADS)

    teklesadik, aklilu; van Griensven, Ann; Anibas, Christian; Huysmans, Marijke

    2016-04-01

    Groundwater storage can have a significant contribution to stream flow, therefore a thorough understanding of the groundwater surface water interaction is of prime important when doing catchment modeling. The aim of this study is to improve the simulation of groundwater - surface water interaction in a catchment model of the upper Zenne River basin located in Belgium. To achieve this objective we used the "Groundwater-Surface water Flow" (GSFLOW) modeling software, which is an integration of the surface water modeling tool "Precipitation and Runoff Modeling system" (PRMS) and the groundwater modeling tool MODFLOW. For this case study, the PRMS model and MODFLOW model were built and calibrated independently. The PRMS upper Zenne River basin model is divided into 84 hydrological response units (HRUs) and is calibrated with flow data at the Tubize gauging station. The spatial discretization of the MODFLOW upper Zenne groundwater flow model consists of 100m grids. Natural groundwater divides and the Brussels-Charleroi canal are used as boundary conditions for the MODFLOW model. The model is calibrated using piezometric data. The GSFLOW results were evaluated against a SWAT model application and field observations of groundwater-surface water interactions along a cross section of the Zenne River and riparian zone. The field observations confirm that there is no exchange of groundwater beyond the Brussel-Charleroi canal and that the interaction at the river bed is relatively low. The results show that there is a significant difference in the groundwater simulations when using GSFLOW versus SWAT. This indicates that the groundwater component representation in the SWAT model could be improved and that a more realistic implementation of the interactions between groundwater and surface water is advisable. This could be achieved by integrating SWAT and MODFLOW.

  14. Water at an electrochemical interface - a simulation study

    SciTech Connect

    Willard, Adam; Reed, Stewart; Madden, Paul; Chandler, David

    2008-08-22

    The results of molecular dynamics simulations of the properties of water in an aqueous ionic solution close to an interface with a model metallic electrode are described. In the simulations the electrode behaves as an ideally polarizable hydrophilic metal, supporting image charge interactions with charged species, and it is maintained at a constant electrical potential with respect to the solution so that the model is a textbook representation of an electrochemical interface through which no current is passing. We show how water is strongly attracted to and ordered at the electrode surface. This ordering is different to the structure that might be imagined from continuum models of electrode interfaces. Further, this ordering significantly affects the probability of ions reaching the surface. We describe the concomitant motion and configurations of the water and ions as functions of the electrode potential, and we analyze the length scales over which ionic atmospheres fluctuate. The statistics of these fluctuations depend upon surface structure and ionic strength. The fluctuations are large, sufficiently so that the mean ionic atmosphere is a poor descriptor of the aqueous environment near a metal surface. The importance of this finding for a description of electrochemical reactions is examined by calculating, directly from the simulation, Marcus free energy profiles for transfer of charge between the electrode and a redox species in the solution and comparing the results with the predictions of continuum theories. Significant departures from the electrochemical textbook descriptions of the phenomenon are found and their physical origins are characterized from the atomistic perspective of the simulations.

  15. Humans Running in Place on Water at Simulated Reduced Gravity

    PubMed Central

    Minetti, Alberto E.; Ivanenko, Yuri P.; Cappellini, Germana; Dominici, Nadia; Lacquaniti, Francesco

    2012-01-01

    Background On Earth only a few legged species, such as water strider insects, some aquatic birds and lizards, can run on water. For most other species, including humans, this is precluded by body size and proportions, lack of appropriate appendages, and limited muscle power. However, if gravity is reduced to less than Earth’s gravity, running on water should require less muscle power. Here we use a hydrodynamic model to predict the gravity levels at which humans should be able to run on water. We test these predictions in the laboratory using a reduced gravity simulator. Methodology/Principal Findings We adapted a model equation, previously used by Glasheen and McMahon to explain the dynamics of Basilisk lizard, to predict the body mass, stride frequency and gravity necessary for a person to run on water. Progressive body-weight unloading of a person running in place on a wading pool confirmed the theoretical predictions that a person could run on water, at lunar (or lower) gravity levels using relatively small rigid fins. Three-dimensional motion capture of reflective markers on major joint centers showed that humans, similarly to the Basilisk Lizard and to the Western Grebe, keep the head-trunk segment at a nearly constant height, despite the high stride frequency and the intensive locomotor effort. Trunk stabilization at a nearly constant height differentiates running on water from other, more usual human gaits. Conclusions/Significance The results showed that a hydrodynamic model of lizards running on water can also be applied to humans, despite the enormous difference in body size and morphology. PMID:22815681

  16. Supercritical Fluid Reactions for Coal Processing

    SciTech Connect

    Charles A. Eckert

    1997-11-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we developed a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as one model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane. The Diels-Alder reaction of anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) was selected as a second model system, and it was investigated in supercritical carbon dioxide.

  17. Ion pre-acceleration in fully self-consistent particle-in-cell simulations of supercritical perpendicular reforming shocks in multiple ion species plasmas

    SciTech Connect

    Rekaa, V. L.; Chapman, S. C.; Dendy, R. O.

    2014-08-10

    Supernova remnant and heliopause termination shock plasmas may contain significant populations of minority heavy ions, with relative number densities n{sub α}/n{sub i} up to 50%. Preliminary kinetic simulations of collisionless shocks in these environments showed that the reformation cycle and acceleration mechanisms at quasi-perpendicular shocks can depend on the value of n{sub α}/n{sub i} . Shock reformation unfolds on ion spatio-temporal scales, requiring fully kinetic simulations of particle dynamics, together with the self-consistent electric and magnetic fields. This paper presents the first set of particle-in-cell simulations for two ion species, protons (n{sub p} ) and α-particles (n{sub α}), with differing mass and charge-to-mass ratios, that spans the entire range of n{sub α}/n{sub i} from 0% to 100%. The interplay between the differing gyro length scales and timescales of the ion species is crucial to the time-evolving phenomenology of the shocks, the downstream turbulence, and the particle acceleration at different n{sub α}/n{sub i} . We show how the overall energization changes with n{sub α}/n{sub i} , and relate this to the processes individual ions undergo in the shock region and in the downstream turbulence, and to the power spectra of magnetic field fluctuations. The crossover between shocks dominated by the respective ion species happens when n{sub α}/n{sub i} = 25%, and minority ion energization is strongest in this regime. Energization of the majority ion species scales with injection energy. The power spectrum of the downstream turbulence includes peaks at sequential ion cyclotron harmonics, suggestive of ion ring-beam collective instability.

  18. Assessment and development of an industrial wet oxidation system for burning waste and low upgrade fuels. Final report, Phase 2B: Pilot demonstration of the MODAR supercritical water oxidation process

    SciTech Connect

    Not Available

    1994-01-01

    Stone & Webster Engineering Corporation is Project Manager for the Development and Demonstration of an Industrial Wet Oxidation System for Burning Wastes and Low Grade Fuel. This progr