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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. Solvation in supercritical water

    SciTech Connect

    Cochran, H.D. ); Cummings, P.T.; Karaborni, S. . Dept. of Chemical Engineering)

    1991-01-01

    The aim of this work is to determine the solvation structure in supercritical water composed with that in ambient water and in simple supercritical solvents. Molecular dynamics studies have been undertaken of systems that model ionic sodium and chloride, atomic argon, and molecular methanol in supercritical aqueous solutions using the simple point charge model of Berendsen for water. Because of the strong interactions between water and ions, ionic solutes are strongly attractive in supercritical water, forming large clusters of water molecules around each ion. Methanol is found to be a weakly-attractive solute in supercritical water. The cluster of excess water molecules surrounding a dissolved ion or polar molecule in supercritical aqueous solutions is comparable to the solvent clusters surrounding attractive solutes in simple supercritical fluids. Likewise, the deficit of water molecules surrounding a dissolved argon atom in supercritical aqueous solutions is comparable to that surrounding repulsive solutes in simple supercritical fluids. The number of hydrogen bonds per water molecule in supercritical water was found to be about one third the number in ambient water. The number of hydrogen bonds per water molecule surrounding a central particle in supercritical water was only mildly affected by the identify of the central particle--atom, molecule, or ion. These results should be helpful in developing a qualitative understanding of important processes that occur in supercritical water. 29 refs., 6 figs.

  3. 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.

  4. 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.

  5. Assessment of hydrogen bonding effect on ionization of water from ambient to supercritical region-MD simulation approach

    NASA Astrophysics Data System (ADS)

    Swiatla-Wojcik, D.; Mozumder, A.

    2014-04-01

    We present a novel, molecular dynamics (MD) simulation based, strategy to analyze how the degree of hydrogen bonding may influence the ionization and dissociation of water upon heating from ambient to supercritical temperatures. Calculations show a negligible change in the ionization energy up to 200 °C. At higher temperatures the ionization energy increases due to the decreasing degree of hydrogen bonding. The influence of density (pressure) is pronounced in the supercritical region. The ionization is more energy consuming in the less dense fluid. We also show that high temperature and low density may promote dissociation of the electronically excited water molecules. Implications on the initial radiation chemical yields of the hydrated electron, hydrogen atom and hydroxyl radical are discussed.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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. PMID:25427299

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. Successful treatment with supercritical water oxidation

    SciTech Connect

    Jensen, R.

    1994-06-01

    Supercritical Water Oxidation (SCWO) operates in a totally enclosed system. It uses water at high temperatures and high pressure to chemically change wastes. Oily substances become soluble and complex hydrocarbons are converted into water and carbon dioxide. Research and development on SCWO is described.

  16. The partial pair correlation functions of dense supercritical water

    NASA Astrophysics Data System (ADS)

    Tassaing, T.; Bellissent-Funel, M.-C.; Guillot, B.; Guissani, Y.

    1998-05-01

    Neutron diffraction measurements of heavy water and of two isotopic H2O/D2O mixtures at supercritical state (T = 380 °C and ρD2O = 0.73 g/cm3) are presented. In combining the set of neutron diffraction data with previous X-rays measurements of Yamanaka et al. (J. Chem. Phys., 101 (1994) 9830), it has been possible by using a Monte Carlo method to reach the partial pair correlation functions gOH(r), gHH(r) and gOO(r). The results are compared with molecular-dynamics simulations using the SPCE pair potential for water. These new results confirm that hydrogen bonding is still present in dense supercritical water.

  17. 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.

  18. 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.

  19. 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.

  20. Supercritical methanol for polyethylene terephthalate depolymerization: observation using simulator.

    PubMed

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

    2007-01-01

    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(6)kJ/kmol Produced-DMT. That of PET depolymerization in vapor methanol was 2.84 x 10(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. PMID:16914302

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Containment system for supercritical water oxidation reactor

    SciTech Connect

    Chastagner, P.

    1991-12-31

    This invention is comprised of 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.

  6. 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.

  7. 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.

  8. 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

  9. Gasification of cyanobacterial in supercritical water.

    PubMed

    Zhang, Huiwen; Zhu, Wei; Xu, Zhirong; Gong, Miao

    2014-01-01

    Cyanobacterial collected from eutrophic freshwater lakes constituted intractable waste with a rich algae biomass content. Supercritical water gasification (SCWG) was proposed to treat the cyanobacterial and to produce hydrogen for energy. The H 2 yield reached 2.92 mol/kg at reaction conditions of 500 °C, 30 min and 22 MPa; this yield accounted for 26% of the total gaseous products. Abundant ammonia and dissolved reactive phosphorous were concentrated in the liquid product, which could be recovered and used as a liquid fertilizer. Solid residue, which accounted only for about 1% of the wet weight, was mainly composed of coke and ash. The efficiency of H 2 production was better than that from other biomass, because of the abundant organic matter in cyanobacterial. Thus, cyanobacterial are an ideal biomass feedstock for H 2 production from SCWG. PMID:25176482

  10. NMR study of compressed supercritical water

    NASA Astrophysics Data System (ADS)

    Lamb, W. J.; Jonas, J.

    1981-01-01

    The proton spin-lattice relaxation time T1 in water has been measured as a function of pressure in the temperature range 150 to 700°C. This study focuses on the supercritical region (tc=374°C) where the spin-rotation interaction mechanism dominates the observed proton relaxation rate. Since water is an asymmetric top molecule, the analysis of the experimental data involves a number of simplifying assumptions discussed in detail. The experimental finding that in supercritical water the spin-rotation relaxation time T 1SR is a linear function of density ρ, up to relatively high densities (ρ≃ 1.5 ρc) provides rationale for analysis of the NMR experimental data in terms of a model used for dilute gases. The T 1SR data are analyzed on the basis of the assumption that the collision modulated spin-rotation interactions can be described by a single correlation function which is an exponential function of time. Using this procedure, we find that T 1SR/ρ αT-2, i.e.T 1SR/ρ exhibits a stronger temperature dependence than that found (T 1SR/ρ αT-3/2) for many polar and nonpolar gases. The calculated effective cross sections for the transfer of angular momentum σeff which show strong temperature dependence (σeff αT-1.5) are several times larger than the kinetic cross sections. By assuming applicability of expressions derived for isotropic reorientation of spherical-top molecules and using the effective spin-rotation interaction constant as obtained from microwave measurements, we are able to calculate the angular momentum correlation time τJ, over the range of temperatures and densities studied. In the supercritical region τJ⩾τΘ, where τΘ is the reorientational correlation time, and the estimated mean angle of reorientation ΔΘ¯ is in the range 50° to 800°. The T 1SR data are also interpreted in terms of the modified rough hard sphere (RHS) model which for ρ<2ρc takes into account the effect of attractive forces. We find that 1/T 1SR is a linear

  11. Dynamical and structural properties of benzene in supercritical water.

    PubMed

    Nieto-Draghi, Carlos; Bonet Avalos, Josep; Contreras, Oliver; Ungerer, Philippe; Ridard, Jacqueline

    2004-12-01

    We have employed an anisotropic united atom model of benzene (R. O. Contreras, Ph.D. thesis, Universitat Rovira i Virgili 2002) that reproduces the quadrupolar moment of this molecule through the inclusion of seven point charges. We show that this kind of interaction is required to reproduce the solvation of these molecules in supercritical water. We have computed self-diffusion coefficient and Maxwell-Stefan coefficients as well as the shear viscosity for the mixture water-benzene at supercritical conditions. A strong density and composition dependence of these properties is observed. In addition, our simulations are in qualitative agreement with the experimental evidence that, at medium densities (0.6 g/cm(3) and 673 K), almost half of the benzene molecules have one hydrogen bond with water molecules. We also observe that these bonds are longer lived than the corresponding hydrogen bonds between water molecules. Similarly, we obtain an important reduction of the dielectric constant of the mixture with the increment of the amount of benzene molecules at medium and high densities. PMID:15549940

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

    Energy Science and Technology Software Center (ESTSC)

    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

  13. 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)

  14. 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)

  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. 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.

  17. 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.

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

    PubMed

    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. PMID:26395714

  19. 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.

  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. Supercritical water oxidation benchscale testing metallurgical analysis report

    SciTech Connect

    Norby, B.C.

    1993-02-01

    This report describes metallurgical evaluation of witness wires from a series of tests using supercritical water oxidation (SCWO) to process cutting oil containing a simulated radionuclide. The goal of the tests was to evaluate the technology`s ability to process a highly chlorinated waste representative of many mixed waste streams generated in the DOE complex. The testing was conducted with a bench-scale SCWO system developed by the Modell Development Corporation. Significant test objectives included process optimization for adequate destruction efficiency, tracking the radionuclide simulant and certain metals in the effluent streams, and assessment of reactor material degradation resulting from processing a highly chlorinated waste. The metallurgical evaluation described herein includes results of metallographic analysis and Scanning Electron Microscopy analysis of witness wires exposed to the SCWO environment for one test series.

  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. 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.

  5. 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)

  6. Research of a Supercritical Pressure Water Cooled Reactor in Korea

    SciTech Connect

    Bae, Yoon-Yeong; Joo, Hyung-Kook; Jang, Jinsung; Jeong, Yong-Hwan; Song, Jin-ho; Yoon, Han-Young; Yoo, Jung-Yul

    2004-07-01

    In this paper the activities on the supercritical pressure water-cooled reactor (SCWR) in Korea are briefly introduced. Four projects on a SCWR are being conducted in Korea. Three of them are supported by the I-NERI program while one is by KAERI. Two of the I-NERI-supported projects concern suitable materials for supercritical pressure and temperature, and radiation environment. The other I-NERI-supported project surveys numerically and experimentally the proper turbulence modeling for the numerical calculation of heat transfer phenomena at a supercritical condition. Heat transfer at a supercritical condition is being studied at KAERI experimentally using carbon dioxide as a coolant. The test loop is to be completed by the end of 2004. (authors)

  7. 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)

  8. Supercritical water oxidation - Concept analysis for evolutionary Space Station application

    NASA Technical Reports Server (NTRS)

    Hall, John B., Jr.; Brewer, Dana A.

    1986-01-01

    The ability of a supercritical water oxidation (SCWO) concept to reduce the number of processes needed in an evolutionary Space Station design's Environmental Control and Life Support System (ECLSS), while reducing resupply requirements and enhancing the integration of separate ECLSS functions into a single Supercritical Water Oxidation process, is evaluated. While not feasible for an initial operational capability Space Station, the SCWO's application to the evolutionary Space Station configuration would aid the integration of eight ECLSS functions into a single one, thereby significantly reducing program costs.

  9. Treatment of sewage sludge in supercritical water and evaluation of the combined process of supercritical water gasification and oxidation.

    PubMed

    Qian, Lili; Wang, Shuzhong; Xu, Donghai; Guo, Yang; Tang, Xingying; Wang, Longfei

    2015-01-01

    Influences of temperature and oxidation coefficient (n) on sewage sludge treatment in supercritical water and its corresponding reaction mechanism were studied. Moreover, the combined process of supercritical water gasification (SCWG) and supercritical water oxidation (SCWO) was also investigated. The results show that ammonia nitrogen, phenols and pyridines are main refractory intermediates. The weight of solid products at 873K and n=4 is only 3.5wt.% of the initial weight, which is lower than that after combustion. Volatile organics in solid phase have almost released at 723K and n=0. Highest yield of combustible gases was obtained at n=0, and H2 yield can reach 11.81mol/kg at 873K. Furthermore, the combination of SCWG at 723K and SCWO at 873K with a total n=1 is feasible for its good effluent quality and low operation costs. PMID:25461006

  10. Simulated propeller slipstream effects on a supercritical wing

    NASA Technical Reports Server (NTRS)

    Welge, H. R.; Crowder, J. P.

    1978-01-01

    To quantify the installed performance of high speed (M = 0.8) turboprop propulsion systems, an experimental program designed to assess the magnitude of the aerodynamic interference of a propeller slipstream on a supercritical wing has been conducted. The test was conducted in the NASA Ames 14-foot wind tunnel. An ejector-nacelle propeller slipstream simulator was used to produce a slipstream with characteristics typical of advanced propellers presently being investigated. A supercritical wing-body configuration was used to evaluate the interference effects. A traversing total pressure rake was used to make flow field measurements behind the wing and to calibrate the slipstream simulator. The force results indicated that the interference drag amounted to an increase of ten counts or about 3% of the wing-body drag for a two engine configuration at the nominal propeller operating conditions. However, at the higher swirl angles (11 deg vs. 7 deg nominally) the interference drag was favorable by about the same magnitude.

  11. Gasification of diesel oil in supercritical water for fuel cells

    NASA Astrophysics Data System (ADS)

    Pinkwart, Karsten; Bayha, Thomas; Lutter, Wolfgang; Krausa, Michael

    Experiments have demonstrated the reforming of hydrocarbons in supercritical water. The hydrocarbons were reformed in a continuously operated tubular V4A reactor. The influences of four different commercial steam reforming catalysts were analysed. The experimental results showed that n-decane can be converted to a hydrogen-rich gas. Furthermore, experiments with diesel oil showed the possibility of fuel conversion at low temperature with commercial steam reforming catalysts. Low temperatures and the use of catalysts lead to inhibition of coke formation during the process. The supercritical reforming offers the possibility of a new low temperature hydrocarbon conversion process to hydrogen for fuel cell applications.

  12. Treatment of municipal sewage sludge in supercritical water: A review.

    PubMed

    Qian, Lili; Wang, Shuzhong; Xu, Donghai; Guo, Yang; Tang, Xingying; Wang, Laisheng

    2016-02-01

    With increasing construction of wastewater treatment plants and stricter policies, municipal sewage sludge (MSS) disposal has become a serious problem. Treatment of MSS in supercritical water (SCW) can avoid the pre-drying procedure and secondary pollution of conventional methods. SCW treatment methods can be divided into supercritical water gasification (SCWG), supercritical water partial oxidation (SCWPO) and supercritical water oxidation (SCWO) technologies with increasing amounts of oxidants. Hydrogen-rich gases can be generated from MSS by SCWG or SCWPO technology using oxidants less than stoichiometric ratio while organic compounds can be completely degraded by SCWO technology with using an oxidant excess. For SCWG and SCWPO technologies, this paper reviews the influences of different process variables (MSS properties, moisture content, temperature, oxidant amount and catalysts) on the production of gases. For SCWO technology, this paper reviews research regarding the removal of organics with or without hydrothermal flames and the changes in heavy metal speciation and risk. Finally, typical systems for handling MSS are summarized and research needs and challenges are proposed. PMID:26645649

  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 for destruction of polycyclic aromatic hydrocarbons

    SciTech Connect

    Kocher, B.S.; Fullerton, K.L.; Lee, S.

    1994-12-31

    Polycyclic aromatic hydrocarbons (PAHs) represent a large class of hydrocarbons that are considered hazardous to the environment. Large amount of PAHs have been dumped onto open ground in cases such as Town gas sites. These sites represent a major environmental liability due to the difficulty in removing them by conventional methods and the large amount of sites, more than 2,000. Supercritical water oxidation offers a unique method of both removing the contaminates and destroying them in a single stage processing step. The process utilizes the single phase mixture of water and oxygen at supercritical water conditions. This allows for the PAHs to be extracted and destroyed simultaneously. The reaction produces an effluent stream rich in carbon dioxide and water. Town gas soil containing 3.37 wt% contamination was ultra-cleaned in a 1-liter pilot plant to an environmentally acceptable level of less than 200 ppm.

  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. Process for treating effluent from a supercritical water oxidation reactor

    SciTech Connect

    Barnes, C.M.; Shapiro, C.

    1995-12-31

    The present invention relates generally to a method for treating and recycling the effluent from a supercritical water oxidation reactor and more specifically to a method for treating and recycling the effluent by expanding the effluent without extensive cooling. Supercritical water oxidation is the oxidation of fuel, generally waste material, in a body of water under conditions above the thermodynamic critical point of water. The current state of the art in supercritical water oxidation plant effluent treatment is to cool the reactor effluent through heat exchangers or direct quench, separate the cooled liquid into a gas/vapor stream and a liquid/solid stream, expand the separated effluent, and perform additional purification on gaseous, liquid, brine and solid effluent. If acid gases are present, corrosion is likely to occur in the coolers. During expansion, part of the condensed water will revaporize. Vaporization can damage the valves due to cavitation and erosion. The present invention expands the effluent stream without condensing the stream. Radionuclides and suspended solids are more efficiently separated in the vapor phase. By preventing condensation, the acids are kept in the much less corrosive gaseous phase thereby limiting the damage to treatment equipment. The present invention also reduces the external energy consumption, by utilizing the expansion step to also cool the effluent.

  18. Amphoteric reactions of supercritical water with coal models

    SciTech Connect

    Horiuchi, A.K.; Fish, H.T.; Mikita, M.A.

    1988-01-01

    For the past several years this laboratory has been studying water assisted coal liquefaction. Initial experiments were designed to determine whether water could replace all or part of the donor solvent in coal liquefaction. More recent work has focused upon the chemical reactions of coal models in supercritical water. For the past year efforts have centered upon the study of two distinct coal model compound systems (bibenzyls and benzyl phenyl ethers) with water under liquefaction conditions. This research is intended to further evaluate the chemical role of water above its critical temperature in the conversion of coal to a liquefaction product. Results are discussed.

  19. 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

  20. 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.

  1. 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

  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. Acetic acid oxidation and hydrolysis in supercritical water

    SciTech Connect

    Meyer, J.C.; Marrone, P.A.; Tester, J.W.

    1995-09-01

    Acetic acid (CH{sub 3}COOH) hydrolysis and oxidation in supercritical water were examined from 425--600 C and 246 bar at reactor residence times of 4.4 to 9.8 s. Over the range of conditions studied, acetic acid oxidation was globally 0.72 {+-} 0.15 order in acetic acid and 0.27 {+-} 0.15 order in oxygen to a 95% confidence level, with an activation energy of 168 {+-} 21 kJ/mol, a preexponential factor of 10{sup 9.9{+-}1.7}, and an induction time of about 1.5 s at 525 C. Isothermal kinetic measurements at 550 C over the range 160 to 263 bar indicated that pressure or density did not affect the rate of acetic acid oxidation as much as was previously observed in the oxidation of hydrogen or carbon monoxide in supercritical water. Major products of acetic acid oxidation in supercritical water are carbon dioxide, carbon monoxide, methane, and hydrogen. Trace amounts of propenoic acid were occasionally detected. Hydrolysis or hydrothermolysis in the absence of oxygen resulted in approximately 35% conversion of acetic acid at 600 C, 246 bar, and 8-s reactor residence time. Regression of the limited hydrolysis runs assuming a reaction rate first-order in organic gave a global rate expression with a preexponential factor of 10{sup 4.4{+-}1.1} and an activation energy of 94 {+-} 17 kJ/mol.

  4. 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.

  5. Simulation of a Supercritical Fluid Flow with Large Temperature Difference under the Assumption of Constant Pressure

    NASA Astrophysics Data System (ADS)

    Komurasaki, Satoko

    2015-11-01

    Eruption of geothermally heated water from the hydrothermal vent in deep oceans of depth over 2,000 meters is numerically simulated. The hydrostatic pressure of water is assumed to be over 200 atmospheres, and the temperature of heated water is occasionally more than 300°C. Under these conditions, a part of heated water can be in the supercritical state, and the physical properties can change significantly by the temperature. Particularly, thermal diffusivity at the critical temperature becomes so small, which prevents heat diffusion, and the temperature gradients can become high. Simulation of this kind of fluid flow can be carried out only by using a highly robust scheme. In this paper, a scheme for a highly-unsteady-flow computation is introduced, and a supercritical fluid flow with a large temperature difference is simulated at a constant pressure. In the computation, the compressible Navier-Stokes equations are solved using a method for the incompressible equations under constant pressure. The equations are approximated by the multidirectional finite difference method and KK scheme is used to stabilize the high-accuracy computation. This work was partially supported by Grant-in-Aid for Scientific Research from MEXT/JSPS (26610119).

  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. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Separation of ionic species under supercritical water conditions

    SciTech Connect

    Li, L.; Gloyna, E.F.

    1999-04-01

    The unique characteristics of supercritical water (SCW) offer potentially attractive processing options that can be explored for reaction and separation purposes. While supercritical water oxidation (SCWO) can achieve high organic conversion efficiencies, low and relative solubilities of inorganic species in SCW may be further utilized for in situ separation of potential by-products from the SCWO process effluent. This paper describes a novel method for separating ionic species under SCW conditions. The concept is based on relative solubilities of different ionic species in SCW. Laboratory-scale demonstration tests were conducted with a Nylon monomer manufacturing process wastewater containing sodium hydroxide, sodium borate, carboxylic acids, and water. The process achieved (1) effective destruction (> 99%) of organic components in the wastewater; (2) selective precipitation of sodium (> 99.5%) as carbonates produced from oxidation of the organic components; and (3) efficient recovery of boron (> 90%) as boric acid in the reactor effluent. The sodium removal efficiency is governed by the solubilities of sodium carbonates in SCW and, therefore, can be directly improved by increasing process temperature. As a result of the temperature increase, both organic destruction and boron recovery efficiencies may be enhanced. This method of selective separation of ionic species in SCW has potential for a wide range of processing applications.

  12. 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.

  13. 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. PMID:27194442

  14. 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.

  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. 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

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. 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

  2. Thermophysical properties of supercritical water and bond flexibility

    NASA Astrophysics Data System (ADS)

    Shvab, I.; Sadus, Richard J.

    2015-07-01

    Molecular dynamics results are reported for the thermodynamic properties of supercritical water using examples of both rigid (TIP 4 P /2005 ) and flexible (TIP 4 P /2005 f ) transferable interaction potentials. Data are reported for pressure, isochoric and isobaric heat capacities, the thermal expansion coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, speed of sound, self-diffusion coefficient, viscosities, and thermal conductivity. Many of these properties have unusual behavior in the supercritical phase such as maximum and minimum values. The effectiveness of bond flexibility on predicting these properties is determined by comparing the results to experimental data. The influence of the intermolecular potential on these properties is both variable and state point dependent. In the vicinity of the critical density, the rigid and flexible potentials yield very different values for the compressibilities, heat capacities, and thermal expansion coefficient, whereas the self-diffusion coefficient, viscosities, and thermal conductivities are much less potential dependent. Although the introduction of bond flexibility is a computationally expedient way to improve the accuracy of an intermolecular potential, it can be counterproductive in some cases and it is not an adequate replacement for incorporating the effects of polarization.

  3. 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.

  4. Direct energy recovery from primary and secondary sludges by supercritical water oxidation.

    PubMed

    Svanström, M; Modell, M; Tester, J

    2004-01-01

    Supercritical water oxidation (SCWO) oxidizes organic and biological materials virtually completely to benign products without the need for stack gas scrubbing. Heavy metals are recovered as stabilized solid, along with the sand and clay that is present in the feed. The technology has been under development for twenty years. The major obstacle to commercialization has been developing reactors that are not clogged by inorganic solid deposits. That problem has been solved by using tubular reactors with fluid velocities that are high enough to keep solids in suspension. Recently, system designs have been created that reduce the cost of processing sewage sludges below that of incineration. At 10 wt- % dry solids, sludge can be oxidized with virtually complete recovery of the sludge heating value as hot water or high-pressure steam. Liquid carbon dioxide of high purity can be recovered from the gaseous effluent and excess oxygen can be recovered for recycle. The net effect is to reduce the stack to a harmless vent with minimal flow rate of a clean gas. Complete simulations have been developed using physical property models that accurately simulate the thermodynamic properties of sub- and supercritical water in mixtures with O2, N2, CO2, and organics. Capital and operating cost estimates are given for sewage sludge treatment, which are less costly than incineration. The scenario of direct recovery of energy from sludges has inherent benefits compared to other gasification or liquefaction options. PMID:15259956

  5. 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

  6. 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.

  7. Thermal decomposition of substituted phenols in supercritical water

    SciTech Connect

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

    1997-05-01

    The thermal decomposition of cresols, hydroxybenzaldehydes, nitrophenols, and benzenediols was studied in dilute aqueous solutions and in the absence of oxygen at 460 C and 250 atm for residence times around 10 s. Thermolysis under these conditions produced conversions of less than 10% for o-, m-, and p-cresol, whereas hydroxybenzaldehydes and nitrophenols were much more reactive. Global rate expressions are reported for the thermolysis of each hydroxybenzaldehyde and nitrophenol isomer. Phenol was a major product from the decomposition of all of the substituted phenols studied. For a given substituent, ortho-substituted phenols reacted more rapidly than the other isomers. For a given substituted position, nitrophenols reacted more rapidly than hydroxybenzaldehydes, which in turn reacted more rapidly than cresols. These results demonstrate that the treatment of CHO- and NO{sub 2}-substituted phenols by oxidation in supercritical water will involve the oxidation of thermal decomposition products in addition to the oxidation of the original compounds.

  8. Prediction of physical properties of water under extremely supercritical conditions: a molecular dynamics study.

    PubMed

    Sakuma, Hiroshi; Ichiki, Masahiro; Kawamura, Katsuyuki; Fuji-ta, Kiyoshi

    2013-04-01

    The physical properties of water under a wide range of pressure and temperature conditions are important in fundamental physics, chemistry, and geoscience. Molecular simulations are useful for predicting and understanding the physical properties of water at phases extremely different from ambient conditions. In this study, we developed a new five-site flexible induced point charge model to predict the density, static dielectric constant, and transport properties of water in the extremely supercritical phase at high temperatures and pressures of up to 2000 K and 2000 MPa. The model satisfactorily reproduced the density, radial distribution function, static dielectric constant, reorientation time, and self-diffusion coefficients of water above the critical points. We also developed a database of the static dielectric constant, which is useful for discussing the electrical conductivity of aqueous fluids in the earth's crust and mantle. PMID:23574243

  9. 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

  10. Extraction of polychlorinated biphenyl with supercritical carbon dioxide, sulfur hexafluoride and subcritical water.

    PubMed

    Pross, S; Gau, W; Wenclawiak, B W

    2000-05-01

    In the extraction of spiked PCB from soil, three extracting fluids were investigated: supercritical carbon dioxide (CO2), supercritical sulfur hexafluoride (SF6) and subcritical water. Among the tested fluids SF6 appeared to be appropriate especially for the extraction of low polar PCB. CO2 and water were found to be suitable for the quantitative extraction of all PCB. Water was judged as the best because of its low price, good availability and environmental safety. PMID:11227442

  11. 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

  12. Subcritical and supercritical water oxidation of CELSS model wastes

    NASA Astrophysics Data System (ADS)

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

    Controlled-Ecological-Life-Support-System (CELSS) model wastes were wet-oxidized at temperatures from 250 to 500°C, i.e., below and above the critical point of water (374°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°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°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.

  13. Catalytic gasification of wet biomass in supercritical water

    SciTech Connect

    Antal, M.J. Jr.; Matsumura, Yukihiko; Xu, Xiaodong

    1995-12-31

    Wet biomass (water hyacinth, banana trees, cattails, green algae, kelp, etc.) grows rapidly and abundantly around the world. As a biomass crop, aquatic species are particularly attractive because their cultivation does not compete with land-based agricultural activities designed to produce food for consumption or export. However, wet biomass is not regarded as a promising feed for conventional thermochemical conversion processes because the cost associated with drying it is too high. This research seeks to address this problem by employing water as the gasification medium. Prior work has shown that low concentrations of glucose (a model compound for whole biomass) can be completely gasified in supercritical water at 600{degrees}C and 34.5 Wa after a 30 s reaction time. Higher concentrations of glucose (up to 22% by weight in water) resulted in incomplete conversion under these conditions. The gas contained hydrogen, carbon dioxide, carbon monoxide, methane, ethane, propane, and traces of other hydrocarbons. The carbon monoxide and hydrocarbons are easily converted to hydrogen by commercial technology available in most refineries. This prior work utilized capillary tube reactors with no catalyst. A larger reactor system was fabricated and the heterogeneous catalytic gasification of glucose and wet biomass slurry of higher concentration was studied to attain higher conversions.

  14. Destruction of nuclear organic waste by supercritical water oxidation. Scale-up of the process

    SciTech Connect

    Moussiere, S.; Roubaud, A.; Fournel, B.

    2007-07-01

    In order to design and then define appropriate dimensions for a supercritical oxidation reactor, a 2D and 3D simulation of the fluid dynamics and heat transfer during the oxidation process has been performed. The solver used is a commercial code, Fluent 6.2. The turbulent flow field in the reactor, created by the stirrer is taken into account with a k-omega model and a swirl imposed to the fluid. In the 3D case the rotation of the stirrer can be modeled thanks to the sliding mesh model. The reactivity of the system is taken into account with a classical combustion model EDC. Comparisons with experimental temperature measurements validate the ability of the CFD modeling to simulate the supercritical water oxidation process. Simulation results provide us a view inside the reactor on the flow, temperature fields and the oxidation localization and development. Results indicate that the flow can be considered as piston-like, heat transfers are strongly enhanced by the stirring. Hence the scaling up of the reactor volume, to reach a treatment capacity of 1 Kg/h of pure organics, can be done regarding the necessary residence times and temperature distribution needed for a complete destruction of the organic matter. (authors)

  15. 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.

  16. Destruction of explosives and rocket fuels by supercritical water oxidation

    SciTech Connect

    Dyer, R.B.; Buelow, S.J.; Harradine, D.M.; Robinson, J.M.; Foy, B.R.; Atencio, J.H.; Dell'Orco, P.C.; Funk, K.A.; McInroy, R.E.; Rofer, C.K.; Counce, D.A.; Trujillo, P.E. Jr. ); Wander, J.D. )

    1992-01-01

    Traditional methods for disposing of PEPs have been open burning or open detonation (OB/OD); however, regulatory agencies are likely to prohibit OB/OD because of the uncontrolled air emissions and soil contaminations. Likewise, controlled incineration carries a liability for air pollution because large quantities of NO{sub x} are produced in the conventional combustion chemistry of PEPS. Soil and ground water have already been contaminated with PEPs through normal operations at manufacturing plants and military bases. Incineration can be used for decontamination of these soils, with the associated liability for air pollution, but few satisfactory and economic methods exist for ground water decontamination. A clear need exists for improved disposal and destruction methods. The destruction of energetic materials, including propellants, explosives and pyrotechnics (PEPS) by oxidation in supercritical water is described. The focus is on the chemistry of the process. The destruction efficiencies and products of reaction contained in the aqueous and gaseous effluents of several representative PEPs are reported.

  17. Governing chemistry of cellulose hydrolysis in supercritical water.

    PubMed

    Cantero, Danilo A; Bermejo, M Dolores; Cocero, M José

    2015-03-01

    At extremely low reaction times (0.02 s), cellulose was hydrolyzed in supercritical water (T=400 °C and P=25 MPa) to obtain a sugar yield higher than 95 wt%, whereas the 5-hydroxymethylfurfural (5-HMF) yield was lower than 0.01 wt %. If the reaction time was increased to 1 s, the main product was glycolaldehyde (60 wt%). Independently of the reaction time, the yield of 5-HMF was always lower than 0.01 wt%. To evaluate the reaction mechanism of biomass hydrolysis in pressurized water, several parameters (temperature, pressure, reaction time, and reaction medium) were studied for different biomasses (cellulose, glucose, fructose, and wheat bran). It was found that the H(+) and OH(-) ion concentration in the reaction medium as a result of water dissociation is the determining factor in the selectivity. The reaction of glucose isomerization to fructose and the further dehydration to 5-HMF are highly dependent on the ion concentration. By an increase in the pOH/pH value, these reactions were minimized to allow control of 5-HMF production. Under these conditions, the retroaldol condensation pathway was enhanced, instead of the isomerization/dehydration pathway. PMID:25704124

  18. Destruction of explosives and rocket fuels by supercritical water oxidation

    SciTech Connect

    Dyer, R.B.; Buelow, S.J.; Harradine, D.M.; Robinson, J.M.; Foy, B.R.; Atencio, J.H.; Dell`Orco, P.C.; Funk, K.A.; McInroy, R.E.; Rofer, C.K.; Counce, D.A.; Trujillo, P.E. Jr.; Wander, J.D.

    1992-09-01

    Traditional methods for disposing of PEPs have been open burning or open detonation (OB/OD); however, regulatory agencies are likely to prohibit OB/OD because of the uncontrolled air emissions and soil contaminations. Likewise, controlled incineration carries a liability for air pollution because large quantities of NO{sub x} are produced in the conventional combustion chemistry of PEPS. Soil and ground water have already been contaminated with PEPs through normal operations at manufacturing plants and military bases. Incineration can be used for decontamination of these soils, with the associated liability for air pollution, but few satisfactory and economic methods exist for ground water decontamination. A clear need exists for improved disposal and destruction methods. The destruction of energetic materials, including propellants, explosives and pyrotechnics (PEPS) by oxidation in supercritical water is described. The focus is on the chemistry of the process. The destruction efficiencies and products of reaction contained in the aqueous and gaseous effluents of several representative PEPs are reported.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. On the kinetics of phenol oxidation in supercritical water

    SciTech Connect

    Krajnc, M.; Levec, J.

    1996-07-01

    Phenol oxidation in supercritical water was carried out in a tubular laboratory-scale reactor operated at a temperature range of 380 C to 450 C and pressures between 230 and 265 bar. The phenol feed concentrations were between 500 and 1,000 mg/L, while oxygen was fed into the reactor at 50 to 1,000% of the stoichiometric amount needed to oxidize phenol completely to carbon dioxide. Phenol conversions from 16 to 96% were attained as the reactor residence times varied from 15 to 203 s. The oxidation obeys a parallel-consecutive reaction scheme that involves multi-ring, intermediate products such as phenoxyl-phenol, biphenol, dibenzo-dioxin, maleic acid, and succinic acid. Experimental results showed that the phenol disappearance rate is represented well by a power-law kinetic model in which the rate is proportional to the 0.4 power of the oxygen mole fraction and roughly linearly proportional to the phenol mole fraction. The pressure effect on the disappearance rate was appropriately accounted for by introducing the molar volume of the reaction mixture, which was readily calculated by an equation of state. Total organic carbon reduction can be estimated by a lumped kinetic equation. In the P-T region the activation energy of the phenol disappearance was 124.7 kJ/mol.

  7. 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).

  8. Treatment of pulp mill sludges by supercritical water oxidation

    SciTech Connect

    Modell, M.

    1990-07-01

    Supercritical water oxidation (SCWO) is new process that can oxidize organics very effectively at moderate temperatures (400 to 650{degree}C) and high pressure (3700 psi). It is an environmentally acceptable alternative for sludge treatment. In bench scale tests, total organic carbon (TOC) and total organic halide (TOX) reductions of 99 to 99.9% were obtained; dioxin reductions were 95 to 99.9%. A conceptual design for commercial systems has been completed and preliminary economics have been estimated. Comparisons confirm that SCWO is less costly than dewatering plus incineration for treating pulp mill sludges. SCWO can also compete effectively with dewatering plus landfilling where tipping fees exceed $35/yd{sup 3}. In some regions of the US, tipping fees are now $75/yd{sup 3} and rising steadily. In the 1995 to 2000 time frame, SCWO has a good chance of becoming the method of choice. MODEC's objective is to bring the technology to commercial availability by 1993. 10 refs., 6 figs., 19 tabs.

  9. 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.

  10. 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

  11. 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.

  12. Supercritical water oxidation of a model fecal sludge without the use of a co-fuel.

    PubMed

    Miller, A; Espanani, R; Junker, A; Hendry, D; Wilkinson, N; Bollinger, D; Abelleira-Pereira, J M; Deshusses, M A; Inniss, E; Jacoby, W

    2015-12-01

    A continuous supercritical water oxidation reactor was designed and constructed to investigate the conversion of a feces simulant without the use of a co-fuel. The maximum reactor temperature and waste conversion was determined as a function of stoichiometric excess of oxygen in order to determine factor levels for subsequent investigation. 48% oxygen excess showed the highest temperature with full conversion. Factorial analysis was then used to determine the effects of feed concentration, oxygen excess, inlet temperature, and operating pressure on the increase in the temperature of the reacting fluid as well as a newly defined non-dimensional number, NJa representing heat transfer efficiency. Operating pressure and stoichiometric excess oxygen were found to have the most significant impacts on NJa. Feed concentration had a significant impact on fluid temperature increase showing an average difference of 46.4°C between the factorial levels. PMID:26210324

  13. RAS and LES Simulation of the supercritical flow over the waving bed

    NASA Astrophysics Data System (ADS)

    Fu, X.; Ma, H.; Heyman, J.; Mettra, F.; Liu, D.; Ancey, C.

    2013-12-01

    The phenomena of bed forms exist widely in the natural rivers and are still not fully understood. The detailed sediment dynamics near the bed is essential for this problem. However, the fluid dynamics near the bed, which drives the sediment motion, is not clear. In this talk, we focus on the fluid dynamics of supercritical flow over a sinusoidal wavy bed, especially around the wall region. This setup mimics anti-dunes morphology i.e. bedforms that are commonly found in steep mountain streams. In this case, the flow depth and the bedform amplitude have the same order of magnitude with the amplitude of the bedform. To study the detailed fluid flow, a 3-Dimensional numerical simulation of Navier-Stokes equations is performed. Two different models, Reynolds Average Simulation (RAS) and Large Eddy Simulation (LES), are used for the turbulence closure. The two models are validated with experiments carried out on a wavy bed. Particular attention is paid to the fluid shear stress on the wavy bed and the bedform equivalent roughness. LES shows more abilities for this problem. In future, various wavelength and amplitude of the sinus wave will be implemented so that new shear stress formulas and parameterization for the anti-dune roughness in shallow water equations will be proposed.

  14. Re-forming supercritical quasi-parallel shocks. I - One- and two-dimensional simulations

    NASA Technical Reports Server (NTRS)

    Thomas, V. A.; Winske, D.; Omidi, N.

    1990-01-01

    The process of reforming supercritical quasi-parallel shocks is investigated using one-dimensional and two-dimensional hybrid (particle ion, massless fluid electron) simulations both of shocks and of simpler two-stream interactions. It is found that the supercritical quasi-parallel shock is not steady. Instread of a well-defined shock ramp between upstream and downstream states that remains at a fixed position in the flow, the ramp periodically steepens, broadens, and then reforms upstream of its former position. It is concluded that the wave generation process is localized at the shock ramp and that the reformation process proceeds in the absence of upstream perturbations intersecting the shock.

  15. 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.

  16. 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.

  17. Density functional simulations as a tool to probe molecular interactions in wet supercritical CO2

    SciTech Connect

    Glezakou, Vassiliki Alexandra; McGrail, B. Peter

    2013-06-03

    Recent advances in mixed Gaussian and plane wave algorithms have made possible the effective use of density functional theory (DFT) in ab initio molecular dynamics (AIMD) simulations for large and chemically complex models of condensed phase materials. In this chapter, we are reviewing recent progress on the modeling and characterization of co-sequestration processes and reactivity in wet supercritical CO2 (sc-CO2). We examine the molecular transformations of mineral and metal components of a sequestration system in contact with water-bearing scCO2 media and aim to establish a reliable correspondence between experimental observations and theory models with predictive ability and transferability of results in large scale geomechanical simulators. This work is funded by the Department of Energy, Office of Fossil Energy. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory. The Pacific Norhtwest National Laboratory (PNNL) is operated by Battelle for DOE under contract DE-AC06-76RL01830.

  18. Kinetic analysis for ammonia decomposition in supercritical water oxidation of sewage sludge

    SciTech Connect

    Goto, Motonobu; Shiramizu, Daisuke; Kodama, Akio; Hirose, Tsutomu

    1999-11-01

    Supercritical water oxidation was applied to the destruction of municipal excess sewage sludge. The reaction was carried out in a batch reactor with hydrogen peroxide as an oxidant in the temperature range of 723--823 K. Ammonia and acetic acid are found to be refractory intermediates in supercritical water oxidation of organic wastes. Ammonia concentration produced during the reaction was measured as a function of reaction time. The dynamic data were analyzed by a first-order kinetics. The reaction rate constant coincides with those reported in the literature.

  19. Oxidative decoupling mechanisms of monomer recovery from waste tires via partial supercritical water oxidation

    SciTech Connect

    Lanterman, H.B.; Kocher, B.S.; Lee, S.

    1996-12-31

    Ground waste tires can be oxidatively decomposed into recoverable useful chemical species via a controlled, partial supercritical water oxidation. The process feasibility has been demonstrated using a 1-liter semi-batch supercritical water oxidation system that is fabricated of Hastelloy C-276. The typical operating conditions are 370-400{degrees}C and 220-260 atm. The products include C{sub 1}-C{sub 10} hydrocarbons, including isoprene, the monomer of natural rubber. Possible oxidative decoupling mechanisms for the recovery of monomer and preliminary process engineering results are presented in this paper.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. TREATMENT AND PRODUCT RECOVERY: SUPERCRITICAL WATER OXIDATION OF NYLON MONOMER MANUFACTURING WASTE

    EPA Science Inventory

    EPA GRANT NUMBER: R822721C569
    Title: Treatment and Product Recovery: Supercritical Water Oxidation of Nylon Monomer Manufacturing Waste
    Investigator: Earnest F. Gloyna
    Institution: University of Texas at Austin
    EPA Project Officer:<...

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Methane and methanol oxidation in supercritical water: Chemical kinetics and hydrothermal flame studies

    SciTech Connect

    Steeper, R.R.

    1996-01-01

    Supercritical water oxidation (SCWO) is an emerging technology for the treatment of wastes in the presence of a large concentration of water at conditions above water`s thermodynamic critical point. A high-pressure, optically accessible reaction cell was constructed to investigate the oxidation of methane and methanol in this environment. Experiments were conducted to examine both flame and non-flame oxidation regimes. Optical access enabled the use of normal and shadowgraphy video systems for visualization, and Raman spectroscopy for in situ measurement of species concentrations. Flame experiments were performed by steadily injecting pure oxygen into supercritical mixtures of water and methane or methanol at 270 bar and at temperatures from 390 to 510{degrees}C. The experiments mapped conditions leading to the spontaneous ignition of diffusion flames in supercritical water. Above 470{degrees}C, flames spontaneously ignite in mixtures containing only 6 mole% methane or methanol. This data is relevant to the design and operation of commercial SCWO processes that may be susceptible to inadvertent flame formation. Non-flame oxidation kinetics experiments measured rates of methane oxidation in supercritical water at 270 bar and at temperatures from 390 to 442{degrees}C. The initial methane concentration was nominally 0.15 gmol/L, a level representative of commercial SCWO processes. The observed methane concentration histories were fit to a one-step reaction rate expression indicating a reaction order close to two for methane and zero for oxygen. Experiments were also conducted with varying water concentrations (0 to 8 gmol/L) while temperature and initial reactant concentrations were held constant. The rate of methane oxidation rises steadily with water concentration up to about 5 gmol/L and then abruptly falls off at higher concentrations.

  11. Startup Thermal Considerations for Supercritical-Pressure Light Water-Cooled Reactors

    SciTech Connect

    Nakatsuka, Toru; Oka, Yoshiaki; Koshizuka, Seiichi

    2001-06-15

    Supercritical-pressure light water-cooled reactors (SCRs) are innovative systems aimed at high efficiency and cost reduction. The once-through direct-cycle plant system is the leading system of fossil-fired power plants (FPPs). Estimates of the coolability and necessary sizes of the SCR startup systems, sequences, and required equipment for startup are investigated with reference to supercritical FPPs. There are two types of supercritical boilers. One is a constant pressure boiler, and the other is a variable pressure boiler.First, startup of the constant pressure boiler is examined. The reactor starts at a supercritical pressure. A startup bypass system consisting of a flash tank and pressure-reducing valves is required. Second, startup of the variable pressure boiler is investigated. The reactor starts at a subcritical pressure, and the pressure increases with the load. A steam-water separator and a drain tank are required for startup.The results of computer calculations show that with both constant pressure and variable pressure startup, the peak cladding temperature does not exceed the operating limit through startup, and both startup sequences are feasible. The sizes of the components required for the startup systems are assessed. To simplify the plant system and to reduce the component size, variable pressure startup with steam separators in the bypass line appears desirable.

  12. 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

  13. 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.

  14. Fast-Geomimicking using Chemistry in Supercritical Water.

    PubMed

    Dumas, Angela; Claverie, Marie; Slostowski, Cédric; Aubert, Guillaume; Careme, Cristel; Le Roux, Christophe; Micoud, Pierre; Martin, François; Aymonier, Cyril

    2016-08-16

    Herein we introduce a powerful and fast method to produce nanominerals using a bottom up approach. The supercritical hydrothermal flow synthesis is exploited to produce model nanominerals by mimicking natural environments at high temperatures under pressure. This innovative concept is demonstrated with the talc synthesis; this represents a major technical breakthrough since it allows decreasing the mineral-synthesis time from tens of hours to tens of seconds. Through this example, we show these nanominerals exhibit new crystal-chemistry signals and new properties. This approach provides a means to reproduce the early stages of formation of minerals in different natural environments from sedimentary environments (low temperature and pressure) to hydrothermal/metamorphic environments (high temperature and high pressure). PMID:27321954

  15. 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.

  16. Gasification of sewage sludge and other biomass for hydrogen production in supercritical water

    SciTech Connect

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

    1998-12-31

    Digested sewage sludge and other biomass such as wood sawdust can be mixed with a corn starch gel to form a viscous paste. The paste can be delivered to a supercritical flow reactor by means of a cement pump. Different types of feedstocks are used in this work sewage sludge (up to 7.69 wt%) mixed in the corn starch paste. When rapidly heated in a flow reactor at pressures above the critical pressure of water (22 MPa) the paste vaporizes. A packed bed of carbon catalyst in the reactor operating at 650 C causes the tarry vapors to react with water, producing hydrogen, carbon dioxide, and some methane with a trace of carbon monoxide. Thus the authors describe a practical method for the total, supercritical steam reforming of biomass to produce hydrogen at high pressure. The steam reforming process produces effectively no tar. Its only products are a hydrogen rich gas, and a clean water, which can be recycled.

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

    DOE PAGESBeta

    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

  18. 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.

  19. Incorporation of parametric uncertainty into complex kinetic mechanisms: Application to hydrogen oxidation in supercritical water

    SciTech Connect

    Phenix, B.D.; Dinaro, J.L.; Tatang, M.A.; Tester, J.W.; Howard, J.B.; McRae, G.J.

    1998-01-01

    In this study, uncertainty analysis is applied to a supercritical water hydrogen oxidation mechanism to determine the effect of uncertainties in reaction rate constants and species thermochemistry on predicted species concentrations. Forward rate constants and species thermochemistry are assumed to be the sole contributors to uncertainty in the reaction model with all other model parameters and inputs treated as deterministic quantities. Uncertainty propagation is performed using traditional Monte Carlo (MC) simulation and a new, more computationally efficient, probabilistic collocation method called the Deterministic Equivalent Modeling Method (DEMM). The results of both analyses show that there is considerable uncertainty in all predicted species concentrations. The predicted H{sub 2} and O{sub 2} concentrations vary {+-}70% from their median values. Similarly, the HO{sub 2} concentration ranges from +90 to {minus}70% of its median, while the H{sub 2}O{sub 2} concentration varies by +180 to {minus}80%. In addition, the DEMM methodology identified two key model parameters, the standard-state heat of formation of HO{sub 2} radical and the forward rate constant for H{sub 2}O{sub 2} dissociation, as the largest contributors to the uncertainty in the predicted hydrogen and oxygen species concentrations. The analyses further show that the change in model predictions due to the inclusion of real-gas effects, which are potentially important for SCWO process modeling, is small relative to the uncertainty introduced by the model parameters themselves.

  20. 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.

  1. 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.

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

    Energy Science and Technology Software Center (ESTSC)

    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

  3. 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.

  4. Molecular dynamics investigation of the various atomic force contributions to the interfacial tension at the supercritical CO2-water interface.

    PubMed

    Zhao, Lingling; Lin, Shangchao; Mendenhall, Jonathan D; Yuet, Pak K; Blankschtein, Daniel

    2011-05-19

    Sequestration of carbon dioxide (CO(2)) in deep, geological formations involves the injection of supercritical CO(2) into depleted reservoirs containing fluids such as brine or oil. The interfacial tension (IFT) between supercritical CO(2) and the reservoir fluid is an important contribution to the sequestration efficiency. In turn, the IFT is a complex function of the reservoir fluid phase composition, the molecular structure of each reservoir fluid component, and environmental conditions (i.e., temperature and pressure). Molecular dynamics simulations can be used to probe the dependence of the IFT on these factors, since the IFT can be calculated directly from the simulated atomic forces and velocities at system equilibrium using the mechanical definition of the IFT. Here, we examine the contribution of each type of atomic force to the IFT, including bonded and nonbonded forces, as quantified by the anisotropy of the atomic virial tensor. In particular, we first examine a supercritical CO(2)-pure liquid water interface, at typical reservoir conditions (temperature of 343 K and pressure of 20 MPa), as a reference state against which CO(2)-brine systems can be compared. In this system, we note that the interactions between water molecules and between CO(2) molecules ("self" interactions) contribute positively to the IFT, while the interactions between water and CO(2) molecules ("cross" interactions) contribute negatively to the IFT. We find that the magnitude of the water "self" interactions is the dominant contribution. In terms of specific types of forces, we find that nonbonded electrostatic (QQ), bonded angle-bending, and bonded bond-stretching interactions contribute positively to the IFT, while nonbonded Lennard-Jones (LJ) interactions contribute negatively to the IFT. We also find that the balance between the LJ interactions and the bond-stretching interactions, in particular, plays a significant role in determining the magnitude of the IFT. Using

  5. A supercritical water oxidation reactor: The Material Evaluations Reactor (MeR)

    SciTech Connect

    LaJeunesse, C.A.; Rice, S.F.; Bartel, J.J.; Kelley, M.; Seibel, C.A.; Hoffa, L.G.; Eklund, T.F.; Odegard, B.C.

    1992-02-01

    The paper describes the construction and control details of a supercritical water oxidation (SCWO) flow reactor. These details include a description of the Quality Function Deployment process that identified the system requirements and resource allocations, an overview of the SCWO process, and an in-depth description of the reactor itself including both physical and operational design. Supercritical water oxidation to destroy aqueous organic waste is a relatively new technology discovered about twelve years ago at the Massachusetts Institute of Technology. It is not commercialized presently, but shows promise for detoxifying wastes in an efficient, cost-competitive, and environmentally safe manner. Supercritical water oxidation occurs at moderate temperatures and pressures where the ability of water to dissolve hydrocarbons is greatly enhanced. Depending on the feed stream and residence time, the dissolved hydrocarbon reacts with an oxidizer to produce innocuous combustion products. We also report the development of an optical component for this flow reactor that permits the use of laser-based diagnostics, specifically spontaneous Raman scattering, to directly probe the reacting flow. Optical accessibility allows the determination of the concentration of these reactants and the chemical kinetics of the reaction in-situ -- the spatial dependence of mechanical processes, in particular corrosion and deposition, that affect the long term reliability of reactors can also be investigated.

  6. 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.

  7. Oxidation reaction of high molecular weight carboxylic acids in supercritical water.

    PubMed

    Jin, Fangming; Moriya, Takehiko; Enomoto, Heiji

    2003-07-15

    Stearic acid, being a model compound of high molecular weight carboxylic acids, was oxidized in a batch reactor by changing the oxygen supply with an insufficient oxygen supply at a constant reaction time at 420 degrees C. On the basis of the intermediate products identified by GC/MS, NMR, and HPLC analyses and the free-radical reaction mechanism, the oxidation pathways of high molecular weight carboxylic acids in supercritical water are discussed. The reaction of carboxylic acids in supercritical water proceeds with the consecutive oxidation of higher molecular weight carboxylic acids to lower molecular weight carboxylic acids through several major pathways. The attack of the hydroxyl radical occurs not only at the carbons in alpha-, beta-, gamma-positions to a --COOH group but also at the carbons ((omega-1)-carbon and/or omega-carbon) far in the alkyl chain from a --COOH group, which may lead to the formation of dicarboxylic acids. PMID:12901673

  8. 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. PMID:26685114

  9. Water hammer simulator

    SciTech Connect

    Sinha, S.K.; Madia, J.; Dixon, S.

    1995-11-01

    The Consolidated Edison Company of New York, Inc. (Con Edison) has constructed a first-of-a-kind water hammer events simulator for use at its training center. The Learning Center, Con Edison`s central training facility, intends to use the simulator as an educational tool to demonstrate the various mechanisms of the water hammer phenomenon to power plant designers, engineers and operators. The water hammer phenomenon has been studied extensively for the past 15 years for the nuclear industry. However, the acknowledge of the various water hammer mechanisms and the measures to prevent or mitigate water hammer have not been widely disseminated among the operators of fossil-fueled power plants. Con Edison personnel who operate the various generation stations and the New York City steam distribution systems are expected to benefit from the new simulator. Knowledge gained from interacting with the simulator will be very important in helping the Con Edison prevent, mitigate, or accommodate water hammer at its facilities. The water hammer simulator was fabricated in Con Edison`s central machine shop. Details of the design and construction of the simulator were finalized in consultation with Creare, Inc., an engineering research firm, located in Hanover, New Hampshire. The simulator seeks to recreate the essential features of water hammer in steam mines following the buildup of cold (subcooled) water by condensation and steam-water interaction. This paper describes the fabrication, design, testing, and operation of the Con Edison water hammer simulator. A discussion of how Con Edison plans to use the facility at The Learning Center is included.

  10. 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

  11. 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.

  12. 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}

  13. Partial oxidative gasification of municipal sludge in subcritical and supercritical water.

    PubMed

    Xu, Z R; Zhu, W; Htar, Swe Hlaing

    2012-06-01

    Subcritical and supercritical water gasification of dewatered sewage sludge obtained from a typical municipal wastewater treatment plant was investigated in a one-litre high-pressure autoclave at temperatures of 300-400 degrees C and pressures of 17.5-23.5 MPa. The sludge (without catalyst) was gasified at subcritical and supercritical water conditions, with different reaction times ranging from 30 to 60 min. The results showed that gaseous product yield increased with increasing temperature and reaction time. Gas products consisted primarily of hydrogen, carbon dioxide, methane, carbon monoxide and other light hydrocarbons. The liquid products contained high levels of organic matter, ammonia nitrogen and a few heavy metals. Compared with the landfilling of sewage sludge, the solid residues were in accordance with the Chinese standard for sludge quality in co-landfilling even without further treatment. In addition, the heavy metals in solid products exhibited more stable characteristics attributable to the reduced leaching toxicity after supercritical water gasification. PMID:22856292

  14. 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.

  15. 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.

  16. 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)

  17. Two-dimensional numerical simulations of supercritical accretion flows revisited

    SciTech Connect

    Yang, Xiao-Hong; Yuan, Feng; Bu, De-Fu; Ohsuga, Ken E-mail: fyuan@shao.ac.cn

    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 {sub θφ} component of the viscous stress and consider various values of the viscous parameter α. We find that when T {sub θφ} 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 M-dot {sub in}∝r{sup 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 M-dot (r). We find that the density profile can be described by ρ(r)∝r {sup –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.

  18. 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

  19. Stability analysis of a square rod bundle sub-channel in supercritical water reactor

    NASA Astrophysics Data System (ADS)

    Hai-jun, Wang; Ting, You; Lei, Zhang; Hong-fang, Gu; Yu-shan, Luo; Ji-lian, Bian

    2013-07-01

    Extensive investigations on the flow and heat transfer behavior in SCWR fuel assembly have been undertaken worldwide. However, stability analysis of supercritical water in the sub-channels of tight lattices is still lacking. In this paper, the flow stability of a fuel bundle channel with square pitches has been analyzed using commercial CFD code-ANSYS Fluent. Typical dynamic instability of Density Wave Oscillation (DWO) has occurred in heated channel containing fluids at supercritical pressure. A further discussion about the impacts of various operational parameters (e.g. power input, system pressure, mass velocity, inlet temperature, etc) shows that the system becomes more stable as system pressure and/or mass flow rate increases. An increase in inlet temperature also has a stabilizing effect on the system.

  20. 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. PMID:26277952

  1. 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

  2. Effects of water on biodiesel fuel production by supercritical methanol treatment.

    PubMed

    Kusdiana, Dadan; Saka, Shiro

    2004-02-01

    In the conventional transesterification of fats/vegetable oils for biodiesel production, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst effectiveness, all of which result in a low conversion. The objective of this study was, therefore, to investigate the effect of water on the yield of methyl esters in transesterification of triglycerides and methyl esterification of fatty acids as treated by catalyst-free supercritical methanol. The presence of water did not have a significant effect on the yield, as complete conversions were always achieved regardless of the content of water. In fact, the present of water at a certain amount could enhance the methyl esters formation. For the vegetable oil containing water, three types of reaction took place; transesterification and hydrolysis of triglycerides and methyl esterification of fatty acids proceeded simultaneously during the treatment to produce a high yield. These results were compared with those of methyl esters prepared by acid- and alkaline-catalyzed methods. The finding demonstrated that, by a supercritical methanol approach, crude vegetable oil as well as its wastes could be readily used for biodiesel fuel production in a simple preparation. PMID:14607489

  3. 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.

  4. Dynamics of supercritical methanol of varying density from first principles simulations: Hydrogen bond fluctuations, vibrational spectral diffusion, and orientational relaxation

    NASA Astrophysics Data System (ADS)

    Yadav, Vivek Kumar; Chandra, Amalendu

    2013-06-01

    A first principles study of the dynamics of supercritical methanol is carried out by means of ab initio molecular dynamics simulations. In particular, the fluctuation dynamics of hydroxyl stretch frequencies, hydrogen bonds, dangling hydroxyl groups, and orientation of methanol molecules are investigated for three different densities at 523 K. Apart from the dynamical properties, various equilibrium properties of supercritical methanol such as the local density distributions and structural correlations, hydrogen bonding aspects, frequency-structure correlations, and dipole distributions of methanol molecules are also investigated. In addition to the density dependence of various equilibrium and dynamical properties, their dependencies on dispersion interactions are also studied by carrying out additional simulations using a dispersion corrected density functional for all the systems. It is found that the hydrogen bonding between methanol molecules decreases significantly as we move to the supercritical state from the ambient one. The inclusion of dispersion interactions is found to increase the number of hydrogen bonds to some extent. Calculations of the frequency-structure correlation coefficient reveal that a statistical correlation between the hydroxyl stretch frequency and the nearest hydrogen-oxygen distance continues to exist even at supercritical states of methanol, although it is weakened with increase of temperature and decrease of density. In the supercritical state, the frequency time correlation function is found to decay with two time scales: One around or less than 100 fs and the other in the region of 250-700 fs. It is found that, for supercritical methanol, the times scales of vibrational spectral diffusion are determined by an interplay between the dynamics of hydrogen bonds, dangling OD groups, and inertial rotation of methanol molecules and the roles of these various components are found to vary with density of the supercritical solvent. Effects

  5. 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.

  6. Interdroplet attractive forces in AOT water-in-oil microemulsions formed in subcritical and supercritical solvents

    SciTech Connect

    Tingey, J.M.; Fulton, J.L.; Smith, R.D. )

    1990-03-08

    The van der Waals attractive interactions between aqueous droplets in water-in-oil type microemulsions have been investigated for a range of continuous-phase solvents including the alkanes from methane to isooctane and the noble gases, krypton and xenon. Hamaker constants for water droplets with surfactant shells of the sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in subcritical and supercritical solvents were calculated by using Lifshitz theory and the resulting interaction potential calculations qualitatively account for many features of the phase behavior of these systems.

  7. Direct liquefaction of Dunaliella tertiolecta for bio-oil in sub/supercritical ethanol-water.

    PubMed

    Chen, Yu; Wu, Yulong; Zhang, Peiling; Hua, Derun; Yang, Mingde; Li, Chun; Chen, Zhen; Liu, Ji

    2012-11-01

    This paper presents bio-oil preparation by direct liquefaction of Dunaliella tertiolecta (D. tertiolecta) with sub/supercritical ethanol-water as the medium in a batch autoclave with high temperature and high pressure. The results indicated that ethanol and water showed synergistic effects on direct liquefaction of D. tertiolecta. The maximum bio-oil yield was 64.68%, with an optimal D. tertiolecta conversion of 98.24% in sub/supercritical ethanol-water. The detailed chemical compositional analysis of the bio-oil was performed using an EA, FT-IR, and GC-MS. The empirical formulas of the bio-oil obtained using the ethanol-water co-solvent (40%, v/v) and sole water as the reaction medium were CH(1.52)O(0.14)N(0.06) and CH(1.43)O(0.23)N(0.09), with calorific values of 34.96 and 29.80 MJ kg(-1), respectively. XPS and SEM results showed that ethanol-water is a very effective reaction medium in the liquefaction. A plausible reaction mechanism of the main chemical component in D. tertiolecta is proposed based on our results and the literatures. PMID:22989646

  8. 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).

  9. 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.

  10. 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.

  11. Oxidation of substituted phenols in supercritical water. Final technical report, September 1992--August 1996

    SciTech Connect

    Savage, P.E.

    1996-11-01

    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 reused. Oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of model pollutants in supercritical water. The decomposition of cresols, hydroxybenzaidehydes, nitrophenols, and benzenediols was studied in dilute aqueous solutions in both the presence and absence of oxygen at 460{degrees}C and 250 atm. Experimental data from the oxidation of these compounds were fit to global, power-law rate expressions. The resulting rate laws showed that the reactivity of the different isomers at 460{degrees}C was in the order of ortho > para > meta for cresols and hydroxybenzaldehydes. Moreover, the CHO-substituted phenol was more reactive than the analogous CH{sub 3}-substituted phenol, and all of these substituted phenols were more reactive than phenol itself. Identifying and quantifying the reaction products of incomplete oxidation allowed us to assemble a general reaction network for the oxidation of cresols in supercritical water. This network comprises parallel primary paths to phenol, to a hydroxybenzaldehyde, and to ring-opening products. The hydroxybenzaldehyde reacts through parallel paths to phenol and to ring-opening products. Phenol also reacts via two parallel paths, but these lead to phenol dimers; and ring-opening products. The dimers are eventually converted to ring-opening products, and the ring-opening products are ultimately converted to CO{sub 2} The relative rates of the different paths in the reaction network are strong functions of the location of the substituent on the phenolic ring.

  12. 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.

  13. 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. PMID:24520696

  14. 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)

  15. 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.

  16. 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.

  17. 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).

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Kinetics of the catalytic oxidation of phenol over manganese oxide in supercritical water

    SciTech Connect

    Oshima, Yoshito; Tomita, Kengo; Koda, Seiichiro

    1999-11-01

    A kinetic analysis was made for the phenol disappearance rate in catalytic oxidation of phenol over MnO{sub 2} in supercritical water at a fixed temperature of 425 C and pressures between 22.7 and 27.2 MPa. The nonsupported MnO{sub 2} catalyst possessed a strong activity for promoting phenol oxidation, though the overall reaction rate was appreciably influenced by internal mass-transfer resistance. From the kinetic analysis on the reaction rate of the phenol disappearance, the global rate expression of the surface reaction was obtained, where the reaction orders with respect to phenol, oxygen, and water were almost unity, 0.7, and {minus}2.0, respectively. A Langmuir-type mechanism, in which phenol and oxygen adsorbed on the catalytic sites and water adsorbed on the same site to inhibit the phenol and oxygen adsorption, was proposed to explain the reaction orders for phenol, oxygen, and water.

  5. 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

  6. Catalytic oxidation of phenol over MnO{sub 2} in supercritical water

    SciTech Connect

    Yu, J.; Savage, P.E.

    1999-10-01

    Bulk MnO{sub 2} was used as a catalyst for phenol oxidation in supercritical water at 380--420 C and 219--300 atm in a flow reactor. The bulk MnO{sub 2} catalyst enhances both the phenol disappearance and CO{sub 2} formation rates during supercritical water oxidation (SCWO), but it does not affect the selectivity to CO{sub 2} or to the phenol dimers at a given phenol conversion. The role of the catalyst appears to be accelerating the rate of formation of phenoxy radicals, which then react in the fluid phase by the same mechanism operative for noncatalytic SCWO of phenol. The rates of phenol disappearance and CO{sub 2} formation are sensitive to the phenol and O{sub 2} concentrations but independent of the water density. Both power-law and dual site Langmuir-Hinshelwood-Hougen-Watson (LHHW) rate laws were developed to correlate the catalytic kinetics. Results show that SCWO reactor volumes can be reduced by an order of magnitude if bulk MnO{sub 2} is used as the catalyst and by yet another order of magnitude if a supported oxidation catalyst is used.

  7. Preliminary corrosion studies of candidate materials for supercritical water oxidation reactor systems. Master's thesis

    SciTech Connect

    Orzalli, J.C.

    1994-05-01

    An experimental test facility has been designed and constructed for investigation of the corrosion behavior of candidate materials in a supercritical water oxidation environment. The high temperatures (500 deg C) and high pressures (300 atm) required in this process, made the experimental apparatus construction and control a complex engineering problem. The facility consists of two systems. The first is an exposure autoclave internal volume 850 ml, with associated monitoring and control systems for conducting long term exposure testing of test coupons and U-bends. The second is an electrochemical cell with a potentiostat and frequency response analyzer for conducting Electronic Impedance Spectroscopy (EIS) in the supercritical water environment. Exposure testing of three candidate materials; Inconel 625, Hastelloy C-276 and 316 stainless steel was conducted at three temperature regimes corresponding to three locations in a SCWO waste treatment system. Preliminary results are presented in an environment of demineralized water as a control. Experimental results indicate evidence of a film on the materials characterized by slight weight gain. Light and confocal laser light microscopic evaluations revealed the presence of localized pitting corrosion on the Inconel 625.

  8. IAEA coordinated research project on thermal-hydraulics of Supercritical Water-Cooled Reactors (SCWRs)

    SciTech Connect

    Yamada, K.; Aksan, S. N.

    2012-07-01

    The Supercritical Water-Cooled Reactor (SCWR) is an innovative water-cooled reactor concept, which uses supercritical pressure water as reactor coolant. It has been attracting interest of many researchers in various countries mainly due to its benefits of high thermal efficiency and simple primary systems, resulting in low capital cost. The IAEA started in 2008 a Coordinated Research Project (CRP) on Thermal-Hydraulics of SCWRs as a forum to foster the exchange of technical information and international collaboration in research and development. This paper summarizes the activities and current status of the CRP, as well as major progress achieved to date. At present, 15 institutions closely collaborate in several tasks. Some organizations have been conducting thermal-hydraulics experiments and analysing the data, and others have been participating in code-to-test and/or code-to-code benchmark exercises. The expected outputs of the CRP are also discussed. Finally, the paper introduces several IAEA activities relating to or arising from the CRP. (authors)

  9. Applications of supercritical fluids.

    PubMed

    Brunner, Gerd

    2010-01-01

    This review discusses supercritical fluids in industrial and near-to-industry applications. Supercritical fluids are flexible tools for processing materials. Supercritical fluids have been applied to mass-transfer processes, phase-transition processes, reactive systems, materials-related processes, and nanostructured materials. Some applications are already at industrial capacity, whereas others remain under development. In addition to extraction, application areas include impregnation and cleaning, multistage countercurrent separation, particle formation, coating, and reactive systems such as hydrogenation, biomass gasification, and supercritical water oxidation. Polymers are modified with supercritical fluids, and colloids and emulsions as well as nanostructured materials exhibit interesting phenomena when in contact with supercritical fluids that can be industrially exploited. For these applications to succeed, the properties of supercritical fluids in combination with the materials processed must be clearly determined and fundamental knowledge of the complex behavior must be made readily available. PMID:22432584

  10. 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

  11. Status on R and D Planning for Supercritical Water Cooled Reactor Systems in the 6. European Framework Programme

    SciTech Connect

    Starflinger, J.; Schulenberg, T.; Aksan, N.; Bittermann, D.; Heikinheimo, L.; Rimpault, G.

    2004-07-01

    On July 30, 2003, EURATOM signed the charter to join the Generation IV International Forum and thus to contribute to innovative reactor design and development. Among other concepts, supercritical water cooled reactor systems shall be foreseen as their contribution. In order to support this international forum, a dedicated budget for R and D of innovative concepts is planned for the 6. European Framework Programme of the European Commission. Currently, a detailed work plan for supercritical water cooled reactor systems is being worked out, in order to be presented and decided by the European Commission thereafter. It shall include: - Design studies of a thermal reactor core, its reactor pressure vessel internals and of the balance of plant. - Study of a fast reactor option for sustainable use of fuel and for Plutonium management. - Study of the corrosion behavior and other performances of candidate materials at supercritical pressures. - Detailed investigations of heat transfer and pressure drop at supercritical pressures and at part load operation conditions of the reactor. - Design code improvements and verifications. - Conceptual design and analyses of a suitable safety system. As a result, the program shall enable a thorough assessment of the supercritical water cooled reactor system with a view to determine its future potential. This summary report shall give an overview of the contributions, which are planned to be provided by the EURATOM partners in France, Finland, Germany, Hungary, Switzerland, The Netherlands and The Czech Republic. (authors)

  12. 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. PMID:23867097

  13. 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.

  14. 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)

  15. Effective recovery of harmful metal ions from squid wastes using subcritical and supercritical water treatments.

    PubMed

    Tavakoli, Omid; Yoshida, Hiroyuki

    2005-04-01

    The Japanese common squid wastes contained high concentration of metal ions such as 31.7 ppm Cd(II), 264.0 ppm Cu(II), and 140.0 ppm Zn(II). The use of sub- and supercritical water treatment has been investigated as a new method of recovering heavy metals from squid wastes. The reactions were carried out in the temperature range of 443-653 K, a pressure range of 0.792-30 MPa, and reaction times of 1-40 min. The wastes were decomposed into soluble proteins, organic acids, amino acids, and so on in the aqueous phase, and the fat and oil were extracted by sub- and supercritical water. The maximum yields on concentration of Cd(II), Cu(II), and Zn(II) in the solid, fat, and oil phases were found at 653, 573, and 513-573 K, respectively. The aqueous phase showed the lowest concentration of the metal ions (0.05-0.5 ppm). The distribution coefficient of metal ions in the fat, solid, and oil phases to aqueous phase were examined and found highest in the fat phase (max. 48 000). The solid phase (max. 39,000) and oil phase (max. 245) showed the second and third highest. Moreover, the fat and oil phases produced during this method act as chelating agents to catch metal ions with an order of recovery of Cu2+ > Zn2+ > Cd2+ and Zn2+ > Cu2+ > Cd2+, respectively. PMID:15871276

  16. Supercritical water oxidation of tannery sludge: stabilization of chromium and destruction of organics.

    PubMed

    Zou, Daoan; Chi, Yong; Dong, Jun; Fu, Chao; Wang, Fei; Ni, Mingjiang

    2013-10-01

    The supercritical water oxidation (SCWO) of industrial tannery sludge was investigated to understand the simultaneous destruction of organic pollutants and recovery of high content chromium. Experiments were performed in a batch reactor at temperatures of 350-500 °C, reaction time of 150-300 s and different oxygen ratios, to exhibit the effect of operation conditions. Results showed that removal efficiency of chemical oxygen demand (COD) increased with higher temperature, larger oxidant amount and reaction time; a maximum value of 96% was obtained. Meanwhile, destruction yield was much higher under supercritical conditions than that in subcritical water. In addition, removal efficiency of Cr from sludge reached more than 98% under all conditions; higher temperature played a positive role. Further, leaching toxicity tests of heavy metals in solid products were conducted based on toxicity characteristic leaching procedure. All heavy metals except nickel showed a greatly reduced leaching toxicity through their stabilization. The chromium oxide recovered in ash was amorphous below 550 °C, so that the structure of Cr could not be identified by X-ray diffraction pattern. Special attention should be paid on nickel as its leaching toxicity increased due to the corrosion of reactor surface under severe reaction conditions. PMID:23916746

  17. 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.

  18. 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.

  19. 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.

  20. 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%

  1. 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.

  2. Migration behavior of supercritical and liquid CO2 in a stratified system: Experiments and numerical simulations

    NASA Astrophysics Data System (ADS)

    Oh, Junho; Kim, Kue-Young; Han, Weon Shik; Park, Eungyu; Kim, Jeong-Chan

    2015-10-01

    Multiple scenarios of upward CO2 migration driven by both injection-induced pressure and buoyancy force were investigated in a horizontally and vertically stratified core utilizing a core-flooding system with a 2-D X-ray scanner. Two reservoir-type scenarios were considered: (1) the terrestrial reservoir scenario (10 MPa and 50°C), where CO2 exists in a supercritical state and (2) the deep-sea sediment reservoir scenario (28 MPa and 25°C), where CO2 is stored in the liquid phase. The core-flooding experiments showed a 36% increase in migration rate in the vertical core setting compared with the horizontal setting, indicating the significance of the buoyancy force under the terrestrial reservoir scenario. Under both reservoir conditions, the injected CO2 tended to find a preferential flow path (low capillary entry pressure and high-permeability (high-k) path) and bypass the unfavorable pathways, leaving low CO2 saturation in the low-permeability (low-k) layers. No distinctive fingering was observed as the CO2 moved upward, and the CO2 movement was primarily controlled by media heterogeneity. The CO2 saturation in the low-k layers exhibited a more sensitive response to injection rates, implying that the increase in CO2 injection rates could be more effective in terms of storage capacity in the low-k layers in a stratified reservoir. Under the deep-sea sediment condition, the storage potential of liquid CO2 was more than twice as high as that of supercritical CO2 under the terrestrial reservoir scenario. In the end, multiphase transport simulations were conducted to assess the effects of heterogeneity on the spatial variation of pressure buildup, CO2 saturation, and CO2 flux. Finally, we showed that a high gravity number (Ngr) tended to be more influenced by the heterogeneity of the porous media.

  3. 'Structure, Dynamics and Vibrational Spectrum of Supercritical CO2/H2O Mixtures from Ab Initio Molecular Dynamics as a Function of Water Cluster Formation

    SciTech Connect

    Glezakou, Vassiliki Alexandra; Rousseau, Roger J.; Dang, Liem X.; McGrail, B. Peter

    2010-08-21

    We have studied the effect of water in the supercritical phase of CO2 as a function of water self-association using DFT-based molecular dynamics simulations. The dependence of the intermolecular and intramolecular structure and dynamic properties upon water concentration in the supercritical CO2/H2O phase at a density of 0.81g/cm3 and temperature of 318.15K is investigated in detail and compared to previous studies of the pure sc-CO2 system and Monte-Carlo simulations of water in sc-CO2 phase. Analysis of radial and orientational distribution functions of the intermolecular interactions shows that the presence of water molecules does not disturb the previously established distorted T-shaped orientation of CO2 molecules, though there is strong evidence of perturbation of the second shell structure which enhances the preference for the slipped parallel orientation in this region. There is also evidence of short-lived hydrogen bonds between CO2 and water molecules. For higher water concentrations, water clustering is observed, consistent with the expected phase separation under these conditions of temperature and pressure. Finally, the water-water and water-CO2 interactions are discussed and analyzed in terms of the water self-association and thermodynamic quantities derived from the corresponding radial distribution functions. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  4. 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.

  5. 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.

  6. 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). PMID:21049923

  7. Synthesizing and dispersing silver nanoparticles in a water-in-supercritical carbon dioxide microemulsion

    SciTech Connect

    Ji, M.; Chen, X.; Wai, C.M.; Fulton, J.L.

    1999-03-24

    Reverse micelles and microemulsions formed in liquid and supercritical carbon dioxide (CO{sub 2}) allow highly polar or polarizable compounds to be dispersed in this nonpolar fluid. However, since the polarizability per unit volume of dense CO{sub 2} is quite low, it is difficult to overcome the strong van der Waals attractive interactions between particles in order to stably suspend macromolecular species. Conventional surfactants by themselves do not form reverse micelles or microemulsions in CO{sub 2} because the van der Waals interdroplet attractions are too high. The use of surfactants or cosurfactants with fluorinated tails provides a layer of a weakly attractive compound covering the highly attractive droplet cores, thus preventing their short-range interactions that would destabilize the system. Using this strategy, the authors describe a method to synthesize and stabilize metallic silver nanoparticles having diameters from 5 to 15 nm in supercritical CO{sub 2} using an optically transparent, water-in-CO{sub 2} microemulsion.

  8. 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

  9. 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.

  10. 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

  11. 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.

  12. 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

  13. 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}.

  14. Ion Pair Asociation in Ultra Supercritical Aqueous Environments: Successful Interplay between Conductance Experiment, Theory and Molecular Simulation.

    SciTech Connect

    Chialvo, Ariel A; Gruszkiewicz, Miroslaw {Mirek} S; Cole, David R

    2010-01-01

    We discuss the interplay between theory, molecular simulation and electric conductance experiments as an important tool for the extraction of ion-pair interaction potentials to make possible the bridging of the density gap between the lowest experimentally attainable conductance measurement and the theoretically reachable zero-density limit of the ion-pair association constant. Then, we predict the density dependence of the Na+!Cl! pair association constant in ultra supercritical steam environments by constraint molecular dynamics simulation over state conditions relevant to the new generation of ultra-supercritical steam power plants. Finally, we draw attention to relevant modeling challenges associated to the behavior of these systems around the zero-density limit and discuss ways to overcome them.

  15. 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.

  16. 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

  17. 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.

  18. Corrosion behavior of a 14Cr-ODS steel in supercritical water

    NASA Astrophysics Data System (ADS)

    Hu, H. L.; Zhou, Z. J.; Liao, L.; Zhang, L. F.; Wang, M.; Li, S. F.; Ge, C. C.

    2013-06-01

    The corrosion behavior of a 14Cr-ODS steel in the supercritical water was investigated using a variety of characterization techniques. Compared with 316L austenitic steel, the 14Cr-ODS steel had better corrosion resistant property. As the increasing of the exposure time, the weight gain increased, but the corrosion rates decreased. The curve of weight gain as a function of time followed a parabolic law. The general weight gain was 0.3476 mg/(dm2 h). A triple layer was observed which consisted of an outer layer, an inner layer and a diffusion layer. The outer layer was iron rich and contained Fe3O4, on which pores were observed. The inner layer and diffusion layer contained mainly (Fe,Cr2)O4. The oxidation mechanism was also discussed.

  19. 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. PMID:22676368

  20. 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.

  1. 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

  2. Pulse radiolysis of supercritical water I. Ractions between hydrophobic and anionic species.

    SciTech Connect

    Cline, J.; Takahashi, K.; Marin, T. W.; Jonah, C. D.; Bartels, D. M.; Chemistry

    2002-12-26

    Reaction rates of solvated electrons with oxygen and with sulfur hexafluoride were measured in hydrothermal and supercritical water using transient absorption spectroscopy and electron pulse radiolysis. Under alkaline conditions, the reaction of hydrogen atoms with hydroxide ions to generate solvated electrons was also observed in the presence of the SF{sub 6} scavenger. At temperatures below 300 C, the rate constants for scavenging by O{sub 2} or SF{sub 6} follow Arrhenius behavior but become increasingly dependent on water density (pressure) at higher temperatures. Above 100 C, the rate constant for the H reaction with OH- falls well below the numbers extrapolated from the Arrhenius behavior in the one atmosphere liquid. At a fixed temperature above the water critical temperature (380 C, T/T{sub c}=1.01), rate constants for all three reactions reach a distinct minimum near 0.45 g/cm3. We propose an explanation for this behavior in terms of the potential of mean force separating an ion (OH- or (e-)aq) from a hydrophobic species (H, O{sub 2}, or SF{sub 6}) in the compressible fluid. The data also reveal an increasing initial yield of atomic hydrogen relative to solvated electrons as water density decreases. The initial yield of H appears to surpass that of solvated electrons when the water density is below 0.6 g/cm3 at 380 C.

  3. 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.

  4. 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

  5. Direct numerical simulations of supercritical fluid mixing layers applied to heptane nitrogen

    NASA Astrophysics Data System (ADS)

    Miller, Richard S.; Harstad, Kenneth G.; Bellan, Josette

    2001-06-01

    Direct numerical simulations (DNS) are conducted of a model hydrocarbon nitrogen mixing layer under supercritical conditions. The temporally developing mixing layer configuration is studied using heptane and nitrogen supercritical fluid streams at a pressure of 60 atm as a model system related to practical hydrocarbon-fuel/air systems. An entirely self-consistent cubic Peng Robinson equation of state is used to describe all thermodynamic mixture variables, including the pressure, internal energy, enthalpy, heat capacity, and speed of sound along with additional terms associated with the generalized heat and mass transport vectors. The Peng Robinson formulation is based on pure-species reference states accurate to better than 1% relative error through comparisons with highly accurate state equations over the range of variables used in this study (600 [less-than-or-eq, slant] T [less-than-or-eq, slant] 1100 K, 40 [less-than-or-eq, slant] p [less-than-or-eq, slant] 80 atm) and is augmented by an accurate curve fit to the internal energy so as not to require iterative solutions. The DNS results of two-dimensional and three-dimensional layers elucidate the unique thermodynamic and mixing features associated with supercritical conditions. Departures from the perfect gas and ideal mixture conditions are quantified by the compression factor and by the mass diffusion factor, both of which show reductions from the unity value. It is found that the qualitative aspects of the mixing layer may be different according to the specification of the thermal diffusion factors whose value is generally unknown, and the reason for this difference is identified by examining the second-order statistics: the constant Bearman Kirkwood (BK) thermal diffusion factor excites fluctuations that the constant Irwing Kirkwood (IK) one does not, and thus enhances overall mixing. Combined with the effect of the mass diffusion factor, constant positive large BK thermal diffusion factors retard

  6. 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.

  7. Limestone-particle-stabilized macroemulsion of liquid and supercritical carbon dioxide in water for ocean sequestration.

    PubMed

    Golomb, D; Barry, E; Ryan, D; Lawton, C; Swett, P

    2004-08-15

    When liquid or supercritical CO2 is mixed with an aqueous slurry of finely pulverized (1-20 microm) limestone (CaCO3) in a high-pressure reactor, a macroemulsion is formed consisting of droplets of CO2 coated with a sheath of CaCO3 particles dispersed in water. The coated droplets are called globules. Depending on the globule diameter and the CaCO3 sheath thickness, the globules sink to the bottom of the water column, are neutrally buoyant, or float on top of the water. The CaCO3 particles are lodged at the CO2/ H2O interface, preventing the coalescence of the CO2 droplets, and thus stabilizing the CO2-in-water emulsion. We describe the expected behavior of a CO2/H2O/CaCO3 emulsion plume released in the deep ocean for sequestration of CO2 in the ocean to ameliorate global warming. Depending on the amount of CO2 injected, the dense plume will descend a few hundred meters while entraining ambient seawater until it acquires neutral buoyancy in the stratified ocean. After equilibration, the globules will rain out from the plume toward the ocean bottom. This mode of CO2 release will prevent acidification of the seawater around the release point, which is a major environmental drawback of ocean sequestration of liquid, unemulsified CO2. PMID:15382876

  8. A universal salt model based on under-ground precipitation of solid salts due to supercritical water `out-salting'

    NASA Astrophysics Data System (ADS)

    Rueslåtten, H.; Hovland, M. T.

    2010-12-01

    One of the common characteristics of planets Earth and Mars is that both host water (H2O) and large accumulations of salt. Whereas Earth’s surface-environment can be regarded as ‘water-friendly’ and ‘salt hostile’, the reverse can be said for the surface of Mars. This is because liquid water is stable on Earth, and the atmosphere transports humidity around the globe, whereas on planet Mars, liquid water is unstable, rendering the atmosphere dry and, therefore, ‘salt-friendly’. The riddle as to how the salt accumulated in various locations on those two planets, is one of long-lasting and great debate. The salt accumulations on Earth are traditionally termed ‘evaporites’, meaning that they formed as a consequence of the evaporation of large masses of seawater. How the accumulations on Mars formed is much harder to explain, as an ocean only existed briefly. Although water molecules and OH-groups may exist in abundance in bound form (crystal water, adsorbed water, etc.), the only place where free water is expected to be stable on Mars is within underground faults, fractures, and crevices. Here it likely occurs as brine or in the form of ice. Based on these conditions, a key to understanding the accumulation of large deposits of salt on both planets is linked to how brines behave in the subsurface when pressurized and heated beyond their supercritical point. At depths greater than about 3 km (P>300 bars) water will no longer boil in a steam phase. Rather, it becomes supercritical and will attain the phase of supercritical water vapor (SCRIW) with a specific gravity of typically 0.3 g/cm3. An important characteristic of SCRIW is its inability to dissolve the common sea salts. The salt dissolved in the brines will therefore precipitate as solid particles when brines (seawater on the Earth) move into the supercritical P&T-domain (T>400°C, P>300 bars). Numerical modeling of a hydrothermal system in the Atlantis II Deep of the Red Sea indicates that a

  9. Kinetics and products from o-cresol oxidation in supercritical water

    SciTech Connect

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

    1995-06-01

    Dilute aqueous solutions of o-cresol (2-methylphenol) were oxidized in a tubular flow reactor at near-critical and supercritical conditions. The power-law rate expression that best correlates the kinetics of o-cresol disappearance is rate = 10{sup 5.7} exp({minus}29,700/RT)[o-cresol]{sup 0.57}[O{sub 2}]{sup 0.22}[H{sub 2}O]{sup 1.44}. The power-law rate expression that best correlates the experimental results for the conversion of organic carbon to CO{sub 2} is rate = 10{sup 6.8} exp({minus}34,000/RT)[TOC]{sup 0.34}[O{sub 2}]{sup 0.73}[H{sub 2}O]{sup 1.18}. All concentrations are in moles per liter, the activation energy is in calories per mole, and the rate is in moles per liter per second. The most abundant products from o-cresol oxidation were typically phenol, 2-hydroxybenzaldehyde, 1,3-benzodioxole, indanone, CO, and CO{sub 2}. 2-Hydroxybenzaldehyde was the major primary product. A reanalysis of published kinetics data for the oxidation of two other ring-containing compounds (pyridine and 4-chlorophenol) in supercritical water revealed that the rate laws previously reported for these two compounds do not provide the best correlation of the experimental data. The authors report the new rate laws, which are similar to those for o-cresol, 2-chlorophenol, and phenol in that the global reaction orders are between 0.55 and 0.9 for the organic compounds and between 0.2 and 0.5 for oxygen.

  10. Local density augmentation of supercritical water probed by 4,4‧-bpyHrad radical: A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Liu, Zhe; Fang, Zhong; Muroya, Yusa; Fu, Haiying; Yan, Yu; Katsumura, Yosuke; Lin, Mingzhang

    2016-07-01

    Solvatochromic shift of 4,4‧-bpyHrad in aqueous solutions at elevated temperatures up to supercritical conditions and in various organic solvents with different dielectric constants, is investigated by pulse-radiolysis technique. 4,4‧-bpyHrad shows a stronger solvent-solute interaction in water than in organic solvents, perhaps due to the hydrogen bond between 4,4‧-bpyHrad and water. At 380 °C, local density augmentation, namely ρlocal-ρbulk, in supercritical water becomes 280 kg m-3 (ρbulk = 208 kg m-3), and the density enhancement factor is 8.9. Density fluctuation maximizes when ρbulk is around 120 kg m-3. Density inhomogeneity decreases as temperature rises, but is still remarkable at 400 °C.

  11. Evaluation of tubular reactor designs for supercritical water oxidation of U.S. Department of Energy mixed waste

    SciTech Connect

    Barnes, C.M.

    1994-12-01

    Supercritical water oxidation (SCWO) is an emerging technology for industrial waste treatment and is being developed for treatment of the US Department of Energy (DOE) mixed hazardous and radioactive wastes. In the SCWO process, wastes containing organic material are oxidized in the presence of water at conditions of temperature and pressure above the critical point of water, 374 C and 22.1 MPa. DOE mixed wastes consist of a broad spectrum of liquids, sludges, and solids containing a wide variety of organic components plus inorganic components including radionuclides. This report is a review and evaluation of tubular reactor designs for supercritical water oxidation of US Department of Energy mixed waste. Tubular reactors are evaluated against requirements for treatment of US Department of Energy mixed waste. Requirements that play major roles in the evaluation include achieving acceptable corrosion, deposition, and heat removal rates. A general evaluation is made of tubular reactors and specific reactors are discussed. Based on the evaluations, recommendations are made regarding continued development of supercritical water oxidation reactors for US Department of Energy mixed waste.

  12. 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

  13. 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.

  14. Oxidation and hydrolysis of acetic acid and methylene chloride in supercritical water as a means of remediation

    SciTech Connect

    Marrone, P.A.; Lachance, R.P.; DiNaro, J.L.

    1995-10-01

    Supercritical water oxidation (SCWO) is a promising technology proposed for the destruction of hazardous organic wastes. Unlike its well known behavior under ambient conditions, water above its critical point (374{degrees}C, 221 bar) has properties similar to that of a nonpolar solvent, primarily due to the effect of a decrease in hydrogen bonding and density that occurs near and above the critical point. The result is that nonpolar organics and oxygen exhibit complete solubility in supercritical water, while polar species such as inorganic salts are insoluble and precipitate out. In the single homogeneous phase formed, oxidation of organics with oxygen in supercritical water is rapid and complete to CO{sub 2} and H{sub 2}O. Organic heteroatoms such as halogens, sulfur, or phosphorus are converted to inorganic acids (HCl, H{sub 2}SO{sub 4}, H{sub 3}PO{sub 4}) which precipitate as salts when neutralized with added base, while nitrogen is converted to N{sub 2} and N{sub 2}O. No NO{sub x} compounds are formed due to the relatively low temperatures that exist in the SCWO process (400 - 650{degrees}C) relative to that of air incineration processes (typically 900 - 1300{degrees}C). Oxidation in supercritical water is thus an appealing means of destroying toxic organic compounds while simultaneously separating out undesired inorganics by precipitation. Applications to decontaminating soils and dilute aqueous wastes are of special interest. Earlier work has demonstrated high destruction efficiencies for various organics in SCWO.

  15. 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. PMID:26087291

  16. 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.

  17. The Effect of Supercritical Water on Microcrack Generation and Crack Healing in the Quartz Constituent of Granite

    NASA Astrophysics Data System (ADS)

    Fujii, Y.; Tanifuji, K.; Takahashi, T.; Stafford, C. E.; Hashida, T.

    2001-12-01

    Supercritical water has properties intermediate between those of gaseous water and liquid water. The density and viscosity of supercritical water is less and diffusivity is greater than that of liquid water. These properties are of great significance when considering the potential development of a supercritical deep-seated geothermal reservoir, where the natural fracture network and permeability may be restricted. We report on experiments that have investigated intragranular microcrack generation and microcrack healing in the quartz constituent of Iidate granite (Fukushima, Japan), at temperature and pressure conditions ranging above and below the supercritical point for water (374 oC/22 MPa), to a maximum of 600 oC and 100 MPa pore fluid pressure. Microstructural data was collated from both permeability experiments and static flow/crack healing experiments conducted in a triaxial cell under isotropic stress conditions, using right cylindrical granite cores saturated in distilled water. The crack healing experiments were performed under a confining pressure of 100 MPa and a constant pore fluid pressure of 50 MPa. The time-dependence of the water/rock interaction, under these conditions, was also determined, with experiments ranging in duration from 0.5 to 96 hours. Permeability experiments were conducted at confining pressures of 20, 25, 50 and 100 MPa. with initial pore fluid pressures approximately 1 MPa higher. Our results show that open crack density increases significantly as both pressure and temperature exceed the critical point for water, with the most significant increases seen at temperatures of 600 oC. All open crack densities show no clear dependence with time. At temperatures of 330 oC, crack healing density increases with both temperature and elapsed time, and increases significantly as the temperature exceeds the critical point for water. However, above temperatures of 450 oC, crack healing density is found to decrease, reaching a low at 550 o

  18. Supercritical water oxidation for the destruction of hazardous waste: better than incineration.

    PubMed

    Al-Duri, Bushra; Alsoqyani, Faihan; Kings, Iain

    2015-12-28

    Supercritical water oxidation (SCWO) is an advanced process mainly employed for the treatment of hazardous stable wastes, otherwise treatable by incineration. It is based on the unique properties of water above its critical point (T(c)=675 K, P(c)=22.2 MPa), making it a superior reaction medium for the destruction of all organics in the presence of oxygen. This work presents preliminary laboratory scale studies on SCWO of nitrogen (N)-containing hazardous hydrocarbons, with a view to enhancing the process performance, using available reagents and non-complex reactor design. This article investigates the destruction of dimethylformamide (DMF), carried out in a continuous (plug flow) reactor system. SCWO of DMF was enhanced by (i) a split-oxidant system, where stoichiometric oxidant was divided between two inlet ports at various ratios and (ii) the addition of isopropyl alcohol (IPA) as a co-fuel, premixed with the feedstock. Testing a range of temperatures, initial DMF concentrations, oxidant ratios, IPA ratios and oxidant split ratios, selected results were presented in terms of % total organic carbon and % N removal. Reaction kinetics were studied and showed a dramatic decrease in the activation energy upon adding IPA. Split-oxidant-feeding enhancement depended on the split ratio and secondary feed position. PMID:26574530

  19. Degradation kinetics of dihydroxyacetone and glyceraldehyde in subcritical and supercritical water

    SciTech Connect

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

    1997-06-01

    Biomass continues to be an important candidate as a renewable resource for energy, chemicals, food, and feedstock. In order to understand the products distribution of cellulose hydrolysis in water, hydrolysis of model compounds of cellulose such as glucose, cellobiose, cellotriose, and cellopentaose is being investigated. One of the important pathways of glucose decomposition was the formation of the C-3 carbon compounds, glyceraldehyde and dihydroxyacetone, which appeared to be isomers and also seemed to have related reaction chemistry. The degradation kinetics of dihydroxyacetone and glyceraldehyde were studied at temperature ranges of 573--673 K, pressures of 25--40 MPa, and residence times from 0.06 to 1.7 s. The reactions of glyceraldehyde gave both dihydroxyacetone and pyruvaldehyde, and yields of dihydroxyacetone were always higher than those of pyruvaldehyde. The reactions of dihydroxyacetone gave glyceraldehyde and pyruvaldehyde, while the yields of pyruvaldehyde were always higher than those of dihydroxyacetone. This pathway involves the reversible isomerization between glyceraldehyde and dihydroxyacetone and their subsequent dehydration to pyruvaldehyde. A model was formulated on the basis of this pathway, and the kinetic rate constants involved were calculated using the experimental results. As the conditions change from subcritical to supercritical, the Arrhenius relationship becomes discontinuous near the critical point of water. At a constant temperature of 673 K, the kinetics constants showed a general increase with an increase in pressure.

  20. Heavy metals stabilization in medical waste incinerator fly ash using alkaline assisted supercritical water technology.

    PubMed

    Jin, Jian; Li, Xiaodong; Chi, Yong; Yan, Jianhua

    2010-12-01

    This study investigated the process of aluminosilicate formation in medical waste incinerator fly ash containing large amounts of heavy metals and treated with alkaline compounds at 375 degrees C and examined how this process affected the mobility and availability of the metals. As a consequence of the treatments, the amount of dissolved heavy metals, and thus their mobility, was greatly reduced, and the metal leaching concentration was below the legislative regulations for metal leachability. Moreover, this process did not produce a high concentration of heavy metals in the effluent. The addition of alkaline compounds such as sodium hydroxide and sodium carbonate can prevent certain heavy metal ions dissolving in water. In comparison with the alkaline-free condition, the extracted concentrations of As, Mn, Pb, Sr and Zn were decreased by about 51.08, 97.22, 58.33, 96.77 and 86.89% by the addition of sodium hydroxide and 66.18, 86.11, 58.33, 83.87 and 81.91% by the addition of sodium carbonate. A mechanism for how the formation of aluminosilicate occurred in supercritical water and affected the mobility and availability of the heavy metals is discussed. The reported results could be useful as basic knowledge for planning new technologies for the hydrothermal stabilization of heavy metals in fly ash. PMID:20430801

  1. 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

  2. Equilibrium partitioning of 2,4-dichlorophenol between water and near-critical and supercritical carbon dioxide

    SciTech Connect

    Akgerman, A.; Carter, B.D. . Chemical Engineering Dept.)

    1994-07-01

    Distribution coefficients of 2,4-dichlorophenol between supercritical carbon dioxide and water are measured at 298.15 and 319.15 K over the pressure range 11-23 MPa using a single-stage equilibrium cell. The data are modeled by the Peng-Robinson equation of state with modified mixing rules. The data are also compared to literature data on distribution coefficients of phenol and p-chlorophenol.

  3. Oxidation behavior of grain boundary engineered alloy 690 in supercritical water environment

    NASA Astrophysics Data System (ADS)

    Xu, P.; Zhao, L. Y.; Sridharan, K.; Allen, T. R.

    2012-03-01

    Nickel-base alloy is an important structural material that is known for its exceptional high temperature oxidation resistance. Oxidation in this alloy at high temperatures occurs to a greater extent along the grain boundaries. Grain boundary engineering (GBE) was applied to modify the grain boundary characteristics of this alloy to affect its oxidation resistance. Specimens with both low level and high level cold works showed a high fraction of special grain boundaries, and were tested for supercritical water oxidation resistance at 500 °C and 24 MPa. Both GBE and as-received samples exhibited mass gain followed by mass loss during 10 weeks of exposure, but the normalized mass change was small and less than 0.12 mg/cm2. GBE samples showed better oxide layer retention compared to the as-received sample. XRD results indicate that nickel oxide, chromium oxide, and spinel oxide were the three main types of oxides that form on as-received and GBE alloy 690. Three distinct regions were identified on the oxidized surface: a flat region with oxide flakes aligning relatively parallel to the surface, a rough region with polygon-type oxide particles randomly distributed on the surface, and a region with aggregated oxide flakes perpendicular to the surface. The flat region of oxidation consisted of (1 1 1) orientated oxide spinel flakes formed on (1 1 1) oriented alloy 690 grains. The flat oxide region was thinner and showed better oxide adhesion compared to the rough region. Chromium oxidation was found only at random grain boundaries, leading to formation of thick Cr2O3 layer on the surface and chromium depletion underneath. None of this oxidation was found at low angle or special boundaries. The chromium oxidation was attributed to fast chromium diffusion through random boundaries and mechanically deformed regions such as scratches left after polishing. It is envisioned that the oxidation behavior of alloy 690 in supercritical water can be tailored by microstructure

  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. SAGE 2D and 3D Simulations of the Explosive Venting of Supercritical Fluids Through Porous Media

    NASA Astrophysics Data System (ADS)

    Weaver, R.; Gisler, G.; Svensen, H.; Mazzini, A.

    2008-12-01

    Magmatic intrusive events in large igneous provinces heat sedimentary country rock leading to the eventual release of volatiles. This has been proposed as a contributor to climate change and other environmental impacts. By means of numerical simulations, we examine ways in which these volatiles can be released explosively from depth. Gases and fluids cooked out of country rock by metamorphic heating may be confined for a time by impermeable clays or other barriers, developing high pressures and supercritical fluids. If confinement is suddenly breached (by an earthquake for example) in such a way that the fluid has access to porous sediments, a violent eruption of a non-magmatic mixture of fluid and sediment may result. Surface manifestations of these events could be hydrothermal vent complexes, kimberlite pipes, pockmarks, or mud volcanoes. These are widespread on Earth, especially in large igneous provinces, as in the Karoo Basin of South Africa, the North Sea off the Norwegian margin, and the Siberian Traps. We have performed 2D and 3D simulations with the Sage hydrocode (from Los Alamos and Science Applications International) of supercritical venting in a variety of geometries and configurations. The simulations show several different patterns of propagation and fracturing in porous or otherwise weakened overburden, dependent on depth, source conditions (fluid availability, temperature, and pressure), and manner of confinement breach. Results will be given for a variety of 2D and 3D simulations of these events exploring the release of volatiles into the atmosphere.

  6. 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.

  7. Pressurised hot water extraction with on-line particle formation by supercritical fluid technology.

    PubMed

    Andersson, J M; Lindahl, S; Turner, C; Rodriguez-Meizoso, I

    2012-10-15

    In this work, an on-line process for pressurised hot water extraction (PHWE) of antioxidants from plants as well as drying of the extract in one step by particle formation based on the use of supercritical carbon dioxide (SC-CO(2)) has been developed. This process has been called WEPO®, water extraction and particle formation on-line. With this process, dried extracts from onion with the same composition of quercetin derivatives as non-dried extracts have been obtained as a fine powder with spherical particles from 250 nm to 4 μm in diameter. The major compounds present in the extract were quercetin-3,4'-diglucoside, quercetin-4'-glucoside and quercetin. An auxiliary inert gas (hot N(2)) was used to enhance the drying process. Parameters such as temperature (120 °C), SC-CO(2) and N(2) pressures (80 and 12.5 bar, respectively) and flow rate of SC-CO(2) (10 ml/min), have been settled by trial-and-error in order to achieve a fine and constant spray formation. Water content, size and morphology, antioxidant capacity and quercetin content of the particles were studied to evaluate the efficiency of the WEPO process. Results were compared with the ones from extracts obtained by continuous flow PHWE followed by freeze-drying. Results showed that both processes gave similar results in terms of antioxidant capacity, concentration of quercetin derivatives and water content, while only WEPO was able to produce defined spherical particles smaller than 4 μm. PMID:23442613

  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. 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.

  10. 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.

  11. 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.

  12. Extraction of weakly reductive and reductive coals with sub- and supercritical water

    SciTech Connect

    Bo Wu; Haoquan Hu; Shiping Huang; Yunming Fang; Xian Li; Meng Meng

    2008-11-15

    On a semi-continuous apparatus, a weakly reductive Shenfu-Dongsheng (SD) coal and a reductive Pingshuo (PS) coal were non-isothermally extracted with sub- and supercritical water to explore the differences between the two coals. The effect of the temperature on the extract formation rate, conversion, and product composition under different pressures was investigated. The extraction results of two coal samples indicate that the extract formation rate has a maximum in the studied temperature range between room temperature and 500{degree}C. The temperature corresponding to the maximum extract formation rate, changing with the pressure, is between 390 and 410{degree}C. The gas yield, extract yield, and conversion of two coals increase with the increasing pressure. In comparison to PS coal, SD coal has a low temperature corresponding to the maximum extract formation rate under the same pressure. Both coals have a main fraction of asphaltene, but SD coal has a higher fraction of oil than PS coal. The main gas components are CO{sub 2}, CH{sub 4}, and H{sub 2}. The gas from PS coal has a higher CH{sub 4} content and lower CO{sub 2} content than that from SD coal. The analysis results of the extraction residue indicated that SD coal has a low residue yield and the residue shows a large surface area and small average pore diameter compared to PS coal. 17 refs., 4 figs., 8 tabs.

  13. Characterization of a spent Ru/C catalyst after gasification of biomass in supercritical water.

    PubMed

    Wambach, J; Schubert, M; Döbeli, M; Vogel, F

    2012-01-01

    Carbon-supported ruthenium catalysts promote the gasification of aqueous organic feed with high efficiency to synthetic natural gas in supercritical water. Ruthenium metal was recently identified as the catalytically active species. [1] Occasionally deactivation is observed. To understand the deactivation, the fresh and several spent catalyst samples were investigated by RBS, ERDA, and XPS. The data revealed a massive reduction of the ruthenium concentration in toto and especially of the surface concentration. Of importance is the almost complete disappearance of the spectral features in the valance band region. Coverage of the ruthenium clusters e.g. with a thin 'carbonaceous' layer, i.e. a kind of fouling, or structural modifications of the ruthenium clusters might be the origin. Additionally, leaching of ruthenium might contribute, but is not considered a major effect, because ruthenium was never found in the liquid effluent of the reactor. The influence of additionally detected corrosion products (Ni, Cr, Fe, Ti) from the stainless steel and the titanium alloy walls seems to be small. No evidence for a deactivation by sulphur could be found. PMID:23211730

  14. 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. PMID:20044251

  15. Effect of ultrasonic impact peening on the corrosion of ferritic-martensitic steels in supercritical water

    NASA Astrophysics Data System (ADS)

    Dong, Ziqiang; Liu, Zhe; Li, Ming; Luo, Jing-Li; Chen, Weixing; Zheng, Wenyue; Guzonas, Dave

    2015-02-01

    Ferritic-Martensitic (F/M) steels are important candidate alloys to be used in the next generation (Generation-IV) SCWRs. In this work, two F/M steels with the same Cr content of around 12 wt.% and varied Si content from 0.6 wt.% to 2.2 wt.% were evaluated in supercritical water (SCW) at 500 °C and 25 MPa for up to 1000 h. The effect of ultrasonic shot peening on the oxidation behavior of these F/M steels have been investigated. The results showed that the oxidation was affected by the Si content as well as the surface modification. The F/M steel with low Si concentration exhibited higher corrosion resistance than that of the alloy with high Si content. Shot peening, which could modify the microstructure at the surface, showed significantly beneficial effect to improving the oxidation resistance. A thin, uniform oxide layer formed on the peened sample could be attributed to the enhanced diffusion of Cr induced by the surface modification.

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

    PubMed

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

    2015-09-01

    To achieve the maximum H2 yield (GYH2), 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 GYH2, CR and TRE were established with Box-Behnken design. GYH2, CR and TRE reached up to 14.32mmol·gTOC(-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 CO2 and H2 were the most abundant gaseous products. As a product of nitrogen-containing organics, NH3 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. PMID:26028557

  17. 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.

  18. Data acquisition testing in supercritical water oxidation using machine cutting oils and metals

    SciTech Connect

    Garcia, K.M.

    1996-12-31

    The Department of Energy, the Navy, and SERDP provided funding for an extensive series of testing of a Supercritical Water Oxidation (SCWO) system. The goal of the testing was to create performance data on the process when dealing with highly chlorinated wastes containing heavy metals, and radionuclides. The testing was performed in a MODAR vessel oxidizer. Performance was measured by the ability of the process to achieve greater than 99.99% destruction of the organic content, to partition the metals and radionuclide surrogates for mass balance, and survive the highly corrosive species in the effluent. The test data has shown that these goals were accomplished. 30 gal/day of highly chlorinated machine cutting oil was treated for 130 hrs. There were no significant corrosion or solids handling problems. This machine cutting oil, TRIM{reg_sign}SOL was chosen by DOE for its complex nature and has proven to be one of the more refractory organic feeds encountered by MODAR. The Navy provided 8 waste streams collected from their shore facilities operation. These paints varied in solids content with wastes such as paint chips, and adhesives. The ninth test run was with all 8 series of wastes combined. The MODAR system successfully treated all of these waste streams providing performance data on the ability of SCWO to treat difficult sludges.

  19. 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

  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. PMID:21420141

  1. Processing of high level waste: Spectroscopic characterization of redox reactions in supercritical water. 1998 annual progress report

    SciTech Connect

    Arrington, C.A. Jr.

    1998-06-01

    'The author is engaged in a collaborative research effort with Los Alamos staff scientists Steven Buelow, Jeanne Robinson, and Bernie Foy all staff members in group CST-6. The work proposed by these LANL staff scientists is directed towards the destruction of complexants and oxidation of chromium and technetium by hydrothermal processing in near critical or supercritical aqueous solutions. The work addresses two areas of investigation related to ongoing efforts at LANL: (1) kinetic studies of oxidation-reduction reactions in supercritical water; (2) measurement of physical properties of ionic solutes in supercritical water. All of the work during this first year was carried out at Los Alamos National Lab. During the Summer program at LANL all equipment and supplies were provided through Dr. Buelow''s program at LANL. The author has now set up a Raman spectroscopy lab at Furman. Using departmental funds he purchased an optical bench, a laser, and a CCD detector, and a grant from the Dreyfus Foundation assisted in the purchase of a Raman spectrometer. He is now able to carry out experiments using the Raman system at Furman. The plan is to continue the Summer collaboration at LANL and carry out experiments at Furman during the academic year.'

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. WATER QUALITY ANALYSIS SIMULATION PROGRAM

    EPA Science Inventory

    The Water Quality Analysis Simulation Program (WASP6), an enhancement of the original WASP (Di Toro et al., 1983; Connolly and Winfield,1984; Ambrose, R.B. et al.,1988). This model helps users interpret and predict water quality responses to natural phenomena and man-made polluti...

  7. Oxidation and thermolysis of methoxy-, nitro-, and hydroxy-substituted phenols in supercritical water

    SciTech Connect

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

    1999-05-01

    The authors have examined the oxidative decomposition of m- and p-methoxyphenol, m-, and p-nitrophenol, and resorcinol and the nonoxidative decomposition of o-, m- and p-methoxyphenol in dilute aqueous solutions at 460 C and 25.3 MPa for residence times on the order of 5 s. The major products from methoxyphenol decomposition in the absence of added oxygen are phenol and hydroxyphenols. The thermolysis kinetics can be described by a power-law rate equation with a reaction order between 0.5 and 1.0, which is consistent with previous studies done at different reaction conditions. Comparing the thermolysis rates for methoxyphenols with those of other substituted phenols showed that the rates are sensitive to both the identity and the location of the substituent. For a given substituent location, NO{sub 2}-substituted phenols reacted more rapidly than either CHO- or OCH{sub 3}-substituted phenols. Additionally, the ortho isomer was always the most reactive. Phenol is a product of incomplete oxidation from the methoxy-phenols and nitrophenols, but no phenol was observed when resorcinol was oxidized. The oxidation kinetics were correlated with power-law rate expressions. The experiments and subsequent kinetics analysis allowed them to separate and quantify the rates of thermolysis and oxidation individually. A comparison of these reactant disappearance rates shows that thermolysis accounts for about 5% of the total rate for m- and p-methoxyphenol during oxidation in supercritical water. Thermolysis accounts for up to 25% of the total rate for m- and p-nitrophenols.

  8. 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. PMID:23627310

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. Micro-PIV measurements of multiphase flow of water and supercritical CO2 in 2D heterogeneous porous micromodels

    NASA Astrophysics Data System (ADS)

    Li, Y.; Kazemifar, F.; Blois, G.; Christensen, K. T.

    2015-12-01

    Multiphase flow of water and supercritical carbon dioxide (CO2) in porous media is central to geological sequestration of CO2 into saline aquifers. However, our fundamental understanding of the coupled flow dynamics of CO2 and water in complex geologic media still remains limited, especially at the pore scale. Recently, studies have been carried out in 2D homogeneous models with the micro-PIV technique, yielding very interesting observations of pore-scale flow transport. The primary aim of this work is to leverage this experimental protocol to quantify the pore-scale flow of water and liquid/supercritical CO2 in 2D heterogeneous porous micromodels under reservoir-relevant conditions. The goal is to capture the dynamics of this multi-phase flow in a porous matrix that mimics the heterogeneity of natural rock. Fluorescent microscopy and the micro-PIV technique are employed to simultaneously measure the spatially-resolved instantaneous velocity field in the water and quantify the instantaneous spatial configuration of both phases. The results for heterogeneous micromodels will be presented and compared with those for homogeneous micromodels, yielding valuable insight into flow processes at the pore scale in natural rock.

  14. 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

  15. The effect of water chemistry on a change in the composition of gas phase in the steam-water path of a supercritical-pressure boiler

    NASA Astrophysics Data System (ADS)

    Belyakov, I. I.; Belokonova, A. F.

    2010-07-01

    We present the results from an experimental research work on studying the behavior of the gas phase in the path of a supercritical-pressure boiler during its operation with different water chemistries, including all-volatile (hydrazine-ammonia), complexone, neutral oxygenated, and combined oxygenated-ammonia chemistries. It is shown that the minimal content of hydrogen in steam is achieved if feedwater is treated with oxygen.

  16. 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

  17. 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...

  18. Hydration of Volcanic Glass with Super-Critical Water and its Effect on Permeability of Volcanic Rocks

    NASA Astrophysics Data System (ADS)

    Isobe, H.

    2006-12-01

    Behavior of high-temperature, high-pressure fluid flow in volcanoes depends on permeability of rocks in fluid paths. High pressure fluids or vapors in volcanoes, which are in super-critical states, are essential factors of volcanic eruptions. Especially, phreatomagmatic eruptions are caused by excess pressures of the fluid degassed from magma body or heated water contacted with magma or high temperature rocks in volcanoes. Alteration processes of rocks and minerals with super-critical fluid can change permeability of rocks by spreading of the fluid path or obstruction with precipitated minerals. In this study, experimental reproduction on the hydration and alteration processes of rocks and minerals with super-critical fluid flow were carried out with a fluid flow apparatus. Starting materials of the experiments are powdered rhyolitic obsidian and dacite. Approximately 55g of the starting material are placed in a SUS316 sample tube. Inner diameter and length of the sample tube are 9.4mm and 572mm, respectively. Temperature gradient of the pressure vessel is controlled by triple electric furnaces. Run products are retrieved by cutting off the sample tube and observed by SEM. Permeability of run products are also measured by gas flow method. Experimental pressure is 50MPa. Flow rate of distilled water at room temperature is 0.1ml / minute pumped by a low speed high-pressure pump. Temperature of the sample is approximately 450°C for rhyolitic glass powder or 420°C for dacite powder at the first half of the sample tube, then decreased to approximately 310°C at the outlet of the sample tube. Run durations are 3 to 8 days. Obsidian grains and groundmass glass of dacite partially dissolved and changed to porous at higher than approximately 400°C. Alteration products of the volcanic glass including clay minerals, cristobalite and plagioclase occur in grain boundaries and cemented grains within a few centimeters from the outlet of the sample tube. Volcanic glass

  19. Monte Carlo simulations of the pressure dependence of the water-acid gas interfacial tensions.

    PubMed

    Biscay, F; Ghoufi, A; Lachet, V; Malfreyt, P

    2009-10-29

    We report two-phase Monte Carlo (MC) simulations of the binary water-acid gas mixtures at high temperature and high pressure. Simulations are performed in the Np(N)AT ensemble in order to reproduce the pressure dependence of the interfacial tensions of the water-CO(2) and water-H(2)S mixtures. The interfacial tension of the binary water-CO(2) mixture is determined from 5 to 45 MPa along the isotherm T = 383 K. Water-H(2)S interfacial tensions are computed along one supercritical isotherm (T = 393 K) in a pressure range of 1-15 MPa. The temperature and pressure conditions investigated here by the MC simulations are typical of the geological storage conditions of these acid gases. The coexisting densities and the compositions of the water-rich and acid-gas-rich phases are compared with experiments and with data calculated from Gibbs ensemble Monte Carlo (GEMC) simulations. PMID:19803493

  20. 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.

  1. 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. PMID:10654784

  2. 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

  3. LBM simulation for CO2 saturation monitoring from elastic velocity and resistivity: Migration of supercritical CO2 in porous media under several PT conditions

    NASA Astrophysics Data System (ADS)

    Tsuji, T.; Yamabe, H.; Matsuoka, T.

    2012-12-01

    . After we simulate supercritical CO2 injection into water-saturated porous media using LBM, we calculate (a) seismic velocity and (b) resistivity from the estimated supercritical CO2 distribution within pore spaces. From these calculations, we obtain seismic velocity and resistivity for various pore structures at several PT conditions. Our preliminary results demonstrate that electric resistivity of the well-sorted grain model is affected by PT conditions. Because the viscosity and density of supercritical CO2 is much changed by PT conditions, CO2 distribution within pore space is different for each PT condition and influences to the resistivity value. Although the estimated relationship between CO2 saturation and resistivity can be modeled by Archie's equation, the parameters used in the equation should be changed by considering PT condition of the injected reservoir. Therefore, the realistic CO2 distribution within pore space should be considered for the quantitative geophysical monitoring. In this study, we further calculate relative permeability for each condition.

  4. 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.

  5. 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. PMID:24628176

  6. 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.

  7. Feasibility Study of Supercritical Light Water Cooled Fast Reactors for Actinide Burning and Electric Power Production, 3rd Quarterly Report

    SciTech Connect

    Mac Donald, Philip Elsworth

    2002-06-01

    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.

  8. 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.

  9. 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.

  10. Study of the excited-state proton-transfer reaction of 5-cyano-2-naphthol in sub- and supercritical water.

    PubMed

    Kobayashi, I; Terazima, M; Kimura, Y

    2012-01-26

    The excited-state proton-transfer (ESPT) reaction of 5-cyano-2-naphthol (5CN2) has been investigated in sub- and supercritical water using time-resolved fluorescence measurements. Under ambient conditions, a very fast decay of the fluorescence from the excited state of normal 5CN2 (ROH*) and a simultaneous increase of the fluorescence from the excited state of the anion species (RO(-)*) were observed, as reported previously. The very high ESPT rate was evaluated as 0.12 ps(-1). With increasing temperature at a constant pressure of 39.0 MPa, the proton transfer became slow. At 615 K and 39.0 MPa, another fluorescence from a new unknown chemical species appeared, which was assigned to the contact ion pair (CIP) of RO(-)* and the hydronium ion. With decreasing pressure at 664 K, the fluorescence from RO(-)* disappeared, and the fluorescence from ROH* and CIP was observed. At the very low density of supercritical water, only the fluorescence decay of ROH* was detected. The reaction dynamics was analyzed with the help of singular value decomposition and spectral decomposition using model functions. The ESPT rate was correlated with the solvent dielectric constant and/or the hydrogen-bonding ability. PMID:22201510

  11. 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". PMID:25915068

  12. Solar Hot Water Hourly Simulation

    Energy Science and Technology Software Center (ESTSC)

    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).

  13. 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

  14. In situ infrared spectroscopic study of brucite carbonation in dry to water-saturated supercritical carbon dioxide.

    PubMed

    Loring, John S; Thompson, Christopher J; Zhang, Changyong; Wang, Zheming; Schaef, Herbert T; Rosso, Kevin M

    2012-05-17

    In geologic carbon sequestration, whereas part of the injected carbon dioxide will dissolve into host brine, some will remain as neat to water saturated supercritical CO(2) (scCO(2)) 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 scCO(2) 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 h reaction period with scCO(2) 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 scCO(2). 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 (MgCO(3)·3H(2)O). Mixtures of nesquehonite and magnesite (MgCO(3)) 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. PMID:22533532

  15. Understanding electrofreezing in water simulations.

    PubMed

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

    2014-08-21

    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. PMID:25149795

  16. PHENOLIC CONTENT AND ANTIOXIDANT ACTIVITY OF SUPERCRITICAL CARBON DIOXIDE-TREATED AND AIR-CLASSIFIED OAT BRAN CONCENTRATE MICROWAVE-IRRADIATED IN WATER OR ETHANOL AT VARYING TEMPERATURES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Oat bran concentrate (OBC) was defatted with supercritical carbon dioxide (SCD), then microwave-irradiated at 50, 100 or 150 deg C for 10 min in water, 50% or 100% ethanol, and extract pH, soluble solids, phenolic content and antioxidant activity were analyzed. OBC was air-classified into five frac...

  17. 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.

  18. 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.

  19. Comparison of supercritical fluid extraction (SFE), Soxhlet and shaking methods for pendimethalin extraction from soils: effect of soil properties and water content

    NASA Astrophysics Data System (ADS)

    Spack, Lionel; Alvarez, Cristina; Martins, Jean M. F.; Tarradellas, Joseph

    1998-09-01

    Supercritical fluid extraction with CO 2 was applied to the analysis of traces of pendimethalin, a herbicide of the dinitroanilines group, in four different natural soils. The Supercritical Fluid Extraction (SFE) method was compared with the classical Soxhlet and shaking methods in terms of ease to run, extraction efficiency, selectivity and reproducibility. The influence of the physico-chemical properties of the soil matrix on herbicide extraction was then evaluated with the SFE method. The supercritical fluid extraction system used in the present study was found to be much easier to run than the other two methods, less time consuming and requires fewer operations as it was optimized for on-line sample clean up. SFE is the most selective of the three tested methods as fewer co-extracts are obtained in the final samples. SFE with CO 2 is particularly powerful because pendimethalin is highly hydrophobic. However, this makes pendimethalin a poor choice for a selectivity study of SFE as it is very rapidly extracted at any CO 2 density. Pendimethalin extraction with supercritical CO 2 was found to be almost complete with average recoveries of 96-99%, similarly to Soxhlet but with a much lower standard deviation (8-10%). The performance of SFE was shown to be unaffected by soil parameters except soil water content. It is demonstrated indeed that extraction efficiency is not linearly related to soil water content, and optimal recovery was found for water contents ranging from 2 to 15% depending on the type of soil. Soil water increases extraction efficiency because water acts as a modifier of the supercritical fluid and increases the penetration of the fluid inside the soil particles (clay swelling). In contrast to SFE and Soxhlet, the efficiency of the shaking method appeared to be partial and strongly dependent on soil properties. Although initial developments should be needed, the various benefits of SFE-CO 2 make this method attractive compared to traditional methods.

  20. 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)

  1. Transparent CoAl2O4 hybrid nano pigment by organic ligand-assisted supercritical water.

    PubMed

    Rangappa, Dinesh; Naka, Takashi; Kondo, Akitsugu; Ishii, Masahiko; Kobayashi, Toshikatsu; Adschiri, Tadafumi

    2007-09-12

    Transparent types of inorganic pigments are important as they can be used in a variety of applications, such as metallic finishing, contrast enhancing luminescent pigments, high-end optical filters, and so on. Currently, the difficulty in producing monodisperse and stable binary metal oxide nano pigments at low temperature hampers the applicability and realization of transparent blue nano pigments. Here, for the first time, we report organic ligand capped CoAl2O4 hybrid transparent nano pigment, which has a particle size less than 8 nm with well-stabilized single nanocrystals, using organic ligand-assisted supercritical water as the reaction medium. The organic ligand capping could effectively inhibit the particle growth and also control the size of nanocrystals. This helps to diminish the scattering effect of the nano blue pigment, realizing a transparent cobalt blue nano pigment without any postheat treatment. PMID:17705377

  2. Synergetic effect of copper-plating wastewater as a catalyst for the destruction of acrylonitrile wastewater in supercritical water oxidation.

    PubMed

    Shin, Young Ho; Lee, Hong-shik; Lee, Young-Ho; Kim, Jaehoon; Kim, Jae-Duck; Lee, Youn-Woo

    2009-08-15

    A new supercritical water oxidation process for the simultaneous treatment of mixed wastewater containing wastewater from acrylonitrile manufacturing processes and copper-plating processes was investigated using a continuous tubular reactor system. Experiments were carried out at temperatures ranging from 400 to 600 degrees C and a pressure of 25 MPa. The residence time was fixed at 2s by changing the flow rates of feeds, depending on reaction temperature. The initial total organic carbon (TOC) concentration of the wastewaters and the O(2) concentration at the reactor inlet were kept constant at 0.49 and 0.74 mol/L. It was confirmed that the copper-plating wastewater accelerated the TOC conversion of acrylonitrile wastewater from 17.6% to 67.3% at a temperature of 450 degrees C. Moreover, copper and copper oxide nanoparticles were generated in the process of supercritical water oxidation (SCWO) of mixed wastewater. 99.8% of copper in mixed wastewater was recovered as solid copper and copper oxides at a temperature of 600 degrees C, with their average sizes ranging from 150 to 160 nm. Our study showed that SCWO provides a synergetic effect for simultaneous treatment of acrylonitrile and copper-plating wastewater. During the reaction, the oxidation rate of acrylonitrile wastewater was enhanced due to the in situ formation of nano-catalysts of copper and/or copper oxides, while the exothermic decomposition of acrylonitrile wastewater supplied enough heat for the recovery of solid copper and copper oxides from copper-plating wastewater. The synergetic effect of wastewater treatment by the newly proposed SCWO process leads to full TOC conversion, color removal, detoxification, and odor elimination, as well as full recovery of copper. PMID:19231072

  3. First principles simulations of fluid water: The radial distribution functions

    NASA Astrophysics Data System (ADS)

    Ortega, José; Lewis, James P.; Sankey, Otto F.

    1997-03-01

    We apply a recently developed first principles but simplified molecular dynamics method to the simulation of water at different conditions. The computational simplicity of this method allows its application to systems containing a significant number of molecules, yet still taking explicitly into account the quantum electronic structure of the system. In the present work we simulate a system of 216 H2O molecules with periodic boundary conditions at two different densities (ρ=1.0 g/cm3 and ρ=0.72 g/cm3 and temperatures ranging from ˜300 K to ˜580 K. The effect of density and temperature on the structure of water is analyzed by means of the partial radial distribution functions gOO, gOH and gHH . We find an important reduction of the hydrogen-bond peak for water at the supercritical conditions ρ= 0.72 g/cm3, T=580 K, in good agreement with recent experimental results.

  4. 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

  5. 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.

  6. Micro-PIV Study of Supercritical CO2-Water Interactions in Porous Micromodels

    NASA Astrophysics Data System (ADS)

    Kazemifar, Farzan; Blois, Gianluca; Christensen, Kenneth T.

    2015-11-01

    Multiphase flow of immiscible fluids in porous media is encountered in numerous natural systems and engineering applications such as enhanced oil recovery (EOR), and CO2 sequestration among others. Geological sequestration of CO2 in saline aquifers has emerged as a viable option for reducing CO2 emissions, and thus it has been the subject of numerous studies in recent years. A key objective is improving the accuracy of numerical models used for field-scale simulations by incorporation/better representation of the pore-scale flow physics. This necessitates experimental data for developing, testing and validating such models. We have studied drainage and imbibition processes in a homogeneous, two-dimensional porous micromodel with CO2 and water at reservoir-relevant conditions. Microscopic particle image velocimetry (micro-PIV) technique was applied to obtain spatially- and temporally-resolved velocity vector fields in the aqueous phase. The results provide new insight into the flow processes at the pore scale.

  7. Experimental methods for the simulation of supercritical CO2 injection at laboratory scale aimed to investigate capillary trapping

    NASA Astrophysics Data System (ADS)

    Trevisan, L.; Illangasekare, T. H.; Rodriguez, D.; Sakaki, T.; Cihan, A.; Birkholzer, J. T.; Zhou, Q.

    2011-12-01

    Geological storage of carbon dioxide in deep geologic formations is being considered as a technical option to reduce greenhouse gas loading to the atmosphere. The processes associated with the movement and stable trapping are complex in deep naturally heterogeneous formations. Three primary mechanisms contribute to trapping; capillary entrapment due to immobilization of the supercritical fluid CO2 within soil pores, liquid CO2 dissolving in the formation water and mineralization. Natural heterogeneity in the formation is expected to affect all three mechanisms. A research project is in progress with the primary goal to improve our understanding of capillary and dissolution trapping during injection and post-injection process, focusing on formation heterogeneity. It is expected that this improved knowledge will help to develop site characterization methods targeting on obtaining the most critical parameters that capture the heterogeneity to design strategies and schemes to maximize trapping. This research combines experiments at the laboratory scale with multiphase modeling to upscale relevant trapping processes to the field scale. This paper presents the results from a set of experiments that were conducted in an intermediate scale test tanks. Intermediate scale testing provides an attractive alternative to investigate these processes under controlled conditions in the laboratory. Conducting these types of experiments is highly challenging as methods have to be developed to extrapolate the data from experiments that are conducted under ambient laboratory conditions to high temperatures and pressures settings in deep geologic formations. We explored the use of a combination of surrogate fluids that have similar density, viscosity contrasts and analogous solubility and interfacial tension as supercritical CO2-brine in deep formations. The extrapolation approach involves the use of dimensionless numbers such as Capillary number (Ca) and the Bond number (Bo). A set of

  8. Accurate Calculation of Solvation Free Energies in Supercritical Fluids by Fully Atomistic Simulations: Probing the Theory of Solutions in Energy Representation.

    PubMed

    Frolov, Andrey I

    2015-05-12

    Accurate calculation of solvation free energies (SFEs) is a fundamental problem of theoretical chemistry. In this work we perform a careful validation of the theory of solutions in energy representation (ER method) developed by Matubayasi et al. [J. Chem. Phys. 2000, 113, 6070-6081] for SFE calculations in supercritical solvents. This method can be seen as a bridge between the molecular simulations and the classical (not quantum) density functional theory (DFT) formulated in energy representation. We performed extensive calculations of SFEs of organic molecules of different chemical natures in pure supercritical CO2 (sc-CO2) and in sc-CO2 with addition of 6 mol % of ethanol, acetone, and n-hexane as cosolvents. We show that the ER method reproduces SFE data calculated by a method free of theoretical approximations (the Bennett's acceptance ratio) with the mean absolute error of only 0.05 kcal/mol. However, the ER method requires by an order less computational resources. Also, we show that the quality of ER calculations should be carefully monitored since the lack of sampling can result into a considerable bias in predictions. The present calculations reproduce the trends in the cosolvent-induced solubility enhancement factors observed in experimental data. Thus, we think that molecular simulations coupled with the ER method can be used for quick calculations of the effect of variation of temperature, pressure, and cosolvent concentration on SFE and hence solubility of bioactive compounds in supercritical fluids. This should dramatically reduce the burden of experimental work on optimizing solvency of supercritical solvents. PMID:26574423

  9. Vibrational Energy Relaxation of Thiocyanate Ions in Liquid-to-Supercritical Light and Heavy Water. A Fermi's Golden Rule Analysis.

    PubMed

    Czurlok, Denis; Gleim, Jeannine; Lindner, Jörg; Vöhringer, Peter

    2014-10-01

    The vibrational relaxation dynamics following an ultrafast nitrile stretching (ν3) excitation of thiocyanate anions dissolved in light and heavy water have been studied over a wide temperature and density range corresponding to the aqueous liquid up to the supercritical phase. In both solvents, the relaxation of the ν3 = 1 state of the anion leads to a direct recovery of the vibrational ground state and involves the resonant transfer of the excess vibrational energy onto the solvent. In light water, the energy-accepting states are provided by the bending-librational combination band (νb + νL), while in heavy water, the relaxation is thermally assisted by virtual acceptor states derived from the stretching-librational/restricted translational hot band (νS - νL,T). The relaxation rate is found to strictly obey Fermi's Golden Rule when the density of resonant solvent states is estimated from the linear infrared spectra of the solute and the pure solvents. PMID:26278447

  10. 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. PMID:27081725

  11. Geoelectrical characterization of carbonate and silicate porous media in the presence of supercritical CO2-water flow

    NASA Astrophysics Data System (ADS)

    Abidoye, Luqman Kolawole; Das, Diganta Bhusan

    2015-10-01

    The relative permittivity (εr) and the electrical conductivity (σ) of porous media are known to be functions of water saturation (S). As such, their measurements can be useful in effective characterisations and monitoring of geological carbon sequestration using geoelectrical measurement techniques. In this work, the effects of pressure, temperature and salt concentration on bulk εr-S and σ-S relationships were investigated for carbonate (limestone) and silicate porous media (both unconsolidated domains) under dynamic and quasi-static supercritical CO2 (scCO2)-brine/water flow. In the silica sand sample, the bulk εr (εb) for scCO2-water decreases as the temperature increases. On the contrary, slight increase was seen in the εb with temperature in the carbonate sample for the scCO2-water system. These trends are more conspicuous at high water saturation. The εb-S curves for the scCO2-water flow in the silica sand also show clear dependency on the domain pressure, where εb increases as the domain pressure increases. Furthermore, the bulk σ (σb), at any particular saturation for the scCO2-brine system rises as the temperature increases with more significant increase found at very high water saturation. Both εb and σb values are found to be greater in the limestone than silica sand porous samples for similar porosity values. Based on different injection rates investigated, we do not find significant dynamic effects in the εb-S and σb-S relationships for the scCO2-brine/water system. As such, geoelectrical characteristics can be taken as reliable in the monitoring of two-phase flow system in the porous media. It can be inferred from the results that the geoelectrical techniques are highly dependent on water saturation. This dependence is more conspicuous at higher water saturation. Different mathematical models examined show their reliability at different water saturation ranges. The polynomial fit developed in this work takes into consideration the fluid

  12. Enhanced coal liquefaction by hydropyrolysis in supercritical fluids. Quarterly report, October-December 1984. [Pyrolysis of benzyl phenyl ether; benzyl phenyl sulfide in water and in water and methanol

    SciTech Connect

    Paulaitis, M.E.; Klein, M.T.; Stiles, A.B.

    1984-01-01

    This research program involves a fundamental investigation of a novel coal liquefaction process that combines pyrolysis, supercritical-fluid solvent extraction, and in situ hydrogen generation through catalytic dissociation of methanol. The experimental work consists of determining: (1) coal pyrolysis reaction pathways, kinetics and mechanisms, and the identity and structure of reaction intermediates, (2) solubilities of coal-derived species in supercritical water, methanol, and water + methanol mixtures, and (3) reaction pathways involved in the generation of hydrogen by catalytic dissociation of methanol to carbon monoxide and hydrogen, and through the shift of carbon monoxide. Both model coal compounds and actual coals are to be studied. 2 refs., 6 figs.

  13. 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.

  14. Feasibility Study of Supercritical Light Water Cooled Reactors for Electric Power Production, Progress Report for Work Through September 2003, 2nd Annual/8th Quarterly Report

    SciTech Connect

    Philip E. MacDonald

    2003-09-01

    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% vs. 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 recirculation and jet pumps, 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 is also in use around the world.

  15. A nanosystem for water-insoluble drugs prepared by a new technology, nanoparticulation using a solid lipid and supercritical fluid.

    PubMed

    Park, Joo Won; Yun, Jeong Min; Lee, Eun Seong; Youn, Yu Seok; Kim, Kab Sig; Oh, Young Taik; Oh, Kyung Teak

    2013-11-01

    While the number and diversity of lead compounds has increased with the development of science technologies, ca. 90 % of new chemical entities under development have shown low aqueous solubility, classified as class II or IV of the biopharmaceutics classification system (BCS). The low aqueous solubility hinders their clinical translations due to low bioavailability and dissolution-limited absorption of orally-administered drugs. Several technologies have been employed to improve the solubility of poorly water-soluble drugs. In this paper, a new method of nanoparticulation using fat and a supercritical fluid (NUFS) for the formulation of hydrophobic drugs was applied to solve the low solubility problem. A typical BCS class II drug, itraconazole, was selected and formulated with hydroxypropyl methylcellulose, emulsification, and anticoagulating agents for NUFS. The non-spherical itraconazole nanoparticles prepared by NUFS were ~300-500 nm in size with a ~15-fold improved dissolution rate compared to non-nanoparticles of itraconazole (i.e., raw itraconazole). In addition, a high drug content of ~46 % by weight and a drug loading efficiency greater than 85 % were achieved. Therefore, the new technology for nano-platforms could be a promising solution for solubilization of poorly water-soluble drugs, resulting in improved bioavailability. PMID:23780798

  16. 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

  17. Molecular dynamics simulation study of ionic hydration and ion association in dilute and 1 molal aqueous sodium chloride solutions from ambient to supercritical conditions

    NASA Astrophysics Data System (ADS)

    Driesner, T.; Seward, T. M.; Tironi, I. G.

    1998-09-01

    The increasing demand for accurate equations of state of fluids under extreme conditions and the need for a detailed microscopic picture of aqueous fluids in some areas of geochemistry (e.g., mineral dissolution/precipitation kinetics) potentially make molecular dynamics (MD) simulations a powerful tool for theoretical geochemistry. We present MD simulations of infinitely dilute and 1 molal aqueous NaCl solutions that have been carried out in order to study the systematics of hydration and ion association over a wide range of conditions from ambient to supercritical and compare them to the available experimental data. In the dilute case, the hydration number of the Na + ion remains essentially constant around 5.5 from ambient to supercritical temperatures when the density is kept constant at 1 g cm -3 but decreases to below 5 along the liquid-vapor curve. In both cases, the average ion-first shell water distance decreases by about 0.03 Å from ambient to near critical temperatures. The Cl - ion shows a slight expansion of the first hydration shell by about 0.02 Å from ambient to near critical temperatures. The geometric definition of the first hydration shell becomes ambiguous due to a shift of the position of the first minimum of the Cl-O radial distribution function. In the case of the 1 molal solution, the contraction of the Na + first hydration shell is similar to that in the dilute case whereas the hydration number decreases drastically from 4.9 to 2.8 due to strong ion association. The released waters are replaced on a near 1:1 basis by chloride ions. Polynuclear clusters as predicted by Oelkers and Helgeson (1993b) are observed in the high temperature systems. The hydration shell of the Cl --ion shows significant deviation from the behavior in dilute systems, that is, at near vapor saturated conditions, the expansion of the hydration shell is significantly larger (0.12 Å from ambient to near critical temperatures). Due to a very large shift of the first

  18. Oxidation of hazardous waste in supercritical water: A comparison of modeling and experimental results for methanol destruction

    SciTech Connect

    Butler, P.B. ); Bergan, N.E.; Bramlette, T.T. ); Pitz, W.J.; Westbrook, C.K. )

    1991-03-17

    Recent experiments at Sandia National Laboratories conducted in conjunction with MODEC Corporation have demonstrated successful clean- up of contaminated water in a supercritical water reactor. These experiments targeted wastes of interest to Department of Energy production facilities. In this paper we present modeling and experimental results for a surrogate waste containing 98% water, 2% methanol, and parts per million of chlorinated hydrocarbons and laser dyes. Our initial modeling results consider only methanol and water. Experimental data are available for inlet and outlet conditions and axial temperature profiles along the outside reactor wall. The purpose of our model is to study the chemical and physical processes inside the reactor. We are particularly interested in the parameters that control the location of the reaction zone. The laboratory-scale reactor operates at 25 MPa., between 300 K and 900 K; it is modeled as a plug-flow reactor with a specified temperature profile. We use Chemkin Real-Gas to calculate mixture density, with the Peng-Robinson equation of state. The elementary reaction set for methanol oxidation and reactions of other C{sub 1} and C{sub 2} hydrocarbons is based on previous models for gas-phase kinetics. Results from our calculations show that the methanol is 99.9% destroyed at 1/3 the total reactor length. Although we were not able to measure composition of the fluid inside the experimental reactor, this prediction occurs near the location of the highest reactor temperature. This indicates that the chemical reaction is triggered by thermal effects, not kinetic rates. Results from ideal-gas calculations show nearly identical chemical profiles inside the reactor in dimensionless distance. However, reactor residence times are overpredicted by nearly 150% using an ideal-gas assumption. Our results indicate that this oxidation process can be successfully modeled using gas-phase chemical mechanisms. 23 refs., 8 figs.

  19. 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.

  20. Simulation of Europa's water plume .

    NASA Astrophysics Data System (ADS)

    Lucchetti, A.; Cremonese, G.; Schneider, N. M.; Plainaki, C.; Mazzotta Epifani, E.; Zusi, M.; Palumbo, P.

    Plumes on Europa would be extremely interesting science and mission targets, particularly due to the unique opportunity to obtain direct information on the subsurface composition, thereby addressing Europa's potential habitability. The existence of water plume on the Jupiter's moon Europa has been long speculated until the recent discover. HST imaged surpluses of hydrogen Lyman alpha and oxygen emissions above the southern hemisphere in December 2012 that are consistent with two 200 km high plumes of water vapor (Roth et al. 2013). In previous works ballistic cryovolcanism has been considered and modeled as a possible mechanism for the formation of low-albedo features on Europa's surface (Fagents et al. 2000). Our simulation agrees with the model of Fagents et al. (2000) and consists of icy particles that follow ballistic trajectories. The goal of such an analysis is to define the height, the distribution and the extension of the icy particles falling on the moon's surface as well as the thickness of the deposited layer. We expect to observe high albedo regions in contrast with the background albedo of Europa surface since we consider that material falling after a cryovolcanic plume consists of snow. In order to understand if this phenomenon is detectable we convert the particles deposit in a pixel image of albedo data. We consider also the limb view of the plume because, even if this detection requires optimal viewing geometry, it is easier detectable in principle against sky. Furthermore, we are studying the loss rates due to impact electron dissociation and ionization to understand how these reactions decrease the intensity of the phenomenon. We expect to obtain constraints on imaging requirements necessary to detect potential plumes that could be useful for ESA's JUICE mission, and in particular for the JANUS camera (Palumbo et al. 2014).

  1. 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…

  2. 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.

  3. Preparation of α-alumina nanoparticles with various shapes via hydrothermal phase transformation under supercritical water conditions

    NASA Astrophysics Data System (ADS)

    Hakuta, Y.; Nagai, N.; Suzuki, Y.-H.; Kodaira, T.; Bando, K. K.; Takashima, H.; Mizukami, F.

    2013-12-01

    Alumina (Al2O3) fine particles are widely used as industrial materials including fillers for metal or plastics, paints, polisher, cosmetics and electric substrates, due to its high hardness, chemical stability, and high thermal conductivity. The performance of those industrial products is closely related to the particle size or shape of the alumina particles used, and thus a new synthetic method to control size, shape, and crystal structure of the aluminum oxide is desired for the improvement of the performance. Hydrothermal phase transformation using various aluminum compounds such as oxide, hydroxide, and salt as a staring material, is known as one of the synthetic methods for producing alumina fine particles; however, the influence about the size and shape of the starting aluminum compounds has been little mentioned, although they strongly affect the size and shape of the final products. In this study, we investigated the influence of the shape, size and crystal structure of the starting aluminum compounds on those of the products, and newly succeeded in the production of rod-like α-Al2O3 nanoparticles from fibrous boehmite nanoparticles using hydrothermal phase transformation under supercritical water conditions.

  4. Corrosion of Alloy 625 and pure chromium in Cl{sup {minus}} containing fluids during supercritical water oxidation (SCWO)

    SciTech Connect

    Wagner, M.; Kolarik, V.; Michelfelder, B.; Juez-Lorenzo, M.; Hirth, T.; Eisenreich, N.; Eyerer, P.

    1999-11-01

    Supercritical water oxidation (SCWO) is an efficient procedure for complete degradation of hazardous residues, converting them into acids, salts, and carbon dioxide. The reactor material, however, is subjected to a highly corrosive fluid and to high pressures at high temperatures. An experimental set-up was designed that allows corrosion studies under these conditions. Alloy 625 and chromium of high purity were studied at 500 C and 46.5 MPa up to 300 h with a model fluid consisting of HCl + H{sub 2}O + NaCl + methanol using H{sub 2}O{sub 2} as oxidant. Alloy 625 forms complex layers with alternating scales consisting of Cr-Mo-Nb-O mixed oxides, and layers containing chlorides, mainly NiCl{sub 2}. Additionally pitting corrosion and local intergranular corrosion were observed. The analysis of the fluid phase by ICP-AES as a function of time showed periods with a strong transition of Ni into the fluid phase and alternating time periods with high Mo and Cr concentrations indicating that alternating mechanisms are controlling the corrosion procedure. On pure chromium, Cr{sub 2}O{sub 3} scales composed of several layers were formed and in wide regions spallation was observed. The reduction of sample thickness and mass changes indicate greater corrosion rates of Cr than Alloy 625.

  5. Influence of Ar-ions irradiation on the oxidation behavior of ferritic-martensitic steel P92 in supercritical water

    NASA Astrophysics Data System (ADS)

    Huang, Xi; Shen, Yinzhong; Zhu, Jun

    2015-02-01

    The corrosion behavior of ferritic-marensitic steel P92 with and without Ar-ions irradiation in supercritical water at 823 K(550 °C)/25 MPa for different exposure times was investigated by a variety of characterization techniques. A distinct difference in oxidation morphology between irradiated and unirradiated samples was observed. The oxide morphology of samples with a relatively moderate radiation intensity was similar with that of samples without irradiation. Many small oxide particles were observed in the region with a relatively high radiation intensity but their size was increased gradually with increasing exposure times. Exfoliation of oxide layer occurred for irradiated samples exposed for 100 h. Chromium-rich oxide layer with a chromium content of more than 20 wt pct along with a small-scale three-layer oxide structures were observed in Ar-ions irradiated samples, arising from the microstructural change in steel samples after the irradiation. Mechanism for the exfoliation of oxide layer is also discussed.

  6. 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

  7. Application of supercritical water to decompose brominated epoxy resin and environmental friendly recovery of metals from waste memory module.

    PubMed

    Li, Kuo; Xu, Zhenming

    2015-02-01

    Waste Memory Modules (WMMs), a particular kind of waste printed circuit board (WPCB), contain a high amount of brominated epoxy resin (BER), which may bring a series of environmental and health problems. On the other hand, metals like gold and copper are very valuable and are important to recover from WMMs. In the present study, an effective and environmental friendly method using supercritical water (SCW) to decompose BER and recover metals from WMMs was developed instead of hydrometallurgy or pyrometallurgy simultaneously. Experiments were conducted under external-catalyst-free conditions with temperatures ranging from 350 to 550 °C, pressures from 25 to 40 MPa, and reaction times from 120 to 360 min in a semibatch-type reactor. The results showed that BER could be quickly and efficiently decomposed under SCW condition, and the mechanism was possibly free radical reaction. After the SCW treatments, the glass fibers and metal foils in the solid residue could be easily liberated and recovered, respectively. The metal recovery rate reached 99.80%. The optimal parameters were determined as 495 °C, 33 MPa, and 305 min on the basis of response surface methodology (RSM). This study provides an efficient and environmental friendly approach for WMMs recycling compared with electrolysis, pyrometallurgy, and hydrometallurgy. PMID:25582426

  8. 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.

  9. In situ mid-infrared spectroscopic titration of forsterite with water in supercritical CO2: Dependence of mineral carbonation on quantitative water speciation

    NASA Astrophysics Data System (ADS)

    Loring, J. S.; Thompson, C. J.; Wang, Z.; Schaef, H. T.; Martin, P.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

    2011-12-01

    Geologic sequestration of carbon dioxide holds promise for helping mitigate CO2 emissions generated from the burning of fossil fuels. Supercritical CO2 (scCO2) plumes containing variable water concentrations (wet scCO2) will displace aqueous solution and dominate the pore space adjacent to caprocks. It is important to understand possible mineral reactions with wet scCO2 to better predict long-term caprock integrity. We introduce novel in situ instrumentation that enables quantitative titrations of reactant minerals with water in scCO2 at temperatures and pressures relevant to target geologic reservoirs. The system includes both transmission and attenuated total reflection mid-infrared optics. Transmission infrared spectroscopy is used to measure concentrations of water dissolved in the scCO2, adsorbed on mineral surfaces, and incorporated into precipitated carbonates. Single-reflection attenuated total reflection infrared spectroscopy is used to monitor water adsorption, mineral dissolution, and carbonate precipitation reactions. Results are presented for the infrared spectroscopic titration of forsterite (Mg2SiO4), a model divalent metal silicate, with water in scCO2 at 100 bar and at both 50 and 75°C. The spectral data demonstrate that the quantitative speciation of water as either dissolved or adsorbed is important for understanding the types, growth rates, and amounts of carbonate precipitates formed. Relationships between dissolved/adsorbed water, water concentrations, and the role of liquid-like adsorbed water are discussed. Our results unify previous in situ studies from our laboratory based on infrared spectroscopy, nuclear magnetic resonance spectroscopy and X-ray diffraction.

  10. 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)

  11. 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

  12. 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

  13. 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

  14. Product composition of the dynamic conversion of brown coal in supercritical water

    SciTech Connect

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

    2007-12-15

    The product composition of the dynamic conversion of brown coal, which was continuously supplied as a water-coal slurry to a flow reactor at 30 MPa, was studied. The temperature of water and coal particles was increased from room temperature to 400{sup o}C (top part of the reactor). The conversion of the organic matter of coal was about 48%, and the products collected at the reactor outlet consisted of solid tar components, substances dissolved and emulsified in water, and volatile substances, whose major constituent was CO{sub 2}. The composition of solid tar components and oils was determined.

  15. 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

  16. 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.

  17. 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. PMID:25200530

  18. Reaction chemistry and phase behavior of lignin in high-temperature and supercritical water.

    PubMed

    Fang, Zhen; Sato, Takafumi; Smith, Richard L; Inomata, Hiroshi; Arai, Kunio; Kozinski, Janusz A

    2008-06-01

    Decomposition of organosolve lignin in water/phenol solutions was studied in a 50 nL micro-reactor coupled with optical, Raman and infrared microscopies at temperatures up to 600 degrees C and water densities up to 1165 kg/m3. It was found that when phenol was used with {lignin+water} mixtures that a homogenous phase was formed that seemed to promote the decomposition of lignin into phenolic fragments by hydrolysis and pyrolysis. Phenol, along with the homogenous reaction conditions also inhibited re-polymerization of the phenolics and promoted oil formation. On the other hand, in the absence of phenol, lignin remained as a heterogeneous phase with water over the range of conditions studied. The homogeneous conditions and conditions for inhibiting char formation by phenol were elucidated and it was found that mixtures of phenol and lignin become homogeneous at 400-600 degrees C and high water densities of 428-683 kg/m3, corresponding to maximum pressures of 93 MPa. These results were further used to propose reaction paths. PMID:17881227

  19. 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.

  20. Reaction of water-saturated supercritical CO2 with forsterite: Evidence for magnesite formation at low temperatures

    NASA Astrophysics Data System (ADS)

    Felmy, Andrew R.; Qafoku, Odeta; Arey, Bruce W.; Hu, Jian Zhi; Hu, Mary; Todd Schaef, H.; 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 (˜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%. PMID:25387488

  2. Nuclear analyses of supercritical water cooled reactor with carbon nano-tube cladding

    SciTech Connect

    Uenohara, Y.; Yamano, N.

    2012-07-01

    The authors have confirmed the feasibility of the dual layer clad comprised of iron and carbon nano-tube to problems of Super Critical Water Reactor cores. Continuous energy Monte Carlo method was applied. The difference between JENDL-3.3 and ENDF-6 was confirmed. Depletion was carried out. (authors)

  3. 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.

  4. In-situ Optical Spectroscopy Investigation of Water and Its influence on Forsterite Transformation in Supercritical CO2

    NASA Astrophysics Data System (ADS)

    Wang, Z.; Thompson, C. J.; Joly, A. G.; Sklarew, D. S.; Poindexter, L.; Rosso, K. M.

    2009-12-01

    Carbon capture and sequestration (CCS) from coal/gas-burning power plants is currently viewed as one of the most promising technologies for mitigating green house gas emissions. This strategy involves injection of supercritical CO2 (scCO2) into deep geological formations such as depleted oil and gas reservoirs and deep saline aquifers. The feasibility of this approach and the ultimate fate of the stored CO2 are determined by the interactions between scCO2, various minerals in the rock formations, and the host fluids. Currently, there is only limited knowledge about both the thermodynamic and kinetic aspects of the physical and chemical processes that occur between scCO2 and relevant minerals, such as metal silicates and metal aluminosilicates, and the role of water activity for catalyzing mineral transformation reactions. In this work, we have developed a modular in situ optical spectroscopic platform that integrates a scCO2 generation and manipulation system with an array of optical and laser spectroscopies including UV-visible, IR, Raman and laser fluorescence spectroscopy. We have used the system to study i) the dissolution and quantification of H2O/D2O in scCO2 and ii) interaction between scCO2 and a model metal silicate, forsterite (Mg2SiO4), and the effects of the presence of water under variable pressure, temperature and water content. Our results showed that H2O and D2O have unique IR spectral features over a broad spectral range from 700 cm-1 to ~ 2900 cm-1 in scCO2 and their concentrations are directly proportional to the characteristic IR bands that correspond to their stretching (D2O) and bending frequencies (both D2O and H2O). These bands offer a unique spectroscopic signature useful for qualitative and quantitative analysis of the properties and reactivity of small amounts of H2O in scCO2.

  5. Multimodel Simulation of Water Flow: Uncertainty Analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Simulations of soil water flow require measurements of soil hydraulic properties which are particularly difficult at the field scale. Laboratory measurements provide hydraulic properties at scales finer than the field scale, whereas pedotransfer functions (PTFs) integrate information on hydraulic pr...

  6. 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.

  7. 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.

  8. Simulation of high-temperature water-CO2 flows in porous media

    NASA Astrophysics Data System (ADS)

    Afanasyev, Andrey

    2010-05-01

    Coupled water and carbon dioxide flows in porous media can take place both in natural volcanic environments and in industrial processes, for example, underground carbon dioxide storage or geothermal energy recovery. Pressures and temperatures in these flows can considerably exceed their values in critical point of water. Nowadays there are no adequate mathematical models that can in aggregate describe both water and water-carbon dioxide mixture properties in sub- and supercritical regions and the dynamics of their flows in such conditions. Thereby the influence of critical conditions on water flows in porous media is not well understood. In the paper cubic equation of state is used to describe water-carbon dioxide mixture in wide range of conditions including critical conditions for mixture. The equation generalizes well known Peng-Robinson equation and can be used to describe properties not only of hydrocarbons but also of carbon-dioxide and water. The real mixture properties measurements are used to determine the equation coefficients. Comparison between experimental measurements and data calculated via the equation of state shows a good agreement between the data. For example the error in water density calculation is less than 10% in the whole range of pressure-enthalpy conditions. Effective and fast algorithms for phase equilibrium calculation via pressure, enthalpy and mixture composition where developed. These thermodynamic variables are the most suitable for trans-critical flow simulations. The developed numerical model that is based on mass and energy conservation laws was used to study hydrothermal system in Solfatara volcano (Campi Flegrei). The flows in porous media that take place in the system are forced by presence of magmatic chamber located at depth of 9 km. Magma degassing makes a hot supercritical plume of water-carbon dioxide mixture that ascends to shallow layers where magmatic fluid mixes with cold meteoric water. The model assumes a source of

  9. 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

  10. Corrosion and microstructural analysis data for AISI 316L and AISI 347H stainless steels after exposure to a supercritical water environment.

    PubMed

    Ruiz, A; Timke, T; van de Sande, A; Heftrich, T; Novotny, R; Austin, T

    2016-06-01

    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

  11. 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

  12. The Mechanism of Diopside-Water-Supercritical CO2 Reaction:Relevance to CO2 Sequestration

    NASA Astrophysics Data System (ADS)

    Jiang, D.; Dong, S.; Zhao, L.; Teng, H.

    2013-12-01

    In order to study fundamental mineral carbonation process and reaction extent relevance to CO2 geological sequestration, in situ Raman spectroscopy was used to detect the silicate mineral diopside (CaMgSi2O6)-H2O-scCO2 reaction. In the experiment, diopside bulk grain (0.09g) and grinded powder (0.09g, 200mesh) were put into the sample pool of in situ Raman spectroscopy apparatus in water-saturated condition (10μlH2O: experimental H2O mole fraction in CO2 is 8.1×10-2, solubility of H2O in CO2 at experimental condition is 4.8×10-3), setting at the temperature of 60 degrees centigrade and the pressure of 7.9MPa. Experiment was done following the Lambert-Beer's law:Iv=KLCI0, which shows that Raman intensity(Iv) is proportional to the substance concentration(C)(K, L and I0 are constant in this experiment). The Raman spectrum analysis was performed at the beginning day, day 13, day 28 and day 42 successively. The results indicate that at day 13, a new peak appeared at 1124cm-1 , revealing that in water-saturated scCO2 condition, diopside is converted to huntite (Mg3Ca(CO3)4). The intensity ratio of diopside(1014cm-1) and huntite varies from 4.51:1(beginning) to 2.59:1(day 13) and then to 3.46:1(day 28). However, at day 42, almost no huntite remained in the experiment settings. According to Beer's law, we can conclude that the concentration of huntite increased firstly and then decreased after day 13 until we could not detect it at day 49. The XRD, SEM and FTIR test at day 49 also support the conclusion above. The huntite might form at the very first stage and then got dissolved into HCO3-; further experiments need to be conducted to detect HCO3-. The Raman test on the bulk grain also shows a similar trend as powder, but the reaction of the grain is much slower than powder. Besides, from the test on the grain at day 28, the water film could been detected 100-150μm above the surface of the grain with the thickness of 50-150μm.

  13. Corrosion properties of oxide dispersion strengthened steels in super-critical water environment

    NASA Astrophysics Data System (ADS)

    Cho, H. S.; Kimura, A.; Ukai, S.; Fujiwara, M.

    2004-08-01

    The effects of alloying elements on corrosion resistance in super critical pressurized water (SCPW) have been investigated to develop corrosion resistant oxide dispersion strengthened (ODS) steels. Corrosion tests were performed in a SCPW (783 K, 25 MPa) environment. Weight gain was measured after exposure to the SCPW. For the improvement of corrosion-resistance, the effects of chromium, aluminum, and yttrium on the corrosion behavior were investigated. The 9-12 wt%Cr ODS steels showed almost similar corrosion behavior with the ordinary ferritic/martensitic steel in the SCPW. However, the addition of high chromium (>13 wt%) and aluminum (4.5 wt%) are very effective to suppress the corrosion in the SCPW. Anodic polarization experiments revealed that the passive current of the ODS steels are lower than the ordinary ferritic/martensitic steels. Addition of aluminum improves the Charpy impact property of the ODS steels.

  14. Process for the oxidation of materials in water at supercritical temperatures utilizing reaction rate enhancers

    SciTech Connect

    Swallow, K.C.; Killilea, W.R.; Hong, G.T.; Bourhis, A.L.

    1993-08-03

    A method is described for substantially completely oxidizing combustible materials in which an aqueous stream bearing the combustible materials is reacted in the presence of an oxidant comprising diatomic oxygen and at a temperature greater than the critical temperature of water and at a pressure greater than about 25 bar, within a reactor for a period of less than about 5 minutes to produce a reaction product stream, wherein the reaction is initiated in the presence of a rate enhancer comprising at least one oxidizing agent in addition to said oxidant selected from the group consisting of ozone, hydrogen peroxide, salts containing persulfate, salts containing permanganate, nitric acid, salts containing nitrate, oxyacids of chlorine and their corresponding salts, hypochlorous acid, salts containing hypochlorite, chlorous acid, salts containing chlorite, chloric acid, salts containing chlorate, perchloric acid, and salts containing perchlorate.

  15. 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.

  16. 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. PMID:27115941

  17. Development of a Holistic Model of the Carleton Supercritical Water Loop (SCWL)

    NASA Astrophysics Data System (ADS)

    Zakharchenko, Alexey

    In contrast to classical design of piping systems such as the Super Critical Water Loop (SCWL), i.e., design by rule or handbook equations, the goal of this thesis is to demonstrate a capability to do design by analysis, i.e., design based on a 3D transient nonlinear coupled holistic macroscopic model of the piping system of the Carleton SCWL. This work focuses on the development of time-efficient and reasonably precise thermal/stress nonlinear analysis of the SCWL piping system, resolving 3D transient fields of interest in the solid and fluid domains of the loop. The analysis makes use of the Dittus-Boelter correlation for computing heat transfer at the fluid-to-solid interface and proposes a simplified methodology for approximation of radial heat transport for turbulent flow in pipes. Using the described analysis methodology, this work provides thermal-mechanical stress analysis of the SCWL, making conclusions about the existing design, providing an example of appropriate operation parameters, and suggesting possible ways to improve the design.

  18. 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.

  19. Dynamic transition in supercritical iron.

    PubMed

    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

  20. 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

  1. 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

  2. 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.

  3. 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

  4. In-situ measurements of the oxidation of AISI 316L(NG) and its constituents (Fe,Cr, Ni) in ultra-supercritical water

    SciTech Connect

    Betova, Iva; Bojinov, Martin; Kinnunen, Petri; Lehtovuori, Viivi; Peltonen, Seppo; Penttila, Sami; Saario, Timo

    2006-07-01

    Several new nuclear reactor designs utilizing supercritical water as coolant are currently being developed. In the European concept the design pressure is 25 MPa and reactor inlet/outlet temperatures 290 deg C/520 deg C. While benefits include better coolant thermal conductivity, increase in efficiency and simpler overall design, many material related questions need to be solved such as oxidation and radiation resistance with simultaneous need to maintain creep strength. This calls for the development of in-situ monitoring methods for the material/environment combination in question. In the present paper, in-situ electrical and electrochemical measurements during oxidation of AISI 316L(NG) and its pure metal constituents (Fe,Cr and Ni) in ultra-supercritical water (500-700 deg C, 30 MPa) have been reproducibly obtained. The oxidation kinetics was followed using the contact electric resistance (CER) and contact electric impedance (CEI) techniques. First attempts have been made to correlate properties of the resulting oxides with the corresponding weight gain data. In addition, impedance spectra of the Ni-Ni contact during oxidation have been reproducibly measured at 500 and 600 deg C. They could be quantitatively interpreted using general considerations of the corrosion process and the Mixed-Conduction Model for oxide films. Preliminary estimates of the diffusion coefficients of principal ionic and electronic current carriers have been obtained and their relevance with respect to available data on Ni oxidation is discussed. (authors)

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Simulation of acid water movement in canals

    NASA Astrophysics Data System (ADS)

    Van Truong, To; Tat Dac, Nguyen; Ngoc Phienc, Huynh

    1996-05-01

    An attempt to tackle the problem of the propagation of acid water in canals is described, and a mathematical model to simulate the acid water movement is developed, in which the jurbanite equilibrium is found to prevail. The processes of settling owing to sedimentation, precipitation and redissolution have been considered in the modelling. Data available from Tan Thanh, in the Plain of Reeds of the Mekong Delta in Viet Nam, are used as a case study.

  10. 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.

  11. Space Simulation Chamber Rescues Water Damaged Books.

    ERIC Educational Resources Information Center

    American School and University, 1981

    1981-01-01

    More than 4,000 valuable water-damaged books were restored by using a space-simulation chamber at the Lockheed Missile and Space Company. It was the fifth time that the chamber has been used for the restoration of valuable books and documents. (Author/MLF)

  12. Molecular Dynamics Simulations of Water Evaporation

    NASA Astrophysics Data System (ADS)

    Wen, Chengyuan; Grest, Gary; Cheng, Shengfeng

    2015-03-01

    The evaporation of water from the liquid/vapor interface is studied via large-scale molecular dynamics simulations for systems of more than a million atoms at 550K and 600K. The TIP4P-2005 water model whose liquid/vapor surface tension is in excellent agreement with experiments is used. Evaporative cooling at the interface is observed from temperature profiles determined from both translational and rotational kinetic energy. During evaporation, the density of water is slightly enhanced near the liquid-vapor interface. The velocity distribution of water molecules in the vapor phase during evaporation at various distances relative to the interface fit a Maxwell-Boltzmann distribution. While our results indicate an imbalance between evaporating and condensing water molecules, local thermal equilibrium is found to hold in addition to mechanical equilibrium. Department of Physics, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA.

  13. Aspects of Supercritical Turbulence: Direct Numerical Simulation of O2/H2 and C7H16/N2 Temporal Mixing Layers

    NASA Technical Reports Server (NTRS)

    Bellan, J.; Okongo, N. A.; Harstad, K. G.; Hutt, John (Technical Monitor)

    2002-01-01

    Results from Direct Numerical Simulations of temporal, supercritical mixing layers for two species systems are analyzed to elucidate species-specific turbulence aspects. The two species systems, O2/H2 and C7HG16/N2, have different thermodynamic characteristics; thus, although the simulations are performed at similar reduced pressure (ratio of the pressure to the critical pressure), the former system is dose to mixture ideality and has a relatively high solubility with respect to the latter, which exhibits strong departures from mixture ideality Due to the specified, smaller initial density stratification, the C7H16/N2 layers display higher growth and increased global molecular mixing as well as larger turbulence levels. However, smaller density gradients at the transitional state for the O2/H2 system indicate that on a local basis, the layer exhibits an enhanced mixing, this being attributed to the increased solubility and to mixture ideality. These thermodynamic features are shown to affect the irreversible entropy production (i.e. the dissipation), which is larger for the O2/H2 layer and is primarily concentrated in high density-gradient magnitude regions that are distortions of the initial density stratification boundary. In contrast, the regions of largest dissipation in the C7H16/N2 layer are located in high density-gradient magnitude regions resulting from the mixing of the two fluids.

  14. 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

  15. 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

  16. 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. PMID:25802060

  17. Hydrogenous Gas Production through Reactions among Supercritical Water, Ironmaking Sludge, and Steelmaking Slag and Recycling of Wastes from Integrated Steel Mills

    NASA Astrophysics Data System (ADS)

    Hayashi, Shoji

    Automobile Shredder Residue (ASR) and Refuse derived fuels (not carbonized and carbonized: YRDF and RDF) as carbonaceous wastes were reacted isothermally with sub-supercritical water (600-695°C, 200 atm) together with a CO2 fixation reagent Ca(OH)2 inside a closed metallic tube reactor (7cm3). Product gas mainly consisted of hydrogen gas and a little methane gas except YRDF. As a whole, gas generated more in order ASR, YRDF, and RDF. Addition of catalysis NaOH or KOH made product gas increase more. KOH was more effective to product gas than NaOH. X-ray diffraction followed that Ca(OH)2 and CaCO3 existed mainly in residues after reaction tests with a CO2 fixation reagent Ca(OH)2 or CaO. Therefore, it was supposed that an overall chemical reaction took place as shown below. BOF steelmaking slag for CO2 fixation provided maximum gas generation 1.42 times as much as molar carbon in a RDF sample with KOH. C + H2O + Ca(OH)2 = CaCO3 + 2H2 Two kinds of wastes from integrated steel mills (sludge from mill scale and activated sludge) were each reacted with supercritical water (600-650°C, 200 atm). Both sludges were effective to generate hydrogenous gas. It was found that harmful cyan in the latter sludge mostly decomposed after reaction. Also, the crushing strength after curing the steelmaking slag bearing residue briquette was not as high as that from Portland cement.

  18. 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

  19. The supercritical profile of the supercritical wing

    NASA Technical Reports Server (NTRS)

    Wagner, O.

    1981-01-01

    The profile wing design for supercritical structures is discussed. Emphasis is placed on the flow of air surrounding the wing and variations in flow fields are examined. Modifications to the profile for flight below transonic level are presented that increase the uplift pressure and permit the achievement of critical Mach numbers on the order of 0.85. The uplift pressure along the upper side of the profile is compared for a classical and a Peaky profile. A comparison of classical and supercritical wing cross sections indicates a flatter upper side, a large nose radius, and a thicker profile to the supercritical wing.

  20. 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.

  1. 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

  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. 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.

  4. 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. PMID:24469309

  5. 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. PMID:20392117

  6. Femtosecond 2DIR spectroscopy of the nitrile stretching vibration of thiocyanate anions in liquid-to-supercritical heavy water. Spectral diffusion and libration-induced hydrogen-bond dynamics.

    PubMed

    Czurlok, Denis; von Domaros, Michael; Thomas, Martin; Gleim, Jeannine; Lindner, Jörg; Kirchner, Barbara; Vöhringer, Peter

    2015-11-28

    Femtosecond two-dimensional infrared (2DIR) spectroscopy was carried out to study the dynamics of vibrational spectral diffusion of the nitrile stretching vibration of thiocyanate anions (S-C≡N(-)) dissolved in liquid-to-supercritical heavy water (D2O). The 2DIR line shapes were used to extract through a nodal slope analysis quantitative information about the correlation function for temporal fluctuations of the CN-stretching frequency. The inverse nodal slope could be fitted phenomenologically by a simple double-exponential decay whose predominant component had a time constant ranging between 300 fs and 1 ps depending on the temperature. The temperature dependence is interpreted in terms of solvent structural fluctuations that are driven by the librational motions of the D2O molecules located in the first solvation shell of the anion. Complementary molecular dynamics simulations of the SCN(-)/D2O system indicate that the breaking and making of hydrogen-bonds between the terminal N-atom of the anion and the D2O molecules are induced by the same solvent-shell librational degrees of freedom that drive the vibrational line broadening dynamics seen in the 2DIR experiment. PMID:26486475

  7. Crew Exploration Vehicle (CEV) Water Landing Simulation

    NASA Technical Reports Server (NTRS)

    Littell, Justin D.; Lawrence, Charles; Carney, Kelly S.

    2007-01-01

    Crew Exploration Vehicle (CEV) water splashdowns were simulated in order to find maximum acceleration loads on the astronauts and spacecraft under various landing conditions. The acceleration loads were used in a Dynamic Risk Index (DRI) program to find the potential risk for injury posed on the astronauts for a range of landing conditions. The DRI results showed that greater risks for injury occurred for two landing conditions; when the vertical velocity was large and the contact angle between the spacecraft and the water impact surface was zero, and when the spacecraft was in a toe down configuration and both the vertical and horizontal landing velocities were large. Rollover was also predicted to occur for cases where there is high horizontal velocity and low contact angles in a toe up configuration, and cases where there was a high horizontal velocity with high contact angles in a toe down configuration.

  8. 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.

  9. 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

  10. 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. PMID:26028160

  11. 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

  12. Reactivity of Forsterite, Lizardite, and Antigorite in Dry to Water-Saturated Supercritical CO2 - An In Situ Infrared Spectroscopic Investigation

    NASA Astrophysics Data System (ADS)

    Loring, J. S.; Thompson, C. J.; Wang, Z.; Schaef, H. T.; Felmy, A. R.; Rosso, K. M.

    2010-12-01

    Geologic carbon sequestration (GCS) is a promising technology for reducing anthropogenic emissions of CO2 into the atmosphere. Olivines and serpentines are potentially important mineral phases in GCS because they are widespread in basalt formations and caprocks, are rich in Ca, Mg, and Fe, and react exothermically with CO2 to form carbonate solids. Previous work in aqueous systems has shown that carbonation rates of serpentines are lower than those of olivines, unless heat or acid pretreatments are applied. To the best of our knowledge, the comparative reactivities of olivines and serpentines have not yet been explored in dry to water saturated supercritical CO2 (scCO2) under conditions relevant to geologic sequestration. In this study, we used in situ infrared spectroscopy to investigate the carbonation of forsterite (Mg2SiO4), a representative of the olivine group and two serpentine polymorphs, antigorite and lizardite (Mg3Si2O5(OH)4). Experiments were carried out at 35 °C and 100 bar using a flow-through system equipped with a high-pressure mid-infrared cell. One ZnSe window of the transmission cell was coated with a thin overlayer of the mineral under investigation. Absorbance spectra were recorded as a function of time for 24 hours after exposing the overlayer to scCO2 containing water at concentrations corresponding to 0%, 50% and 95% saturation. Experiments were also performed with an approximately 2-fold excess concentration of water. In these latter experiments, a controlled temperature gradient was used to intentionally condense a liquid water film on the mineral surfaces. Little reaction was observed for the minerals exposed to dry scCO2. At water concentrations of 50% and 95% saturation, a very thin, liquid-like water film was detected on the mineral surface. A relatively minor extent of reaction occurred, and most of the transformation was observed during the first three hours of the experiments. Much greater reactivity was evident when a thicker

  13. 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

  14. 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. PMID:26574527

  15. 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

  16. 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

  17. Analysis of the terrestrial ion foreshock: 2D Full-Particle simulation of a curved supercritical shock

    NASA Astrophysics Data System (ADS)

    Lembege, B.; Savoini, P.; Stienlet, J.

    2013-05-01

    Two distinct ion populations backstreaming into the solar wind have been clearly evidenced by various space missions within the quasi-perpendicular region of the ion foreshock located upstream of the Earth's Bow shock (i.e. for 45° ≤ Theta_Bn ≤ 90°, where Theta_Bn is the angle between the shock normal and the upstream magnetostatic field): (i) field-aligned ion beams (« FAB ») characterized by a gyrotropic distribution, and (ii) gyro-phase bunched ions («GPB »), characterized by a NON gyrotropic distribution. The origin of these backstreaming ions has not been clearly identified and is presently analyzed with the help of 2D PIC simulation of a curved shock, where full curvature effects, time of flight effects and both electrons and ions dynamics are fully described within a self consistent approach. Present simulations evidence that these two populations can be effectively created directly by the shock front without invoking microinstabilities. The analysis of both individual and statistical ion trajectories evidences that: (i) two new parameters, namely the interaction time DT_inter and distance of penetration L_depth into the shock wave, play a key role and allow to discriminate these two populations. "GPB" population is characterized by a very short interaction time (DT_inter = 1 to 2 Tci) in comparison to the "FAB" population (DT_inter = 2 Tci to 10 Tci) which moves back and forth between the upstream edge of the shock front and the overshoot, where tci is the upstream ion gyroperiod. (ii) the importance of the injection angle (i.e. the angle between the normal of the shock front and the gyration velocity when ions reach the shock) to understand how the reflection process takes place. (iii) "FAB" population drifts along the curved shock front scanning a large Theta_Bn range from 90°. (iv) "GPB" population is embedded within the "FAB" population near the shock front which explains the difficulty to identify such a population in the experimental

  18. 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.

  19. 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.

  20. Supercritical fluid mixing in Diesel Engine Applications

    NASA Astrophysics Data System (ADS)

    Bravo, Luis; Ma, Peter; Kurman, Matthew; Tess, Michael; Ihme, Matthias; Kweon, Chol-Bum

    2014-11-01

    A numerical framework for simulating supercritical fluids mixing with large density ratios is presented in the context of diesel sprays. Accurate modeling of real fluid effects on the fuel air mixture formation process is critical in characterizing engine combustion. Recent work (Dahms, 2013) has suggested that liquid fuel enters the chamber in a transcritical state and rapidly evolves to supercritical regime where the interface transitions from a distinct liquid/gas interface into a continuous turbulent mixing layer. In this work, the Peng Robinson EoS is invoked as the real fluid model due to an acceptable compromise between accuracy and computational tractability. Measurements at supercritical conditions are reported from the Constant Pressure Flow (CPF) chamber facility at the Army Research Laboratory. Mie and Schlieren optical spray diagnostics are utilized to provide time resolved liquid and vapor penetration length measurement. The quantitative comparison presented is discussed. Oak Ridge Associated Universities (ORAU).

  1. 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).

  2. 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

  3. 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.

  4. SIMULATOR FOR WATER RESOURCES IN RURAL BASINS-WQ (SWRRBWQ)

    EPA Science Inventory

    The U.S. Department of Agricultures (USDA) Simulator for Water Resources in Rural Basins Water Quality (SWRRBWQ) was developed to simulate hydrologic, sedimentation, and nutrient and pesticide transport in a large, complex rural watershed. The model operates on a continuous time-...

  5. 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.

  6. 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

  7. Non-degradable triazine substrates of atrazine and cyanuric acid hydrothermally and in supercritical water under the UV-illuminated photocatalytic cooperation.

    PubMed

    Horikoshi, Satoshi; Hidaka, Hisao

    2003-04-01

    Strong oxidation by titanium dioxide photocatalysis can occur by photodegradation of organic contaminants in air and water. Some endocrine disruptors such as 2,4-dichlorophenoxy acetic acid (;;; ), 2,4-dichlorophenol (;;; ), nonylphenol (; ), bisphenol A (), diethyl phthalate (; ), etc. which can be neither biodegraded by bacteria nor degraded thermally can be degraded by TiO(2) photocatalytic treatment. However, incomplete photomineralization partly occurred, when TiO(2) photocatalytic degradation is employed for the treatment of certain endocrine disruptors. For example, no atrazine pesticide having triazine skeleton can be completely mineralized even by a photocatalytic procedure; the photodegradation of atrazine ultimately stops at the intermediate step of cyanuric acid, which cannot be photodegraded even after long illumination times (). In this study, the decomposition of atrazine and cyanuric acid was carried out with a device combining photocatalytic degradation in supercritical water (scH(2)O) or hydrothermal water (hyH(2)O). Atrazine and cyanuric acid can be degraded by the cooperation of either scH(2)O or hyH(2)O and UV illuminated TiO(2)-photocatalytic dispersed system under the fixed pressure of 23 MPa at 623 K or 683 K in a 120-ml Hastelloy batch reactor. The photocatalytic degradation method under high temperature and pressure has found appropriate for the photocatalytic oxidation of acetic acid and 2-chlorobiphenyl under continuous flow conditions at 160 degrees C and 20 atm (). In addition, the wet peroxide oxidation of PCBs by high temperature and pressure has been reported (). The main aims of this research are following. (i): the degradation of atrazine and cyanuric acid within the scH(2)O or hyH(2)O, (ii) the decomposition of atrazine and cyanuric acid catalyzed by TiO(2) particles under scH(2)O or hyH(2)O, and the synergistic effect for several reactions with TiO(2) and scH(2)O or hyH(2)O, and (iii) the mineralization yield of nitrogen and

  8. 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. PMID:25181254

  9. Simulating Crop Phenological Responses to Water Deficits

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Semi-arid crop production systems commonly are characterized by highly variable precipitation, both within and among years. Crop strategies to deal with water deficits are to either avoid or tolerate water stress, and many plant responses to water stress are involved. This chapter examines a fundame...

  10. 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.

  11. 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°...

  12. Inactivation of E. coli K12 in buffered peptone water and apple cider by pilot-plant scale supercritical carbon dioxide system

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There is increasing interest in non-thermal processing to inactivate foodborne pathogens and background microflora in juice products. Non-thermal pasteurization ensures safety and may offer better quality products than thermal pasteurization. Of non-thermal technologies, use of supercritical carbon ...

  13. Simulation of water flow in terrestrial systems

    Energy Science and Technology Software Center (ESTSC)

    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

  14. 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.

  15. Supercritical fuel injection system

    NASA Technical Reports Server (NTRS)

    Marek, C. J.; Cooper, L. P. (Inventor)

    1980-01-01

    a fuel injection system for gas turbines is described including a pair of high pressure pumps. The pumps provide fuel and a carrier fluid such as air at pressures above the critical pressure of the fuel. A supercritical mixing chamber mixes the fuel and carrier fluid and the mixture is sprayed into a combustion chamber. The use of fuel and a carrier fluid at supercritical pressures promotes rapid mixing of the fuel in the combustion chamber so as to reduce the formation of pollutants and promote cleaner burning.

  16. 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.

  17. 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.

  18. 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.

  19. Water vapor permeabilities through polymers: diffusivities from experiments and simulations

    NASA Astrophysics Data System (ADS)

    Seethamraju, Sindhu; Chandrashekarapura Ramamurthy, Praveen; Madras, Giridhar

    2014-09-01

    This study experimentally determines water vapor permeabilities, which are subsequently correlated with the diffusivities obtained from simulations. Molecular dynamics (MD) simulations were used for determining the diffusion of water vapor in various polymeric systems such as polyethylene, polypropylene, poly (vinyl alcohol), poly (vinyl acetate), poly (vinyl butyral), poly (vinylidene chloride), poly (vinyl chloride) and poly (methyl methacrylate). Cavity ring down spectroscopy (CRDS) based methodology has been used to determine the water vapor transmission rates. These values were then used to calculate the diffusion coefficients for water vapor through these polymers. A comparative analysis is provided for diffusivities calculated from CRDS and MD based results by correlating the free volumes.

  20. 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.

  1. ULTRA-SUPERCRITICAL STEAM CORROSION

    SciTech Connect

    Holcomb, G.R.; Alman, D.E.; Bullard, S.B.; Covino, B.S., Jr.; Cramer, S.D.; Ziomek-Moroz, M.

    2003-04-22

    Efficiency increases in fossil energy boilers and steam turbines are being achieved by increasing the temperature and pressure at the turbine inlets well beyond the critical point of water. To allow these increases, advanced materials are needed that are able to withstand the higher temperatures and pressures in terms of strength, creep, and oxidation resistance. As part of a larger collaborative effort, the Albany Research Center (ARC) is examining the steam-side oxidation behavior for ultrasupercritical (USC) steam turbine applications. Initial tests are being done on six alloys identified as candidates for USC steam boiler applications: ferritic alloy SAVE12, austenitic alloy Super 304H, the high Cr-high Ni alloy HR6W, and the nickel-base superalloys Inconel 617, Haynes 230, and Inconel 740. Each of these alloys has very high strength for its alloy type. Three types of experiments are planned: cyclic oxidation in air plus steam at atmospheric pressure, thermogravimetric ana lysis (TGA) in steam at atmospheric pressure, and exposure tests in supercritical steam up to 650 C (1202 F) and 34.5 MPa (5000 psi). The atmospheric pressure tests, combined with supercritical exposures at 13.8, 20.7, 24.6, and 34.5 MPa (2000, 3000, 4000, and 5000 psi) should allow the determination of the effect of pressure on the oxidation process.

  2. 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

  3. 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.

  4. 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...

  5. Enhanced coal liquefaction by pyrolysis in supercritical fluids

    SciTech Connect

    Paulaitis, M.E.; Klein, M.T.; Sandler, S.I.

    1990-11-19

    A fundamental investigation of a novel coal liquefaction process was undertaken which combines pyrolysis and supercritical-fluid solvent extraction. The experimental work consisted of determining: (1) coal pyrolysis reaction pathways, kinetics and mechanisms; (2) equilibrium solubilities of coal-related compounds in supercritical water. Experiments involving model coal compounds (tetralin and 1-methylnaphthalene, phenethyl phenyl ether, 1,3-diphenylpropane, benzyl phenyl ether, benzylamine). 8 refs., 6 figs., 9 tabs.

  6. 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

  7. Current Water Deficit Stress Simulations in Selected Agricultural System Simulation Models

    Technology Transfer Automated Retrieval System (TEKTRAN)

    System models, which adequately simulate plant water stress effects, are valuable tools for developing management practices with improved water use efficiency in agriculture. Plants experience water stress when its supply in the soil fails to meet the demand. Although it is easy to define the conc...

  8. Supercritical gasification for the treatment of o-cresol wastewater.

    PubMed

    Wei, Chao-hai; Hu, Cheng-sheng; Wu, Chao-fei; Yan, Bo

    2006-01-01

    The supercritical water gasification of phenolic wastewater without oxidant was performed to degrade pollutants and produce hydrogen-enriched gases. The simulated o-cresol wastewater was gasified at 440-650 degrees C and 27.6 MPa in a continuous Inconel 625 reactor with the residence time of 0.42-1.25 min. The influence of the reaction temperature, residence time, pressure, catalyst, oxidant and the pollutant concentration on the gasification efficiency was investigated. Higher temperature and longer residence time enhanced the o-cresol gasification. The TOC removal rate and hydrogen gasification rate were 90.6% and 194.6%, respectively, at the temperature of 650 degrees C and the residence time of 0.83 min. The product gas was mainly composed of H2, CO2, CH4 and CO, among which the total molar percentage of H2 and CH4 was higher than 50%. The gasification efficiency decreased with the pollutant concentration increasing. Both the catalyst and oxidant could accelerate the hydrocarbon gasification at a lower reaction temperature, in which the catalyst promoted H2 production and the oxidant enhanced CO2 generation. The intermediates of liquid effluents were analyzed and phenol was found to be the main composition. The results indicate that the supercritical gasification is a promising way for the treatment of hazardous organic wastewater. PMID:17078539

  9. 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.

  10. Simulating Leaf Area of Corn Plants at Contrasting Water Status

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An exponential decay function was fitted with literature data to describe the decrease in leaf expansion rate as leaf water potential decreases. The fitted function was then applied to modify an existing leaf area simulation module in a soil-plant-atmosphere continuum model in order to simulate leaf...

  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. 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

  13. Modeling and Simulation of Water Allocation System Based on Simulated Annealing Hybrid Genetic Algorithm

    NASA Astrophysics Data System (ADS)

    Zhu, Jiulong; Wang, Shijun

    Presently water resource in most watersheds in China is distributed in terms of administrative instructions. This kind of allocation method has many disadvantages and hampers the instructional effect of market mechanism on water allocation. The paper studies South-to-North Water Transfer Project and discusses water allocation of the node lakes along the Project. Firstly, it advanced four assumptions. Secondly, it analyzed constraint conditions of water allocation in terms of present state of water allocation in China. Thirdly, it established a goal model of water allocation and set up a systematic model from the angle of comprehensive profits of water utilization and profits of the node lakes. Fourthly, it discussed calculation method of the model by means of Simulated Annealing Hybrid Genetic Algorithm (SHGA). Finally, it validated the rationality and validity of the model by a simulation testing.

  14. 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

  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. 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.

  17. 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

  18. Ultra Supercritical Steamside Oxidation

    SciTech Connect

    Holcomb, Gordon R.; Cramer, Stephen D.; Covino, Bernard S., Jr.; Bullard, Sophie J.; Ziomek-Moroz, Malgorzata

    2005-01-01

    Ultra supercritical (USC) power plants offer the promise of higher efficiencies and lower emissions, which are goals of the U.S. Department of Energy's Advanced Power Systems Initiatives. 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. Current Advanced Power Systems goals include coal generation at 60% efficiency, which require steam temperatures of up to 760 C. This research examines the steamside oxidation of advanced alloys for use in USC systems, with emphasis placed on alloys for high- and intermediate-pressure turbine sections. Initial results of this research are presented.

  19. Simulation of Multiphase Water-Carbon Dioxide Mixture Flows in Porous Media

    NASA Astrophysics Data System (ADS)

    Afanasyev, A. A.

    2012-04-01

    Two-phase models are widely used for simulation of CO2 storage in saline aquifers. These models support gaseous phase mainly saturated with CO2 and liquid phase mainly saturated with H2O (e.g. TOUGH2 code). For deep aquifers where CO2 injection may result a plume of supercritical CO2 compositional simulation approach must be applied. This approach originated from petrol reservoir simulation studies is based on a cubic equation of state and is also capable only of single-phase states and two-phase states of liquid-gas type. The goal of the present study lies in development of a new mathematical approach for compositional simulation of carbon sequestration processes. The approach is supposed to be capable both of single-phase and two-phase states of liquid-gas type as in classical models and also of two-phase states of liquid-liquid type and three-phase states at high pressure. The liquid-liquid states are formed by two liquids. The first liquid is mainly saturated with water while the second is mainly saturated with CO2. These thermodynamic equilibriums with liquefied CO2 phase can be detected experimentally (Takenouchi et. al., 1964). The three-phase states represent a composition of the two-phase states of liquid-gas and liquid-liquid types. The three phases are water and CO2 in liquid and gaseous states. As liquefied CO2 is negatively buoyant at high pressure the described states can result in non-classical hydrodynamic effects in the aquifer with CO2 sinking and consequently in non-classical structural trapping scenarios. The distinctive feature of the proposed approach lies in the methodology for mixture properties determination. Transport equations and Darcy law are solved together with calculation of the entropy maximum that is reached in thermodynamic equilibrium and determines the mixture composition. To define and solve the problem only one function - mixture thermodynamic potential - is required. The proposed approach was implemented in MUFITS (Multiphase

  20. 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.

  1. 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.

  2. Ultra supercritical steamside oxidation

    SciTech Connect

    Holcomb, Gordon R.; Covino, Bernard S., Jr.; Bullard, Sophie J.; Cramer, Stephen D.; Ziomek-Moroz, Margaret

    2005-01-01

    Ultra supercritical (USC) power plants offer the promise of higher efficiencies and lower emissions, Current goals of the U.S. Department of Energy’s Advanced Power Systems Initiatives include coal generation at 60% efficiency, which would require steam temperatures of up to 760°C. This research examines the steamside oxidation of advanced alloys for use in USC systems, with emphasis placed on alloys for high- and intermediate-pressure turbine sections.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  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. Cycle Simulation of HotWater Fired Absorption Chiller

    NASA Astrophysics Data System (ADS)

    Esaki, Shuji; Iramina, Kazuyasu; Kobayashi, Takahiro; Ohnou, Masayuki; Kaneko, Toshiyuki; Soga, Takashi

    The design limits were examined to determine the lowest temperature for hot water that can be used as a heat source to drive a hot water fired absorption chiller. Advantage was taken of the fact that the cycle calculation method using the minimum temperature difference is quite effective. This minimum temperature difference was the lower of the two temperature differences used to get the logarithmic mean temperature difference that need to design the evaporator, absorber, condenser and generator in an absorption refrigerator. This report proposes a new solution algorithm employing this minimum temperature difference to make a cycle simulation of the hot water fired absorption chiller. It shows the lowest usable temperature for hot water and makes clear the chilled water and cooling water temperature conditions that can provide the lowest temperature.

  10. Direct folding simulation of a long helix in explicit water

    NASA Astrophysics Data System (ADS)

    Gao, Ya; Lu, Xiaoliang; Duan, Lili; Zhang, Dawei; Mei, Ye; Zhang, John Z. H.

    2013-05-01

    A recently proposed Polarizable Hydrogen Bond (PHB) method has been employed to simulate the folding of a 53 amino acid helix (PDB ID 2KHK) in explicit water. Under PHB simulation, starting from a fully extended structure, the peptide folds into the native state as confirmed by measured time evolutions of radius of gyration, root mean square deviation (RMSD), and native hydrogen bond. Free energy and cluster analysis show that the folded helix is thermally stable under the PHB model. Comparison of simulation results under, respectively, PHB and standard nonpolarizable force field demonstrates that polarization is critical for stable folding of this long α-helix.

  11. Conceptual design of a thermalhydraulic loop for multiple test geometries at supercritical conditions named Supercritical Phenomena Experimental Test Apparatus (SPETA)

    NASA Astrophysics Data System (ADS)

    Adenariwo, Adepoju

    The efficiency of nuclear reactors can be improved by increasing the operating pressure of current nuclear reactors. Current CANDU-type nuclear reactors use heavy water as coolant at an outlet pressure of up to 11.5 MPa. Conceptual SuperCritical Water Reactors (SCWRs) will operate at a higher coolant outlet pressure of 25 MPa. Supercritical water technology has been used in advanced coal plants and its application proves promising to be employed in nuclear reactors. To better understand how supercritical water technology can be applied in nuclear power plants, supercritical water loops are used to study the heat transfer phenomena as it applies to CANDU-type reactors. A conceptual design of a loop known as the Supercritical Phenomena Experimental Apparatus (SPETA) has been done. This loop has been designed to fit in a 9 m by 2 m by 2.8 m enclosure that will be installed at the University of Ontario Institute of Technology Energy Research Laboratory. The loop include components to safely start up and shut down various test sections, produce a heat source to the test section, and to remove reject heat. It is expected that loop will be able to investigate the behaviour of supercritical water in various geometries including bare tubes, annulus tubes, and multi-element-type bundles. The experimental geometries are designed to match the fluid properties of Canadian SCWR fuel channel designs so that they are representative of a practical application of supercritical water technology in nuclear plants. This loop will investigate various test section orientations which are the horizontal, vertical, and inclined to investigate buoyancy effects. Frictional pressure drop effects and satisfactory methods of estimating hydraulic resistances in supercritical fluid shall also be estimated with the loop. Operating limits for SPETA have been established to be able to capture the important heat transfer phenomena at supercritical conditions. Heat balance and flow calculations have

  12. 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.

  13. 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.

  14. Simulation Games: The Future of Water Resources Education and Management?

    NASA Astrophysics Data System (ADS)

    Castilla Rho, J. C.; Mariethoz, G.; Rojas, R. F.; Andersen, M. S.; Kelly, B. F.; Holley, C.

    2014-12-01

    Scientists rely on models of the water cycle to describe and predict problems of water scarcity in a changing climate, and to suggest adaptation strategies for securing future water needs. Yet these models are too often complicated for managers, the general public and for students to understand. Simpler modelling environments will help with finding solutions by engaging a broader segment of the population. Such environments will enable education at the earliest stages and collective action. I propose that simulation games can be an effective communication platform between scientists and 'non-experts' and that such games will shed light on problems of pollution and overuse of water resources. In the same way as pilots use flight simulators to become proficient at flying aircraft, simulation games—if underpinned by good science—can be used to educate the public, students and managers about how to best manage our water resources. I aim to motivate young scientists to think about using games to advance water education and management.

  15. 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 ...

  16. Simulations of Convective Excitation of Internal Waves in Water

    NASA Astrophysics Data System (ADS)

    Lecoanet, D.; Quataert, E.; Vasil, G. M.; Brown, B. P.; Oishi, J.

    2014-12-01

    Convection adjacent to stable stratification can excite internal waves. These convectively excited internal waves can transport energy, momentum, and other quantities in a variety of geophysical and atmospherical contexts, including in the Earth's stratosphere, and the radiative zones of stars. To better understand the excitation mechanism, we perform simplified 2D simulations of a recent experiment by Perrard et al. (2013). The simulations are run using the new, very flexible, pseudo-spectral code Dedalus. The experiment and simulations exploit water's density maximum at 4C: a linear temperature profile includes both convectively unstable and stably stratified regions. The simulations and experiment show qualitatively similar excitation spectra. We then test two heuristic models of internal wave excitation by convection, the interface forcing mechanism and the deep excitation mechanism. To test these, we run linear simulations of the simulation. In one case, we solve the linear wave equation, with a boundary condition mimicking the motions of the interface from the simulations. This successfully reproduces the low frequency waves, but overestimates the excitation of high frequency waves. This is because high frequency convective motions are nonlinear, but the interface forcing simulation treats them as linear. Next, we test the deep excitation mechanism by solving the linear wave equation with a source term related to the Reynolds stress in the convective region. This successfully reproduces all waves, and the correlation between the linear model and the full simulation is about 0.95. This suggests that the deep excitation mechanism most accurately explains the wave generation in this system.

  17. Pore connectivity, electrical conductivity, and partial water saturation: Network simulations

    NASA Astrophysics Data System (ADS)

    Li, M.; Tang, Y. B.; Bernabé, Y.; Zhao, J. Z.; Li, X. F.; Bai, X. Y.; Zhang, L. H.

    2015-06-01

    The electrical conductivity of brine-saturated rock is predominantly dependent on the geometry and topology of the pore space. When a resistive second phase (e.g., air in the vadose zone and oil/gas in hydrocarbon reservoirs) displaces the brine, the geometry and topology of the pore space occupied by the electrically conductive phase are changed. We investigated the effect of these changes on the electrical conductivity of rock partially saturated with brine. We simulated drainage and imbibition as invasion and bond percolation processes, respectively, in pipe networks assumed to be perfectly water-wet. The simulations included the formation of a water film in the pipes invaded by the nonwetting fluid. During simulated drainage/imbibition, we measured the changes in resistivity index as well as a number of relevant microstructural parameters describing the portion of the pore space saturated with water. Except Euler topological number, all quantities considered here showed a significant level of "universality," i.e., insensitivity to the type of lattice used (simple cubic, body-centered cubic, or face-centered cubic). Hence, the coordination number of the pore network appears to be a more effective measure of connectivity than Euler number. In general, the simulated resistivity index did not obey Archie's simple power law. In log-log scale, the resistivity index curves displayed a substantial downward or upward curvature depending on the presence or absence of a water film. Our network simulations compared relatively well with experimental data sets, which were obtained using experimental conditions and procedures consistent with the simulations. Finally, we verified that the connectivity/heterogeneity model proposed by Bernabé et al. (2011) could be extended to the partial brine saturation case when water films were not present.

  18. A MODFLOW Infiltration Device Package for Simulating Storm Water Infiltration.

    PubMed

    Jeppesen, Jan; Christensen, Steen

    2015-01-01

    This article describes a MODFLOW Infiltration Device (INFD) Package that can simulate infiltration devices and their two-way interaction with groundwater. The INFD Package relies on a water balance including inflow of storm water, leakage-like seepage through the device faces, overflow, and change in storage. The water balance for the device can be simulated in multiple INFD time steps within a single MODFLOW time step, and infiltration from the device can be routed through the unsaturated zone to the groundwater table. A benchmark test shows that the INFD Package's analytical solution for stage computes exact results for transient behavior. To achieve similar accuracy by the numerical solution of the MODFLOW Surface-Water Routing (SWR1) Process requires many small time steps. Furthermore, the INFD Package includes an improved representation of flow through the INFD sides that results in lower infiltration rates than simulated by SWR1. The INFD Package is also demonstrated in a transient simulation of a hypothetical catchment where two devices interact differently with groundwater. This simulation demonstrates that device and groundwater interaction depends on the thickness of the unsaturated zone because a shallow groundwater table (a likely result from storm water infiltration itself) may occupy retention volume, whereas a thick unsaturated zone may cause a phase shift and a change of amplitude in groundwater table response to a change of infiltration. We thus find that the INFD Package accommodates the simulation of infiltration devices and groundwater in an integrated manner on small as well as large spatial and temporal scales. PMID:25187115

  19. 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.

  20. 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.

  1. 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).

  2. Decontamination of Tritiated-Water Using Super-hydrophobic Pt-Catalyst Synthesized with Water-in-Supercritical CO{sub 2}

    SciTech Connect

    Youichi Enokida; Kayo Sawada |; Ryosuke Shimizu; Ichiro Yamamoto

    2008-01-15

    Tritium, {sup 3}H, is one of the hydrogen isotopes, created in coolant of a fission reactor and to be utilized as fuel for nuclear fusion reactors. Since a large amount of tritium will be contained in a fusion reactor or in a fission reactor, a small fraction of the tritiated chemical species, in most cases, tritiated water, may leak to the environment. Tritium is, however, a radioactive isotope whose specific radioactivity is 4 x 10{sup 17} Bq kg{sup -1}, and easy to transfer in human body, its confinement is very important from the safety aspect. One of the problems of tritium confinement and decontamination of tritiated chemical species is related with necessity of its isotope separation from lighter hydrogen isotopes, {sup 2}H and {sup 1}H. Most of principles for the isotope separations are based on fractionations of isotopes in different chemical species. A large fractionation for hydrogen isotopes is observed in a chemical exchange of hydrogen atoms between water, Q{sub 2}O, and hydrogen gas, Q{sub 2}, where 'Q' denotes one of the hydrogen isotopes. Heavier isotopes are enriched significantly into Q{sub 2}O rather than Q{sub 2}. Therefore practical method of tritium removal would be established by hydrogen isotope separation with chemical exchange of water and hydrogen gas. At first, we prepared a catalyst, by reducing Pt{sup 4+} in reversed micelles where the reducing agent, aqueous solution of sodium tetra borohydrate, NaBH{sub 4} was also contained in reversed micelles prepared separately. In this situation, micelles containing Pt{sup 4+} and reducing reagent collided and produced Pt nanoparticles, which were expected to be impregnated in the hydrophobic structure after depressurization. After this type of earlier experiment we determined a mass of impregnated Pt by total dissolution of gauze with aqua regia followed by concentration measurement of Pt with ICP-AES. We performed several trials, unfortunately, however, the mass of Pt deposited on the gauze

  3. 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

  4. 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

  5. Direct Phase Equilibrium Simulations of NIPAM Oligomers in Water.

    PubMed

    Boţan, Vitalie; Ustach, Vincent; Faller, Roland; Leonhard, Kai

    2016-04-01

    NIPAM (N-isopropylacrylamide)-based polymers in water show many interesting properties in experiments, including a lower critical solution temperature (LCST) at 305 K and a conformational transition of single chains at the same temperature. The results of many simulation studies suggest that standard force fields are able to describe the conformational transition and the phase equilibrium well. We show by performing long molecular dynamics simulations of the direct liquid-liquid phase equilibrium of NIPAM trimers in water that there is no LCST in the expected temperature range for any of the force fields under study. The results show further that the relaxation times of single-chain simulations are considerably longer than anticipated. Conformational transitions of single polymers can therefore not necessarily be used as surrogates for a real phase transition. PMID:26991504

  6. 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

  7. 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

  8. 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.

  9. 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).

  10. 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

  11. 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

  12. 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

  13. 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.

  14. 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

  15. 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.

  16. Microwave Extraction of Water from Lunar Regolith Simulant

    NASA Astrophysics Data System (ADS)

    Ethridge, Edwin; 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 or `permafrost'. Currently a Lunar Lander Exploration Program is expected to land at the lunar pole to determine if water is present. The detection of water from the permafrost is an important goal for NASA. Extraction of water from lunar permafrost would be a valuable In-Situ Resource for Utilization (ISRU) in human life support and as a fuel. The use of microwave processing could 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 simulant. Water was collected in a cryogenic cold trap even with soil temperature well below 0 °C. The results of microwave extraction of water experiments will be presented.

  17. The influence of water and supercritical CO2 on the frictional strength and velocity dependence of montmorillonite and muscovite and the potential for fault zone reactivation in CO2 storage reservoirs

    NASA Astrophysics Data System (ADS)

    Samuelson, Jon

    2013-04-01

    Recent research indicates that CO2 is capable of inducing swelling in clay minerals in a similar fashion to water, though to a more modest extent. It is therefore of importance for feasibility studies of the geological storage of CO2 to understand if the addition of CO2 to clay rich fault zones has the potential to cause significant frictional weakening, similar to that associated with water. We conduct velocity-stepping direct shear experiments on pre-pressed plates (49 mm long x 35 mm wide x ~1 mm thick), of montmorillonite and muscovite. An effective normal stress of 35 MPa is used in all experiments, which is roughly equivalent to the effective overburden stress expected in many storage projects. Temperature was held constant at ~48 °C, consistent with previous experiments which indicated CO2 induced swelling in montmorillonite. Pore fluid conditions are the main variable in this suite of experiments, in which the frictional strength of each clay mineral is analyzed oven-dry (attached to vacuum), saturated with deionized (DI) water, and oven-dry saturated with supercritical CO2. Pore pressure is maintained at 15 MPa for the water and CO2 saturated experiments (?n=50 MPa, PH20-CO2=15 MPa). Shearing velocity is varied systematically from approximately 11 μm/s to 0.2, 1.1, 11, 1.1, and 0.2 μm/s in order to determine the rate and state friction parameters, a, b, and DC. Additionally, microstructural analysis of the post-shear clay gouges is conducted in an effort to understand the rheology behind changes observed in frictional properties. Preliminary results of experiments on montmorillonite show an overconsolidation peak at strains of approximately 0.3 for each of the oven-dry and water and CO2 saturated experiments. Peak friction (μP) for oven-dry montmorillonite is 0.53, decaying to a steady state friction (μSS) of 0.51. For DI-saturated montmorillonite μP=0.11 and μSS=0.10. CO2-saturated montmorillonite displays frictional strength between that of dry

  18. The influence of water and supercritical CO2 on the frictional strength and velocity dependence of swelling (montmorillonite and saponite) and non-swelling (muscovite and illite) clays and the potential for fault zone reactivation in CO2 storage reservoirs

    NASA Astrophysics Data System (ADS)

    Samuelson, J. E.

    2012-12-01

    Recent research indicates that CO2 is capable of inducing swelling in clay minerals in a similar fashion to water, though to a more modest extent. It is therefore of importance for feasibility studies of the geological storage of CO2 to understand if the addition of CO2 to clay rich fault zones has the potential to cause significant frictional weakening, similar to that associated with water. We conduct velocity-stepping direct shear experiments on pre-pressed plates (49 mm long x 35 mm wide x ~1 mm thick), of montmorillonite and saponite, both known swelling clays, as well as plates of illite and muscovite also important phyllosilicate minerals in faults, though non-swelling. An effective normal stress of 35 MPa is used in all experiments, which is roughly equivalent to the effective overburden stress expected in many storage projects. Temperature was held constant at ~ 48 °C, consistent with previous experiments which indicated CO2 induced swelling in montmorillonite. Pore fluid conditions are the main variable in this suite of experiments, in which the frictional strength of each clay mineral is analyzed dry (open to atmospheric conditions), saturated with deionized (DI) water, and saturated with supercritical CO2. Pore pressure is maintained at 15 MPa for the water and CO2 saturated experiments (σn=50 MPa, PH20/CO2=15 MPa). Shearing velocity is varied systematically from approximately 11 μm/s to 0.2, 1.1, 11, 1.1, and 0.2 μm/s in order to determine the rate and state friction parameters, a, b, and DC. Additionally, microstructural analysis of the post-shear clay gouges is conducted in an effort to understand the rheology behind changes observed in frictional properties. Initial experiments on montmorillonite show an overconsolidation peak at strains of approximately 0.3 for each of the dry and water and CO2 saturated experiments. Peak friction (μP) for dry montmorillonite is 0.18, decaying to a steady state friction (μss) of 0.13. For DI

  19. SD-GIS-based temporal-spatial simulation of water quality in sudden water pollution accidents

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Qin, Yu; Huang, Mingxiang; Sun, Qiang; Li, Shun; Wang, Liqiang; Yu, Chaohui

    2011-07-01

    System dynamics (SD) is well suited for studying dynamic nonlinear complex systems. In this paper, SD is applied to a rapid-onset water pollution accident using a 1-D water quality model and a conceptual GIS-SD framework is constructed to simulate the temporal-spatial changes of pollutant concentration. Based on the component GIS and the SD model, a prototype system of water quality simulation in water pollution accidents is developed. The data collected on the spot in the Songhua River water pollution accident in November 2005 were used for model parameter calibration and model validation. The results showed that: (1) the constructed model could simulate the changes of nitrobenzene concentration with time in the Songhua River water pollution accident, especially during the peak concentration and at the arrival time of peak concentration, and that the simulated values and the on-the-spot monitored values corresponded with each other well; (2) the scenario simulation could be made by adjusting parameters u (longitudinal current velocity), E (longitudinal diffusion coefficient), and k (decay rate coefficient). Such a model can provide decision makers with quantitative information to optimize related emergency response measures.

  20. Molecular dynamics simulations of water permeation across Nafion membrane interfaces.

    PubMed

    Daly, Kevin B; Benziger, Jay B; Panagiotopoulos, Athanassios Z; Debenedetti, Pablo G

    2014-07-24

    Permeation of water across the membrane/vapor and membrane/liquid-water interfaces of Nafion is studied using nonequilibrium molecular dynamics (NEMD) simulations, providing direct calculations of mass-transfer resistance. Water mass transfer within one nanometer of the vapor interface is shown to be 2 orders of magnitude slower than at any other point within the membrane, in qualitative agreement with permeation experiments. This interfacial resistance is much stronger than the resistance suggested by prior simulation work calculating self-diffusivity near the interface. The key difference between the prior approach and the NEMD approach is that the NEMD approach implicitly incorporates changes in solubility in the direction normal to the interface. Water is shown to be very insoluble near the vapor interface, which is rich in hydrophobic perfluorocarbon chains, in agreement with advancing contact angle experiments. Hydrophilic side chains are buried beneath this hydrophobic layer and aligned toward the interior of the membrane. Hydrophilic pores are not exposed to the vapor interface as proposed in prior theoretical work. At the membrane/liquid-water interface, highly swollen polymer chains extend into the liquid-water phase, forming a nanoscopically rough interface that is consistent with atomic force microscopy experiments. In these swollen conformations, hydrophilic side chains are exposed to the liquid-water phase, suggesting that the interface is hydrophilic, in agreement with receding contact angle experiments. The mass-transfer resistance of this interface is negligible compared to that of the bulk, in qualitative agreement with permeation experiments. The water activity at the vapor and liquid-water interfaces are nearly the same, yet large conformational and transport differences are observed, consistent with a mass-transfer-based understanding of Schroeder's paradox for Nafion. PMID:24971638

  1. 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.

  2. Molecular dynamics simulation of liquid water: Hybrid density functionals

    SciTech Connect

    Todorova, T; Seitsonen, A; Hutter, J; Kuo, W; Mundy, C

    2005-09-12

    The structure, dynamical and electronic properties of liquid water utilizing different hybrid density functionals were tested within the plane wave framework of first principles molecular dynamics simulations. The computational approach, which employs modified functionals with short-ranged Hartree-Fock exchange, was first tested in calculations of the structural and bonding properties of the water dimer and cyclic water trimer. Liquid water simulations were performed at the state point of 350 K at the experimental density. Simulations included three different hybrid functionals, a meta functional, four gradient corrected functionals, the local density and Hartree-Fock approximation. It is found that hybrid functionals are superior in reproducing the experimental structure and dynamical properties as measured by the radial distribution function and self diffusion constant when compared to the pure density functionals. The local density and Hartree-Fock approximations show strongly over- and under-structured liquids, respectively. Hydrogen bond analysis shows that the hybrid functionals give slightly smaller averaged numbers of hydrogen bonds and similar hydrogen bond populations as pure density functionals. The average molecular dipole moments in the liquid from the three hybrid functionals are lower than from the corresponding pure density functionals.

  3. Simulated Water Delivery to Lunar Permanently Shadowed Regions

    NASA Astrophysics Data System (ADS)

    Moores, John

    2015-11-01

    A set of Monte Carlo simulations was run to examine water diffusion across the lunar surface and specifically to the Permanently Shadowed Regions (PSRs). This work extends the results of Schorghofer (2014) to latitudes above 5º from the pole and to specific PSRs and is accomplished using a separately derived model to independently test Schorghofer’s (2014) results. The model was validated using the results of Schorghofer (2014) at the 5º latitude line, replicating all of the behaviors of that model, but with slightly different values for the total number of tracer particles arriving and their fractionation.25 times fewer particles were able to survive to arrive within 1º of the pole, as compared to those that were able to arrive within 5º of the pole. For the PSRs themselves, 1.87% of particles were eventually sequestered within the PSRs by the end of our simulations. Examining the amount of water which could be transported over geological time reveals that sufficient water moves via migration to (1) supply the hydrogen signals observed by LEND, (Mitrofanov et al., 2012), (2) the frost at Haworth Crater (Gladstone et al., 2012) as well as to explain (3) the high level of water seen in the soils of Cabeus Crater in the LCROSS experiment (Colaprete et al., 2010) without the need to invoke another water supply mechanism.In all cases, the average time required for migration was small with average arrival times of less than a lunar day following an impact. Substantial differences were observed in the amount of water accreted by the different PSRs with Cabeus Crater accreting by far the most water per square meter. Faustini and the Haworth Lowlands have the next highest delivery, receiving ~60% each as much water as Cabeus per square meter. Shackleton has the lowest water delivery, receiving only ~5% as much water per square meter as Cabeus. The simulated results show a clear latitudinal trend with more water emplaced at lower latitudes. Yet, the data show very

  4. 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.

  5. Reverse micelle and microemulsion phases in supercritical fluids

    SciTech Connect

    Fulton, J.L.; Smith, R.D.

    1988-05-19

    The surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) was used to form reverse micelle and microemulsion phases in supercritical ethane and propane for systems consisting of 80-100% alkane by weight. Phase diagrams obtained from view cell studies of microemulsion phases formed in supercritical fluids are reported and shown to be strongly dependent on pressure. The properties of these solutions were also characterized by conductivity, density, and surfactant solubility measurements. The solubility of AOT in ethane and propane over a range of pressures shows behavior typical of solids in supercritical fluids. The maximum water-to-surfactant ratio (W/sub 0/) increased dramatically in both ethane and propane systems as pressure was increased. At 300 bar and 103/sup 0/C, the supercritical propane-surfactant system is capable of solubilizing much more water (W/sub 0/ = 12) than the supercritical ethane-surfactant system (W/sub 0/ = 4) at 300 bar and 37/sup 0/C. Some of the important thermodynamic contributions that are likely responsible for this pressure-dependent phase behavior are discussed, and potential applications of this new class of solvents are considered.

  6. Lidar simulation. [measurement of atmospheric water vapor via optical radar

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The feasibility of measuring atmospheric water vapor via orbital lidar is estimated. The calculation starts with laser radar equations representing backscatter with and without molecular line absorption; the magnitudes of off-line backscatter are demonstrated. Extensive prior data on water line strengths are summarized to indicate the available sensitivity to water vapor concentration. Several lidar situations are considered starting with uniform and perturbed atmospheres at 0, 3, 10 and 20 kM (stratosphere) altitudes. These simulations are indicative of results to be obtained in ground truth measurements (ground-based and airborne). An approximate treatment of polar observations is also given. Vertical atmospheric soundings from orbit and from ground stations are calculated. Errors are discussed as regards their propagation through the lidar equation to render the measured water vapor concentration imprecise; conclusions are given as to required laser energy and feasible altitude resolution.

  7. The properties of water: insights from quantum simulations.

    PubMed

    Paesani, Francesco; Voth, Gregory A

    2009-04-30

    The properties of water play a central role in many phenomena of relevance to different areas of science, including physics, chemistry, biology, geology, and climate research. Although well studied for decades, the behavior of water under different conditions and in different environments still remains mysterious and often surprising. In this article, various efforts aimed at providing a comprehensive representation of the water properties at a molecular level through computer modeling and simulation will be described. In particular, the unique role played by the hydrogen-bond network will be examined, first in liquid water, then in the solvation of model biological compounds, and finally in ice, especially highlighting the important effects related to the quantization of the nuclear motion. PMID:19385690

  8. Water-Silica Force Field for Simulating Nanodevices

    PubMed Central

    Cruz-Chu, Eduardo R.; Aksimentiev, Aleksei; Schulten, Klaus

    2008-01-01

    Amorphous silica is an inorganic material that is central for many nanotechnology appplications, such as nanoelectronics, microfluidics, and nanopore technology. In order to use molecular dynamics (MD) simulations to study the behavior of biomolecules with silica, we developed a force field for amorphous silica surfaces based on their macroscopic wetting properties that is compatible with the CHARMM force field and TIP3P water model. The contact angle of a water droplet with silica served as a criterion to tune the intermolecular interactions. The resulting force field was used to study the permeation of water through silica nanopores, illustrating the influence of the surface topography and the intermolecular parameters on permeation kinetics. We find that minute modeling of the amorphous surface is critical for MD studies, since the particular arrangement of surface atoms controls sensitively electrostatic interactions between silica and water. PMID:17064100

  9. 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.

  10. Pressure-induced transformations in computer simulations of glassy water

    NASA Astrophysics Data System (ADS)

    Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

    2013-11-01

    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.

  11. 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

  12. 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.

  13. Market Simulations for Irrigation Water Rights: A Hypothetical Case Study

    NASA Astrophysics Data System (ADS)

    Wong, Benedict D. C.; Eheart, J. Wayland

    1983-10-01

    The efficiency of two marketable water rights systems in a lentic (lakelike) structure is assessed quantitatively for a case study based on hypothetical irrigation water use. Water rights are simulated on the bases of (1) the expected values of water rights to the users and (2) perfect foresight on the parts of users, and the economic outcomes of these markets are evaluated from both ex ante and ex post perspectives. The market outcomes are compared to the optimal (efficient) scheme and to two alternative nonmarket policies. Distributional aspects of the markets are examined on the basis of individual payoff. Simulation results show that higher efficiency is obtained for the two market systems than for the nonmarket policies and that the market systems recoup about 95% of the economic value of the optimal distribution. The results suggest that most of the 5% efficiency loss should be attributed to the design of the market system itself (i.e., the restrictions imposed by the definition of the rights and/or the water rights allocation policy), rather than the users' inability to predict future events.

  14. 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.

  15. 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

  16. 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.

  17. Is there a third order phase transition for supercritical fluids?

    PubMed

    Zhu, Jinglong; Zhang, Pingwen; Wang, Han; Site, Luigi Delle

    2014-01-01

    We prove that according to Molecular Dynamics (MD) simulations of liquid mixtures of Lennard-Jones (L-J) particles, there is no third order phase transition in the supercritical regime beyond Andrew's critical point. This result is in open contrast with recent theoretical studies and experiments which instead suggest not only its existence but also its universality regarding the chemical nature of the fluid. We argue that our results are solid enough to go beyond the limitations of MD and the generic character of L-J models, thus suggesting a rather smooth liquid-vapor thermodynamic behavior of fluids in supercritical regime. PMID:24410228

  18. Simulating subsurface heterogeneity improves large-scale water resources predictions

    NASA Astrophysics Data System (ADS)

    Hartmann, A. J.; Gleeson, T.; Wagener, T.; Wada, Y.

    2014-12-01

    Heterogeneity is abundant everywhere across the hydrosphere. It exists in the soil, the vadose zone and the groundwater. In large-scale hydrological models, subsurface heterogeneity is usually not considered. Instead average or representative values are chosen for each of the simulated grid cells, not incorporating any sub-grid variability. This may lead to unreliable predictions when the models are used for assessing future water resources availability, floods or droughts, or when they are used for recommendations for more sustainable water management. In this study we use a novel, large-scale model that takes into account sub-grid heterogeneity for the simulation of groundwater recharge by using statistical distribution functions. We choose all regions over Europe that are comprised by carbonate rock (~35% of the total area) because the well understood dissolvability of carbonate rocks (karstification) allows for assessing the strength of subsurface heterogeneity. Applying the model with historic data and future climate projections we show that subsurface heterogeneity lowers the vulnerability of groundwater recharge on hydro-climatic extremes and future changes of climate. Comparing our simulations with the PCR-GLOBWB model we