Supercritical Water Experimental Setup for µSR

NASA Astrophysics Data System (ADS)

Liu, Guangdong; Chen, Yanggang; Morrison, Alexander H.; Koda, Akihiro; Percival, Paul W.; Ghandi, Khashayar

The Canadian design for Generation IV nuclear reactors uses supercritical water (SCW, water above its critical point of 374 °C, 221 bar (1 bar = 100 kPa)) as the coolant. Supercritical water-cooled reactors (SCWRs) are designed towards sustainability, economic benefits, improved safety, and longer lifespan. Despite the potential advantages of SCWRs, we know very little about the kinetics of radiolysis products that are formed in them because of the limitations of experimental instruments under the extreme conditions of SCW. The radiolysis products can accumulate over time and create a very corrosive environment. Our group has developed and tested an apparatus suitable for muon spin rotation (µSR) studies of water and aqueous solutions up to 550 °C and 250 bar, close to the conditions at the reactor outlet of the proposed Canadian SCWR design (625 °C and 250 bar). The reaction kinetics information obtained from our setup, together with computer simulations, will aid us in developing chemical control strategies to minimize corrosion in SCWRs.

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experimental investigation on heat transfer and frictional characteristics of vertical upward rifled tube in supercritical CFB boiler

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Dong; Pan, Jie; Zhu, Xiaojing

2011-02-15

Water wall design is a key issue for supercritical Circulating Fluidized Bed (CFB) boiler. On account of the good heat transfer performance, rifled tube is applied in the water wall design of a 600 MW supercritical CFB boiler in China. In order to investigate the heat transfer and frictional characteristics of the rifled tube with vertical upward flow, an in-depth experiment was conducted in the range of pressure from 12 to 30 MPa, mass flux from 230 to 1200 kg/(m{sup 2} s), and inner wall heat flux from 130 to 720 kW/m{sup 2}. The wall temperature distribution and pressure dropmore » in the rifled tube were obtained in the experiment. The normal, enhanced and deteriorated heat transfer characteristics were also captured. In this paper, the effects of pressure, inner wall heat flux and mass flux on heat transfer characteristics are analyzed, the heat transfer mechanism and the frictional resistance performance are discussed, and the corresponding empirical correlations are presented. The experimental results show that the rifled tube can effectively prevent the occurrence of departure from nucleate boiling (DNB) and keep the tube wall temperature in a permissible range under the operating condition of supercritical CFB boiler. (author)« less

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.

Benchmark of ReaxFF force field for subcritical and supercritical water.

PubMed

Manzano, Hegoi; Zhang, Weiwei; Raju, Muralikrishna; Dolado, Jorge S; López-Arbeloa, Iñigo; van Duin, Adri C T

2018-06-21

Water in the subcritical and supercritical states has remarkable properties that make it an excellent solvent for oxidation of hazardous chemicals, waste separation, and green synthesis. Molecular simulations are a valuable complement to experiments in order to understand and improve the relevant sub- and super-critical reaction mechanisms. Since water molecules under these conditions can act not only as a solvent but also as a reactant, dissociative force fields are especially interesting to investigate these processes. In this work, we evaluate the capacity of the ReaxFF force field to reproduce the microstructure, hydrogen bonding, dielectric constant, diffusion, and proton transfer of sub- and super-critical water. Our results indicate that ReaxFF is able to simulate water properties in these states in very good quantitative agreement with the existing experimental data, with the exception of the static dielectric constant that is reproduced only qualitatively.

Effects of supercritical carbon dioxide (SC-CO(2)) oil extraction on the cell wall composition of almond fruits.

PubMed

Femenia, A; García-Marín, M; Simal, S; Rosselló, C; Blasco, M

2001-12-01

Extraction of oil from almond fruits using supercritical carbon dioxide (SC-CO(2)) was carried out at 50 degrees C and 330 bar on three sets of almonds: raw almond seeds, raw almond kernels, and toasted almond seeds. Three different oil extraction percentages were applied on each set ranging from approximately 15 to 16%, from approximately 27 to 33%, and from approximately 49 to 64%. Although no major changes were detected in the fatty acid composition between fresh and partially defatted samples, carbohydrate analysis of partially defatted materials revealed important changes in cell wall polysaccharides from almond tissues. Thus, at low extraction percentages (up to approximately 33%), pectic polysaccharides and hemicellulosic xyloglucans were the main type of polymers affected, suggesting the modification of the cell wall matrix, although without breakage of the walls. Then, as supercritical fluid extraction (SCFE) continues and higher extraction rates are achieved (up to approximately 64%), a major disruption of the cell wall occurred as indicated by the losses of all major types of cell wall polysaccharides, including cellulose. These results suggest that, under the conditions used for oil extraction using SC-CO(2), fatty acid chains are able to exit the cells through nonbroken walls; the modification of the pectin-hemicellulose network might have increased the porosity of the wall. However, as high pressure is being applied, there is a progressive breakage of the cell walls allowing the free transfer of the fatty acid chains from inside the cells. These findings might contribute to providing the basis for the optimization of SCFE procedures based on plant food sources.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Corradini, D.; Rovere, M.; Gallo, P., E-mail: gallop@fis.uniroma3.it

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 howmore » 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.« less

Spontaneous Ignition of Hydrothermal Flames in Supercritical Ethanol Water Solutions

NASA Technical Reports Server (NTRS)

Hicks, Michael C.; Hegde, Uday G.; Kojima, Jun J.

2017-01-01

Results are reported from recent tests where hydrothermal flames spontaneously ignited in a Supercritical Water Oxidation (SCWO) Test Cell. Hydrothermal flames are generally categorized as flames that occur when appropriate concentrations of fuel and oxidizer are present in supercritical water (SCW); i.e., water at conditions above its critical point (218 atm and 374 C). A co-flow injector was used to inject fuel, comprising an aqueous solution of 30-vol to 50-vol ethanol, and air into a reactor held at constant pressure and filled with supercritical water at approximately 240 atm and 425 C. Hydrothermal flames auto-ignited and quickly stabilized as either laminar or turbulent diffusion flames, depending on the injection velocities and test cell conditions. Two orthogonal views, one of which provided a backlit shadowgraphic image, provided visual observations. Optical emission measurements of the steady state flame were made over a spectral range spanning the ultraviolet (UV) to the near infrared (NIR) using a high-resolution, high-dynamic-range spectrometer. Depending on the fuel air flow ratios varying degrees of sooting were observed and are qualitatively compared using light absorption comparisons from backlit images.

Numerical investigation of heat transfer in parallel channels with water at supercritical pressure.

PubMed

Shitsi, Edward; Kofi Debrah, Seth; Yao Agbodemegbe, Vincent; Ampomah-Amoako, Emmanuel

2017-11-01

Thermal phenomena such as heat transfer enhancement, heat transfer deterioration, and flow instability observed at supercritical pressures as a result of fluid property variations have the potential to affect the safety of design and operation of Supercritical Water-cooled Reactor SCWR, and also challenge the capabilities of both heat transfer correlations and Computational Fluid Dynamics CFD physical models. These phenomena observed at supercritical pressures need to be thoroughly investigated. An experimental study was carried out by Xi to investigate flow instability in parallel channels at supercritical pressures under different mass flow rates, pressures, and axial power shapes. Experimental data on flow instability at inlet of the heated channels were obtained but no heat transfer data along the axial length was obtained. This numerical study used 3D numerical tool STAR-CCM+ to investigate heat transfer at supercritical pressures along the axial lengths of the parallel channels with water ahead of experimental data. Homogeneous axial power shape HAPS was adopted and the heating powers adopted in this work were below the experimental threshold heating powers obtained for HAPS by Xi. The results show that the Fluid Centre-line Temperature FCLT increased linearly below and above the PCT region, but flattened at the PCT region for all the system parameters considered. The inlet temperature, heating power, pressure, gravity and mass flow rate have effects on WT (wall temperature) values in the NHT (normal heat transfer), EHT (enhanced heat transfer), DHT (deteriorated heat transfer) and recovery from DHT regions. While variation of all other system parameters in the EHT and PCT regions showed no significant difference in the WT and FCLT values respectively, the WT and FCLT values respectively increased with pressure in these regions. For most of the system parameters considered, the FCLT and WT values obtained in the two channels were nearly the same. The

Structural behavior of supercritical fluids under confinement

NASA Astrophysics Data System (ADS)

Ghosh, Kanka; Krishnamurthy, C. V.

2018-01-01

The existence of the Frenkel line in the supercritical regime of a Lennard-Jones (LJ) fluid shown through molecular dynamics (MD) simulations initially and later corroborated by experiments on argon opens up possibilities of understanding the structure and dynamics of supercritical fluids in general and of the Frenkel line in particular. The location of the Frenkel line, which demarcates two distinct physical states, liquidlike and gaslike within the supercritical regime, has been established through MD simulations of the velocity autocorrelation (VACF) and radial distribution function (RDF). We, in this article, explore the changes in the structural features of supercritical LJ fluid under partial confinement using atomistic walls. The study is carried out across the Frenkel line through a series of MD simulations considering a set of thermodynamics states in the supercritical regime (P =5000 bar, 240 K ≤T ≤1500 K ) of argon well above the critical point. Confinement is partial, with atomistic walls located normal to z and extending to "infinity" along the x and y directions. In the "liquidlike" regime of the supercritical phase, particles are found to be distributed in distinct layers along the z axis with layer spacing less than one atomic diameter and the lateral RDF showing amorphous-like structure for specific spacings (packing frustration) and non-amorphous-like structure for other spacings. Increasing the rigidity of the atomistic walls is found to lead to stronger layering and increased structural order. For confinement with reflective walls, layers are found to form with one atomic diameter spacing and the lateral RDF showing close-packed structure for the smaller confinements. Translational order parameter and excess entropy assessment confirms the ordering taking place for atomistic wall and reflective wall confinements. In the "gaslike" regime of the supercritical phase, particle distribution along the spacing and the lateral RDF exhibit features

Structural behavior of supercritical fluids under confinement.

PubMed

Ghosh, Kanka; Krishnamurthy, C V

2018-01-01

The existence of the Frenkel line in the supercritical regime of a Lennard-Jones (LJ) fluid shown through molecular dynamics (MD) simulations initially and later corroborated by experiments on argon opens up possibilities of understanding the structure and dynamics of supercritical fluids in general and of the Frenkel line in particular. The location of the Frenkel line, which demarcates two distinct physical states, liquidlike and gaslike within the supercritical regime, has been established through MD simulations of the velocity autocorrelation (VACF) and radial distribution function (RDF). We, in this article, explore the changes in the structural features of supercritical LJ fluid under partial confinement using atomistic walls. The study is carried out across the Frenkel line through a series of MD simulations considering a set of thermodynamics states in the supercritical regime (P=5000 bar, 240K≤T≤1500K) of argon well above the critical point. Confinement is partial, with atomistic walls located normal to z and extending to "infinity" along the x and y directions. In the "liquidlike" regime of the supercritical phase, particles are found to be distributed in distinct layers along the z axis with layer spacing less than one atomic diameter and the lateral RDF showing amorphous-like structure for specific spacings (packing frustration) and non-amorphous-like structure for other spacings. Increasing the rigidity of the atomistic walls is found to lead to stronger layering and increased structural order. For confinement with reflective walls, layers are found to form with one atomic diameter spacing and the lateral RDF showing close-packed structure for the smaller confinements. Translational order parameter and excess entropy assessment confirms the ordering taking place for atomistic wall and reflective wall confinements. In the "gaslike" regime of the supercritical phase, particle distribution along the spacing and the lateral RDF exhibit features not

Kinetics of Supercritical Water Oxidation

DTIC Science & Technology

1995-12-31

milestone and Sandia Technical Report. A much-needed report describing in detail the operation of the Supercritical Fluids Reactor (SFR) was also...years. In addition, the literature research required to arrive at this optimal design will be used to improve the performance of the Supercritical Fluids ...the Supercritical Fluids Reactor (SFR)" (Sandia National Laboratories Report SAND-8203, Livermore, CA, 1995). R. R. Steeper, "Methane and Methanol

Supercritical water oxidation treatment of textile sludge.

PubMed

Zhang, Jie; Wang, Shuzhong; Li, Yanhui; Lu, Jinling; Chen, Senlin; Luo, XingQi

2017-08-01

In this work, we studied the supercritical water oxidation (SCWO) of the textile sludge, the hydrothermal conversion of typical textile compounds and the corrosion properties of stainless steel 316. Moreover, the influence mechanisms of NaOH during these related processes were explored. The results show that decomposition efficiency for organic matter in liquid phase of the textile sludge was improved with the increment of reaction temperature or oxidation coefficient. However, the organic substance in solid phase can be oxidized completely in supercritical water. Serious coking occurred during the high pressure water at 250-450°C for the Reactive Orange 7, while at 300 and 350°C for the polyvinyl alcohol. The addition of NaOH not only accelerated the destruction of organic contaminants in the SCWO reactor, but effectively inhibited the dehydration conversion of textile compounds during the preheating process, which was favorable for the treatment system of textile sludge. The corrosion experiment results indicate that the stainless steel 316 could be competent for the body materials of the reactor and the heat exchangers. Furthermore, there was prominent enhancement of sodium hydroxide for the corrosion resistance of 316 in subcritical water. On the contrary the effect was almost none during SCWO.

Field-portable supercritical CO{sub 2} extractor

DOEpatents

Wright, B.W.; Zemanian, T.S.; Robins, W.H.; Woodcock, L.J.

1997-06-10

The present invention is an apparatus for extracting organic compounds from solid materials. A generator vessel has a removable closure for receiving a solid or liquid solvent which is heated with a resistive heating element to a gaseous or supercritical phase. The removable closure is unencumbered because the side wall is penetrated with an outlet for the gaseous or supercritical solvent. The generator vessel further has a pressure transducer that provides an electronic signal related to pressure of the gaseous or supercritical solvent. The apparatus of the present invention further includes at least one extraction cell having a top and a bottom and a wall extending there between, wherein the bottom is sealably penetrated by an inlet for gaseous or supercritical solvent received through a manifold connected to the outlet, the top having an easy-open removable closure cap, and the wall having an outlet port. Finally, a permeable sample cartridge is included for holding the solid materials and to provide radial-flow of the extraction fluid, which is placed within the extraction cell. 10 figs.

Field-portable supercritical CO.sub.2 extractor

DOEpatents

Wright, Bob W.; Zemanian, Thomas S.; Robins, William H.; Woodcock, Leslie J.

1997-01-01

The present invention is an apparatus for extracting organic compounds from solid materials. A generator vessel has a removable closure for receiving a solid or liquid solvent which is heated with a resistive heating element to a gaseous or supercritical phase. The removable closure is unencumbered because the side wall is penetrated with an outlet for the gaseous or supercritical solvent. The generator vessel further has a pressure transducer that provides an electronic signal related to pressure of the gaseous or supercritical solvent. The apparatus of the present invention further includes at least one extraction cell having a top and a bottom and a wall extending therebetween, wherein the bottom is sealably penetrated by an inlet for gaseous or supercritical solvent received through a manifold connected to the outlet, the top having an easy-open removable closure cap, and the wall having an outlet port. Finally, a permeable sample cartridge is included for holding the solid materials and to provide radial-flow of the extraction fluid, which is placed within the extraction cell.

Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

NASA Astrophysics Data System (ADS)

Marin, Timothy W.; Janik, Ireneusz; Bartels, David M.; Chipman, Daniel M.

2017-05-01

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381 °C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. Using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.

Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

DOE PAGES

Marin, Timothy W.; Janik, Ireneusz; Bartels, David M.; ...

2017-05-17

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381°C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as themore » water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. As a result, using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.« less

Techniques, applications and future prospects of diamond anvil cells for studying supercritical water systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Jr., R.L.; Fang, Z.; Tohoku)

In this review, diamond anvil type cells (DACs) are reviewed as a method for studying supercritical water systems. The hydrothermal DAC provides easy and safe experimental access to high pressure (30-3000 MPa) and high temperature (400-800 C) regions and the device allows exploration of supercritical systems at high density (400-1200 kg/m{sup 3}), which is usually difficult or costly with batch or flow systems. In the first part of this review, characteristics of DACs regarding anvil type, DAC type, anvil alignment, heating, analytical methods, pressure and temperature determination, gasket, loading, physical size are discussed with emphasis on DACs that can bemore » used to generate conditions of interest for understanding supercritical water systems. In the second part of this review, applications and key findings of studies on supercritical water systems from geology, chemical, biomass, energy, environmental, polymer, and materials related fields are discussed. Some of the key findings determined with DAC are related to the dissolution or existence of phases at conditions of high temperature and high pressure, however, DAC has been used in many quantitative studies to determine fundamental properties such as speeds of sound, phase behavior, solubilities, partition coefficients and viscosities. Future prospects for DAC as a method for exploring supercritical water systems include combination of DAC with transmission electron microscopy (TEM) for studying nanostructures, use of high-speed streak cameras to study high-speed reactions, combustions, and energetic materials, use of time-dependent loads to study kinetics, precipitation and crystallization phenomena, the use of DAC with synchrotron radiation to follow reaction and material processes in situ, and the many modifications that can be made to DAC anvils and rapid heating methods such as lasers and masers used in conjunction with in situ techniques. The DAC is a highly versatile instrument and should find

Supercritical convection, critical heat flux, and coking characteristics of propane

NASA Technical Reports Server (NTRS)

Rousar, D. C.; Gross, R. S.; Boyd, W. C.

1984-01-01

The heat transfer characteristics of propane at subcritical and supercritical pressure were experimentally evaluated using electrically heated Monel K-500 tubes. A design correlation for supercritical heat transfer coefficient was established using the approach previously applied to supercritical oxygen. Flow oscillations were observed and the onset of these oscillations at supercritical pressures was correlated with wall-to-bulk temperature ratio and velocity. The critical heat flux measured at subcritical pressure was correlated with the product of velocity and subcooling. Long duration tests at fixed heat flux conditions were conducted to evaluate coking on the coolant side tube wall and coking rates comparable to RP-1 were observed.

Inhibition effect in supercritical water oxidation of hydroquinone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thammanayakatip, C.; Oshima, Yoshito; Koda, Seiichiro

1998-05-01

In the oxidation reactions of hydroquinone under a supercritical conditions (temperature of 683 K and pressure of 24.5 MPa), the conversion was found to become saturated despite the very fast initial reaction. This behavior was quite different from that under a subcritical condition (temperature of 633 K and pressure of 24.5 MPa). Under both conditions, p-benzoquinone was found to be an important intermediate. The yield of CO{sub 2} was very small, which indicates a strong inhibition effect of hydroquinone and/or its derivatives. These inhibition phenomena should be taken into account very carefully in the application of supercritical water oxidation formore » treating waste organic materials where a complete decomposition is very important.« less

Development of an Accelerated Methodology to Study Degradation of Materials in Supercritical Water for Application in High Temperature Power Plants

NASA Astrophysics Data System (ADS)

Rodriguez, David

The decreasing supply of fossil fuel sources, coupled with the increasing concentration of green house gases has placed enormous pressure to maximize the efficiency of power generation. Increasing the outlet temperature of these power plants will result in an increase in operating efficiency. By employing supercritical water as the coolant in thermal power plants (nuclear reactors and coal power plants), the plant efficiency can be increased to 50%, compared to traditional reactors which currently operate at 33%. The goal of this dissertation is to establish techniques to characterize the mechanical properties and corrosion behavior of materials exposed to supercritical water. Traditionally, these tests have been long term exposure tests spanning months. The specific goal of this dissertation is to develop a methodology for accelerated estimation of corrosion rates in supercritical water that can be sued as a screening tool to select materials for long term testing. In this study, traditional methods were used to understand the degradation of materials in supercritical water and establish a point of comparison to the first electrochemical studies performed in supercritical water. Materials studied included austenitic steels (stainless steel 304, stainless steel 316 and Nitronic 50) and nickel based alloys (Inconel 625 and 718). Surface chemistry of the oxide layer was characterized using scanning electron microscopy, X-ray diffraction, FT-IR, Raman and X-ray photoelectron spectroscopies. Stainless steel 304 was subjected to constant tensile load creep tests in water at a pressure of 27 MPa and at temperatures of 200 °C, 315 °C and supercritical water at 450 °C for 24 hours. It was determined that the creep rate for stainless steel 304 exposed to supercritical water would be unacceptable for use in service. It was observed that the formation of hematite was favored in subcritical temperatures, while magnetite was formed in the supercritical region. Corrosion of

Code Development in Coupled PARCS/RELAP5 for Supercritical Water Reactor

DOE PAGES

Hu, Po; Wilson, Paul

2014-01-01

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

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.

SUPERCRITICAL WATER OXIDATION MODEL DEVELOPMENT FOR SELECTED EPA PRIORITY POLLUTANTS

EPA Science Inventory

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

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

PubMed

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

2015-12-10

This study examined the effects of sub- and supercritical water pretreatments on the physicochemical properties of crab shell α-chitin and its enzymatic degradation to obtain N,N'-diacetylchitobiose (GlcNAc)2. Following sub- and supercritical water pretreatments, the protein in the crab shell was removed and the residue of crab shell contained α-chitin and CaCO3. Prolonged pretreatment led to α-chitin decomposition. The reaction of pure α-chitin in sub- and supercritical water pretreatments was investigated separately; we observed lower mean molecular weight and weaker hydrogen bonds compared with untreated α-chitin. (GlcNAc)2 yields from enzymatic degradation of subcritical (350 °C, 7 min) and supercritical water (400 °C, 2.5 min) pretreated crab shell were 8% and 6%, compared with 0% without any pretreatment. This study shows that sub- and supercritical water pretreatments of crab shell provide to an alternative method to the use of acid and base for decalcification and deproteinization of crab shell required for (GlcNAc)2 production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Accelerated Stress Corrosion Crack Initiation of Alloys 600 and 690 in Hydrogenated Supercritical Water

NASA Astrophysics Data System (ADS)

Moss, Tyler; Was, Gary S.

2017-04-01

The objective of this study is to determine whether stress corrosion crack initiation of Alloys 600 and 690 occurs by the same mechanism in subcritical and supercritical water. Tensile bars of Alloys 690 and 600 were strained in constant extension rate tensile experiments in hydrogenated subcritical and supercritical water from 593 K to 723 K (320 °C to 450 °C), and the crack initiation behavior was characterized by high-resolution electron microscopy. Intergranular cracking was observed across the entire temperature range, and the morphology, structure, composition, and temperature dependence of initiated cracks in Alloy 690 were consistent between hydrogenated subcritical and supercritical water. Crack initiation of Alloy 600 followed an Arrhenius relationship and did not exhibit a discontinuity or change in slope after crossing the critical temperature. The measured activation energy was 121 ± 13 kJ/mol. Stress corrosion crack initiation in Alloy 690 was fit with a single activation energy of 92 ± 12 kJ/mol across the entire temperature range. Cracks were observed to propagate along grain boundaries adjacent to chromium-depleted metal, with Cr2O3 observed ahead of crack tips. All measures of the SCC behavior indicate that the mechanism for stress corrosion crack initiation of Alloy 600 and Alloy 690 is consistent between hydrogenated subcritical and supercritical water.

Modeling of biomass to hydrogen via the supercritical water pyrolysis process

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 reasonablemore » 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.« less

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.

Oxidation of Alloy 600 and Alloy 690: Experimentally Accelerated Study in Hydrogenated Supercritical Water

NASA Astrophysics Data System (ADS)

Moss, Tyler; Cao, Guoping; Was, Gary S.

2017-04-01

The objective of this study is to determine whether the oxidation of Alloys 600 and 690 in supercritical water occurs by the same mechanism in subcritical water. Coupons of Alloys 690 and 600 were exposed to hydrogenated subcritical and supercritical water from 633 K to 673 K (360 °C to 400 °C) and the oxidation behavior was observed. By all measures of oxide character and behavior, the oxidation process is the same above and below the supercritical line. Similar oxide morphologies, structures, and chemistries were observed for each alloy across the critical point, indicating that the oxidation mechanism is the same in both subcritical and supercritical water. Oxidation results in a multi-layer oxide structure composed of particles of NiO and NiFe2O4 formed by precipitation on the outer surface and a chromium-rich inner oxide layer formed by diffusion of oxygen to the metal-oxide interface. The inner oxide on Alloy 600 is less chromium rich than that observed on Alloy 690 and is accompanied by preferential oxidation of grain boundaries. The inner oxide on Alloy 690 initially forms by internal oxidation before a protective layer of chromium-rich MO is formed with Cr2O3 at the metal-oxide interface. Grain boundaries in Alloy 690 act as fast diffusion paths for chromium that forms a protective Cr2O3 layer at the surface, preventing grain boundary oxidation from occurring.

Surface chemistry and corrosion behavior of Inconel 625 and 718 in subcritical, supercritical, and ultrasupercritical water

NASA Astrophysics Data System (ADS)

Rodriguez, David; Merwin, Augustus; Karmiol, Zachary; Chidambaram, Dev

2017-05-01

Corrosion behavior of Inconel 625 and 718 in subcritical, supercritical and ultrasupercritical water was studied as a function of temperature and time. The change in the chemistry of the as-received surface film on Inconel 625 and 718 after exposure to subcritical water at 325 °C and supercritical water at 425 °C and 527.5 °C for 2 h was studied. After exposure to 325 °C subcritical water, the CrO42- based film formed; however minor quantities of NiFexCr2-xO4 spinel compounds were observed. The oxide film formed on both alloys when exposed to supercritical water at 425 °C consisted of NiFexCr2-xO4 spinel. The surface films on both alloys were identified as NiFe2O4 when exposed to supercritical water at 527.5 °C. To characterize the fully developed oxide layer, studies were conducted at test solution temperatures of 527.5 and 600 °C. Samples were exposed to these temperatures for 24, 96, and 200 h. Surface chemistry was analyzed using X-ray diffraction, as well as Raman and X-ray photoelectron spectroscopies. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. The differences in corrosion behavior of the two alloys are attributed to the lower content of chromium and increased iron content of Inconel 718 as compared to Inconel 625.

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.

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.

Corrosion behavior of ceramic-coated ZIRLO™ exposed to supercritical water

NASA Astrophysics Data System (ADS)

Mandapaka, Kiran K.; Cahyadi, Rico S.; Yalisove, Steven; Kuang, Wenjun; Sickafus, K.; Patel, Maulik K.; Was, Gary S.

2018-01-01

The corrosion behavior of ceramic coated ZIRLO™ tubing was evaluated in a supercritical water (SCW) environment to determine its behavior in high temperature water. Two coating architectures were analyzed; a 4 bi-layer TiAlN/TiN coating with Ti bond coat, and a TiN monolithic coating with Ti bond layer on ZIRLO™ tubes using cathodic arc physical vapor deposition (CA-PVD) technique. Femtosecond laser ablation was used to introduce reproducible defects in some of the coated tubes. On exposure to deaerated supercritical water at 542 °C for 48 h, coated tubes exhibited significantly higher weight gain compared to uncoated ZIRLO™. Examination revealed formation of a uniform ZrO2 layer beneath the coating of a thickness similar to that on the uncoated tube inner surface. The defects generated during the coating process acted as preferential paths for diffusion of oxygen resulting in the oxidation of substrate ZIRLO™. However, there was no delamination of the coating. There were insignificant differences in the oxidation weight gain between laser ablated and non-ablated tubes and the laser induced defects did not spread beyond their original size.

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.

Experimental study on heat transfer to supercritical water flowing through tubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2012-07-01

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

Estimation of the degree of hydrogen bonding between quinoline and water by ultraviolet-visible absorbance spectroscopy in sub- and supercritical water

NASA Astrophysics Data System (ADS)

Osada, Mitsumasa; Toyoshima, Katsunori; Mizutani, Takakazu; Minami, Kimitaka; Watanabe, Masaru; Adschiri, Tadafumi; Arai, Kunio

2003-03-01

UV-visible spectra of quinoline was measured in sub- and supercritical water (25 °Cwater was estimated from solvatochromic shifts in the π-π* absorbance band. Hydrogen bonding decreased with increasing temperature from 25 to 360 °C. At supercritical conditions (380 °Cwater was large (0.5<ρr<1.5). In this condition, local density around quinoline was lower than bulk density, namely negative solvation, and it led to the cleavage of hydrogen bonding between quinoline and water.

Water-in-Supercritical CO2 Microemulsion Stabilized by a Metal Complex.

PubMed

Luo, Tian; Zhang, Jianling; Tan, Xiuniang; Liu, Chengcheng; Wu, Tianbin; Li, Wei; Sang, Xinxin; Han, Buxing; Li, Zhihong; Mo, Guang; Xing, Xueqing; Wu, Zhonghua

2016-10-17

Herein we propose for the first time the utilization of a metal complex for forming water-in-supercritical CO 2 (scCO 2 ) microemulsions. The water solubility in the metal-complex-stabilized microemulsion is significantly improved compared with the conventional water-in-scCO 2 microemulsions stabilized by hydrocarbons. Such a microemulsion provides a promising route for the in situ CO 2 reduction catalyzed by a metal complex at the water/scCO 2 interface. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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:<...

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

PubMed

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

2016-01-08

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Oxidation of stainless steel 316 and Nitronic 50 in supercritical and ultrasupercritical water

NASA Astrophysics Data System (ADS)

Rodriguez, David; Chidambaram, Dev

2015-08-01

Corrosion of stainless steel 316 and Nitronic 50 exposed to supercritical and ultrasupercritical water was studied as a function of temperature and exposure time. Post-exposure surface analysis was performed using Raman and X-ray photoelectron spectroscopies to determine the chemistry of the oxides formed as a result of the exposure. When exposed to supercritical water, Nitronic 50 and stainless steel 316 were observed to have similar weight gains; however, stainless steel 316 was found to gain less weight than Nitronic 50 in exposure tests performed in ultrasupercritical water. Stainless steel 316 developed surface films primarily composed of iron oxides, while the surface of Nitronic 50 contained a mixture of iron, chromium and manganese oxides. Based on these analyses, the differences in weight gain and oxidation characteristics of the two materials are attributed to the higher concentration of Cr and Mn in Nitronic 50 compared to stainless steel 316.

Supercritical Fluids Processing of Biomass to Chemicals and Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olson, Norman K.

2011-09-28

The main objective of this project is to develop and/or enhance cost-effective methodologies for converting biomass into a wide variety of chemicals, fuels, and products using supercritical fluids. Supercritical fluids will be used both to perform reactions of biomass to chemicals and products as well as to perform extractions/separations of bio-based chemicals from non-homogeneous mixtures. This work supports the Biomass Program’s Thermochemical Platform Goals. Supercritical fluids are a thermochemical approach to processing biomass that, while aligned with the Biomass Program’s interests in gasification and pyrolysis, offer the potential for more precise and controllable reactions. Indeed, the literature with respect tomore » the use of water as a supercritical fluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”« less

Combined processes of ozonation and supercritical water oxidation for landfill leachate degradation.

PubMed

Scandelai, Ana Paula Jambers; Cardozo Filho, Lúcio; Martins, Danielly Cruz Campos; Freitas, Thabata Karoliny Formicoli de Souza; Garcia, Juliana Carla; Tavares, Célia Regina Granhen

2018-04-25

Leachate is a highly variable, heterogeneous and recalcitrant wastewater generated in landfills which may contain high concentrations of many organic and inorganic compounds, hampering the application of a single technique in its treatment. Therefore, this paper assessed leachate degradation through supercritical water oxidation (ScWO) as well as combined processes of ozonation and supercritical water oxidation (O 3 /ScWO and ScWO/O 3 ), a yet innovative combination. Ozonation was carried out at different reaction times (30-120 min). ScWO was developed at 600 °C, 23 MPa, and spatial time (τ) from 29 to 52 s. A combination of ozonation (30 min) and supercritical water oxidation process (O 3 -30'/ScWO) was the most efficient technique for the degradation of the leachate assessed. These conditions enabled to remove high values of apparent and true color (92% and 97%, respectively), biochemical oxygen demand (BOD 5,20 ) (95%), chemical oxygen demand (COD) (92%), total organic carbon (TOC) (79%), nitrite (78%), nitrate (84%), total (96%), dissolved (96%) and suspended (94%) solids. In addition, the combined process presented significant decrease in electric conductivity (EC) (68%) and less leachate turbidity removal (43%). Except for ammonia and nitrite, all parameters of the leachate treated by O 3 -30'/ScWO met the specifications of Brazilian legislation (CONAMA Resolutions No. 357/2005 and No. 430/2011) for the disposal of wastewater in water bodies. Besides, both processes are considered to be clean technologies. This shows the great possibility of applying the O 3 /ScWO combination to landfills leachates. Copyright © 2018 Elsevier Ltd. All rights reserved.

Water extractable arabinoxylan aerogels prepared by supercritical CO2 drying.

PubMed

Marquez-Escalante, Jorge; Carvajal-Millan, Elizabeth; Miki-Yoshida, Mario; Alvarez-Contreras, Lorena; Toledo-Guillén, Alma Rosa; Lizardi-Mendoza, Jaime; Rascón-Chu, Agustín

2013-05-14

Water extractable arabinoxylan (WEAX) aerogels were prepared by extracting the solvent from the alcogels (WEAX hydrogels with an alcohol as the solvent) with carbon dioxide under supercritical conditions. WEAX aerogels were characterized using scanning electron microscopy and adsorption and desorption nitrogen isotherms. The micrographs indicate a heterogeneous porous network structure in WEAX aerogel. Adsorption/desorption nitrogen isotherms of this material were type IV, which confirm that this material possess a mesoporous structure. WEAX aerogels rehydration capability was evaluated and the water absorption mechanism was determined. The WEAX aerogels water absorption mechanism was non-Fickian (n = 0.54).

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.

Development of Theoretical Methods for Predicting Solvent Effects on Reaction Rates in Supercritical Water Oxidation Processes

DTIC Science & Technology

2003-06-12

Raghunath Behera, Belinda Bashore, Richard Jendrejak and Susan C. Tucker*, “How local density enhancements influence solute reaction rates in supercritical...water,” National Meeting of the American Chemical Society, San Diego, CA, April 2001. Raghunath Behera, Belinda Bashore, Richard Jendrejak and... Raghunath Behera, Belinda Bashore, Richard Jendrejak and Susan C. Tucker*, “How local density enhancements influence solute reaction rates in supercritical

Core design of a direct-cycle, supercritical-water-cooled fast breeder reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jevremovic, T.; Oka, Yoshiaki; Koshizuka, Seiichi

1994-10-01

The conceptual design of a direct-cycle fast breeder reactor (FBR) core cooled by supercritical water is carried out as a step toward a low-cost FBR plant. The supercritical water does not exhibit change of phase. The turbines are directly driven by the core outlet coolant. In comparison with a boiling water reactor (BWR), the recirculation systems, steam separators, and dryers are eliminated. The reactor system is much simpler than the conventional steam-cooled FBRs, which adopted Loeffler boilers and complicated coolant loops for generating steam and separating it from water. Negative complete and partial coolant void reactivity are provided without muchmore » deterioration in the breeding performances by inserting thin zirconium-hydride layers between the seeds and blankets in a radially heterogeneous core. The net electric power is 1245 MW (electric). The estimated compound system doubling time is 25 yr. The discharge burnup is 77.7 GWd/t, and the refueling period is 15 months with a 73% load factor. The thermal efficiency is high (41.5%), an improvement of 24% relative to a BWR's. The pressure vessel is not thick at 30.3 cm.« less

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

Production of cellulose II from native cellulose by near- and supercritical water solubilization.

PubMed

Sasaki, Mitsuru; Adschiri, Tadafumi; Arai, Kunio

2003-08-27

We explored conditions for dissolving microcrystalline cellulose in high-temperature and high-pressure water without catalyst and in order to produce cellulose II in a rapid and selective manner. For understanding reactions of microcrystalline cellulose in subcritical and supercritical water, its solubilization treatment was conducted using a continuous-flow-type microreactor. It was found that cellulose could dissolve in near- and supercritical water at short treatment times of 0.02-0.4 s, resulting in the formation of cellulose II in relatively high yield after the treatment. Next, characteristics of the cellulose II obtained were investigated. As a result, it was confirmed that the relative crystallinity index and the degree of polymerization of the cellulose II were high values ranging from 80 to 60% and from 50 to 30%, respectively. From these findings, it was suggested that this method had high potential as an alternative technique for the conventional cellulose II production method.

Adsorption behaviors of supercritical Lennard-Jones fluid in slit-like pores.

PubMed

Li, Yingfeng; Cui, Mengqi; Peng, Bo; Qin, Mingde

2018-05-18

Understanding the adsorption behaviors of supercritical fluid in confined space is pivotal for coupling the supercritical technology and the membrane separation technology. Based on grand canonical Monte Carlo simulations, the adsorption behaviors of a Lennard-Jones (LJ) fluid in slit-like pores at reduced temperatures over the critical temperature, T c *  = 1.312, are investigated; and impacts of the wall-fluid interactions, the pore width, and the temperature are taken into account. It is found that even if under supercritical conditions, the LJ fluid can undergo a "vapor-liquid phase transition" in confined space, i.e., the adsorption density undergoes a sudden increase with the bulk density. A greater wall-fluid attractive potential, a smaller pore width, and a lower temperature will bring about a stronger confinement effect. Besides, the adsorption pressure reaches a local minimum when the bulk density equals to a certain value, independent of the wall-fluid potential or pore width. The insights in this work have both practical and theoretical significances. Copyright © 2018 Elsevier Inc. All rights reserved.

Multi-Phase Equilibrium and Solubilities of Aromatic Compounds and Inorganic Compounds in Sub- and Supercritical Water: A Review.

PubMed

Liu, Qinli; Ding, Xin; Du, Bowen; Fang, Tao

2017-11-02

Supercritical water oxidation (SCWO), as a novel and efficient technology, has been applied to wastewater treatment processes. The use of phase equilibrium data to optimize process parameters can offer a theoretical guidance for designing SCWO processes and reducing the equipment and operating costs. In this work, high-pressure phase equilibrium data for aromatic compounds+water systems and inorganic compounds+water systems are given. Moreover, thermodynamic models, equations of state (EOS) and empirical and semi-empirical approaches are summarized and evaluated. This paper also lists the existing problems of multi-phase equilibria and solubility studies on aromatic compounds and inorganic compounds in sub- and supercritical water.

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.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 ismore » 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.« less

UV spectral shift of benzene in sub- and supercritical water

NASA Astrophysics Data System (ADS)

Kometani, Noritsugu; Takemiya, Koji; Yonezawa, Yoshiro; Amita, Fujitsugu; Kajimoto, Okitsugu

2004-08-01

UV absorption spectra of benzene have been measured over the wide range of temperature and pressure from the ambient state to the supercritical state ( T = 400 °C and P = 40 MPa). The analysis of the spectral shift of benzene in water relative to that in the gas indicates that at T = 380 and 390 °C the local solvent density around benzene is likely to be depressed below the bulk density for densities near the critical density. It is found that π-hydrogen bond between benzene and water becomes evident with lowering temperature below T = 340 °C.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamada, K.; Aksan, S. N.

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,more » 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)« less

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Quin RS; Thompson, Christopher J.; Loring, John S.

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 laboratorymore » 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

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

Methane and Methanol Oxidation in Supercritical Water: Chemical Kinetics and Hydrothermal Flame Studies

DTIC Science & Technology

1996-01-01

water at 270 bar and at temperatures from 390 to 442 ’C. The initial methane concentration was nominally 0.15 gmol/L, a level representa- tive of...compounds appropriate for treatment with SCWO technology (Modell, 1989). Since then, the need to understand reaction chemistry has motivated extensive...understand the physics and chemistry controlling oxidation in supercritical water; to contribute to combustion science by performing fundamental studies in a

Critical size of crystalline ZrO(2) nanoparticles synthesized in near- and supercritical water and supercritical isopropyl alcohol.

PubMed

Becker, Jacob; Hald, Peter; Bremholm, Martin; Pedersen, Jan S; Chevallier, Jacques; Iversen, Steen B; Iversen, Bo B

2008-05-01

Nanocrystalline ZrO(2) samples with narrow size distributions and mean particle sizes below 10 nm have been synthesized in a continuous flow reactor in near and supercritical water as well as supercritical isopropyl alcohol using a wide range of temperatures, pressures, concentrations and precursors. The samples were comprehensively characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS), and the influence of the synthesis parameters on the particle size, particle size distribution, shape, aggregation and crystallinity was studied. On the basis of the choice of synthesis parameters either monoclinic or tetragonal zirconia phases can be obtained. The results suggest a critical particle size of 5-6 nm for nanocrystalline monoclinic ZrO(2) under the present conditions, which is smaller than estimates reported in the literature. Thus, very small monoclinic ZrO(2) particles can be obtained using a continuous flow reactor. This is an important result with respect to improvement of the catalytic properties of nanocrystalline ZrO(2).

Determination of fat- and water-soluble vitamins by supercritical fluid chromatography: A review.

PubMed

Tyśkiewicz, Katarzyna; Dębczak, Agnieszka; Gieysztor, Roman; Szymczak, Tomasz; Rój, Edward

2018-01-01

Vitamins are compounds that take part in all basic functions of an organism but also are subject of number of studies performed by different researchers. Two groups of vitamins are distinguished taking into consideration their solubility. Chromatography with supercritical CO 2 has found application in the determination, separation, and quantitative analyses of both fat- and water-soluble vitamins. The methods of vitamins separation have developed and improved throughout the years. Both groups of compounds were separated using supercritical fluid chromatography with different detection on different stationary phases. The main aim of this review is to provide an overview of the studies of vitamins separation that have been determined so far. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supercritical fluid extraction of selected pharmaceuticals from water and serum.

PubMed

Simmons, B R; Stewart, J T

1997-01-24

Selected drugs from benzodiazepine, anabolic agent and non-steroidal anti-inflammatory drug (NSAID) therapeutic classes were extracted from water and serum using a supercritical CO2 mobile phase. The samples were extracted at a pump pressure of 329 MPa, an extraction chamber temperature of 45 degrees C, and a restrictor temperature of 60 degrees C. The static extraction time for all samples was 2.5 min and the dynamic extraction time ranged from 5 to 20 min. The analytes were collected in appropriate solvent traps and assayed by modified literature HPLC procedures. Analyte recoveries were calculated based on peak height measurements of extracted vs. unextracted analyte. The recovery of the benzodiazepines ranged from 80 to 98% in water and from 75 to 94% in serum. Anabolic drug recoveries from water and serum ranged from 67 to 100% and 70 to 100%, respectively. The NSAIDs were recovered from water in the 76 to 97% range and in the 76 to 100% range from serum. Accuracy, precision and endogenous peak interference, if any, were determined for blank and spiked serum extractions and compared with classical sample preparation techniques of liquid-liquid and solid-phase extraction reported in the literature. For the benzodiazepines, accuracy and precision for supercritical fluid extraction (SFE) ranged from 1.95 to 3.31 and 0.57 to 1.25%, respectively (n = 3). The SFE accuracy and precision data for the anabolic agents ranged from 4.03 to 7.84 and 0.66 to 2.78%, respectively (n = 3). The accuracy and precision data reported for the SFE of the NSAIDs ranged from 2.79 to 3.79 and 0.33 to 1.27%, respectively (n = 3). The precision of the SFE method from serum was shown to be comparable to the precision obtained with other classical preparation techniques.

Water-gas shift reaction on alumina-supported Pt-CeO x catalysts prepared by supercritical fluid deposition

DOE PAGES

Deal, Jacob W.; Le, Phong; Corey, C. Blake; ...

2016-08-25

Alumina-supported platinum catalysts, both with and without ceria, were prepared by supercritical fluid deposition and evaluated for activity for water-gas shift reaction. The organometallic precursor, platinum(II) acetylacetonate, was deposited from solution in supercritical carbon dioxide. Analysis of the catalysts by high resolution scanning transmission electron microscopy indicated that platinum was present in the form of highly dispersed metal nanoparticles. Pretreatment of the alumina-supported ceria in hydrogen prior to the deposition of the platinum precursor resulted in more platinum nucleated on ceria than non-pretreated alumina-supported ceria but varied in both particle size and structure. The ceria-containing catalyst that was not pretreatedmore » exhibited a more uniform particle size, and the Pt particles were encapsulated in crystalline ceria. Reaction rate measurements showed that the catalyst was more active for water-gas shift, with reaction rates per mass of platinum that exceeded most literature values for water-gas shift reaction on Pt-CeO x catalysts. The high activity was attributed to the significant fraction of platinum/ceria interfacial contact. We found that these results show the promise of supercritical fluid deposition as a scalable means of synthesizing highly active supported metal catalysts that offer efficient utilization of precious metals.« less

Effects of Cr Content and Surface Finishes on Oxidation Behaviors of Austenitic Fe-Cr-Ni Alloys Exposed in Supercritical Water (SCW)

NASA Astrophysics Data System (ADS)

Xing, Bo

The scope of this work was to characterize the corrosion resistance of candidate austenitic alloys in supercritical water for the use of the fuel cladding material within the Canadian supercritical water-cooled reactor (SCWR) concept. A series of Commercial austenitic stainless steels (SS) and alloys were exposed to supercritical water for different exposure times up to 500 hours. Two surface finishes were applied - a coarse grinding with 120 grit abrasive or polishing with either 1200 grit or 0.05 microm alumina suspension. Gravimetric measurements and electron microscopy techniques were used to evaluate the oxidation behaviors of tested alloys. The superior corrosion resistance of alloy 310S was benefited from a critical Cr content of 25 wt.%. The surface finish played a significant role to vary the oxidation behavior of alloys containing slightly less than the critical Cr content. However, Oxide exfoliation was observed on low Cr content alloys.

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. Copyright © 2014 Elsevier Ltd. All rights reserved.

Supercritical water gasification of biomass: Thermodynamic constraints.

PubMed

Castello, Daniele; Fiori, Luca

2011-08-01

In the present work, the supercritical water gasification (SCWG) of biomass is analyzed with a view to outlining the possible thermodynamic constraints that must be taken into account to develop this new process. In particular, issues concerning the formation of solid carbon and the process heat duty are discussed. The analysis is conducted by means of a two-phase non-stoichiometric thermodynamic model, based on Gibbs free energy minimization. Results show that char formation at equilibrium only occurs at high biomass concentrations, with a strong dependence on biomass composition. As regards the process heat duty, SCWG is mostly endothermic when biomass concentration is low, although a very small amount of oxidizing agent is able to make the process exothermic, with only a small loss in the heating value of the syngas produced. Copyright © 2011 Elsevier Ltd. All rights reserved.

Numerical investigation of supercritical LNG convective heat transfer in a horizontal serpentine tube

NASA Astrophysics Data System (ADS)

Han, Chang-Liang; Ren, Jing-Jie; Dong, Wen-Ping; Bi, Ming-Shu

2016-09-01

The submerged combustion vaporizer (SCV) is indispensable general equipment for liquefied natural gas (LNG) receiving terminals. In this paper, numerical simulation was conducted to get insight into the flow and heat transfer characteristics of supercritical LNG on the tube-side of SCV. The SST model with enhanced wall treatment method was utilized to handle the coupled wall-to-LNG heat transfer. The thermal-physical properties of LNG under supercritical pressure were used for this study. After the validation of model and method, the effects of mass flux, outer wall temperature and inlet pressure on the heat transfer behaviors were discussed in detail. Then the non-uniformity heat transfer mechanism of supercritical LNG and effect of natural convection due to buoyancy change in the tube was discussed based on the numerical results. Moreover, different flow and heat transfer characteristics inside the bend tube sections were also analyzed. The obtained numerical results showed that the local surface heat transfer coefficient attained its peak value when the bulk LNG temperature approached the so-called pseudo-critical temperature. Higher mass flux could eliminate the heat transfer deteriorations due to the increase of turbulent diffusion. An increase of outer wall temperature had a significant influence on diminishing heat transfer ability of LNG. The maximum surface heat transfer coefficient strongly depended on inlet pressure. Bend tube sections could enhance the heat transfer due to secondary flow phenomenon. Furthermore, based on the current simulation results, a new dimensionless, semi-theoretical empirical correlation was developed for supercritical LNG convective heat transfer in a horizontal serpentine tube. The paper provided the mechanism of heat transfer for the design of high-efficiency SCV.

Surfactant/Supercritical Fluid Cleaning of Contaminated Substrates

NASA Technical Reports Server (NTRS)

White, Gary L.

1997-01-01

CFC's and halogenated hydrocarbon solvents have been the solvents of choice to degrease and otherwise clean precision metal parts to allow proper function. Recent regulations have, however, rendered most of these solvents unacceptable for these purposes. New processes which are being used or which have been proposed to replace these solvents usually either fail to remove water soluble contaminants or produce significant aqueous wastes which must then be disposed of. In this work, a new method for cleaning surfaces will be investigated. Solubility of typical contaminants such as lubricating greases and phosphatizing bath residues will be studied in several surfactant/supercritical fluid solutions. The effect of temperature, pressure, and the composition of the cleaning mixture on the solubility of oily, polar, and ionic contaminants will be investigated. A reverse micellar solution in a supercritical light hydrocarbon solvent will be used to clean samples of industrial wastes. A reverse micellar solution is one where water is dissolved into a non-polar solvent with the aid of a surfactant. The solution will be capable of dissolving both water-soluble contaminants and oil soluble contaminants. Once the contaminants have been dissolved into the solution they will be separated from the light hydrocarbon and precipitated by a relatively small pressure drop and the supercritical solvent will be available for recycle for reuse. The process will be compared to the efficacy of supercritical CO2 cleaning by attempting to clean the same types of substrates and machining wastes with the same contaminants using supercritical CO2. It is anticipated that the supercritical CO2 process will not be capable of removing ionic residues.

Pilot-scale laboratory waste treatment by supercritical water oxidation.

PubMed

Oshima, Yoshito; Hayashi, Rumiko; Yamamoto, Kazuo

2006-01-01

Supercritical water oxidation (SCWO) is a reaction in which organics in an aqueous solution can be oxidized by O2 to CO2 and H2O at a very high reaction rate. In 2003, The University of Tokyo constructed a facility for the SCWO process, the capacity of which is approximately 20 kl/year, for the purpose of treating organic laboratory waste. Through the operation of this facility, we have demonstrated that most of the organics in laboratory waste including halogenated organic compounds can be successfully treated without the formation of dioxines, suggesting that SCWO is useful as an alternative technology to the conventional incineration process.

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

PubMed

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

2012-01-01

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

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

Geologic controls on supercritical geothermal resources above magmatic intrusions.

PubMed

Scott, Samuel; Driesner, Thomas; Weis, Philipp

2015-07-27

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

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.

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.

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.

Oxidation reactions of solid carbonaceous and resinous substances in supercritical water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koda, S.

Recent kinetic studies, particularly those by means of shadowgraphy and X-ray radiography, for supercritical water oxidation of solid carbonaceous and resinous substances have revealed the importance of the O{sub 2} mass transfer process over the intrinsic surface reaction at higher temperatures. The mass transfer processes, internal and external one, should be incorporated in designing SCWO processes for solid substances and related processes such as catalytic SCWO. Some model calculation efforts of late are briefly described. Finally, fundamental information required for future development is itemed.

A supercritical airfoil experiment

NASA Technical Reports Server (NTRS)

Mateer, G. G.; Seegmiller, H. L.; Hand, L. A.; Szodruck, J.

1994-01-01

The purpose of this investigation is to provide a comprehensive data base for the validation of numerical simulations. The objective of the present paper is to provide a tabulation of the experimental data. The data were obtained in the two-dimensional, transonic flowfield surrounding a supercritical airfoil. A variety of flows were studied in which the boundary layer at the trailing edge of the model was either attached or separated. Unsteady flows were avoided by controlling the Mach number and angle of attack. Surface pressures were measured on both the model and wind tunnel walls, and the flowfield surrounding the model was documented using a laser Doppler velocimeter (LDV). Although wall interference could not be completely eliminated, its effect was minimized by employing the following techniques. Sidewall boundary layers were reduced by aspiration, and upper and lower walls were contoured to accommodate the flow around the model and the boundary-layer growth on the tunnel walls. A data base with minimal interference from a tunnel with solid walls provides an ideal basis for evaluating the development of codes for the transonic speed range because the codes can include the wall boundary conditions more precisely than interference connections can be made to the data sets.

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.

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

PubMed

Lock, Nina; Bremholm, Martin; Christensen, Mogens; Almer, Jonathan; Chen, Yu-Sheng; Iversen, Bo B

2009-12-14

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

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Supercritical fluid particle design for poorly water-soluble drugs (review).

PubMed

Sun, Yongda

2014-01-01

Supercritical fluid particle design (SCF PD) offers a number of routes to improve solubility and dissolution rate for enhancing the bioavailability of poorly water-soluble drugs, which can be adopted through an in-depth knowledge of SCF PD processes and the molecular properties of active pharmaceutical ingredients (API) and drug delivery system (DDS). Combining with research experiences in our laboratory, this review focuses on the most recent development of different routes (nano-micron particles, polymorphic particles, composite particles and bio-drug particles) to improve solubility and dissolution rate of poorly water-soluble drugs, covering the fundamental concept of SCF and the principle of SCF PD processes which are typically used to control particle size, shape, morphology and particle form and hence enable notable improvement in the dissolution rate of the poorly water-soluble drugs. The progress of the industrialization of SCF PD processes in pharmaceutical manufacturing environment with scaled-up plant under current good manufacturing process (GMP) specification is also considered in this review.

Supercritical carbon dioxide for textile applications and recent developments

NASA Astrophysics Data System (ADS)

Eren, H. A.; Avinc, O.; Eren, S.

2017-10-01

In textile industry, supercritical carbon dioxide (scCO2), possessing liquid-like densities, mostly find an application on textile dyeing processes such as providing hydrophobic dyes an advantage on dissolving. Their gas-like low viscosities and diffusion properties can result in shorter dyeing periods in comparison with the conventional water dyeing process. Supercritical carbon dioxide dyeing is an anhydrous dyeing and this process comprises the usage of less energy and chemicals when compared to conventional water dyeing processes leading to a potential of up to 50% lower operation costs. The advantages of supercritical carbon dioxide dyeing method especially on synthetic fiber fabrics hearten leading textile companies to alter their dyeing method to this privileged waterless dyeing technology. Supercritical carbon dioxide (scCO2) waterless dyeing is widely known and applied green method for sustainable and eco-friendly textile industry. However, not only the dyeing but also scouring, desizing and different finishing applications take the advantage of supercritical carbon dioxide (scCO2). In this review, not only the principle, advantages and disadvantages of dyeing in supercritical carbon dioxide but also recent developments of scCO2 usage in different textile processing steps such as scouring, desizing and finishing are explained and commercial developments are stated and summed up.

Enzyme microheterogeneous hydration and stabilization in supercritical carbon dioxide.

PubMed

Silveira, Rodrigo L; Martínez, Julian; Skaf, Munir S; Martínez, Leandro

2012-05-17

Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.

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.

Supercritical water pyrolysis of sewage sludge.

PubMed

Ma, Wenchao; Du, Guiyue; Li, Jian; Fang, Yuanhao; Hou, Li'an; Chen, Guanyi; Ma, Degang

2017-01-01

Municipal sewage sludge (SS) from wastewater treatment plant containing high water content (>85wt.%), lead to the difficulty of co-combustion with MSW or coal due to the high cost of drying. This study explores an alternative method by supercritical water (SCW) pyrolysis of sewage sludge (SS) in a high pressure reaction vessel. The effects of temperature and moisture content of SS on yield and composition of the products (bio-oil, bio char and non-condensable gas) were studied. A temperature of 385°C and moisture content of 85wt.% were found to be the optimum conditions for the maximum bio-oil production of 37.23wt.%, with a higher heating value of 31.08MJ/kg. In the optimum condition, the yields of aliphatic hydrocarbon and phenols were about 29.23wt.% and 12.51wt.%, respectively. The physical and chemical properties of bio-char were analyzed by using XRF and BET. Results of GC analyses of NCG showed that it has the maximum HHV of 13.39MJ/m 3 at 445°C and moisture content of 85wt.%. The reaction path from SS to bio-oil through SCW pyrolysis was given. Moreover, carbon balance was calculated for the optimal condition, and finding out that 64.27wt.% of the carbon content was transferred from SS to bio-oil. Finally, this work demonstrates that the SCW pyrolysis is a promising disposal method for SS. Copyright © 2016. Published by Elsevier Ltd.

Supercritical carbon dioxide-based sterilization of decellularized heart valves

PubMed Central

Hennessy, Ryan S.; Jana, Soumen; Tefft, Brandon J.; Helder, Meghana R.; Young, Melissa D.; Hennessy, Rebecca R.; Stoyles, Nicholas J.; Lerman, Amir

2017-01-01

Objective The goal of this research project encompasses finding the most efficient and effective method of decellularized tissue sterilization. Background Aortic tissue grafts have been utilized to repair damaged or diseased valves. Although, the tissues for grafting are collected aseptically, it does not eradicate the risk of contamination nor disease transfer. Thus, sterilization of grafts is mandatory. Several techniques have been applied to sterilize grafts; however, each technique shows drawbacks. In this study, we compared several sterilization techniques: supercritical carbon dioxide, electrolyzed water, gamma radiation, ethanol-peracetic acid, and hydrogen peroxide for impact on the sterility and mechanical integrity of porcine decellularized aortic valves. Methods Valve sterility was characterized by histology, microbe culture, and electron microscopy. Uniaxial tensile testing was conducted on the valve cusps along their circumferential orientation to study these sterilization techniques on their integrity. Results Ethanol-peracetic acid and supercritical carbon dioxide treated valves were found to be sterile. The tensile strength of supercritical carbon dioxide treated valves (4.28 ± 0.22 MPa) was higher to those valves treated with electrolyzed water, gamma radiation, ethanol-peracetic acid and hydrogen peroxide (1.02 ± 0.15, 1.25 ± 0.25, 3.53 ± 0.41 and 0.37 ± 0.04 MPa, respectively). Conclusions Superior sterility and integrity were found in the decellularized porcine aortic valves with supercritical carbon dioxide sterilization. This sterilization technique may hold promise for other decellularized soft tissues. Summary Sterilization of grafts is essential. Supercritical carbon dioxide, electrolyzed water, gamma radiation, ethanol-peracetic acid, and hydrogen peroxide techniques were compared for impact on sterility and mechanical integrity of porcine decellularized aortic valves. Ethanol-peracetic acid and supercritical carbon dioxide treated

Supercritical carbon dioxide-based sterilization of decellularized heart valves.

PubMed

Hennessy, Ryan S; Jana, Soumen; Tefft, Brandon J; Helder, Meghana R; Young, Melissa D; Hennessy, Rebecca R; Stoyles, Nicholas J; Lerman, Amir

2017-02-01

The goal of this research project encompasses finding the most efficient and effective method of decellularized tissue sterilization. Aortic tissue grafts have been utilized to repair damaged or diseased valves. Although, the tissues for grafting are collected aseptically, it does not eradicate the risk of contamination nor disease transfer. Thus, sterilization of grafts is mandatory. Several techniques have been applied to sterilize grafts; however, each technique shows drawbacks. In this study, we compared several sterilization techniques: supercritical carbon dioxide, electrolyzed water, gamma radiation, ethanol-peracetic acid, and hydrogen peroxide for impact on the sterility and mechanical integrity of porcine decellularized aortic valves. Valve sterility was characterized by histology, microbe culture, and electron microscopy. Uniaxial tensile testing was conducted on the valve cusps along their circumferential orientation to study these sterilization techniques on their integrity. Ethanol-peracetic acid and supercritical carbon dioxide treated valves were found to be sterile. The tensile strength of supercritical carbon dioxide treated valves (4.28 ± 0.22 MPa) was higher to those valves treated with electrolyzed water, gamma radiation, ethanol-peracetic acid and hydrogen peroxide (1.02 ± 0.15, 1.25 ± 0.25, 3.53 ± 0.41 and 0.37 ± 0.04 MPa, respectively). Superior sterility and integrity were found in the decellularized porcine aortic valves with supercritical carbon dioxide sterilization. This sterilization technique may hold promise for other decellularized soft tissues. Sterilization of grafts is essential. Supercritical carbon dioxide, electrolyzed water, gamma radiation, ethanol-peracetic acid, and hydrogen peroxide techniques were compared for impact on sterility and mechanical integrity of porcine decellularized aortic valves. Ethanol-peracetic acid and supercritical carbon dioxide treated valves were found to be sterile using histology, microbe

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

Formation of ZnO at zinc oxidation by near- and supercritical water under the constant electric field

NASA Astrophysics Data System (ADS)

Shishkin, A. V.; Sokol, M. Ya.; Shatrova, A. V.; Fedyaeva, O. N.; Vostrikov, A. A.

2014-12-01

The work has detected an influence of a constant electric field (up to E = 300 kV/m) on the structure of a nanocrystalline layer of zinc oxide, formed on the surface of a planar zinc anode in water under supercritical (673 K and 23 MPa) and near-critical (673 K and 17. 5 MPa) conditions. The effect of an increase of zinc oxidation rate with an increase in E is observed under supercritical conditions and is absent at near-critical ones. Increase in the field strength leads to the formation of a looser structure in the inner part of the zinc oxide layer.

Corrosion of low alloy steel containing 0.5% chromium in supercritical CO2-saturated brine and water-saturated supercritical CO2 environments

NASA Astrophysics Data System (ADS)

Wei, Liang; Gao, Kewei; Li, Qian

2018-05-01

The corrosion behavior of P110 low-Cr alloy steel in supercritical CO2-saturated brine (aqueous phase) and water-saturated supercritical CO2 (SC CO2 phase) was investigated. The results show that P110 steel primarily suffered general corrosion in the aqueous phase, while severe localized corrosion occurred in the SC CO2 phase. The formation of corrosion product scale on P110 steel in the aqueous phase divided into three stages: formation of the initial corrosion layer containing amorphous Cr(OH)3, FeCO3 and a small amount of Fe3C; transformation of initial corrosion layer to mixed layer, which consisted of FeCO3 and a small amount of Cr(OH)3 and Fe3C; growth and dissolution of the mixed layer. Finally, only a single mixed layer covered on the steel in the aqueous phase. However, the scale formed in SC CO2 phase consisted of two layers: the inner mixed layer and the dense outer FeCO3 crystalline layer.

Titania nanospheres from supercritical fluids.

PubMed

Darr, J A; Kellici, S; Rehman, I U

2005-06-01

Surfactant-coated amorphous titania nanospheres have been synthesised using templating 'water-in-supercritical carbon dioxide' emulsion droplets; the process represents a clean and controlled method for the manufacture of high-purity nanoparticles.

Biodiesel production from Spirulina microalgae feedstock using direct transesterification near supercritical methanol condition.

PubMed

Mohamadzadeh Shirazi, Hamed; Karimi-Sabet, Javad; Ghotbi, Cyrus

2017-09-01

Microalgae as a candidate for production of biodiesel, possesses a hard cell wall that prevents intracellular lipids leaving out from the cells. Direct or in situ supercritical transesterification has the potential for destruction of microalgae hard cell wall and conversion of extracted lipids to biodiesel that consequently reduces the total energy consumption. Response surface methodology combined with central composite design was applied to investigate process parameters including: Temperature, Time, Methanol-to-dry algae, Hexane-to-dry algae, and Moisture content. Thirty-two experiments were designed and performed in a batch reactor, and biodiesel efficiency between 0.44% and 99.32% was obtained. According to fatty acid methyl ester yields, a quadratic experimental model was adjusted and the significance of parameters was evaluated using analysis of variance (ANOVA). Effects of single and interaction parameters were also interpreted. In addition, the effect of supercritical process on the ultrastructure of microalgae cell wall using scanning electron spectrometry (SEM) was surveyed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Enhancing the solubility and bioavailability of poorly water-soluble drugs using supercritical antisolvent (SAS) process.

PubMed

Abuzar, Sharif Md; Hyun, Sang-Min; Kim, Jun-Hee; Park, Hee Jun; Kim, Min-Soo; Park, Jeong-Sook; Hwang, Sung-Joo

2018-03-01

Poor water solubility and poor bioavailability are problems with many pharmaceuticals. Increasing surface area by micronization is an effective strategy to overcome these problems, but conventional techniques often utilize solvents and harsh processing, which restricts their use. Newer, green technologies, such as supercritical fluid (SCF)-assisted particle formation, can produce solvent-free products under relatively mild conditions, offering many advantages over conventional methods. The antisolvent properties of the SCFs used for microparticle and nanoparticle formation have generated great interest in recent years, because the kinetics of the precipitation process and morphologies of the particles can be accurately controlled. The characteristics of the supercritical antisolvent (SAS) technique make it an ideal tool for enhancing the solubility and bioavailability of poorly water-soluble drugs. This review article focuses on SCFs and their properties, as well as the fundamentals of overcoming poorly water-soluble drug properties by micronization, crystal morphology control, and formation of composite solid dispersion nanoparticles with polymers and/or surfactants. This article also presents an overview of the main aspects of the SAS-assisted particle precipitation process, its mechanism, and parameters, as well as our own experiences, recent advances, and trends in development. Copyright © 2017 Elsevier B.V. All rights reserved.

Wall shear measurement in sand-water mixture flows

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yucel, O.; Grad, W.H.

1975-07-01

The wall shear stress was measured in clear-water and sand-water mixture flows with the use of a flush-mounting hot-film shear-sensor. Data were obtained with 2 shear-sensors and 2 different sands (d50 = 0.45 mm and d50 = 0.88 mm) with solids concentrations of up to Cmax = 1.6% by vol, and for flow Reynolds number of 10/sup 5/ < RD < 6 x 10/sup 5/. The measured sensor wall shear stresses were compared with the true wall shear stresses obtained with the energy head loss measurements conducted in a pipeline system. The results of the tests in the clear-water flowsmore » confirmed the relationship between the sensor power output, Ps, and the wall shear stress, tauo, given by tauo1/3 = APs + B, in which A and B are calibration coefficients. The tests with the low-concentration sand-water mixtures in a vertical pipe indicated that for the present range of experiments, sensor power outputs with the mixtures exceeded those for clear-water by an average of 5%. It is shown that the shear sensors are delicate but accurate instruments that can be used for the measurement of the wall shear stress. (13 refs.)« less

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.

Polycyclic aromatic hydrocarbon formation during the gasification of sewage sludge in sub- and supercritical water: Effect of reaction parameters and reaction pathways.

PubMed

Gong, Miao; Wang, Yulan; Fan, Yujie; Zhu, Wei; Zhang, Huiwen; Su, Ying

2018-02-01

The formation of polycyclic aromatic hydrocarbon is a widespread issue during the supercritical water gasification of sewage sludge, which directly reduces the gasification efficiency and restricts the technology practical application. The changes of the concentrations and forms as well as the synthesis rate of polycyclic aromatic hydrocarbons in the residues from supercritical water gasification of dewatered sewage sludge were investigated to understand influence factors and the reaction pathways. Results showed that the increase of reaction temperature during the heating period favours directly concentration of polycyclic aromatic hydrocarbon (especially higher-molecular-weight), especially when it raise above 300 °C. Lower heating and cooling rate essentially extend the total reaction time. Higher polycyclic aromatic hydrocarbon concentration and higher number of rings were generally promoted by lower heating and cooling rate, longer reaction time and higher reaction temperature. The lower-molecular-weight polycyclic aromatic hydrocarbons can be directly generated through the decomposition of aromatic-containing compounds in sewage sludge, as well as 3-ring and 4-ring polycyclic aromatic hydrocarbons can be formed by aromatization of steroids. Possible mechanisms of reaction pathways of supercritical water gasification of sewage sludge were also proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iouri I. Balachov; Takao Kobayashi; Francis Tanzella

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 andmore » 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.« less

Corrosion behavior of oxide dispersion strengthened ferritic steels in supercritical water

NASA Astrophysics Data System (ADS)

Gao, Wenhua; Guo, Xianglong; Shen, Zhao; Zhang, Lefu

2017-04-01

The corrosion resistance of three different Cr content oxide dispersion strengthened (ODS) ferritic steels in supercritical water (SCW) and their passive films formed on the surface have been investigated. The results show that the dissolved oxygen (DO) and chemical composition have significant influence on the corrosion behavior of the ODS ferritic steels. In 2000 ppb DO SCW at 650 °C, the 14Cr-4Al ODS steel forms a tri-layer oxide film and the surface morphologies have experienced four structures. For the tri-layer oxide film, the middle layer is mainly Fe-Cr spinel and the Al is gradually enriched in the inner layer.

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 ...

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.

New Class of Amphiphiles Designed for Use in Water-in-Supercritical CO2 Microemulsions.

PubMed

Sagisaka, Masanobu; Ogiwara, Shunsuke; Ono, Shinji; James, Craig; Yoshizawa, Atsushi; Mohamed, Azmi; Rogers, Sarah E; Heenan, Richard K; Yan, Ci; Peach, Jocelyn Alice; Eastoe, Julian

2016-11-29

Water-in-supercritical CO 2 microemulsions formed using the hybrid F-H surfactant sodium 1-oxo-1-[4-(perfluorohexyl)phenyl]hexane-2-sulfonate, FC6-HC4, have recently been shown to have the highest water-solubilizing power ever reported. FC6-HC4 demonstrated the ability to outperform not only other surfactants but also other FCm-HCn analogues containing different fluorocarbon and hydrocarbon chain lengths (Sagisaka, M. et al. Langmuir 2015, 31, 7479-7487). With the aim of clarifying the key structural features of this surfactant, this study examined the phase behavior and water/supercritical CO 2 aggregate formation of 1-oxo-1-[4-(perfluorohexyl)phenyl]hexane (Nohead FC6-HC4), which is an FC6-HC4 analogue but now, interestingly, without the sulfonate headgroup. Surprisingly, Nohead FC6-HC4, which would not normally be identified as a classic surfactant, yielded transparent single-phase W/CO 2 microemulsions with polar cores able to solubilize a water-soluble dye, even at pressures and temperatures so low as to approach the critical point of CO 2 (e.g., ∼100 bar at 35 °C). High-pressure small-angle scattering (SANS) measurements revealed the transparent phases to consist of ellipsoidal nanodroplets of water. The morphology of these droplets was shown to be dependent on the pressure, Nohead FC6-HC4 concentration, and water-to-surfactant molar ratio. Despite having almost the same structure as Nohead FC6-HC4, analogues containing both shorter and longer hydrocarbons were unable to form W/CO 2 microemulsion droplets. This shows the importance of the role of the hydrocarbon chain in the stabilization of W/CO 2 microemulsions. A detailed examination of the mechanism of Nohead FC6-HC4 adsorption onto the water surface suggests that the hexanoyl group protrudes into the aqueous core, allowing for association between the carbonyl group and water.

Selection of inactivation medium for fungal spores in clinical wastes by supercritical carbon dioxide.

PubMed

Noman, Efaq; Norulaini Nik Ab Rahman, Nik; Al-Gheethi, Adel; Nagao, Hideyuki; Talip, Balkis A; Ab Kadir, Omar

2018-05-21

The present study aimed to select the best medium for inactivation of Aspergillus fumigatus, Aspergillus spp. in section Nigri, A. niger, A. terreus var. terreus, A. tubingensis, Penicillium waksmanii, P. simplicissimum, and Aspergillus sp. strain no. 145 spores in clinical wastes by using supercritical carbon dioxide (SC-CO 2 ). There were three types of solutions used including normal saline, seawater, distilled water, and physiological saline with 1% of methanol; each solution was tested at 5, 10, and 20 mL of the water contents. The experiments were conducted at the optimum operating parameters of supercritical carbon dioxide (30 MPa, 75 °C, 90 min). The results showed that the inactivation rate was more effective in distilled water with the presence of 1% methanol (6 log reductions). Meanwhile, the seawater decreases inactivation rate more than normal saline (4.5 vs. 5.1 log reduction). On the other hand, the experiments performed with different volumes of distilled water (5, 10, and 20 mL) indicated that A. niger spores were completely inactivated with 10 mL of distilled water. The inactivation rate of fungal spores decreased from 6 to 4.5 log as the amount of distilled water increased from 10 to 20 mL. The analysis for the spore morphology of A. fumigatus and Aspergillus spp. in section Nigri using scanning electron microscopy (SEM) has revealed the role of temperature and pressure in the SC-CO 2 in the destruction of the cell walls of the spores. It can be concluded that the distilled water represent the best medium for inactivation of fungal spores in the clinical solid wastes by SC-CO 2 .

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.

Experimental investigation of wall shock cancellation and reduction of wall interference in transonic testing

NASA Technical Reports Server (NTRS)

Ferri, A.; Roffe, G.

1975-01-01

A series of experiments were performed to evaluate the effectiveness of a three-dimensional land and groove wall geometry and a variable permeability distribution to reduce the interference produced by the porous walls of a supercritical transonic test section. The three-dimensional wall geometry was found to diffuse the pressure perturbations caused by small local mismatches in wall porosity permitting the use of a relatively coarse wall porosity control to reduce or eliminate wall interference effects. The wall porosity distribution required was found to be a sensitive function of Mach number requiring that the Mach number repeatability characteristics of the test apparatus be quite good. The effectiveness of a variable porosity wall is greatest in the upstream region of the test section where the pressure differences across the wall are largest. An effective variable porosity wall in the down stream region of the test section requires the use of a slightly convergent test section geometry.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong

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 formore » 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.« less

Supercritical water oxidation of dioxins and furans in waste incinerator fly ash, sewage sludge and industrial soil.

PubMed

Zainal, Safari; Onwudili, Jude A; Williams, Paul T

2014-08-01

Three environmental samples containing dioxins and furans have been oxidized in the presence of hydrogen peroxide under supercritical water oxidation conditions. The samples consisted of a waste incinerator fly ash, sewage sludge and contaminated industrial soil. The reactor system was a batch, autoclave reactor operated at temperatures between 350 degrees C and 450degrees C, corresponding to pressures of approximately 20-33.5 MPa and with hydrogen peroxide concentrations from 0.0 to 11.25 vol%. Hydrogen peroxide concentration and temperature/pressure had a strong positive effect on the oxidation of dioxins and furans. At the highest temperatures and pressure of supercritical water oxidation of 4500C and 33.5 MPa and with 11.25 vol% of hydrogen peroxide, the destruction efficiencies of the individual polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) isomers were between 90% and 99%. There did not appear to be any significant differences in the PCDD/PCDF destruction efficiencies in relation to the different sample matrices of the waste incinerator fly ash, sewage sludge and contaminated industrial soil.

Supercritical CO(2) fluid extraction of crystal water from trehalose dihydrate. Efficient production of form II (T(alpha)) phase.

PubMed

Akao, Ken-ichi; Okubo, Yusei; Inoue, Yoshio; Sakurai, Minoru

2002-10-11

Form II is a kind of metastable crystalline form of trehalose anhydrate, and it is easily converted to the dihydrate crystal by absorbing water in moist atmosphere at room temperature (Akao et al., Carbohydr. Res. 2001, 334, 233-241). It can be utilized as an edible and nontoxic desiccant, and thus its efficient production from the dihydrate is significant from a viewpoint of industrial applications. In this study, we attempt to extract crystal water from the dihydrate using supercritical CO(2). We examine the dependence of extraction efficiency on the extraction time, the temperature and pressure of the fluid. Then, FTIR measurements are carried out to detect the extracted water and to identify the polymorphic phase of the sugar sample after the extraction treatment. In particular, the so-called first derivative euclidean distance analysis for IR spectra is shown to be quite useful for the structural identification. Consequently, we demonstrate that form II is produced from the dihydrate through supercritical CO(2) fluid extraction if appropriate temperature and pressure conditions (around 80 degrees C and 20 MPa) are maintained.

Supercritical Fuel Measurements

DTIC Science & Technology

2012-09-01

TERMS Fuels, supercritical fluids , stimulated scattering, Brillouin scattering, Rayleigh scattering, elastic properties, thermal properties 16...10 Supercritical Cell and Fluid Handling ....................................................................................... 11...motion in supercritical fluids . Thus, the method can perform diagnostics on the heat transfer of high-temperature and high-pressure fuels, measuring

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

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

PubMed

Jo, Yeon-Ji; Kim, Jae-Hyeong; Jung, Kyung-Hun; Min, Sang-Gi; Chun, Ji-Yeon

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.

Green Walls as an Approach in Grey Water Treatment

NASA Astrophysics Data System (ADS)

Rysulova, Martina; Kaposztasova, Daniela; Vranayova, Zuzana

2017-10-01

Grey water contributes significantly to waste water parameters such as biochemical oxygen demand (BOD), chemical oxygen demand (COD), total suspended solids (TSS), total phosphorus (Ptotal), total nitrogen (Ntotal), ammonium, boron, metals, salts, surfactants, synthetic chemicals, oils and greases, xenobiotic substances and microorganisms. Concentration of these pollutants and the water quality highlights the importance of treatment process in grey water systems. Treatment technologies operating under low energy and maintenance are usually preferred, since they are more cost effective for users. Treatment technologies based on natural processes represent an example of such technology including vegetated wall. Main aim of this paper is to introduce the proposal of vegetated wall managing grey water and brief characteristic of proposed system. Is expected that prepared experiment will establish the purifying ability and the potential of green wall application as an efficient treatment technology.

Hot and cold water as a supercritical solvent

NASA Astrophysics Data System (ADS)

Fuentevilla, Daphne Anne

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

Study of Variable Turbulent Prandtl Number Model for Heat Transfer to Supercritical Fluids in Vertical Tubes

NASA Astrophysics Data System (ADS)

Tian, Ran; Dai, Xiaoye; Wang, Dabiao; Shi, Lin

2018-06-01

In order to improve the prediction performance of the numerical simulations for heat transfer of supercritical pressure fluids, a variable turbulent Prandtl number (Prt) model for vertical upward flow at supercritical pressures was developed in this study. The effects of Prt on the numerical simulation were analyzed, especially for the heat transfer deterioration conditions. Based on the analyses, the turbulent Prandtl number was modeled as a function of the turbulent viscosity ratio and molecular Prandtl number. The model was evaluated using experimental heat transfer data of CO2, water and Freon. The wall temperatures, including the heat transfer deterioration cases, were more accurately predicted by this model than by traditional numerical calculations with a constant Prt. By analyzing the predicted results with and without the variable Prt model, it was found that the predicted velocity distribution and turbulent mixing characteristics with the variable Prt model are quite different from that predicted by a constant Prt. When heat transfer deterioration occurs, the radial velocity profile deviates from the log-law profile and the restrained turbulent mixing then leads to the deteriorated heat transfer.

Dehydrating and Sterilizing Wastes Using Supercritical CO2

NASA Technical Reports Server (NTRS)

Brown, Ian J.

2006-01-01

A relatively low-temperature process for dehydrating and sterilizing biohazardous wastes in an enclosed life-support system exploits (1) the superior mass-transport properties of supercritical fluids in general and (2) the demonstrated sterilizing property of supercritical CO2 in particular. The wastes to be treated are placed in a chamber. Liquid CO2, drawn from storage at a pressure of 850 psi (approx.=5.9 MPa) and temperature of 0 C, is compressed to pressure of 2 kpsi (approx.=14 MPa) and made to flow into the chamber. The compression raises the temperature to 10 C. The chamber and its contents are then further heated to 40 C, putting the CO2 into a supercritical state, in which it kills microorganisms in the chamber. Carrying dissolved water, the CO2 leaves the chamber through a back-pressure regulator, through which it is expanded back to the storage pressure. The expanded CO2 is refrigerated to extract the dissolved water as ice, and is then returned to the storage tank at 0 C

[Supercritical and near-critical fluid solvents assisted reaction and separation processes].

PubMed

Song, R; Zeng, J; Zhong, B

2001-11-01

The tunability of supercritical and near-critical fluid (S/NCF) solvents offers environmental improvements and economic advantages from improved performances and flexibility for separation and reaction processes through density changes or cosolvents. The paper reviews the sustainable reaction and separation processes in S/NCF solvents such as supercritical carbon dioxide and near-critical water.

Liposomes Size Engineering by Combination of Ethanol Injection and Supercritical Processing.

PubMed

Santo, Islane Espirito; Campardelli, Roberta; Albuquerque, Elaine Cabral; Vieira De Melo, Silvio A B; Reverchon, Ernesto; Della Porta, Giovanna

2015-11-01

Supercritical fluid extraction using a high-pressure packed tower is proposed not only to remove the ethanol residue from liposome suspensions but also to affect their size and distribution leading the production of nanosomes. Different operating pressures, temperatures, and gas to liquid ratios were explored and ethanol was successfully extracted up to a value of 400 ppm; liposome size and distribution were also reduced by the supercritical processing preserving their integrity, as confirmed by Z-potential data and Trasmission Electron Microscopy observations. Operating at 120 bar and 38°C, nanosomes with a mean diameter of about 180 ± 40 nm and good storage stability were obtained. The supercritical processing did not interfere on drug encapsulation, and no loss of entrapped drug was observed when the water-soluble fluorescein was loaded as a model compound. Fluorescein encapsulation efficiency was 30% if pure water was used during the supercritical extraction as processing fluid; whereas an encapsulation efficiency of 90% was obtained if the liposome suspension was processed in water/fluorescein solution. The described technology is easy to scale up to an industrial production and merge in one step the solvent extraction, liposome size engineering, and an excellent drug encapsulation in a single operation unit. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

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

PubMed

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

2012-01-01

Xanthophylls, including zeaxanthin, are considered dietary supplements with a potentially positive impact on age-related macular degeneration. Using pilot-scale column fractionation coupled with supercritical anti-solvent (SAS) recrystallization, highly pure zeaxanthin particulates were prepared from ultrasonic extracts of the microalgae, Nannochloropsis oculata, grown in sea water. Column partition chromatography increased the concentration of zeaxanthin from 36.2 mg/g of the ultrasonic extracts to 425.6 mg/g of the collected column fractions. A response surface methodology was systematically designed for the SAS process by changing feed concentration, CO(2) flow rate and anti-solvent pressure. Zeaxanthin-rich particles with a purity of 84.2% and a recovery of 85.3% were produced using supercritical anti-solvent recrystallization from the column eluate at a feed concentration of 1.5 mg/mL, CO(2) flow rate of 48.6 g/min and pressure of 135 bar. Copyright © 2011 Elsevier Ltd. All rights reserved.

Supercritical Fuel Pyrolysis

DTIC Science & Technology

2010-05-30

supercritical fluids . These temperatures and pressures will also cause the fuel to undergo pyrolytic reactions, which have the potential of forming...With regard to physical properties, supercritical fluids have highly variable densities, no surface tension, and transport properties (i.e., mass...effects in supercritical fluids , often affecting chemical reaction pathways by facilitating the formation of certain transition states [6]. Because

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.

Supercritical water oxidation for the destruction of toxic organic wastewaters: a review.

PubMed

Veriansyah, Bambang; Kim, Jae-Duck

2007-01-01

The destruction of toxic organic wastewaters from munitions demilitarization and complex industrial chemical clearly becomes an overwhelming problem if left to conventional treatment processes. Two options, incineration and supercritical water oxidation (SCWO), exist for the complete destruction of toxic organic wastewaters. Incinerator has associated problems such as very high cost and public resentment; on the other hand, SCWO has proved to be a very promising method for the treatment of many different wastewaters with extremely efficient organic waste destruction 99.99% with none of the emissions associated with incineration. In this review, the concepts of SCWO, result and present perspectives of application, and industrial status of SCWO are critically examined and discussed.

Corrosion and stress corrosion cracking in supercritical water

NASA Astrophysics Data System (ADS)

Was, G. S.; Ampornrat, P.; Gupta, G.; Teysseyre, S.; West, E. A.; Allen, T. R.; Sridharan, K.; Tan, L.; Chen, Y.; Ren, X.; Pister, C.

2007-09-01

Supercritical water (SCW) has attracted increasing attention since SCW boiler power plants were implemented to increase the efficiency of fossil-based power plants. The SCW reactor (SCWR) design has been selected as one of the Generation IV reactor concepts because of its higher thermal efficiency and plant simplification as compared to current light water reactors (LWRs). Reactor operating conditions call for a core coolant temperature between 280 °C and 620 °C at a pressure of 25 MPa and maximum expected neutron damage levels to any replaceable or permanent core component of 15 dpa (thermal reactor design) and 100 dpa (fast reactor design). Irradiation-induced changes in microstructure (swelling, radiation-induced segregation (RIS), hardening, phase stability) and mechanical properties (strength, thermal and irradiation-induced creep, fatigue) are also major concerns. Throughout the core, corrosion, stress corrosion cracking, and the effect of irradiation on these degradation modes are critical issues. This paper reviews the current understanding of the response of candidate materials for SCWR systems, focusing on the corrosion and stress corrosion cracking response, and highlights the design trade-offs associated with certain alloy systems. Ferritic-martensitic steels generally have the best resistance to stress corrosion cracking, but suffer from the worst oxidation. Austenitic stainless steels and Ni-base alloys have better oxidation resistance but are more susceptible to stress corrosion cracking. The promise of grain boundary engineering and surface modification in addressing corrosion and stress corrosion cracking performance is discussed.

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.

Supercritical Fuel Pyrolysis

DTIC Science & Technology

2007-05-28

be supercritical fluids . These temperatures and pressures will also cause the fuel to undergo pyrolytic reactions, which have the potential of forming...physical properties, supercritical fluids have highly variable densities, no surface tension, and transport properties (i.e., mass, energy, and momentum...are very dependent on pressure, chemical reaction rates in supercritical fluids can be highly pressure-dependent [6-9]. The kinetic reaction rate

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.

Impregnation of Fenofibrate on mesoporous silica using supercritical carbon dioxide.

PubMed

Bouledjouidja, Abir; Masmoudi, Yasmine; Van Speybroeck, Michiel; Schueller, Laurent; Badens, Elisabeth

2016-02-29

Low oral bioavailability can be circumvented by the formulation of the poorly water soluble drug in ordered mesoporous silica (OMS-L-7). Fenofibrate is an orally administered, poorly water-soluble active pharmaceutical ingredient (API), used clinically to lower lipid levels. Fenofibrate was loaded into silica using two methods: incipient wetness and supercritical impregnation. This study investigates the impact of loading and the impact of varying supercritical carbon dioxide (scCO2) processing conditions. The objective is to enhance Fenofibrate loading into silica while reducing degree of the drug crystallinity, so as to increase the drug's dissolution rate and its bioavailability. The comparison of both impregnation processes was made in terms of impregnation yields and duration as well as physical characterization of the drug. While incipient wetness method led to a Fenofibrate loading up to 300 mgdrug/gsilica in 48 h of impregnation, the supercritical impregnation method yielded loading up to 485 mgdrug/gsilica in 120 min of impregnation duration, at 16 MPa and 308 K, with a low degree of crystallinity (about 1%) comparable to the crystallinity observed via the solvent method. In addition to the enhancement of impregnation efficiency, the supercritical route provides a solvent-free alternative for impregnation. Copyright © 2015 Elsevier B.V. All rights reserved.

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".

Co-detoxification of transformer oil-contained PCBs and heavy metals in medical waste incinerator fly ash under sub- and supercritical water.

PubMed

Wang, Chunfeng; Zhu, Nengmin; Wang, Yanmin; Zhang, Fushen

2012-01-17

The simultaneous detoxification processes of transformer oil-contained PCBs and heavy metals in medical waste incinerator (MWI) fly ash were developed under sub- and supercritical water. The addition of MWI fly ash to transformer oil-contained PCBs was found to increase the destruction efficiency of PCBs, at the same time, it facilitated reducing the leaching concentration of toxic metals from residues (obtained after reaction) for harmless disposal. In this study, we elucidated primarily the catalysis possibility of heavy metals in raw MWI fly ash for PCBs degradation by adopting the sequential extraction procedure. For both MWI fly ashes, more than 90% destruction efficiency of PCBs was achieved at ≥375 °C for 30 min, and trichlorobenzene (TCB) existing in the transformer oil was also completely decomposed. The correlation of catalytic performance to PCBs degradation was discussed based on structural characteristics and dechlorinated products. Likewise, such process rendered residues innocuous through supercritical water treatment for reuse or disposal in landfill.

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

PubMed

Kamarei, Fahimeh; Vajda, Péter; Guiochon, Georges

2013-09-20

This paper compares two methods used for the preparative purification of a mixture of (S)-, and (R)-naproxen on a Whelk-O1 column, using either high performance liquid chromatography or supercritical fluid chromatography. The adsorption properties of both enantiomers were measured by frontal analysis, using methanol-water and methanol-supercritical carbon dioxide mixtures as the mobile phases. The measured adsorption data were modeled, providing the adsorption isotherms and their parameters, which were derived from the nonlinear fit of the isotherm models to the experimental data points. The model used was a Bi-Langmuir isotherm, similar to the model used in many enantiomeric separations. These isotherms were used to calculate the elution profiles of overloaded elution bands, assuming competitive Bi-Langmuir behavior of the two enantiomers. The analysis of these profiles provides the basis for a comparison between supercritical fluid chromatographic and high performance liquid chromatographic preparative scale separations. It permits an illustration of the advantages and disadvantages of these methods and a discussion of their potential performance. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

2000-01-01

This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

Wollastonite Carbonation in Water-Bearing Supercritical CO2: Effects of Particle Size.

PubMed

Min, Yujia; Li, Qingyun; Voltolini, Marco; Kneafsey, Timothy; Jun, Young-Shin

2017-11-07

The performance of geologic CO 2 sequestration (GCS) can be affected by CO 2 mineralization and changes in the permeability of geologic formations resulting from interactions between water-bearing supercritical CO 2 (scCO 2 ) and silicates in reservoir rocks. However, without an understanding of the size effects, the findings in previous studies using nanometer- or micrometer-size particles cannot be applied to the bulk rock in field sites. In this study, we report the effects of particle sizes on the carbonation of wollastonite (CaSiO 3 ) at 60 °C and 100 bar in water-bearing scCO 2 . After normalization by the surface area, the thickness of the reacted wollastonite layer on the surfaces was independent of particle sizes. After 20 h, the reaction was not controlled by the kinetics of surface reactions but by the diffusion of water-bearing scCO 2 across the product layer on wollastonite surfaces. Among the products of reaction, amorphous silica, rather than calcite, covered the wollastonite surface and acted as a diffusion barrier to water-bearing scCO 2 . The product layer was not highly porous, with a specific surface area 10 times smaller than that of the altered amorphous silica formed at the wollastonite surface in aqueous solution. These findings can help us evaluate the impacts of mineral carbonation in water-bearing scCO 2 .

Primordial black hole and wormhole formation by domain walls

NASA Astrophysics Data System (ADS)

Deng, Heling; Garriga, Jaume; Vilenkin, Alexander

2017-04-01

In theories with a broken discrete symmetry, Hubble sized spherical domain walls may spontaneously nucleate during inflation. These objects are subsequently stretched by the inflationary expansion, resulting in a broad distribution of sizes. The fate of the walls after inflation depends on their radius. Walls smaller than a critical radius fall within the cosmological horizon early on and collapse due to their own tension, forming ordinary black holes. But if a wall is large enough, its repulsive gravitational field becomes dominant much before the wall can fall within the cosmological horizon. In this ``supercritical'' case, a wormhole throat develops, connecting the ambient exterior FRW universe with an interior baby universe, where the exponential growth of the wall radius takes place. The wormhole pinches off in a time-scale comparable to its light-crossing time, and black holes are formed at its two mouths. As discussed in previous work, the resulting black hole population has a wide distribution of masses and can have significant astrophysical effects. The mechanism of black hole formation has been previously studied for a dust-dominated universe. Here we investigate the case of a radiation-dominated universe, which is more relevant cosmologically, by using numerical simulations in order to find the initial mass of a black hole as a function of the wall size at the end of inflation. For large supercritical domain walls, this mass nearly saturates the upper bound according to which the black hole cannot be larger than the cosmological horizon. We also find that the subsequent accretion of radiation satisfies a scaling relation, resulting in a mass increase by about a factor of 2.

Primordial black hole and wormhole formation by domain walls

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Heling; Garriga, Jaume; Vilenkin, Alexander, E-mail: heling.deng@tufts.edu, E-mail: garriga@cosmos.phy.tufts.edu, E-mail: vilenkin@cosmos.phy.tufts.edu

In theories with a broken discrete symmetry, Hubble sized spherical domain walls may spontaneously nucleate during inflation. These objects are subsequently stretched by the inflationary expansion, resulting in a broad distribution of sizes. The fate of the walls after inflation depends on their radius. Walls smaller than a critical radius fall within the cosmological horizon early on and collapse due to their own tension, forming ordinary black holes. But if a wall is large enough, its repulsive gravitational field becomes dominant much before the wall can fall within the cosmological horizon. In this ''supercritical'' case, a wormhole throat develops, connectingmore » the ambient exterior FRW universe with an interior baby universe, where the exponential growth of the wall radius takes place. The wormhole pinches off in a time-scale comparable to its light-crossing time, and black holes are formed at its two mouths. As discussed in previous work, the resulting black hole population has a wide distribution of masses and can have significant astrophysical effects. The mechanism of black hole formation has been previously studied for a dust-dominated universe. Here we investigate the case of a radiation-dominated universe, which is more relevant cosmologically, by using numerical simulations in order to find the initial mass of a black hole as a function of the wall size at the end of inflation. For large supercritical domain walls, this mass nearly saturates the upper bound according to which the black hole cannot be larger than the cosmological horizon. We also find that the subsequent accretion of radiation satisfies a scaling relation, resulting in a mass increase by about a factor of 2.« less

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

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

NASA Astrophysics Data System (ADS)

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

2009-10-01

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

Advanced Supercritical Carbon Dioxide Brayton Cycle Development

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Mark; Sienicki, James; Moisseytsev, Anton

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 CO 2 (S-CO 2)more » 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-CO 2 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-through labyrinth seals was

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.

Study on influence of three kinds of stress on crack propagation in butt welds of spiral coil waterwall for ultra supercritical boiler

NASA Astrophysics Data System (ADS)

Yan, Zhenrong; Si, Jun

2017-09-01

The spiral coil waterwall is the main pressure parts and the core functional components of Ultra Supercritical Boiler. In the process of operation, the spiral coil waterwall is under the combined action of welding residual stress, installation defects stress and working fluid stress, Cracks and crack propagation are easy to occur in butt welds with defects. In view of the early cracks in the butt welds of more T23 water cooled walls, in this paper, the influence of various stresses on the crack propagation in the butt welds of spiral coil waterwall was studied by numerical simulation. Firstly, the welding process of T23 water cooled wall tube was simulated, and the welding residual stress field was obtained. Then,on the basis, put the working medium load on the spiral coil waterwall, the supercoated stress distribution of the welding residual stress and the stress of the working medium is obtained. Considering the bending moment formed by stagger joint which is the most common installation defects, the stress field distribution of butt welds in T23 water-cooled wall tubes was obtained by applying bending moment on the basis of the stress field of the welding residual stress and the working medium stress. The results show that, the welding residual stress is small, the effect of T23 heat treatment after welding to improve the weld quality is not obvious; The working medium load plays a great role in the hoop stress of the water cooled wall tube, and promotes the cracks in the butt welds; The axial stress on the water cooled wall tube produced by the installation defect stress is obvious, the stagger joint, and other installation defects are the main reason of crack propagation of spiral coil waterwall. It is recommended that the control the bending moment resulting from the stagger joint not exceed 756.5 NM.

A numerical solution of the Navier-Stokes equations for supercritical fluid thermodynamic analysis

NASA Technical Reports Server (NTRS)

Heinmiller, P. J.

1971-01-01

An explicit numerical solution of the compressible Navier-Stokes equations is applied to the thermodynamic analysis of supercritical oxygen in the Apollo cryogenic storage system. The wave character is retained in the conservation equations which are written in the basic fluid variables for a two-dimensional Cartesian coordinate system. Control-volume cells are employed to simplify imposition of boundary conditions and to ensure strict observance of local and global conservation principles. Non-linear real-gas thermodynamic properties responsible for the pressure collapse phenomonon in supercritical fluids are represented by tabular and empirical functions relating pressure and temperature to density and internal energy. Wall boundary conditions are adjusted at one cell face to emit a prescribed mass flowrate. Scaling principles are invoked to achieve acceptable computer execution times for very low Mach number convection problems. Detailed simulations of thermal stratification and fluid mixing occurring under low acceleration in the Apollo 12 supercritical oxygen tank are presented which model the pressure decay associated with de-stratification induced by an ordinary vehicle maneuver and heater cycle operation.

Supercritical Carbon Dioxide and Its Potential as a Life-Sustaining Solvent in a Planetary Environment

PubMed Central

Budisa, Nediljko; Schulze-Makuch, Dirk

2014-01-01

Supercritical fluids have different properties compared to regular fluids and could play a role as life-sustaining solvents on other worlds. Even on Earth, some bacterial species have been shown to be tolerant to supercritical fluids. The special properties of supercritical fluids, which include various types of selectivities (e.g., stereo-, regio-, and chemo-selectivity) have recently been recognized in biotechnology and used to catalyze reactions that do not occur in water. One suitable example is enzymes when they are exposed to supercritical fluids such as supercritical carbon dioxide: enzymes become even more stable, because they are conformationally rigid in the dehydrated state. Furthermore, enzymes in anhydrous organic solvents exhibit a “molecular memory”, i.e., the capacity to “remember” a conformational or pH state from being exposed to a previous solvent. Planetary environments with supercritical fluids, particularly supercritical carbon dioxide, exist, even on Earth (below the ocean floor), on Venus, and likely on Super-Earth type exoplanets. These planetary environments may present a possible habitat for exotic life. PMID:25370376

Supercritical carbon dioxide and its potential as a life-sustaining solvent in a planetary environment.

PubMed

Budisa, Nediljko; Schulze-Makuch, Dirk

2014-08-08

Supercritical fluids have different properties compared to regular fluids and could play a role as life-sustaining solvents on other worlds. Even on Earth, some bacterial species have been shown to be tolerant to supercritical fluids. The special properties of supercritical fluids, which include various types of selectivities (e.g., stereo-, regio-, and chemo-selectivity) have recently been recognized in biotechnology and used to catalyze reactions that do not occur in water. One suitable example is enzymes when they are exposed to supercritical fluids such as supercritical carbon dioxide: enzymes become even more stable, because they are conformationally rigid in the dehydrated state. Furthermore, enzymes in anhydrous organic solvents exhibit a "molecular memory", i.e., the capacity to "remember" a conformational or pH state from being exposed to a previous solvent. Planetary environments with supercritical fluids, particularly supercritical carbon dioxide, exist, even on Earth (below the ocean floor), on Venus, and likely on Super-Earth type exoplanets. These planetary environments may present a possible habitat for exotic life.

Numerical design of streamlined tunnel walls for a two-dimensional transonic test

NASA Technical Reports Server (NTRS)

Newman, P. A.; Anderson, E. C.

1978-01-01

An analytical procedure is discussed for designing wall shapes for streamlined, nonporous, two-dimensional, transonic wind tunnels. It is based upon currently available 2-D inviscid transonic and boundary layer analysis computer programs. Predicted wall shapes are compared with experimental data obtained from the NASA Langley 6 by 19 inch Transonic Tunnel where the slotted walls were replaced by flexible nonporous walls. Comparisons are presented for the empty tunnel operating at a Mach number of 0.9 and for a supercritical test of an NACA 0012 airfoil at zero lift. Satisfactory agreement is obtained between the analytically and experimentally determined wall shapes.

Supercritical fluid processing of drug nanoparticles in stable suspension.

PubMed

Pathak, Pankaj; Meziani, Mohammed J; Desai, Tarang; Foster, Charles; Diaz, Julian A; Sun, Ya-Ping

2007-07-01

Significant effort has been directed toward the development of drug formulation and delivery techniques, especially for the drug of no or poor aqueous solubility. Among various strategies to address the solubility issue, the reduction of drug particle sizes to the nanoscale has been identified as a potentially effective and broadly applicable approach. Complementary to traditional methods, supercritical fluid techniques have found unique applications in the production and processing of drug particles. Here we report the application of a newly developed supercritical fluid processing technique, Rapid Expansion of a Supercritical Solution into a Liquid Solvent, to the nanosizing of potent antiparasitic drug Amphotericin B particles. A supercritical carbon dioxide-cosolvent system was used for the solubilization and processing of the drug. The process produced well-dispersed nanoscale Amphotericin B particles suspended in an aqueous solution, and the suspension was intrinsically stable or could be further stabilized in the presence of water-soluble polymers. The properties of the drug nanoparticles were found to be dependent on the type of cosolvent used. The results on the use of dimethyl sulfoxide and methanol as cosolvents and their effects on the properties of nanosized Amphotericin B particles are presented and discussed.

Preparing silica aerogel monoliths via a rapid supercritical extraction method.

PubMed

Carroll, Mary K; Anderson, Ann M; Gorka, Caroline A

2014-02-28

A procedure for the fabrication of monolithic silica aerogels in eight hours or less via a rapid supercritical extraction process is described. The procedure requires 15-20 min of preparation time, during which a liquid precursor mixture is prepared and poured into wells of a metal mold that is placed between the platens of a hydraulic hot press, followed by several hours of processing within the hot press. The precursor solution consists of a 1.0:12.0:3.6:3.5 x 10(-3) molar ratio of tetramethylorthosilicate (TMOS):methanol:water:ammonia. In each well of the mold, a porous silica sol-gel matrix forms. As the temperature of the mold and its contents is increased, the pressure within the mold rises. After the temperature/pressure conditions surpass the supercritical point for the solvent within the pores of the matrix (in this case, a methanol/water mixture), the supercritical fluid is released, and monolithic aerogel remains within the wells of the mold. With the mold used in this procedure, cylindrical monoliths of 2.2 cm diameter and 1.9 cm height are produced. Aerogels formed by this rapid method have comparable properties (low bulk and skeletal density, high surface area, mesoporous morphology) to those prepared by other methods that involve either additional reaction steps or solvent extractions (lengthier processes that generate more chemical waste).The rapid supercritical extraction method can also be applied to the fabrication of aerogels based on other precursor recipes.

Preparing Silica Aerogel Monoliths via a Rapid Supercritical Extraction Method

PubMed Central

Gorka, Caroline A.

2014-01-01

A procedure for the fabrication of monolithic silica aerogels in eight hours or less via a rapid supercritical extraction process is described. The procedure requires 15-20 min of preparation time, during which a liquid precursor mixture is prepared and poured into wells of a metal mold that is placed between the platens of a hydraulic hot press, followed by several hours of processing within the hot press. The precursor solution consists of a 1.0:12.0:3.6:3.5 x 10-3 molar ratio of tetramethylorthosilicate (TMOS):methanol:water:ammonia. In each well of the mold, a porous silica sol-gel matrix forms. As the temperature of the mold and its contents is increased, the pressure within the mold rises. After the temperature/pressure conditions surpass the supercritical point for the solvent within the pores of the matrix (in this case, a methanol/water mixture), the supercritical fluid is released, and monolithic aerogel remains within the wells of the mold. With the mold used in this procedure, cylindrical monoliths of 2.2 cm diameter and 1.9 cm height are produced. Aerogels formed by this rapid method have comparable properties (low bulk and skeletal density, high surface area, mesoporous morphology) to those prepared by other methods that involve either additional reaction steps or solvent extractions (lengthier processes that generate more chemical waste).The rapid supercritical extraction method can also be applied to the fabrication of aerogels based on other precursor recipes. PMID:24637334

Supercritical water oxidation of quinazoline: Reaction kinetics and modeling.

PubMed

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

2017-03-01

This paper presents a first quantitative kinetic model for supercritical water oxidation (SCWO) of quinazoline that describes the formation and interconversion of intermediates and final products at 673-873 K. The set of 11 reaction pathways for phenol, pyrimidine, naphthalene, NH 3 , etc, involved in the simplified reaction network proved sufficient for fitting the experimental results satisfactorily. We validated the model prediction ability on CO 2 yields at initial quinazoline loading not used in the parameter estimation. Reaction rate analysis and sensitivity analysis indicate that nearly all reactions reach their thermodynamic equilibrium within 300 s. The pyrimidine yielding from quinazoline is the dominant ring-opening pathway and provides a significant contribution to CO 2 formation. Low sensitivity of NH 3 decomposition rate to concentration confirms its refractory nature in SCWO. Nitrogen content in liquid products decreases whereas that in gaseous phase increases as reaction time prolonged. The nitrogen predicted by the model in gaseous phase combined with the experimental nitrogen in liquid products gives an accurate nitrogen balance of conversion process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Supercritical fluid attachment of palladium nanoparticles on aligned carbon nanotubes.

PubMed

Ye, Xiang-Rong; Lin, Yuehe; Wai, Chien M; Talbot, Jan B; Jin, Sungho

2005-06-01

Nanocomposite materials consisting of Pd nanoparticles deposited on aligned multi-walled carbon nanotubes have been fabricated through hydrogen reduction of palladium-beta-diketone precursor in supercritical carbon dioxide. The supercritical fluid processing allowed deposition of high-density Pd nanoparticles (approximately 5-10 nm) on both as-grown (unfunctionalized) and functionalized (using HNO3 oxidation) nanotubes. However, the wet processing for functionalization results in pre-agglomerated, bundle-shaped nanotubes, thus significantly reducing the effective surface area for Pd particle deposition, although the bundling provides more secure, lock-in-place positioning of nanotubes and Pd catalyst particles. The nanotube bundling is substantially mitigated by Pd nanoparticle deposition on the unfunctionalized and geometrically separated nanotubes, which provides much higher catalyst surface area. Such nanocomposite materials utilizing geometrically secured and aligned nanotubes can be useful for providing much enhanced catalytic activities to chemical and electrochemical reactions (e.g., fuel cell reactions), and eliminate the need for tedious catalyst recovery process after the reaction is completed.

Supercritical water gasification of sewage sludge: gas production and phosphorus recovery.

PubMed

Acelas, Nancy Y; López, Diana P; Brilman, D W F Wim; Kersten, Sascha R A; Kootstra, A Maarten J

2014-12-01

In this study, the feasibility of the gasification of dewatered sewage sludge in supercritical water (SCW) for energy recovery combined with P-recovery from the solid residue generated in this process was investigated. SCWG temperature (400°C, 500°C, 600°C) and residence time (15min, 30min, 60min) were varied to investigate their effects on gas production and the P recovery by acid leaching. The results show that the dry gas composition for this uncatalyzed gasification of sewage sludge in SCW mainly comprised of CO2, CO, CH4, H2, and some C2-C3 compounds. Higher temperatures and longer residence times favored the production of H2 and CH4. After SCWG, more than 95% of the P could be recovered from the solid residue by leaching with acids. SCWG combined with acid leaching seems an effective method for both energy recovery and high P recovery from sewage sludge. Copyright © 2014 Elsevier Ltd. All rights reserved.

Supercritical Fluid Fractionation of JP-8

DTIC Science & Technology

1991-12-26

applications, such as coffee decaffeination , spice extraction, and lipids purification. The processing principles have also long been well known and ipracticed...PRINCIPLES OF SUPERCRITICAL FLUID EXTRACTION 8 A. Background on Supercritical Fluid Solubility 8 B. Supercritical Fluid Extraction Process ...Operation I0 1. Batch Extraction of Solid Materials 10 2. Counter-Current Continuous SCF Processing of Liquid 15 Products 3. Supercritical Fluid Extraction vs

Fluorescent single walled nanotube/silica composite materials

DOEpatents

Dattelbaum, Andrew M.; Gupta, Gautam; Duque, Juan G.; Doorn, Stephen K.; Hamilton, Christopher E.; DeFriend Obrey, Kimberly A.

2013-03-12

Fluorescent composites of surfactant-wrapped single-walled carbon nanotubes (SWNTs) were prepared by exposing suspensions of surfactant-wrapped carbon nanotubes to tetramethylorthosilicate (TMOS) vapor. Sodium deoxycholate (DOC) and sodium dodecylsulphate (SDS) were the surfactants. No loss in emission intensity was observed when the suspension of DOC-wrapped SWNTs were exposed to the TMOS vapors, but about a 50% decrease in the emission signal was observed from the SDS-wrapped SWNTs nanotubes. The decrease in emission was minimal by buffering the SDS/SWNT suspension prior to forming the composite. Fluorescent xerogels were prepared by adding glycerol to the SWNT suspensions prior to TMOS vapor exposure, followed by drying the gels. Fluorescent aerogels were prepared by replacing water in the gels with methanol and then exposing them to supercritical fluid drying conditions. The aerogels can be used for gas sensing.

Determination of Organic Partitioning Coefficients in Water-Supercritical CO 2 Systems by Simultaneous in Situ UV and Near-Infrared Spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bryce, David A.; Shao, Hongbo; Cantrell, Kirk J.

2016-06-07

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 switchingmore » 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.« less

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

2016-06-07

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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, andmore » models for process design and optimization.« less

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

USDA-ARS?s Scientific Manuscript database

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...

The effect of the rigidity of perfluoropolyether surfactant on its behavior at the water/supercritical carbon dioxide interface.

PubMed

Lu, Lanyuan; Berkowitz, Max L

2005-11-24

We performed a series of molecular dynamics simulations to study the PFPE (perfluoropolyether) and PE (polyether) surfactant monolayers at the water/supercritical carbon dioxide interface. Molecular differences between fluorocarbon surfactant PFPE and its hydrocarbon analogue PE were analyzed. We observed that values of intramolecular bonded interaction parameters which are related to chain rigidity determine the monolayer surface pressure. We show that "good" and "bad" properties of PFPE/PE surfactants are connected to conformational entropy. These results are consistent with our previous micellar simulations.

Subaqueous ice-contact fans: Depositional systems characterised by highly aggradational supercritical flow conditions

NASA Astrophysics Data System (ADS)

Lang, Joerg; Winsemann, Jutta

2015-04-01

Subaqueous ice-contact fans are deposited by high-energy plane-wall jets from subglacial conduits into standing water bodies. Highly aggradational conditions during flow expansion and deceleration allow for the preservation of bedforms related to supercritical flows, which are commonly considered rare in the depositional record. We present field examples from gravelly and sandy subaqueous ice-contact fan successions, which indicate that deposition by supercritical flows might be considered as a characteristic feature of these depositional systems. The studied successions were deposited in deep ice-dammed lakes, which formed along the margins of the Middle Pleistocene Scandinavian ice sheets across Northern Germany. The gravel-rich subaqueous fan deposits are dominated by large scour-fills (up to 25 m wide and 3 m) deep and deposits of turbulent hyperconcentrated flows, which are partly attributed to supercritical flow conditions (Winsemann et al., 2009). Scours (up to 4.5 m wide and 0.9 m deep) infilled by gravelly backsets are observed above laterally extensive erosional surfaces and are interpreted as deposits of cyclic steps. Laterally discontinuous beds of low-angle cross-stratified gravel are interpreted as antidune deposits. Downflow and up-section the gravel-rich deposits pass into sand-rich successions, which include deposits of chutes-and-pools, breaking antidunes, stationary antidunes and humpback dunes (Lang and Winsemann, 2013). Deposits of chutes-and-pools and breaking antidunes are characterised by scour-fills (up to 4 m wide and 1.2 m deep) comprising backsets or gently dipping sigmoidal foresets. Stationary antidune deposits consist of laterally extensive sinusoidal waveforms with long wavelengths (1-12 m) and low amplitudes (0.1-0.5 m), which formed under quasi-steady flows at the lower limit of the supercritical flow stage and high rates of sedimentation. Humpback dunes are characterised by divergent sigmoidal foresets and are interpreted as

An experimental investigation of the subcritical and supercritical flow about a swept semispan wing

NASA Technical Reports Server (NTRS)

Lockman, W. K.; Seegmiller, H. L.

1983-01-01

An experimental investigation of the turbulent, subcritical and supercritical flow over a swept, semispan wing in a solid wall wind tunnel is described. The program was conducted over a range of Mach numbers, Reynolds numbers, and angles of attack to provide a variety of test cases for assessment of wing computer codes and tunnel wall interference effects. Wing flows both without and with three dimensional flow separation are included. Data include mean surface pressures for both the wing and tunnel walls; surface oil flow patterns on the wing; and mean velocity, flow field surveys. The results are given in tabular form and presented graphically to illustrate some of the effects of the test parameters. Comparisons of the wing pressure data with the results from two inviscid wing codes are also shown to assess the importance of viscous flow and tunnel wall effects.

Simulation of one-sided heating of boiler unit membrane-type water walls

NASA Astrophysics Data System (ADS)

Kurepin, M. P.; Serbinovskiy, M. Yu.

2017-03-01

This study describes the results of simulation of the temperature field and the stress-strain state of membrane-type gastight water walls of boiler units using the finite element method. The methods of analytical and standard calculation of one-sided heating of fin-tube water walls by a radiative heat flux are analyzed. The methods and software for input data calculation in the finite-element simulation, including thermoelastic moments in welded panels that result from their one-sided heating, are proposed. The method and software modules are used for water wall simulation using ANSYS. The results of simulation of the temperature field, stress field, deformations and displacement of the membrane-type panel for the boiler furnace water wall using the finite-element method, as well as the results of calculation of the panel tube temperature, stresses and deformations using the known methods, are presented. The comparison of the known experimental results on heating and bending by given moments of membrane-type water walls and numerical simulations is performed. It is demonstrated that numerical results agree with high accuracy with the experimental data. The relative temperature difference does not exceed 1%. The relative difference of the experimental fin mutual turning angle caused by one-sided heating by radiative heat flux and the results obtained in the finite element simulation does not exceed 8.5% for nondisplaced fins and 7% for fins with displacement. The same difference for the theoretical results and the simulation using the finite-element method does not exceed 3% and 7.1%, respectively. The proposed method and software modules for simulation of the temperature field and stress-strain state of the water walls are verified and the feasibility of their application in practical design is proven.

Combined Extraction Processes of Lipid from Chlorella vulgaris Microalgae: Microwave Prior to Supercritical Carbon Dioxide Extraction

PubMed Central

Dejoye, Céline; Vian, Maryline Abert; Lumia, Guy; Bouscarle, Christian; Charton, Frederic; Chemat, Farid

2011-01-01

Extraction yields and fatty acid profiles from freeze-dried Chlorella vulgaris by microwave pretreatment followed by supercritical carbon dioxide (MW-SCCO2) extraction were compared with those obtained by supercritical carbon dioxide extraction alone (SCCO2). Work performed with pressure range of 20–28 Mpa and temperature interval of 40–70 °C, gave the highest extraction yield (w/w dry weight) at 28 MPa/40 °C. MW-SCCO2 allowed to obtain the highest extraction yield (4.73%) compared to SCCO2 extraction alone (1.81%). Qualitative and quantitative analyses of microalgae oil showed that palmitic, oleic, linoleic and α-linolenic acid were the most abundant identified fatty acids. Oils obtained by MW-SCCO2 extraction had the highest concentrations of fatty acids compared to SCCO2 extraction without pretreatment. Native form, and microwave pretreated and untreated microalgae were observed by scanning electronic microscopy (SEM). SEM micrographs of pretreated microalgae present tearing wall agglomerates. After SCCO2, microwave pretreated microalgae presented several micro cracks; while native form microalgae wall was slightly damaged. PMID:22272135

CHARACTERIZING PIPE WALL DEMAND: IMPLICATIONS FOR WATER QUALITY MODELING

EPA Science Inventory

It has become generally accepted that water quality can deteriorate in a distribution system through reactions in the bulk phase and/or at the pipe wall. These reactions may be physical, chemical or microbiological in nature. Perhaps one of the most serious aspects of water qua...

Supercritical Carbon Dioxide Regeneration of Activated Carbon Loaded with Contaminants from Rocky Mountain Arsenal Well Water.

DTIC Science & Technology

1982-05-01

PROCESSING COST OF ACTIVATED CHARCOAL REGENERATION BY SUPERCRITICAL CARBON DIOXIDE PROCESS ........................... 25 l IV-4 SENSITIVITY OF GAC...PROCESSING COSTS TO GAC WORKING CAPACITY ................................. 27 IV-5 ESTIMATED PROCESSING COST OF ACTIVATED CHARCOAL REGENERATION BY THERMAL...34 VI-2 COMPARISON OF THREE GRANULAR ACTIVATED CARBONS - SUPERCRITICAL CO2 REACTIVATION - GRANULAR CARBON ISOTHERMS - PHASE I RAW DATA

Bedforms formed by experimental supercritical density flows

NASA Astrophysics Data System (ADS)

Naruse, Hajime; Izumi, Norihiro; Yokokawa, Miwa; Muto, Tetsuji

2014-05-01

This study reveals characteristics and formative conditions of bedforms produced by saline density flows in supercritical flow conditions, especially focusing on the mechanism of the formation of plane bed. The motion of sediment particles forming bedforms was resolved by high-speed cameras (1/1000 frame/seconds). Experimental density flows were produced by mixtures of salt water (1.01-1.04 in density) and plastic particles (1.5 in specific density, 140 or 240 mm in diameter). Salt water and plastic particles are analogue materials of muddy water and sand particles in turbidity currents respectively. Acrylic flume (4.0 m long, 2.0 cm wide and 0.5 m deep) was submerged in an experimental tank (6.0 m long, 1.8 m wide and 1.2 m deep) that was filled by clear water. Features of bedforms were observed when the bed state in the flume reached equilibrium condition. The experimental conditions range 1.5-4.2 in densimetric Froude number and 0.2-0.8 in Shields dimensionless stress. We report the two major discoveries as a result of the flume experiments: (1) Plane bed under Froude-supercritical flows and (2) Geometrical characteristics of cyclic steps formed by density flows. (1) Plane bed was formed under the condition of supercritical flow regime. In previous studies, plane bed has been known to be formed by subcritical unidirectional flows (ca. 0.8 in Froude number). However, this study implies that plane bed can also be formed by supercritical conditions with high Shields dimensionless stress (>0.4) and very high Froude number (> 4.0). This discovery may suggest that previous estimations of paleo-hydraulic conditions of parallel lamination in turbidites should be reconsidered. The previous experimental studies and data from high-speed camera suggest that the region of plane bed formation coincides with the region of the sheet flow developments. The particle transport in sheet flow (thick bedload layer) induces transform of profile of flow shear stress, which may be

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

Design and study of water supply system for supercritical unit boiler in thermal power station

NASA Astrophysics Data System (ADS)

Du, Zenghui

2018-04-01

In order to design and optimize the boiler feed water system of supercritical unit, the establishment of a highly accurate controlled object model and its dynamic characteristics are prerequisites for developing a perfect thermal control system. In this paper, the method of mechanism modeling often leads to large systematic errors. Aiming at the information contained in the historical operation data of the boiler typical thermal system, the modern intelligent identification method to establish a high-precision quantitative model is used. This method avoids the difficulties caused by the disturbance experiment modeling for the actual system in the field, and provides a strong reference for the design and optimization of the thermal automation control system in the thermal power plant.

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

Water Walls for Life Support

NASA Technical Reports Server (NTRS)

Hammoudeh, Mona (Inventor); Flynn, Michael T. (Inventor); Gormly, Sherwin J. (Inventor); Richardson, Tra-My Justine (Inventor)

2017-01-01

A method and associated system for processing waste gases, liquids and solids, produced by human activity, to separate (i) liquids suitable for processing to produce potable water, (ii) solids and liquids suitable for construction of walls suitable for enclosing a habitat volume and for radiation shielding, and (iii) other fluids and solids that are not suitable for processing. A forward osmosis process and a reverse osmosis process are sequentially combined to reduce fouling and to permit accumulation of different processable substances. The invention may be used for long term life support of human activity.

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

PubMed

Fiori, Luca; Valbusa, Michele; Castello, Daniele

2012-10-01

The supercritical water gasification (SCWG) of biomass for H(2) production is analyzed in terms of process development and energetic self-sustainability. The conceptual design of a plant is proposed and the SCWG process involving several substrates (glycerol, microalgae, sewage sludge, grape marc, phenol) is simulated by means of AspenPlus™. The influence of various parameters - biomass concentration and typology, reaction pressure and temperature - is analyzed. The process accounts for the possibility of exploiting the mechanical energy of compressed syngas (later burned to sustain the SCWG reaction) through expansion in turbines, while purified H(2) is fed to fuel cells. Results show that the SCWG reaction can be energetically self-sustained if minimum feed biomass concentrations of 15-25% are adopted. Interestingly, the H(2) yields are found to be maximal at similar feed concentrations. Finally, an energy balance is performed showing that the whole process could provide a net power of about 150 kW(e)/(1000 kg(feed)/h). Copyright © 2012 Elsevier Ltd. All rights reserved.

FLOW SEPARATION CONDITIONS AT PIPE WALLS OF WATER DISTRIBUTION MAINS

EPA Science Inventory

Biofilm formations on pipe walls have been found in potable water distribution mains. The biofilm layers contribute to accelerated corrosion rates, increased flow resistance, and formation of encrustations that may deteriorate drinking water quality. Research to evaluate the depe...

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

D.M. McEligot; K. G. Condie; G. E. McCreery

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 Generationmore » IV program.« less

Synthesis of praseodymium-ion-doped perovskite nanophosphor in supercritical water

NASA Astrophysics Data System (ADS)

Hakuta, Yukiya; Sue, Kiwamu; Takashima, Hiroshi

2018-05-01

We report the synthesis of praseodymium-doped calcium strontium titanate nanoparticles, (Ca0.6Sr0.4)0.997Pr0.002TiO3 (PCSTO), using hydrothermal synthesis under supercritical water conditions and the production of red luminescence. Starting solutions were prepared by dissolving calcium nitrate, strontium nitrate, titanium hydroxide sols, and praseodymium nitrate in distilled water. We investigated the effect of the reaction temperature, concentration, and pH of the starting solution on the luminescence properties. Synthesis was conducted at temperatures of 200 °C–400 °C, a reaction pressure of 30 MPa, and for reaction times of 4–20 s. The Pr concentration was set to 0.2 mol% relative to the (Ca0.6Sr0.4) ions. We also investigated the effect of high temperature annealing on the luminescence properties of the PCSTO nanoparticles. Particle characteristics were evaluated using x-ray diffraction, a scanning transmission electron microscope (STEM) equipped with an energy-dispersive x-ray spectrometer, and a fluorometer. Single-phase perovskite particles were obtained at hydrothermal reaction temperatures of over 300 °C even for a reaction time of several seconds. STEM images showed that the particles had cubic-like shapes with diameters of 8–13 nm and that they were chemically homogeneous. The PCSTO nanoparticles exhibited sharp red luminescence at 612 nm corresponding to the f–f transition of Pr3+ ions. Moreover, annealing at 1000 °C led to particle growth, achieving diameters of 40 nm and an increase in the quantum efficiency to around 12.0%.

Measuring water adsorption on mineral surfaces in air, CO2, and supercritical CO2 with a quartz-crystal microbalance

NASA Astrophysics Data System (ADS)

Bryan, C. R.; Wells, R. K.; Burton, P. D.; Heath, J. E.; Dewers, T. A.; Wang, Y.

2011-12-01

Carbon sequestration via underground storage in geologic formations is a proposed approach for reducing industrial CO2 emissions. However, current models for carbon injection and long-term storage of supercritical CO2 (scCO2) do not consider the development and stability of adsorbed water films at the scCO2-hydrophilic mineral interface. The thickness and properties of the water films control the surface tension and wettability of the mineral surface, and on the core scale, affect rock permeability, saturation, and capillary properties. The film thickness is strongly dependent upon the activity of water in the supercritical fluid, which will change as initially anhydrous scCO2 absorbs water from formation brine. As described in a companion paper by the coauthors, the thickness of the adsorbed water layer is controlled by the disjoining pressure; structural and van der Waals components dominate at low water activity, while electrostatic forces become more important with increasing film thickness (higher water activities). As scCO2 water activity and water layer thickness increase, concomitant changes in mineral surface properties and reservoir/caprock hydrologic properties will affect the mobility of the aqueous phase and of scCO2. Moreover, the development of a water layer may be critical to mineral dissolution reactions in scCO2. Here, we describe the use of a quartz-crystal microbalance (QCM) to monitor adsorption of water by mineral surfaces. QCMs utilize a piezoelectrically-stimulated quartz wafer to measure adsorbed or deposited mass via changes in vibrational frequency. When used to measure the mass of adsorbed liquid films, the frequency response of the crystal must be corrected for the viscoelastic, rather than elastic, response of the adsorbed layer. Results are presented for adsorption to silica in N2 and CO2 at one bar, and in scCO2. Additional data are presented for water uptake by clays deposited on a QCM wafer. In this case, water uptake occurs by the

Spatial and temporal modeling of sub- and supercritical thermal energy storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tse, LA; Ganapathi, GB; Wirz, RE

2014-05-01

This paper describes a thermodynamic model that simulates the discharge cycle of a single-tank thermal energy storage (TES) system that can operate from the two-phase (liquid-vapor) to supercritical regimes for storage fluid temperatures typical of concentrating solar power plants. State-of-the-art TES design utilizes a two-tank system with molten nitrate salts; one major problem is the high capital cost of the salts (International Renewable Energy Agency, 2012). The alternate approach explored here opens up the use of low-cost fluids by considering operation at higher pressures associated with the two-phase and supercritical regimes. The main challenge to such a system is itsmore » high pressures and temperatures which necessitate a relatively high-cost containment vessel that represents a large fraction of the system capital cost. To mitigate this cost, the proposed design utilizes a single-tank TES system, effectively halving the required wall material. A single-tank approach also significantly reduces the complexity of the system in comparison to the two-tank systems, which require expensive pumps and external heat exchangers. A thermodynamic model is used to evaluate system performance; in particular it predicts the volume of tank wall material needed to encapsulate the storage fluid. The transient temperature of the tank is observed to remain hottest at the storage tank exit, which is beneficial to system operation. It is also shown that there is an optimum storage fluid loading that generates a given turbine energy output while minimizing the required tank wall material. Overall, this study explores opportunities to further improve current solar thermal technologies. The proposed single-tank system shows promise for decreasing the cost of thermal energy storage. (C) 2014 Elsevier Ltd. All rights reserved.« less

Advanced Thermal Storage for Central Receivers with Supercritical Coolants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kelly, Bruce D.

2010-06-15

The principal objective of the study is to determine if supercritical heat transport fluids in a central receiver power plant, in combination with ceramic thermocline storage systems, offer a reduction in levelized energy cost over a baseline nitrate salt concept. The baseline concept uses a nitrate salt receiver, two-tank (hot and cold) nitrate salt thermal storage, and a subcritical Rankine cycle. A total of 6 plant designs were analyzed, as follows: Plant Designation Receiver Fluid Thermal Storage Rankine Cycle Subcritical nitrate salt Nitrate salt Two tank nitrate salt Subcritical Supercritical nitrate salt Nitrate salt Two tank nitrate salt Supercritical Lowmore » temperature H2O Supercritical H2O Two tank nitrate salt Supercritical High temperature H2O Supercritical H2O Packed bed thermocline Supercritical Low temperature CO2 Supercritical CO2 Two tank nitrate salt Supercritical High temperature CO2 Supercritical CO2 Packed bed thermocline Supercritical Several conclusions have been drawn from the results of the study, as follows: 1) The use of supercritical H2O as the heat transport fluid in a packed bed thermocline is likely not a practical approach. The specific heat of the fluid is a strong function of the temperatures at values near 400 °C, and the temperature profile in the bed during a charging cycle is markedly different than the profile during a discharging cycle. 2) The use of supercritical CO2 as the heat transport fluid in a packed bed thermocline is judged to be technically feasible. Nonetheless, the high operating pressures for the supercritical fluid require the use of pressure vessels to contain the storage inventory. The unit cost of the two-tank nitrate salt system is approximately $24/kWht, while the unit cost of the high pressure thermocline system is nominally 10 times as high. 3) For the supercritical fluids, the outer crown temperatures of the receiver tubes are in the range of 700 to 800 °C. At temperatures of 700 °C and above

Supercritical transitiometry of polymers.

PubMed

Randzio, S L; Grolier, J P

1998-06-01

Employing supercritical fluids (SCFs) during polymers processing allows the unusual properties of SCFs to be exploited for making polymer products that cannot be obtained by other means. A new supercritical transitiometer has been constructed to permit study of the interactions of SCFs with polymers during processing under well-defined conditions of temperature and pressure. The supercritical transitiometer allows pressure to be exerted by either a supercritical fluid or a neutral medium and enables simultaneous determination of four basic parameters of a transition, i.e., p, T, Δ(tr)H and Δ(tr)V. This permits determination of the SCF effect on modification of the polymer structure at a given pressure and temperature and defines conditions to allow reproducible preparation of new polymer structures. Study of a semicrystalline polyethylene by this method has defined conditions for preparation of new microfoamed phases with good mechanical properties. The low densities and microporous structures of the new materials may make them useful for applications in medicine, pharmacy, or the food industry, for example.

Small angle x ray scattering studies of reverse micelles in supercritical fluids

NASA Astrophysics Data System (ADS)

Pfund, D. M.; Fulton, J. L.

1994-10-01

The nature of aggregates formed in a supercritical fluid determines its solvent power and selectivity. Small angle X ray scattering (SAXS) is a powerful tool for studying the properties of aggregates with sizes in the 10(angstrom) to 200(angstrom) range. It is also useful in studying those interparticle interactions which operate over a similar distance. The authors have used SAXS to examine the aggregates formed in pure fluids, in mixtures and in fluid/surfactant/water systems. The scattered intensity as a function of angle depends on the geometry, polydispersity, X ray contrast, and interaction strength of the particles as well as on the phase behavior of the system. In this paper the authors present the results of modeling the X-ray scattering from AOT/water reverse micelles in supercritical propane and in propane/carbon dioxide mixtures. They examine the effect of dilution with CO2 anti-solvent on the phase behavior of the system and on the strength of intermicellar attractions. A better understanding of these systems must be obtained before the applications of supercritical reverse micelle systems to extractions, reactions, and enhanced oil recovery can be fully developed.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loring, John S.; Schaef, Herbert T.; Thompson, Christopher J.

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 tomore » 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.« less

Extraction of aucubin from seeds of Eucommia ulmoides Oliv. using supercritical carbon dioxide.

PubMed

Li, Hui; Hu, Jiangyu; Ouyang, Hui; Li, Yanan; Shi, Hui; Ma, Chengjin; Zhang, Yongkang

2009-01-01

Supercritical CO2 was used as solvent for the extraction of aucubin from the seeds of Eucommia ulmoides Oliv. The co-solvent composition was tested and extraction conditions were optimized. Results showed that the best co-solvent was a water-ethanol mixture (1 + 3, v/v), and the highest yield was obtained when the extraction was performed under 26 MPa at extraction and separation temperatures of 55 and 30 degrees C for 120 min, using 6 mL co-solvent/g material at a CO2 flow rate of 20 L/h. In a comparison of the supercritical CO2 and Soxhlet extraction methods, the Soxhlet method needed 3 h to extract 10 g material, whereas the supercritical CO2 extraction technique needed only 2 h to extract 100 g material, thus showing a high extraction capability. The supercritical CO2 extraction produced a higher yield, with a lower cost for the extraction. Owing to the advantages of low extraction temperature, high yield, and ease of separating the product from the solvent, supercritical CO2 extraction is likely to be developed into an ideal technique for the extraction of aucubin, a compound with thermal instability, from the seeds of this plant.

Electrodeposition of metals from supercritical fluids

PubMed Central

Ke, Jie; Su, Wenta; Howdle, Steven M.; George, Michael W.; Cook, David; Perdjon-Abel, Magda; Bartlett, Philip N.; Zhang, Wenjian; Cheng, Fei; Levason, William; Reid, Gillian; Hyde, Jason; Wilson, James; Smith, David C.; Mallik, Kanad; Sazio, Pier

2009-01-01

Electrodeposition is a widely used materials-deposition technology with a number of unique features, in particular, the efficient use of starting materials, conformal, and directed coating. The properties of the solvent medium for electrodeposition are critical to the technique's applicability. Supercritical fluids are unique solvents which give a wide range of advantages for chemistry in general, and materials processing in particular. However, a widely applicable approach to electrodeposition from supercritical fluids has not yet been developed. We present here a method that allows electrodeposition of a range of metals from supercritical carbon dioxide, using acetonitrile as a co-solvent and supercritical difluoromethane. This method is based on a careful selection of reagent and supporting electrolyte. There are no obvious barriers preventing this method being applied to deposit a range of materials from many different supercritical fluids. We present the deposition of 3-nm diameter nanowires in mesoporous silica templates using this methodology. PMID:19706479

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.

Supercritical fluid chromatography

NASA Astrophysics Data System (ADS)

Vigdergauz, M. S.; Lobachev, A. L.; Lobacheva, I. V.; Platonov, I. A.

1992-03-01

The characteristic features of supercritical fluid chromatography (SCFC) are examined and there is a brief historical note concerning the development of the method. Information concerning the use of supercritical fluid chromatography in the analysis of objects of different nature is presented in the form of a table. The roles of the mobile and stationary phases in the separation process and the characteristic features of the apparatus and of the use of the method in physicochemical research are discussed. The bibliography includes 364 references.

Didanosine polymorphism in a supercritical antisolvent process.

PubMed

Bettini, R; Menabeni, R; Tozzi, R; Pranzo, M B; Pasquali, I; Chierotti, M R; Gobetto, R; Pellegrino, L

2010-04-01

Solid-state properties of active ingredients are crucial in pharmaceutical development owing to their significant clinical and economical implications. In the present work we investigated the solid-state properties and the solubility in water of didanosine, DDI, re-crystallized from a dimethylsulfoxide solution using supercritical CO(2) as an antisolvent (SAS process) for comparison with the commercially available drug product. We also applied modern solid-state NMR (SS NMR) techniques, namely 2D (1)H DQ CRAMPS (Combined Rotation And Multiple Pulse Spectroscopy) and (1)H-(13)C on- and off-resonance CP (cross polarization) FSLG-HETCOR experiments, known for providing reliable information about (1)H-(1)H and (1)H-(13)C intra- and intermolecular proximities, in order to address polymorphism issues arising from the crystallization of a new form in the supercritical process. A new polymorph of didanosine was obtained from the supercritical antisolvent process and characterized by means of 1D and 2D multinuclear ((1)H, (13)C, (15)N) SS NMR. The particle size of the new crystal phase was reduced by varying the antisolvent density through a pressure increase. The structural differences between the commercial product and the SAS re-crystallized DDI are highlighted by X-ray diffractometry and well described by solid-state NMR. The carbon C6 (13)C chemical shift suggests that both commercial and re-crystallized didanosine samples are in the enol form. The analysis of homo- and heteronuclear proximities obtained by means of 2D NMR experiments shows that commercial and SAS re-crystallized DDI possess very similar molecular conformation and hydrogen bond network, but different packing. The new polymorph proved to be a metastable form at ambient conditions, showing higher solubility in water and lower stability to mechanical stress. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Behavior of water in supercritical CO2: adsorption and capillary condensation in porous media

NASA Astrophysics Data System (ADS)

Heath, J. E.; Bryan, C. R.; Dewers, T. A.; Wang, Y.

2011-12-01

The chemical potential of water in supercritical CO2 (scCO2) may play an important role in water adsorption, capillary condensation, and evaporation under partially saturated conditions at geologic CO2 storage sites, especially if initially anhydrous CO2 is injected. Such processes may affect residual water saturations, relative permeability, shrink/swell of clays, and colloidal transport. We have developed a thermodynamic model of water or brine film thickness as a function of water relative humidity in scCO2. The model is based on investigations of liquid water configuration in the vadose zone and uses the augmented Young-Laplace equation, which incorporates both adsorptive and capillary components. The adsorptive component is based on the concept of disjoining pressure, which reflects force per area normal to the solid and water/brine-scCO2 interfaces. The disjoining pressure includes van der Waals, electrostatic, and structural interactions. The van der Waals term includes the effects of mutual dissolution of CO2 and water in the two fluid phases on partial molar volumes, dielectric coefficients, and refractive indices. Our approach treats the two interfaces as asymmetric surfaces in terms of charge densities and electrostatic potentials. We use the disjoining pressure isotherm to evaluate the type of wetting (e.g., total or partial wetting) for common reservoir and caprock minerals and kerogen. The capillary component incorporates water activity and is applied to simple pore geometries with slits and corners. Finally, we compare results of the model to a companion study by the coauthors on measurement of water adsorption to mineral phases using a quartz-crystal microbalance. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Oxy-combustor operable with supercritical fluid

DOEpatents

Brun, Klaus; McClung, Aaron M.; Owston, Rebecca A.

2017-04-04

An oxy-combustor is provided which comprises a combustion vessel including at least one solid fuel slurry inlet port, at least one oxygen inlet port and at least one supercritical fluid inlet port, wherein the combustion vessel is operable at an operating pressure of at least 1,100 psi; an interior of the combustion vessel comprises a combustion chamber and a supercritical fluid infusion chamber surrounding at least a part of the combustion chamber, the supercritical fluid infusion chamber and the combustion chamber are separated by a porous liner surrounding the combustion chamber, and the supercritical infusion chamber is located between the porous liner and an outer casing of the combustion vessel.

Experimental study on the heat transfer characteristics of a nuclear reactor containment wall cooled by gravitationally falling water

NASA Astrophysics Data System (ADS)

Pasek, Ari D.; Umar, Efrison; Suwono, Aryadi; Manalu, Reinhard E. E.

2012-06-01

Gravitationally falling water cooling is one of mechanism utilized by a modern nuclear Pressurized Water Reactor (PWR) for its Passive Containment Cooling System (PCCS). Since the cooling is closely related to the safety, water film cooling characteristics of the PCCS should be studied. This paper deals with the experimental study of laminar water film cooling on the containment model wall. The influences of water mass flow rate and wall heat rate on the heat transfer characteristic were studied. This research was started with design and assembly of a containment model equipped with the water cooling system, and calibration of all measurement devices. The containment model is a scaled down model of AP 1000 reactor. Below the containment steam is generated using electrical heaters. The steam heated the containment wall, and then the temperatures of the wall in several positions were measure transiently using thermocouples and data acquisition. The containment was then cooled by falling water sprayed from the top of the containment. The experiments were done for various wall heat rate and cooling water flow rate. The objective of the research is to find the temperature profile along the wall before and after the water cooling applied, prediction of the water film characteristic such as means velocity, thickness and their influence to the heat transfer coefficient. The result of the experiments shows that the wall temperatures significantly drop after being sprayed with water. The thickness of water film increases with increasing water flow rate and remained constant with increasing wall heat rate. The heat transfer coefficient decreases as film mass flow rate increase due to the increases of the film thickness which causes the increasing of the thermal resistance. The heat transfer coefficient increases slightly as the wall heat rate increases. The experimental results were then compared with previous theoretical studied.

Advanced degradation of brominated epoxy resin and simultaneous transformation of glass fiber from waste printed circuit boards by improved supercritical water oxidation processes.

PubMed

Liu, Kang; Zhang, Zhiyuan; Zhang, Fu-Shen

2016-10-01

This work investigated various supercritical water oxidation (SCWO) systems, i.e. SCWO1 (only water), SCWO2 (water+H2O2) and SCWO3 (water+H2O2/NaOH), for waste printed circuit boards (PCBs) detoxification and recycling. Response surface methodology (RSM) was applied to optimize the operating conditions of the optimal SCWO3 systems. The optimal reaction conditions for debromination were found to be the NaOH of 0.21g, the H2O2 volume of 9.04mL, the time of 39.7min, maximum debromination efficiency of 95.14%. Variance analysis indicated that the factors influencing debromination efficiency was in the sequence of NaOH>H2O2>time. Mechanism studies indicated that the dissociated ions from NaOH in supercritical water promoted the debromination of brominated epoxy resins (BERs) through an elimination reaction and nucleophilic substitution. HO2, produced by H2O2 could induce the oxidation of phenol ring to open (intermediates of BERs), which were thoroughly degraded to form hydrocarbons, CO2, H2O and NaBr. In addition, the alkali-silica reaction between OH(-) and SiO2 induced the phase transformation of glass fibers, which were simultaneously converted into anorthite and albite. Waste PCBs in H2O2/NaOH improved SCWO system were fully degraded into useful products and simultaneously transformed into functional materials. These findings are helpful for efficient recycling of waste PCBs. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Theoretical and Experimental Investigation of the Lift and Drag Characteristics of Hydrofoils at Subcritical and Supercritical Speeds

NASA Technical Reports Server (NTRS)

Wadlin, Kenneth L; Shuford, Charles L , Jr; Mcgehee, John R

1955-01-01

A theoretical and experimental investigation at subcavitation speeds was made of the effect of the free-water surface and rigid boundaries on the lift and drag of an aspect-ratio-10 hydrofoil at both subcritical and supercritical speeds and of an aspect ratio-4 hydrofoil at supercritical speeds. Approximate theoretical solutions for the effects of the free-water surface and rigid boundaries on drag at subcritical speeds are developed. An approximate theoretical solution for the effects of these boundaries on drag at subcritical speeds is also presented. The agreement between theory and experiment at both supercritical and subcritical speeds is satisfactory for engineering calculations of hydrofoil characteristics from aerodynamic data. The experimental investigation indicated no appreciable effect of the limiting speed of wave propagation on lift-curve slope or angle of zero lift. It also showed that the increase in drag as the critical speed is approached from the supercritical range is gradual. The result is contrary to the abrupt increase at the critical speed predicted by theory.

First-wall structural analysis of the self-cooled water blanket concept

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Brien, D.A.; Steiner, D.; Embrechts, M.J.

1986-01-01

A novel blanket concept recently proposed utilizes water with small amounts of dissolved lithium compound as both coolant and breeder. The inherent simplicity of this idea should result in an attractive breeding blanket for fusion reactors. In addition, the available base of relevant information accumulated through water-cooled fission reactor programs should greatly facilitate the R and D effort required to validate this concept. First-wall and blanket designs have been developed first for the tandem mirror reactor (TMR) due to the obvious advantages of this geometry. First-wall and blanket designs will also be developed for toroidal reactors. A simple plate designmore » with coolant tubes welded on the back (side away from plasma) was chosen as the first wall for the TMR application. Dimensions and materials were chosen to minimize temperature differences and thermal stresses. A finite element code (STRAW), originally developed for the analysis of core components subjected to high-pressure transients in the fast breeder program, was utilized to evaluate stresses in the first wall.« less

Decoration of multi-walled carbon nanotubes with metal nanoparticles in supercritical carbon dioxide medium as a novel approach for the modification of screen-printed electrodes.

PubMed

Moreno, Virginia; Llorent-Martínez, Eulogio J; Zougagh, Mohammed; Ríos, Angel

2016-12-01

A supercritical carbon dioxide medium was used for the decoration of functionalized multi-walled carbon nanotubes (MWCNTs) with metallic nanoparticles. This procedure allowed the rapid and simple decoration of carbon nanotubes with the selected metallic nanoparticles. The prepared nanomaterials were used to modify screen-printed electrodes, improving their electrochemical properties and allowing to obtain a wide range of working electrodes based on carbon nanotubes. These electrodes were applied to the amperometric determination of vitamin B6 in food and pharmaceutical samples as an example of the analytical potentiality of the electrodes thus prepared. Using Ru-nanoparticles-MWCNTs as the working electrode, a linear dynamic range between 2.6×10 -6 and 2×10 -4 molL -1 and a limit of detection of 0.8×10 -6 molL -1 were obtained. These parameters represented a minimum 3-fold increase in sensitivity compared to the use of bare MWCNTs or other carbon-based working electrodes. Copyright © 2016 Elsevier B.V. All rights reserved.

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

2014-10-03

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. Copyright © 2014. Published by Elsevier B.V.

Wall extensibility and cell hydraulic conductivity decrease in enlarging stem tissues at low water potentials.

PubMed

Nonami, H; Boyer, J S

1990-08-01

Measurements with a guillotine psychrometer (H Nonami, JS Boyer [1990] Plant Physiol 94: 1601-1609) indicate that the inhibition of stem growth at low water potentials (low psi(w)) is accompanied by decreases in cell wall extensibility and tissue hydraulic conductance to water that eventually limit growth rate in soybean (Glycine max L. Merr.). To check this conclusion, we measured cell wall properties and cell hydraulic conductivities with independent techniques in soybean seedlings grown and treated the same way, i.e. grown in the dark and exposed to low psi(w) by transplanting dark grown seedlings to vermiculite of low water content. Wall properties were measured with an extensiometer modified for intact plants, and conductances were measured with a cell pressure probe in intact plants. Theory was developed to relate the wall measurements to those with the psychrometer. In the elongation zone, the plastic deformability of the walls decreased when measured with the extensiometer while growth was inhibited at low psi(w). It increased during a modest growth recovery. This behavior was the same as that for the wall extensibility observed previously with the psychrometer. Tissue that was killed before measurement with the extensiometer also showed a similar response, indicating that changes in wall extensibility represented changes in wall physical properties and not rates of wall biosynthesis. The elastic compliance (reciprocal of bulk elastic modulus) did not change in the elongating or mature tissue. The hydraulic conductivity of cortical cells decreased in the elongating tissue and increased slightly during growth recovery in a response similar to that observed with the psychrometer. We conclude that the plastic properties of the cell walls and the conductance of the cells to water were decreased at low psi(w) but that the elastic properties of the walls were of little consequence in this response.

Supercritical impregnation and optical characterization of loaded foldable intraocular lenses using supercritical fluids.

PubMed

Bouledjouidja, Abir; Masmoudi, Yasmine; Li, Yanfeng; He, Wei; Badens, Elisabeth

2017-10-01

To prepare drug-loaded intraocular lenses (IOLs) used to combine cataract surgery with postoperative complication treatment through supercritical impregnation while preserving their optical properties. Aix-Marseille Université, CNRS, Centrale Marseille, Laboratoire de Mécanique, Modélisation & Procédés Propres, Marseille, France, and He University Eye Hospital, Liaoning Province, China. Experimental study. Supercritical impregnations of commercial foldable IOLs used in cataract surgery with ciprofloxacin (an antibiotic) and dexamethasone 21-phosphate disodium salt (an antiinflammatory drug) were performed in a noncontinuous mode. Impregnation amounts were determined through drug-release kinetic studies. The optical characterizations of IOLs were determined by evaluating the dioptric power and the imaging quality by determining the modulating transfer function (MTF) at a specified spatial frequency according to the International Organization for Standardization (ISO 11979-2:2014). Transparent IOLs presenting an effective impregnation were obtained with a prolonged drug delivery during approximately 10 days. Optical characterizations (dioptric powers and MTF values) show preserved optical properties after supercritical treatment/impregnation. Supercritical treatments/impregnations do not damage the optical properties of IOLs and are therefore adequate for the preparation of delivery devices used for cataract surgery. Copyright © 2017. Published by Elsevier Inc.

Water-walled microfluidics for high-optical finesse cavities

NASA Astrophysics Data System (ADS)

Maayani, Shai; Martin, Leopoldo L.; Carmon, Tal

2016-01-01

In submerged microcavities there is a tradeoff between resonant enhancement for spatial water and light overlap. Why not transform the continuously resonating optical mode to be fully contained in a water microdroplet per se? Here we demonstrate a sustainable 30-μm-pure water device, bounded almost completely by free surfaces, enabling >1,000,000 re-circulations of light. The droplets survive for >16 h using a technique that is based on a nano-water bridge from the droplet to a distant reservoir to compensate for evaporation. More than enabling a nearly-perfect optical overlap with water, atomic-level surface smoothness that minimizes scattering loss, and ~99% coupling efficiency from a standard fibre. Surface tension in our droplet is 8,000 times stronger than gravity, suggesting a new class of devices with water-made walls, for new fields of study including opto-capillaries.

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.

Phase Domain Walls in Weakly Nonlinear Deep Water Surface Gravity Waves.

PubMed

Tsitoura, F; Gietz, U; Chabchoub, A; Hoffmann, N

2018-06-01

We report a theoretical derivation, an experimental observation and a numerical validation of nonlinear phase domain walls in weakly nonlinear deep water surface gravity waves. The domain walls presented are connecting homogeneous zones of weakly nonlinear plane Stokes waves of identical amplitude and wave vector but differences in phase. By exploiting symmetry transformations within the framework of the nonlinear Schrödinger equation we demonstrate the existence of exact analytical solutions representing such domain walls in the weakly nonlinear limit. The walls are in general oblique to the direction of the wave vector and stationary in moving reference frames. Experimental and numerical studies confirm and visualize the findings. Our present results demonstrate that nonlinear domain walls do exist in the weakly nonlinear regime of general systems exhibiting dispersive waves.

Phase Domain Walls in Weakly Nonlinear Deep Water Surface Gravity Waves

NASA Astrophysics Data System (ADS)

Tsitoura, F.; Gietz, U.; Chabchoub, A.; Hoffmann, N.

2018-06-01

We report a theoretical derivation, an experimental observation and a numerical validation of nonlinear phase domain walls in weakly nonlinear deep water surface gravity waves. The domain walls presented are connecting homogeneous zones of weakly nonlinear plane Stokes waves of identical amplitude and wave vector but differences in phase. By exploiting symmetry transformations within the framework of the nonlinear Schrödinger equation we demonstrate the existence of exact analytical solutions representing such domain walls in the weakly nonlinear limit. The walls are in general oblique to the direction of the wave vector and stationary in moving reference frames. Experimental and numerical studies confirm and visualize the findings. Our present results demonstrate that nonlinear domain walls do exist in the weakly nonlinear regime of general systems exhibiting dispersive waves.

Effect of temperature and dissolved oxygen on stress corrosion cracking behavior of P92 ferritic-martensitic steel in supercritical water environment

NASA Astrophysics Data System (ADS)

Zhang, Z.; Hu, Z. F.; Zhang, L. F.; Chen, K.; Singh, P. M.

2018-01-01

The effect of temperature and dissolved oxygen (DO) on stress corrosion cracking (SCC) of P92 martensitic steel in supercritical water (SCW) was investigated using slow strain rate test (SSRT) and fractography analysis. The SSRT was carried out at temperatures of 400, 500, 600 °C in deaerated supercritical water and at DO contents of 0, 200, 500 ppb at the temperature of 600 °C, respectively. The results of SSRT show that the decrease of ductility at the temperature of 400 °C may be related to the dynamic strain aging (DSA) of P92 steel. The degradation of the mechanical properties in SCW is the joint effect of temperature and SCC. Compared with the effect of temperature, DO in SCW has no significant effect on the SCC susceptibility of P92 steel. The observation of oxide layer shows that large numbers of pores are nucleated in the oxide layer, which is related to vacancy accumulation and hydrogen generated in the oxide layer. Under the combined action of the growth stress and tensile stress, micro cracks, nucleated from the pores in the oxide layer, are easily propagated intergranularly outward to the surface of specimen, and fewer cracks can extend inward along the intrinsic pores to the inner oxide/metal interface, which is the reason for the exfoliation of oxide films.

Mechanical analysis of the strains generated by water tension in plant stems. Part I: stress transmission from the water to the cell walls.

PubMed

Alméras, Tancrède; Gril, Joseph

2007-11-01

Plant tissues shrink and swell in response to changes in water pressure. These strains can be easily measured, e.g., at the surface of tree stems, to obtain indirect information about plant water status and other physiological parameters. We developed a mechanical model to clarify how water pressure is transmitted to cell walls and causes shrinkage of plant tissues, particularly in the case of thick-walled cells such as wood fibers. Our analysis shows that the stress inside the fiber cell walls is lower than the water tension. The difference is accounted for by a stress transmission factor that depends on two main effects. The first effect is the dilution of the stress through the cell wall, because water acts at the lumen border and is transmitted to the outer border of the cell, which has a larger circumference. The second effect is the partial conversion of radial stress into tangential stress. Both effects are quantified as functions of parameters of the cell wall structure and its mechanical properties.

Bond cleavage of lignin model compounds into aromatic monomers using supported metal catalysts in supercritical water

PubMed Central

Yamaguchi, Aritomo; Mimura, Naoki; Shirai, Masayuki; Sato, Osamu

2017-01-01

More efficient use of lignin carbon is necessary for carbon-efficient utilization of lignocellulosic biomass. Conversion of lignin into valuable aromatic compounds requires the cleavage of C–O ether bonds and C–C bonds between lignin monomer units. The catalytic cleavage of C–O bonds is still challenging, and cleavage of C–C bonds is even more difficult. Here, we report cleavage of the aromatic C–O bonds in lignin model compounds using supported metal catalysts in supercritical water without adding hydrogen gas and without causing hydrogenation of the aromatic rings. The cleavage of the C–C bond in bibenzyl was also achieved with Rh/C as a catalyst. Use of this technique may greatly facilitate the conversion of lignin into valuable aromatic compounds. PMID:28387304

Effects of supercritical environment on hydrocarbon-fuel injection

NASA Astrophysics Data System (ADS)

Shin, Bongchul; Kim, Dohun; Son, Min; Koo, Jaye

2017-04-01

In this study, the effects of environment conditions on decane were investigated. Decane was injected in subcritical and supercritical ambient conditions. The visualization chamber was pressurized to 1.68 MPa by using nitrogen gas at a temperature of 653 K for subcritical ambient conditions. For supercritical ambient conditions, the visualization chamber was pressurized to 2.52 MPa by using helium at a temperature of 653 K. The decane injection in the pressurized chamber was visualized via a shadowgraph technique and gradient images were obtained by a post processing method. A large variation in density gradient was observed at jet interface in the case of subcritical injection in subcritical ambient conditions. Conversely, for supercritical injection in supercritical ambient conditions, a small density gradient was observed at the jet interface. In a manner similar to that observed in other cases, supercritical injection in subcritical ambient conditions differed from supercritical ambient conditions such as sphere shape liquid. Additionally, there were changes in the interface, and the supercritical injection core width was thicker than that in the subcritical injection. Furthermore, in cases with the same injection conditions, the change in the supercritical ambient normalized core width was smaller than the change in the subcritical ambient normalized core width owing to high specific heat at the supercritical injection and small phase change at the interface. Therefore, the interface was affected by the changing ambient condition. Given that the effect of changing the thermodynamic properties of propellants could be essential for a variable thrust rocket engine, the effects of the ambient conditions were investigated experimentally.

Fayalite Dissolution and Siderite Formation in Water-Saturated Supercritical CO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Odeta; Kovarik, Libor; Kukkadapu, Ravi K.

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 upmore » 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.« less

Geothermal energy production with supercritical fluids

DOEpatents

Brown, Donald W.

2003-12-30

There has been invented a method for producing geothermal energy using supercritical fluids for creation of the underground reservoir, production of the geothermal energy, and for heat transport. Underground reservoirs are created by pumping a supercritical fluid such as carbon dioxide into a formation to fracture the rock. Once the reservoir is formed, the same supercritical fluid is allowed to heat up and expand, then is pumped out of the reservoir to transfer the heat to a surface power generating plant or other application.

7. NHP, Water Turbine Section, north end of east wall ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

7. NHP, Water Turbine Section, north end of east wall of 1908-1909 vaulted concrete standpipe foundation. View is to the Northeast. - Nunn Hydroelectric Plant, On Madison River, Ennis, Madison County, MT

Dynamics of Supercritical Flows

DTIC Science & Technology

2012-08-26

to Supercritical Environment of Relevance to Rocket, Gas turbine , and Diesel Engines,” 37th AIAA Aerospace Science Meeting and Exhibit, AIAA...Visual Characteristics of a Round Jet into a Sub- to Supercritical Environment of Relevance to Rocket, Gas turbine , and Diesel Engines,” 37th AIAA...Relevance to Rocket, Gas turbine , and Diesel Engines,” 37th AIAA Aerospace Science Meeting and Exhibit, AIAA, Washington, DC, 11-14 Jan. 1999. 26Chehroudi

International contributions to IAEA-NEA heat transfer databases for supercritical fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leung, L. K. H.; Yamada, K.

2012-07-01

An IAEA Coordinated Research Project on 'Heat Transfer Behaviour and Thermohydraulics Code Testing for SCWRs' is being conducted to facilitate collaboration and interaction among participants from 15 organizations. While the project covers several key technology areas relevant to the development of SCWR concepts, it focuses mainly on the heat transfer aspect, which has been identified as the most challenging. Through the collaborating effort, large heat-transfer databases have been compiled for supercritical water and surrogate fluids in tubes, annuli, and bundle subassemblies of various orientations over a wide range of flow conditions. Assessments of several supercritical heat-transfer correlations were performed usingmore » the complied databases. The assessment results are presented. (authors)« less

The NASA Langley Laminar-Flow-Control (LFC) experiment on a swept, supercritical airfoil: Design overview

NASA Technical Reports Server (NTRS)

Harris, Charles D.; Harvey, William D.; Brooks, Cuyler W., Jr.

1988-01-01

A large-chord, swept, supercritical, laminar-flow-control (LFC) airfoil was designed and constructed and is currently undergoing tests in the Langley 8 ft Transonic Pressure Tunnel. The experiment was directed toward evaluating the compatibility of LFC and supercritical airfoils, validating prediction techniques, and generating a data base for future transport airfoil design as part of NASA's ongoing research program to significantly reduce drag and increase aircraft efficiency. Unique features of the airfoil included a high design Mach number with shock free flow and boundary layer control by suction. Special requirements for the experiment included modifications to the wind tunnel to achieve the necessary flow quality and contouring of the test section walls to simulate free air flow about a swept model at transonic speeds. Design of the airfoil with a slotted suction surface, the suction system, and modifications to the tunnel to meet test requirements are discussed.

Enhancing power cycle efficiency for a supercritical Brayton cycle power system using tunable supercritical gas mixtures

DOEpatents

Wright, Steven A.; Pickard, Paul S.; Vernon, Milton E.; Radel, Ross F.

2017-08-29

Various technologies pertaining to tuning composition of a fluid mixture in a supercritical Brayton cycle power generation system are described herein. Compounds, such as Alkanes, are selectively added or removed from an operating fluid of the supercritical Brayton cycle power generation system to cause the critical temperature of the fluid to move up or down, depending upon environmental conditions. As efficiency of the supercritical Brayton cycle power generation system is substantially optimized when heat is rejected near the critical temperature of the fluid, dynamically modifying the critical temperature of the fluid based upon sensed environmental conditions improves efficiency of such a system.

Water-polysaccharide interactions in the primary cell wall of Arabidopsis thaliana from polarization transfer solid-state NMR.

PubMed

White, Paul B; Wang, Tuo; Park, Yong Bum; Cosgrove, Daniel J; Hong, Mei

2014-07-23

Polysaccharide-rich plant cell walls are hydrated under functional conditions, but the molecular interactions between water and polysaccharides in the wall have not been investigated. In this work, we employ polarization transfer solid-state NMR techniques to study the hydration of primary-wall polysaccharides of the model plant, Arabidopsis thaliana. By transferring water (1)H polarization to polysaccharides through distance- and mobility-dependent (1)H-(1)H dipolar couplings and detecting it through polysaccharide (13)C signals, we obtain information about water proximity to cellulose, hemicellulose, and pectins as well as water mobility. Both intact and partially extracted cell wall samples are studied. Our results show that water-pectin polarization transfer is much faster than water-cellulose polarization transfer in all samples, but the extent of extraction has a profound impact on the water-polysaccharide spin diffusion. Removal of calcium ions and the consequent extraction of homogalacturonan (HG) significantly slowed down spin diffusion, while further extraction of matrix polysaccharides restored the spin diffusion rate. These trends are observed in cell walls with similar water content, thus they reflect inherent differences in the mobility and spatial distribution of water. Combined with quantitative analysis of the polysaccharide contents, our results indicate that calcium ions and HG gelation increase the amount of bound water, which facilitates spin diffusion, while calcium removal disrupts the gel and gives rise to highly dynamic water, which slows down spin diffusion. The recovery of spin diffusion rates after more extensive extraction is attributed to increased water-exposed surface areas of the polysaccharides. Water-pectin spin diffusion precedes water-cellulose spin diffusion, lending support to the single-network model of plant primary walls in which a substantial fraction of the cellulose surface is surrounded by pectins.

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.

Supercritical methanol for polyethylene terephthalate depolymerization: Observation using simulator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Genta, Minoru; Iwaya, Tomoko; Sasaki, Mitsuru

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 beneficialmore » 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.« less

Wall Extensibility and Cell Hydraulic Conductivity Decrease in Enlarging Stem Tissues at Low Water Potentials 1

PubMed Central

Nonami, Hiroshi; Boyer, John S.

1990-01-01

Measurements with a guillotine psychrometer (H Nonami, JS Boyer [1990] Plant Physiol 94: 1601-1609) indicate that the inhibition of stem growth at low water potentials (low ψw) is accompanied by decreases in cell wall extensibility and tissue hydraulic conductance to water that eventually limit growth rate in soybean (Glycine max L. Merr.). To check this conclusion, we measured cell wall properties and cell hydraulic conductivities with independent techniques in soybean seedlings grown and treated the same way, i.e. grown in the dark and exposed to low ψw by transplanting dark grown seedlings to vermiculite of low water content. Wall properties were measured with an extensiometer modified for intact plants, and conductances were measured with a cell pressure probe in intact plants. Theory was developed to relate the wall measurements to those with the psychrometer. In the elongation zone, the plastic deformability of the walls decreased when measured with the extensiometer while growth was inhibited at low ψw. It increased during a modest growth recovery. This behavior was the same as that for the wall extensibility observed previously with the psychrometer. Tissue that was killed before measurement with the extensiometer also showed a similar response, indicating that changes in wall extensibility represented changes in wall physical properties and not rates of wall biosynthesis. The elastic compliance (reciprocal of bulk elastic modulus) did not change in the elongating or mature tissue. The hydraulic conductivity of cortical cells decreased in the elongating tissue and increased slightly during growth recovery in a response similar to that observed with the psychrometer. We conclude that the plastic properties of the cell walls and the conductance of the cells to water were decreased at low ψw but that the elastic properties of the walls were of little consequence in this response. PMID:16667664

View of east and south (rear) walls, water wheels and ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

View of east and south (rear) walls, water wheels and generators, interior of Childs Powerhouse. Looking southeast - Childs-Irving Hydroelectric Project, Childs System, Childs Powerhouse, Forest Service Road 708/502, Camp Verde, Yavapai County, AZ

Bio-oil production from biomass via supercritical fluid extraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durak, Halil, E-mail: halildurak@yyu.edu.tr

2016-04-18

Supercritical fluid extraction is used for producing bio-fuel from biomass. Supercritical fluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercritical fluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds weremore » identified by GC-MS obtained in acetone and ethanol respectively.« less

Methane storage in nanoporous material at supercritical temperature over a wide range of pressures

PubMed Central

Wu, Keliu; Chen, Zhangxin; Li, Xiangfang; Dong, Xiaohu

2016-01-01

The methane storage behavior in nanoporous material is significantly different from that of a bulk phase, and has a fundamental role in methane extraction from shale and its storage for vehicular applications. Here we show that the behavior and mechanisms of the methane storage are mainly dominated by the ratio of the interaction between methane molecules and nanopores walls to the methane intermolecular interaction, and a geometric constraint. By linking the macroscopic properties of the methane storage to the microscopic properties of a system of methane molecules-nanopores walls, we develop an equation of state for methane at supercritical temperature over a wide range of pressures. Molecular dynamic simulation data demonstrates that this equation is able to relate very well the methane storage behavior with each of the key physical parameters, including a pore size and shape and wall chemistry and roughness. Moreover, this equation only requires one fitted parameter, and is simple, reliable and powerful in application. PMID:27628747

Non-catalytic transfer hydrogenation in supercritical CO2 for coal liquefaction

NASA Astrophysics Data System (ADS)

Elhussien, Hussien

This thesis presents the results of the investigation on developing and evaluating a low temperature (<150°C) non - catalytic process using a hydrogen transfer agent (instead of molecu-lar hydrogen) for coal dissolution in supercritical CO2. The main idea behind the thesis was that one hydrogen atom from water and one hydrogen atom from the hydrogen transfer agent (HTA) were used to hydrogenate the coal. The products of coal dissolution were non-polar and polar while the supercritical CO2, which enhanced the rates of hydrogenation and dissolution of the non-polar molecules and removal from the reaction site, was non-polar. The polar modifier (PM) for CO2 was added to the freed to aid in the dissolution and removal of the polar components. The addition of a phase transfer agent (PTA) allowed a seamless transport of the ions and by-product between the aqueous and organic phases. DDAB, used as the PTA, is an effective phase transfer catalyst and showed enhancement to the coal dissolution process. COAL + DH- +H 2O → COAL.H2 + DHO-- This process has a great feature due to the fact that the chemicals were obtained without requir-ing to first convert coal to CO and H2 units as in indirect coal liquefaction. The experiments were conducted in a unique reactor set up that can be connected through two lines. one line to feed the reactor with supercritical CO 2 and the other connected to gas chromatograph. The use of the supercritical CO2 enhanced the solvent option due to the chemical extraction, in addition to the low environmental impact and energy cost. In this thesis the experiment were conducted at five different temperatures from atmos-pheric to 140°C, 3000 - 6000 psi with five component of feed mixture, namely water, HTA, PTA, coal, and PM in semi batch vessels reactor system with a volume of 100 mL. The results show that the chemicals were obtained without requiring to first convert coal to CO and H2 units as in indirect coal liquefaction. The results show that

Using supercritical fluids to refine hydrocarbons

DOEpatents

Yarbro, Stephen Lee

2015-06-09

A system and method for reactively refining hydrocarbons, such as heavy oils with API gravities of less than 20 degrees and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure, using a selected fluid at supercritical conditions. A reaction portion of the system and method delivers lightweight, volatile hydrocarbons to an associated contacting unit which operates in mixed subcritical/supercritical or supercritical modes. Using thermal diffusion, multiphase contact, or a momentum generating pressure gradient, the contacting unit separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques.

Enhanced Reduction of Few-Layer Graphene Oxide via Supercritical Water Gasification of Glycerol

PubMed Central

Arcelus-Arrillaga, Pedro; Millan, Marcos; Suelves, Isabel

2017-01-01

A sustainable and effective method for de-oxygenation of few-layer graphene oxide (FLGO) by glycerol gasification in supercritical water (SCW) is described. In this manner, reduction of FLGO and valorization of glycerol, in turn catalyzed by FLGO, are achieved simultaneously. The addition of glycerol enhanced FLGO oxygen removal by up to 59% due to the in situ hydrogen generation as compared to the use of SCW only. Physicochemical characterization of the reduced FLGO (rFLGO) showed a high restoration of the sp2-conjugated carbon network. FLGO sheets with a starting C/O ratio of 2.5 are reduced by SCW gasification of glycerol to rFLGO with a C/O ratio of 28.2, above those reported for hydrazine-based methods. Additionally, simultaneous glycerol gasification resulted in the concurrent production of H2, CO, CH4 and valuable hydrocarbons such as alkylated and non-alkylated long chain hydrocarbon (C12–C31), polycyclic aromatic hydrocarbons (PAH), and phthalate, phenol, cresol and furan based compounds. PMID:29240720

Noble-metal-free bimetallic alloy nanoparticle-catalytic gasification of phenol in supercritical water

DOE PAGES

Jia, Lijuan; Yu, Jiangdong; Chen, Yuan; ...

2017-08-01

The exploration of non-noble-metal catalysts for high efficiency gasification of biomass in supercritical water (SCW) is of great significance for the sustainable development. A series of Ni–M (M = Co or Zn) bimetallic nanoparticles supported on graphitized carbon black were synthesized and examined as catalysts for gasification of phenol in SCW. We found that a nearly complete gasification of phenol can be achieved even at a low temperature of 450 °C with the bimetallic nanoparticles catalysts. Kinetic study indicated the activation energy for phenol gasification were 20.4 ± 2.6 and 43.6 ± 2.6 kJ/mol for Ni20Zn15 and Ni20Co15 catalyst, respectively.more » Furthermore, XRD, XPS and TEM were performed to characterize the catalysts and the results showed the formation of NiCo and NiZn alloy phase. Catalyst recycling experiments were also conducted to evaluate the stability of the catalysts. The characterization of used catalysts suggest that the severe agglomeration of nanoparticles leads to the decrease in catalytic activity.« less

Noble-metal-free bimetallic alloy nanoparticle-catalytic gasification of phenol in supercritical water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Lijuan; Yu, Jiangdong; Chen, Yuan

The exploration of non-noble-metal catalysts for high efficiency gasification of biomass in supercritical water (SCW) is of great significance for the sustainable development. A series of Ni–M (M = Co or Zn) bimetallic nanoparticles supported on graphitized carbon black were synthesized and examined as catalysts for gasification of phenol in SCW. We found that a nearly complete gasification of phenol can be achieved even at a low temperature of 450 °C with the bimetallic nanoparticles catalysts. Kinetic study indicated the activation energy for phenol gasification were 20.4 ± 2.6 and 43.6 ± 2.6 kJ/mol for Ni20Zn15 and Ni20Co15 catalyst, respectively.more » Furthermore, XRD, XPS and TEM were performed to characterize the catalysts and the results showed the formation of NiCo and NiZn alloy phase. Catalyst recycling experiments were also conducted to evaluate the stability of the catalysts. The characterization of used catalysts suggest that the severe agglomeration of nanoparticles leads to the decrease in catalytic activity.« less

Pulsed supercritical synthesis of anatase TiO₂ nanoparticles in a water-isopropanol mixture studied by in situ powder X-ray diffraction.

PubMed

Rostgaard Eltzholtz, Jakob; Tyrsted, Christoffer; Ørnsbjerg Jensen, Kirsten Marie; Bremholm, Martin; Christensen, Mogens; Becker-Christensen, Jacob; Brummerstedt Iversen, Bo

2013-03-21

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.

Effect of cold work on the stress corrosion cracking behavior of Alloy 690 in supercritical water environment

NASA Astrophysics Data System (ADS)

Chen, Kai; Du, Donghai; Gao, Wenhua; Guo, Xianglong; Zhang, Lefu; Andresen, Peter L.

2018-01-01

The stress corrosion cracking (SCC) behavior of Alloy 690 with 0, 20% and 30% cold work (CW) was studied in supercritical water (SCW) environment with an emphasis on CW and creep on the CGRs (CGR). SCC and creep CGRs increased with %CW, which correlated hardness very well. Microscopic characterization of the crack tip and fracture surface showed obvious cavity-like features, which is clear evidence of creep attack. The creep CGRs in inert gas were comparable to the SCC CGRs in SCW, indicating that creep is a major factor in crack growth. Increasing level of CW was found to increase the creep susceptibility, and high activation energies for creep crack growth were observed between 500 °C and 550 °C.

Anomalous sorption of supercritical fluids on polymer thin films.

PubMed

Wang, Xiaochu; Sanchez, Isaac C

2006-10-24

Unusual sorption has been reported in thin polymer films exposed to near-critical CO2. When the supercritical fluid approaches the critical point, the film appears to thicken, but it is not clear whether the film swells or there is an adsorption layer on the film surface. A combination of the gradient theory of inhomogeneous systems and the Sanchez-Lacombe equation of state has been used to investigate this phenomenon. It is shown analytically that surface adsorption on an attractive surface is proportional to the compressibility of the fluid. We have also investigated numerically the sorption of supercritical CO2 on poly(dimethylsiloxane) and polyisobutylene, and supercritical 1,1-difluoroethane on polystyrene. By calculating the Gibbs adsorption and adsorption layer thickness of the supercritical fluids, we found in all cases (different substrates, different supercritical fluids) that maximum adsorption occurs when the supercritical fluid is near its compressibility maximum.

Control of the rate of cell enlargement: Excision, wall relaxation, and growth-induced water potentials.

PubMed

Boyer, J S; Cavalieri, A J; Schulze, E D

1985-04-01

A new guillotine thermocouple psychrometer was used to make continuous measurements of water potential before and after the excision of elongating and mature regions of darkgrown soybean (Glycine max L. Merr.) stems. Transpiration could not occur, but growth took place during the measurement if the tissue was intact. Tests showed that the instrument measured the average water potential of the sampled tissue and responded rapidly to changes in water potential. By measuring tissue osmotic potential (Ψ s ), turgor pressure (Ψ p ) could be calculated. In the intact plant, Ψ s and Ψ p were essentially constant for the entire 22 h measurement, but Ψ s was lower and Ψ p higher in the elongating region than in the mature region. This caused the water potential in the elongating region to be lower than in the mature region. The mature tissue equilibrated with the water potential of the xylem. Therefore, the difference in water potential between mature and elongating tissue represented a difference between the xylem and the elongating region, reflecting a water potential gradient from the xylem to the epidermis that was involved in supplying water for elongation. When mature tissue was excised with the guillotine, Ψ s and Ψ p did not change. However, when elongating tissue was excised, water was absorbed from the xylem, whose water potential decreased. This collapsed the gradient and prevented further water uptake. Tissue Ψ p then decreased rapidly (5 min) by about 0.1 MPa in the elongating tissue. The Ψ p decreased because the cell walls relaxed as extension, caused by Ψ p , continued briefly without water uptake. The Ψ p decreased until the minimum for wall extension (Y) was reached, whereupon elongation ceased. This was followed by a slow further decrease in Y but no additional elongation. In elongating tissue excised with mature tissue attached, there was almost no effect on water potential or Ψ p for several hours. Nevertheless, growth was reduced

Pore-scale imaging of capillary trapped supercritical CO2 as controlled by water-wet vs. CO2-wet media and grain shapes

NASA Astrophysics Data System (ADS)

Chaudhary, K.; Cardenas, M.; Wolfe, W. W.; Maisano, J. A.; Ketcham, R. A.; Bennett, P.

2013-12-01

The capillary trapping of supercritical CO2 (s-CO2) is postulated to comprise up to 90% of permanently trapped CO2 injected during geologic sequestration. Successive s-CO2/brine flooding experiments under reservoir conditions showed that water-wet rounded beads trapped 15% of injected s-CO2 both as clusters and as individual ganglia, whereas CO2¬-wet beads trapped only 2% of the injected s-CO2 as minute pockets in pore constrictions. Angular water-wet grains trapped 20% of the CO2 but flow was affected by preferential flow. Thus, capillary trapping is a viable mechanism for the permanent CO2 storage, but its success is constrained by the media wettability.

Large Eddy Simulation of Supercritical CO2 Through Bend Pipes

NASA Astrophysics Data System (ADS)

He, Xiaoliang; Apte, Sourabh; Dogan, Omer

2017-11-01

Supercritical Carbon Dioxide (sCO2) is investigated as working fluid for power generation in thermal solar, fossil energy and nuclear power plants at high pressures. Severe erosion has been observed in the sCO2 test loops, particularly in nozzles, turbine blades and pipe bends. It is hypothesized that complex flow features such as flow separation and property variations may lead to large oscillations in the wall shear stresses and result in material erosion. In this work, large eddy simulations are conducted at different Reynolds numbers (5000, 27,000 and 50,000) to investigate the effect of heat transfer in a 90 degree bend pipe with unit radius of curvature in order to identify the potential causes of the erosion. The simulation is first performed without heat transfer to validate the flow solver against available experimental and computational studies. Mean flow statistics, turbulent kinetic energy, shear stresses and wall force spectra are computed and compared with available experimental data. Formation of counter-rotating vortices, named Dean vortices, are observed. Secondary flow pattern and swirling-switching flow motions are identified and visualized. Effects of heat transfer on these flow phenomena are then investigated by applying a constant heat flux at the wall. DOE Fossil Energy Crosscutting Technology Research Program.

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.

Supercritical fluid technology: concepts and pharmaceutical applications.

PubMed

Deshpande, Praful Balavant; Kumar, G Aravind; Kumar, Averineni Ranjith; Shavi, Gopal Venkatesh; Karthik, Arumugam; Reddy, Meka Sreenivasa; Udupa, Nayanabhirama

2011-01-01

In light of environmental apprehension, supercritical fluid technology (SFT) exhibits excellent opportunities to accomplish key objectives in the drug delivery sector. Supercritical fluid extraction using carbon dioxide (CO(2)) has been recognized as a green technology. It is a clean and versatile solvent with gas-like diffusivity and liquid-like density in the supercritical phase, which has provided an excellent alternative to the use of chemical solvents. The present commentary provides an overview of different techniques using supercritical fluids and their future opportunity for the drug delivery industry. Some of the emerging applications of SFT in pharmaceuticals, such as particle design, drug solubilization, inclusion complex, polymer impregnation, polymorphism, drug extraction process, and analysis, are also covered in this review. The data collection methods are based on the recent literature related to drug delivery systems using SFT platforms. SFT has become a much more versatile and environmentally attractive technology that can handle a variety of complicated problems in pharmaceuticals. This cutting-edge technology is growing predominantly to surrogate conventional unit operations in relevance to the pharmaceutical production process. Supercritical fluid technology has recently drawn attention in the field of pharmaceuticals. It is a distinct conception that utilizes the solvent properties of supercritical fluids above their critical temperature and pressure, where they exhibit both liquid-like and gas-like properties, which can enable many pharmaceutical applications. For example, the liquid-like properties provide benefits in extraction processes of organic solvents or impurities, drug solubilization, and polymer plasticization, and the gas-like features facilitate mass transfer processes. It has become a much more versatile and environmentally attractive technology that can handle a variety of complicated problems in pharmaceuticals. This review is

Forsterite Carbonation in Wet Supercritical CO2 and Sodium Citrate

NASA Astrophysics Data System (ADS)

Qiu, L.; Schaef, T.; Wang, Z.; Miller, Q.; McGrail, P.

2013-12-01

Lin Qiu1*, Herbert T. Schaef2, Zhengrong Wang1, Quin R.S. Miller3, BP McGrail2 1. Yale University, New Haven, CT, USA 2. Pacific Northwest National Laboratory, Richland, WA, USA 3. University of Wyoming, Laramie, WY, USA Geologic reservoirs for managing carbon emissions (mostly CO2) have expanded over the last 5 years to include unconventional formations including basalts and fractured shales. Recently, ~1000 metric tons of CO2 was injected into the Columbia River Basalt (CRB) in Eastern Washington as part of the Wallula Pilot Project, Big Sky Regional Carbon Partnership. Based on reservoir conditions, the injected CO2 is present as a supercritical fluid that dissolves into the formation water over time, and reacts with basalt components to form carbonate minerals. In this paper, we discuss mineral transformation reactions occurring when the forsterite (Mg2SiO4) is exposed to wet scCO2 in equilibrium with pure water and sodium citrate solutions. Forsterite was selected as it is an important olivine group mineral present in igneous and mafic rocks. Citrate was selected as it has been shown to enhance mineral dissolution and organic ligands are possible degradation products of the microbial communities present in the formational waters of the CRB. For the supercritical phase, transformation reactions were examined by in situ high pressure x-ray diffraction (HXRD) in the presence of supercritical carbon dioxide (scCO2) in contact with water and sodium citrate solutions at conditions relevant to carbon sequestration. Experimental results show close-to-complete dissolution of forsterite in contact with scCO2 equilibrated with pure water for 90 hours (90 bar and 50°C). Under these conditions, thin films of water coated the mineral surface, providing a mechanism for silicate dissolution and transport of cations necessary for carbonate formation. The primary crystalline component initially detected with in situ HXRD was the hydrated magnesium carbonate, nesquehonite [Mg

On-line coupling of supercritical fluid extraction and chromatographic techniques.

PubMed

Sánchez-Camargo, Andrea Del Pilar; Parada-Alfonso, Fabián; Ibáñez, Elena; Cifuentes, Alejandro

2017-01-01

This review summarizes and discusses recent advances and applications of on-line supercritical fluid extraction coupled to liquid chromatography, gas chromatography, and supercritical fluid chromatographic techniques. Supercritical fluids, due to their exceptional physical properties, provide unique opportunities not only during the extraction step but also in the separation process. Although supercritical fluid extraction is especially suitable for recovery of non-polar organic compounds, this technique can also be successfully applied to the extraction of polar analytes by the aid of modifiers. Supercritical fluid extraction process can be performed following "off-line" or "on-line" approaches and their main features are contrasted herein. Besides, the parameters affecting the supercritical fluid extraction process are explained and a "decision tree" is for the first time presented in this review work as a guide tool for method development. The general principles (instrumental and methodological) of the different on-line couplings of supercritical fluid extraction with chromatographic techniques are described. Advantages and shortcomings of supercritical fluid extraction as hyphenated technique are discussed. Besides, an update of the most recent applications (from 2005 up to now) of the mentioned couplings is also presented in this review. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical models for supercritical fluid extraction.

PubMed

Huang, Zhen; Shi, Xiao-Han; Jiang, Wei-Juan

2012-08-10

For the proper design of supercritical fluid extraction processes, it is essential to have a sound knowledge of the mass transfer mechanism of the extraction process and the appropriate mathematical representation. In this paper, the advances and applications of kinetic models for describing supercritical fluid extraction from various solid matrices have been presented. The theoretical models overviewed here include the hot ball diffusion, broken and intact cell, shrinking core and some relatively simple models. Mathematical representations of these models have been in detail interpreted as well as their assumptions, parameter identifications and application examples. Extraction process of the analyte solute from the solid matrix by means of supercritical fluid includes the dissolution of the analyte from the solid, the analyte diffusion in the matrix and its transport to the bulk supercritical fluid. Mechanisms involved in a mass transfer model are discussed in terms of external mass transfer resistance, internal mass transfer resistance, solute-solid interactions and axial dispersion. The correlations of the external mass transfer coefficient and axial dispersion coefficient with certain dimensionless numbers are also discussed. Among these models, the broken and intact cell model seems to be the most relevant mathematical model as it is able to provide realistic description of the plant material structure for better understanding the mass-transfer kinetics and thus it has been widely employed for modeling supercritical fluid extraction of natural matters. Copyright © 2012 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rother, Gernot; Vlcek, Lukas; Gruszkiewicz, Miroslaw

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 formore » 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.« less

Design of Test Loops for Forced Convection Heat Transfer Studies at Supercritical State

NASA Astrophysics Data System (ADS)

Balouch, Masih N.

Worldwide research is being conducted to improve the efficiency of nuclear power plants by using supercritical water (SCW) as the working fluid. One such SCW reactor considered for future development is the CANDU-Supercritical Water Reactor (CANDU-SCWR). For safe and accurate design of the CANDU-SCWR, a detailed knowledge of forced-convection heat transfer in SCW is required. For this purpose, two supercritical fluid loops, i.e. a SCW loop and an R-134a loop are developed at Carleton University. The SCW loop is designed to operate at pressures as high as 28 MPa, temperatures up to 600 °C and mass fluxes of up to 3000 kg/m2s. The R-134a loop is designed to operate at pressures as high as 6 MPa, temperatures up to 140 °C and mass fluxes in the range of 500-6000 kg/m2s. The test loops designs allow for up to 300 kW of heating power to be imparted to the fluid. Both test loops are of the closed-loop design, where flow circulation is achieved by a centrifugal pump in the SCW loop and three parallel-connected gear pumps in the R-134a loop, respectively. The test loops are pressurized using a high-pressure nitrogen cylinder and accumulator assembly, which allows independent control of the pressure, while simultaneously dampening pump induced pressure fluctuations. Heat exchangers located upstream of the pumps control the fluid temperature in the test loops. Strategically located measuring instrumentation provides information on the flow rate, pressure and temperature in the test loops. The test loops have been designed to accommodate a variety of test-section geometries, ranging from a straight circular tube to a seven-rod bundle, achieving heat fluxes up to 2.5 MW/m2 depending on the test-section geometry. The design of both test loops allows for easy reconfiguration of the test-section orientation relative to the gravitational direction. All the test sections are of the directly-heated design, where electric current passing through the pressure retaining walls of the

Effects of spatial gradients in thermophysical properties on the topology of turbulence in heated channel flow of supercritical fluids

NASA Astrophysics Data System (ADS)

Azih, Chukwudi; Yaras, Metin I.

2018-01-01

The current literature suggests that large spatial gradients of thermophysical properties, which occur in the vicinity of the pseudo-critical thermodynamic state, may result in significant variations in forced-convection heat transfer rates. Specifically, these property gradients induce inertia- and buoyancy-driven phenomena that may enhance or deteriorate the turbulence-dominated heat convection process. Through direct numerical simulations, the present study investigates the role of coherent flow structures in channel geometries for non-buoyant and buoyant flows of supercritical water, with buoyant configurations involving wall-normal oriented gravitational acceleration and downstream-oriented gravitational acceleration. This sequence of simulations enables the evaluation of the relative contributions of inertial and buoyancy phenomena to heat transfer variations. In these simulations, the state of the working fluid is in the vicinity of the pseudo-critical point. The uniform wall heat flux and the channel mass flux are specified such that the heat to mass flux ratio is 3 kJ/kg, with an inflow Reynolds number of 12 000 based on the channel hydraulic diameter, the area-averaged inflow velocity, and fluid properties evaluated at the bulk temperature and pressure of the inflow plane. In the absence of buoyancy forces, notable reductions in the density and viscosity in close proximity of the heated wall are observed to promote generation of small-scale vortices, with resultant breakdown into smaller scales as they interact with preexisting larger near-wall vortices. This interaction results in a reduction in the overall thermal mixing at particular wall-normal regions of the channel. Under the influence of wall-normal gravitational acceleration, the wall-normal density gradients are noted to enhance ejection motions due to baroclinic vorticity generation on the lower wall, thus providing additional wall-normal thermal mixing. Along the upper wall, the same mechanism

Nested subcritical flows within supercritical systems

NASA Technical Reports Server (NTRS)

Hendricks, R. C.; Braun, M. J.; Wheeler, R. L., III; Mullen, R. L.

1985-01-01

In supercritical systems the design inlet and outlet pressures are maintained above the thermaodynamic critical pressure P sub C. Designers rely on this simple rule of thumb to circumvent problems associated with a subcritical pressure regime nested within the supercritical pressure system along with the uncertainties in heat transfer, fluid mechanics, and thermophysical property variations. The simple rule of thumb is adequate in many low-power designs but is inadequate for high-performance turbomachines and linear systems, where nested two-phase regions can exist. Examples for a free-jet expansion with backpressure greater than P sub C and a rotor (bearing) with ambient pressure greater than P sub C illustrate the existence of subcritical pressure regimes nested within supercritical systems.

A three step supercritical process to improve the dissolution rate of eflucimibe.

PubMed

Rodier, Elisabeth; Lochard, Hubert; Sauceau, Martial; Letourneau, Jean-Jacques; Freiss, Bernard; Fages, Jacques

2005-10-01

The aim of this study is to improve the dissolution properties of a poorly-soluble active substance, Eflucimibe by associating it with gamma-cyclodextrin. To achieve this objective, a new three-step process based on supercritical fluid technology has been proposed. First, Eflucimibe and cyclodextrin are co-crystallized using an anti-solvent process, dimethylsulfoxide being the solvent and supercritical carbon dioxide being the anti-solvent. Second, the co-crystallized powder is held in a static mode under supercritical conditions for several hours. This is the maturing step. Third, in a final stripping step, supercritical CO(2) is flowed through the matured powder to extract the residual solvent. The coupling of the first two steps brings about a significant synergistic effect to improve the dissolution rate of the drug. The nature of the entity obtained at the end of each step is discussed and some suggestions are made as to what happens in these operations. It is shown the co-crystallization ensures a good dispersion of both compounds and is rather insensitive to the operating parameters tested. The maturing step allows some dissolution-recrystallization to occur thus intensifying the intimate contact between the two compounds. Addition of water is necessary to make maturing effective as this is governed by the transfer properties of the medium. The stripping step allows extraction of the residual solvent but also removes some of the Eflucimibe which is the main drawback of this final stage.

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.

Structure of solvates of o-hydroxybenzoic acid in supercritical CO2-cosolvent media, according to molecular dynamics data

NASA Astrophysics Data System (ADS)

Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.

2015-03-01

Three-component supercritical carbon dioxide-cosolvent (methanol, ethanol, water)- o-hydroxybenzoic acid ( o-HBA) mixtures at a density of 0.7 g/cm3 and temperatures of 318 and 348 K are simulated by means of molecular dynamics. The solvate structures are investigated. It is shown that the solvation mechanism of o-HBA (particularly the o-HBA molecule forming a stable solvate complex with one molecule of a cosolvent via a hydrogen bond through the carboxyl group) does not depend on the temperature or the cosolvent. It is noted that the form of the cosolvent in a supercritical fluid varies: alcohols are distributed in the bulk in the form of monomers and hydrogen-bonded dimers, and water molecules tend to form microclusters along with chained and spatially branched structures by means of hydrogen bonds. It is established that the local molar fraction of cosolvent around the solvate complexes grows. It is concluded that the solvation of o-HBA is determined by the behavior of cosolvent in media of supercritical CO2.

An experimental study of wall adaptation and interference assessment using Cauchy integral formula

NASA Technical Reports Server (NTRS)

Murthy, A. V.

1991-01-01

This paper summarizes the results of an experimental study of combined wall adaptation and residual interference assessment using the Cauchy integral formula. The experiments were conducted on a supercritical airfoil model in the Langley 0.3-m Transonic Cryogenic Tunnel solid flexible wall test section. The ratio of model chord to test section height was about 0.7. The method worked satisfactorily in reducing the blockage interference and demonstrated the primary requirement for correcting for the blockage effects at high model incidences to correctly determine high lift characteristics. The studies show that the method has potential for reducing the residual interference to considerably low levels. However, corrections to blockage and upwash velocities gradients may still be required for the final adapted wall shapes.

Effects of salinity and the extent of water on supercritical CO2-induced phlogopite dissolution and secondary mineral formation.

PubMed

Shao, Hongbo; Ray, Jessica R; Jun, Young-Shin

2011-02-15

To ensure the viability of geologic CO2 sequestration (GCS), we need a holistic understanding of reactions at supercritical CO2 (scCO2)-saline water-rock interfaces and the environmental factors affecting these interactions. This research investigated the effects of salinity and the extent of water on the dissolution and surface morphological changes of phlogopite [KMg2.87Si3.07Al1.23O10(F,OH)2], a model clay mineral in potential GCS sites. Salinity enhanced the dissolution of phlogopite and affected the location, shape, size, and phase of secondary minerals. In low salinity solutions, nanoscale particles of secondary minerals formed much faster, and there were more nanoparticles than in high salinity solutions. The effect of water extent was investigated by comparing scCO2-H2O(g)-phlogopite and scCO2-H2O(l)-phlogopite interactions. Experimental results suggested that the presence of a thin water film adsorbed on the phlogopite surface caused the formation of dissolution pits and a surface coating of secondary mineral phases that could change the physical properties of rocks. These results provide new information for understanding reactions at scCO2-saline water-rock interfaces in deep saline aquifers and will help design secure and environmentally sustainable CO2 sequestration projects.

TUBEWALL: a passive solar thermo-siphoning, field-fabricated, water storage wall system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, F.; Hemker, P.

1980-01-01

The basic component of TUBEWALL is a water-filled thin-wall cylindrical tube with an insulating foam vertical partition insert that divides the inside of the tube into a thin collector water compartment (solar side) and a larger storage water compartment (room side). The two compartments are connected at the top and bottom by means of circulation holes in the foam partition. When the sun strikes the solar side of the tube, the thin layer of collector water is heated, thermosiphons through the top opening in the partition into the larger storage compartment on the room side, and is replaced with coolmore » water drawn from the bottom of the storage through the bottom hole in the partition. Night back-siphonage is prevented by a thin flap valve over the top circulation hole. The tubes may by used between wall studs having a low-cost fiberglass/tedlar double glazing. The tubes can be covered on the room side with drywall and heat transferred to the living space by indirect radiation, and either natural air convection through top and bottom vent slots or by fan. Alternatively, the tubes can be left exposed for direct radiation.« less

Turbulent convective heat transfer of methane at supercritical pressure in a helical coiled tube

NASA Astrophysics Data System (ADS)

Wang, Chenggang; Sun, Baokun; Lin, Wei; He, Fan; You, Yingqiang; Yu, Jiuyang

2018-02-01

The heat transfer of methane at supercritical pressure in a helically coiled tube was numerically investigated using the Reynolds Stress Model under constant wall temperature. The effects of mass flux ( G), inlet pressure ( P in) and buoyancy force on the heat transfer behaviors were discussed in detail. Results show that the light fluid with higher temperature appears near the inner wall of the helically coiled tube. When the bulk temperature is less than or approach to the pseudocritical temperature ( T pc ), the combined effects of buoyancy force and centrifugal force make heavy fluid with lower temperature appear near the outer-right of the helically coiled tube. Beyond the T pc , the heavy fluid with lower temperature moves from the outer-right region to the outer region owing to the centrifugal force. The buoyancy force caused by density variation, which can be characterized by Gr/ Re 2 and Gr/ Re 2.7, enhances the heat transfer coefficient ( h) when the bulk temperature is less than or near the T pc , and the h experiences oscillation due to the buoyancy force. The oscillation is reduced progressively with the increase of G. Moreover, h reaches its peak value near the T pc . Higher G could improve the heat transfer performance in the whole temperature range. The peak value of h depends on P in. A new correlation was proposed for methane at supercritical pressure convective heat transfer in the helical tube, which shows a good agreement with the present simulated results.

Supercritical carbon dioxide design strategies: from drug carriers to soft killers.

PubMed

Aguiar-Ricardo, Ana; Bonifácio, Vasco D B; Casimiro, Teresa; Correia, Vanessa G

2015-12-28

The integrated use of supercritical carbon dioxide (scCO(2)) and micro- and nanotechnologies has enabled new sustainable strategies for the manufacturing of new medications. 'Green' scCO(2)-based methodologies are well suited to improve either the synthesis or materials processing leading to the assembly of three-dimensional multifunctional constructs. By using scCO(2) either as C1 feedstock or as solvent, simple, economic, efficient and clean routes can be designed to synthesize materials with unique properties such as polyurea dendrimers and oxazoline-based polymers/oligomers. These new biocompatible, biodegradable and water-soluble polymeric materials can be engineered into multifunctional constructs with antimicrobial activity, targeting moieties, labelling units and/or efficiently loaded with therapeutics. This mini-review highlights the particular features exhibited by these materials resulting directly from the followed supercritical routes. © 2015 The Author(s).

Supercritical synthesis of biodiesel.

PubMed

Bernal, Juana M; Lozano, Pedro; García-Verdugo, Eduardo; Burguete, M Isabel; Sánchez-Gómez, Gregorio; López-López, Gregorio; Pucheault, Mathieu; Vaultier, Michel; Luis, Santiago V

2012-07-23

The synthesis of biodiesel fuel from lipids (vegetable oils and animal fats) has gained in importance as a possible source of renewable non-fossil energy in an attempt to reduce our dependence on petroleum-based fuels. The catalytic processes commonly used for the production of biodiesel fuel present a series of limitations and drawbacks, among them the high energy consumption required for complex purification operations and undesirable side reactions. Supercritical fluid (SCF) technologies offer an interesting alternative to conventional processes for preparing biodiesel. This review highlights the advances, advantages, drawbacks and new tendencies involved in the use of supercritical fluids (SCFs) for biodiesel synthesis.

Micelle-hosted palladium nanoparticles catalyze citral molecule hydrogenation in supercritical carbon dioxide.

PubMed

Meric, Pascal; Yu, Kai Man K; Tsang, Shik Chi

2004-09-28

A new approach of employing metal particles in micelles for the hydrogenation of organic molecules in the presence of fluorinated surfactant and water in supercritical carbon dioxide has very recently been introduced. This is allegedly to deliver many advantages for carrying out catalysis including the use of supercritical carbon dioxide (scCO2) as a greener solvent. Following this preliminary account, the present work aims to provide direct visual evidence on the formation of metal microemulsions and to investigate whether metal located in the soft micellar assemblies could affect reaction selectivity. Synthesis of Pd nanoparticles in perfluorohydrocarboxylate anionic micelles in scCO2 is therefore carried out in a stainless steel batch reactor at 40 degrees C and in a 150 bar CO2/H2 mixture. Homogeneous dispersion of the microemulsion containing Pd nanoparticles in scCO2 is observed through a sapphire window reactor at W0 ratios (molar water-to-surfactant ratios) ranging from 2 to 30. It is also evidenced that the use of micelle assemblies as new metal catalyst nanocarriers could indeed exert a great influence on product selectivity. The hydrogenation of a citral molecule that contains three reducible groups (aldehyde, double bonds at the 2,3-position and the 6,7-position) is studied. An unusually high selectivity toward citronellal (a high regioselectivity toward the reduction of the 2,3-unsaturation) is observed in supercritical carbon dioxide. On the other hand, when the catalysis is carried out in the conventional liquid or vapor phase over the same reaction time, total hydrogenation of the two double bonds is achieved. It is thought that the high kinetic reluctance for double bond hydrogenation of the citral molecule at the hydrophobic end (the 6,7-position) is due to the unique micelle environment that is in close proximity to the metal surface in supercritical carbon dioxide that guides a head-on attack of the molecule toward the core metal particle.

The development of a self-streamlining flexible walled transonic test section

NASA Technical Reports Server (NTRS)

Goodyer, M. J.; Wolf, S. W. D.

1980-01-01

This design eliminates the uncertainties in data from conventional transonic test sections. Sidewalls are rigid, and the flexible floor and ceiling are positioned by motorized jacks controlled by on-line computer to minimize run times. The tunnel-computer combination is self-streamlining without reference to the model. Data is taken from the model only when the walls are good streamlines, and is corrected for the small, known but inevitable residual interferences. Two-dimensional validation testing in the Mach range up to about 0.85 where the walls are just supercritical shows good agreement with reference data using a height:chord ratio of 1.5. Techniques are under development to extend Mach number above 1. This work has demonstrated the feasibility of almost eliminating wall interferences, improving flow quality, and reducing power requirements or increasing Reynolds number. Extensions to three-dimensional testing are outlined.

Supercritical fluid chromatographic resolution of water soluble isomeric carboxyl/amine terminated peptides facilitated via mobile phase water and ion pair formation.

PubMed

Patel, M A; Riley, F; Ashraf-Khorassani, M; Taylor, L T

2012-04-13

Both analytical scale and preparative scale packed column supercritical fluid chromatography (SFC) have found widespread applicability for chiral separations of multiple polar pharmaceutical candidates. However, SFC is rapidly becoming an achiral technique. More specifically, ion pair SFC is finding greater utility for separation of ionic analytes such as amine salts and organic sulfonates. The key to this success is, in part, the incorporation of additives such as trifluoroacetic acid and ammonium acetate into the mobile phase in association with a wide variety of both bonded silica stationary phases and high purity bare silica. Ion pairing SFC coupled with evaporative light scattering detection and mass spectrometric detection is presented here for the separation of water soluble, uncapped, isomeric peptide pairs that differ in amino acid arrangement. The separation is best achieved on either diol-bonded silica or bare silica with 1-5% (w/w) water as a significant ingredient in the mobile phase. Nitrogenous stationary phases such as 2-ethylpyridine, which had been very successful for the separation of capped peptides failed to yield the desired separation regardless of the mobile phase composition. A HILIC type retention mechanism is postulated for the separation of both isomeric uncapped peptide pairs. Copyright © 2012 Elsevier B.V. All rights reserved.

Effect of supercritical fluid density on nanoencapsulated drug particle size using the supercritical antisolvent method.

PubMed

Kalani, Mahshid; Yunus, Robiah

2012-01-01

The reported work demonstrates and discusses the effect of supercritical fluid density (pressure and temperature of supercritical fluid carbon dioxide) on particle size and distribution using the supercritical antisolvent (SAS) method in the purpose of drug encapsulation. In this study, paracetamol was encapsulated inside L-polylactic acid, a semicrystalline polymer, with different process parameters, including pressure and temperature, using the SAS process. The morphology and particle size of the prepared nanoparticles were determined by scanning electron microscopy and transmission electron microscopy. The results revealed that increasing temperature enhanced mean particle size due to the plasticizing effect. Furthermore, increasing pressure enhanced molecular interaction and solubility; thus, particle size was reduced. Transmission electron microscopy images defined the internal structure of nanoparticles. Thermal characteristics of nanoparticles were also investigated via differential scanning calorimetry. Furthermore, X-ray diffraction pattern revealed the changes in crystallinity structure during the SAS process. In vitro drug release analysis determined the sustained release of paracetamol in over 4 weeks.

Effect of supercritical fluid density on nanoencapsulated drug particle size using the supercritical antisolvent method

PubMed Central

Kalani, Mahshid; Yunus, Robiah

2012-01-01

The reported work demonstrates and discusses the effect of supercritical fluid density (pressure and temperature of supercritical fluid carbon dioxide) on particle size and distribution using the supercritical antisolvent (SAS) method in the purpose of drug encapsulation. In this study, paracetamol was encapsulated inside L-polylactic acid, a semicrystalline polymer, with different process parameters, including pressure and temperature, using the SAS process. The morphology and particle size of the prepared nanoparticles were determined by scanning electron microscopy and transmission electron microscopy. The results revealed that increasing temperature enhanced mean particle size due to the plasticizing effect. Furthermore, increasing pressure enhanced molecular interaction and solubility; thus, particle size was reduced. Transmission electron microscopy images defined the internal structure of nanoparticles. Thermal characteristics of nanoparticles were also investigated via differential scanning calorimetry. Furthermore, X-ray diffraction pattern revealed the changes in crystallinity structure during the SAS process. In vitro drug release analysis determined the sustained release of paracetamol in over 4 weeks. PMID:22619552

Numerical Study on the Heat Transfer of Carbon Dioxide in Horizontal Straight Tubes under Supercritical Pressure

PubMed Central

Yang, Mei

2016-01-01

Cooling heat transfer of supercritical CO2 in horizontal straight tubes with wall is numerically investigated by using FLUENT. The results show that almost all models are able to present the trend of heat transfer qualitatively, and the stand k−ε with enhanced wall treatment model shows the best agreement with the experimental data, followed by LB low Re turbulence model. Then further studies are discussed on velocity, temperature and turbulence distributions. The parameters which are defined as the criterion of buoyancy effect on convection heat transfer are introduced to judge the condition of the fluid. The relationships among the inlet temperature, outlet temperature, the mass flow rate, the heat flux and the diameter are discussed and the difference between the cooling and heating of CO2 are compared. PMID:27458729

Subcritical and supercritical technology for the production of second generation bioethanol.

PubMed

Rostagno, Mauricio A; Prado, Juliana M; Mudhoo, Ackmez; Santos, Diego T; Forster-Carneiro, Tânia; Meireles, M Angela A

2015-01-01

There is increased interest in reducing our reliance on fossil fuels and increasing the share of renewable raw materials in our energy supply chain due to environmental and economic concerns. Ethanol is emerging as a potential alternative to liquid fuels due to its eco-friendly characteristics and relatively low production costs. As ethanol is currently produced from commodities also used for human and animal consumption, there is an urgent need of identifying renewable raw materials that do not pose a competitive problem. Lignocellulosic agricultural residues are an ideal choice since they can be effectively hydrolyzed to fermentable sugars and integrated in the context of a biorefinery without competing with the food supply chain. However, the conventional hydrolysis methods still have major issues that need to be addressed. These issues are related to the processing rate and generation of fermentation inhibitors, which can compromise the quality of the product and the cost of the process. As the knowledge of the processes taking place during hydrolysis of agricultural residues is increasing, new techniques are being exploited to overcome these drawbacks. This review gives an overview of the state-of-the-art of hydrolysis with subcritical and supercritical water in the context of reusing agricultural residues for the production of suitable substrates to be processed during the fermentative production of bioethanol. Presently, subcritical and/or supercritical water hydrolysis has been found to yield low sugar contents mainly due to concurrent competing degradation of sugars during the hydrothermal processes. In this line of thinking, the present review also revisits the recent applications and advances to provide an insight of future research trends to optimize on the subcritical and supercritical process kinetics.

Controllable synthesis of Ce{sub 1-x}Zr{sub x}O{sub 2} hollow nanospheres via supercritical anti-solvent precipitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang Haoxi; Post-Doctor Station for Science and Technology of Chemical Engineering and Technology, Tianjin University, Tianjin 300072; Post-Doctor Workstation for Science and Technology, Shandong Haihua Group Co. Ltd, Weifang, Shandong 262737

2012-01-15

Nanocrystalline Ce{sub 1-x}Zr{sub x}O{sub 2} hollow nanospheres were successfully synthesized via supercritical anti-solvent precipitation using supercritical CO{sub 2} as the anti-solvent. It was found that the as-produced samples exhibited hollow spherical structures with uniform diameters ranging from 30 to 50 nm and the sphere walls were composed of various oriented nanocrystallites, with sizes of 3-7 nm. The results of high-resolution transmission electron microscopy showed that the formation of the hollow structures could be controlled by adjusting the solution concentration. The results of temperature-programmed reduction and oxygen storage capacity measurements showed that the hollow nanospheres had enhanced redox properties. A possiblemore » mechanism for the formation of Ce{sub 1-x}Zr{sub x}O{sub 2} hollow nanospheres has also been proposed and experimental investigated.« less

The vacuum system reform and test of the super-critical 600mw unit

NASA Astrophysics Data System (ADS)

Yan, Tao; Wan, Zhonghai; Lu, Jin; Chen, Wen; Cai, Wen

2017-11-01

The deficiencies of the designed vacuum system of the super-critical unit is pointed out in this paper, and then it is reformed by the steam ejector. The experimental results show that the vacuum of the condenser can be improved, the coal consumption can be reduced and the plant electricity consumption can be lowered dramatically at a small cost of the steam energy consumption. Meanwhile, the water-ring vacuum pumps cavitation problems can be solved.

Single-Walled Carbon Nanotubes as Fluorescence Biosensors for Pathogen Recognition in Water Systems

DOE PAGES

Upadhyayula, Venkata K. K.; Ghoshroy, Soumitra; Nair, Vinod S.; ...

2008-01-01

Tmore » he possibility of using single-walled carbon nanotubes (SWCNs) aggregates as fluorescence sensors for pathogen recognition in drinking water treatment applications has been studied. Batch adsorption study is conducted to adsorb large concentrations of Staphylococcus aureus aureus SH 1000 and Escherichia coli pKV-11 on single-walled carbon nanotubes. Subsequently the immobilized bacteria are detected with confocal microscopy by coating the nanotubes with fluorescence emitting antibodies. he Freundlich adsorption equilibrium constant ( k ) for S.aureus and E.coli determined from batch adsorption study was found to be 9 × 10 8 and 2 × 10 8  ml/g, respectively. he visualization of bacterial cells adsorbed on fluorescently modified carbon nanotubes is also clearly seen. he results indicate that hydrophobic single-walled carbon nanotubes have excellent bacterial adsorption capacity and fluorescent detection capability. his is an important advancement in designing fluorescence biosensors for pathogen recognition in water systems.« less

Hydroelectric voltage generation based on water-filled single-walled carbon nanotubes.

PubMed

Yuan, Quanzi; Zhao, Ya-Pu

2009-05-13

A DFT/MD mutual iterative method was employed to give insights into the mechanism of voltage generation based on water-filled single-walled carbon nanotubes (SWCNTs). Our calculations showed that a constant voltage difference of several mV would generate between the two ends of a carbon nanotube, due to interactions between the water dipole chains and charge carriers in the tube. Our work validates this structure of a water-filled SWCNT as a promising candidate for a synthetic nanoscale power cell, as well as a practical nanopower harvesting device at the atomic level.

Investigation of Instabilities and Heat Transfer Phenomena in Supercritical Fuels at High Heat Flux and Temperatures

NASA Technical Reports Server (NTRS)

Linne, Diane L.; Meyer, Michael L.; Braun, Donald C.; Keller, Dennis J.

2000-01-01

A series of heated tube experiments was performed to investigate fluid instabilities that occur during heating of supercritical fluids. In these tests, JP-7 flowed vertically through small diameter tubes at supercritical pressures. Test section heated length, diameter, mass flow rate, inlet temperature, and heat flux were varied in an effort to determine the range of conditions that trigger the instabilities. Heat flux was varied up to 4 BTU/sq in./s, and test section wall temperatures reached as high as 1950 F. A statistical model was generated to explain the trends and effects of the control variables. The model included no direct linear effect of heat flux on the occurrence of the instabilities. All terms involving inlet temperature were negative, and all terms involving mass flow rate were positive. Multiple tests at conditions that produced instabilities provided inconsistent results. These inconsistencies limit the use of the model as a predictive tool. Physical variables that had been previously postulated to control the onset of the instabilities, such as film temperature, velocity, buoyancy, and wall-to-bulk temperature ratio, were evaluated here. Film temperatures at or near critical occurred during both stable and unstable tests. All tests at the highest velocity were stable, but there was no functional relationship found between the instabilities and velocity, or a combination of velocity and temperature ratio. Finally, all of the unstable tests had significant buoyancy at the inlet of the test section, but many stable tests also had significant buoyancy forces.

Fundamental study of CO2-H2O-mineral interactions for carbon sequestration, with emphasis on the nature of the supercritical fluid-mineral interface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bryan, Charles R.; Dewers, Thomas A.; Heath, Jason E.

2013-09-01

In the supercritical CO2-water-mineral systems relevant to subsurface CO2 sequestration, interfacial processes at the supercritical fluid-mineral interface will strongly affect core- and reservoir-scale hydrologic properties. Experimental and theoretical studies have shown that water films will form on mineral surfaces in supercritical CO2, but will be thinner than those that form in vadose zone environments at any given matric potential. The theoretical model presented here allows assessment of water saturation as a function of matric potential, a critical step for evaluating relative permeabilities the CO2 sequestration environment. The experimental water adsorption studies, using Quartz Crystal Microbalance and Fourier Transform Infrared Spectroscopymore » methods, confirm the major conclusions of the adsorption/condensation model. Additional data provided by the FTIR study is that CO2 intercalation into clays, if it occurs, does not involve carbonate or bicarbonate formation, or significant restriction of CO2 mobility. We have shown that the water film that forms in supercritical CO2 is reactive with common rock-forming minerals, including albite, orthoclase, labradorite, and muscovite. The experimental data indicate that reactivity is a function of water film thickness; at an activity of water of 0.9, the greatest extent of reaction in scCO2 occurred in areas (step edges, surface pits) where capillary condensation thickened the water films. This suggests that dissolution/precipitation reactions may occur preferentially in small pores and pore throats, where it may have a disproportionately large effect on rock hydrologic properties. Finally, a theoretical model is presented here that describes the formation and movement of CO2 ganglia in porous media, allowing assessment of the effect of pore size and structural heterogeneity on capillary trapping efficiency. The model results also suggest possible engineering approaches for optimizing trapping capacity and

Novel Supercritical Carbon Dioxide Power Cycle Utilizing Pressured Oxy-combustion in Conjunction with Cryogenic Compression

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brun, Klaus; McClung, Aaron; Davis, John

2014-03-31

features 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

Progressive Inhibition by Water Deficit of Cell Wall Extensibility and Growth along the Elongation Zone of Maize Roots Is Related to Increased Lignin Metabolism and Progressive Stelar Accumulation of Wall Phenolics1

PubMed Central

Fan, Ling; Linker, Raphael; Gepstein, Shimon; Tanimoto, Eiichi; Yamamoto, Ryoichi; Neumann, Peter M.

2006-01-01

Water deficit caused by addition of polyethylene glycol 6000 at −0.5 MPa water potential to well-aerated nutrient solution for 48 h inhibited the elongation of maize (Zea mays) seedling primary roots. Segmental growth rates in the root elongation zone were maintained 0 to 3 mm behind the tip, but in comparison with well-watered control roots, progressive growth inhibition was initiated by water deficit as expanding cells crossed the region 3 to 9 mm behind the tip. The mechanical extensibility of the cell walls was also progressively inhibited. We investigated the possible involvement in root growth inhibition by water deficit of alterations in metabolism and accumulation of wall-linked phenolic substances. Water deficit increased expression in the root elongation zone of transcripts of two genes involved in lignin biosynthesis, cinnamoyl-CoA reductase 1 and 2, after only 1 h, i.e. before decreases in wall extensibility. Further increases in transcript expression and increased lignin staining were detected after 48 h. Progressive stress-induced increases in wall-linked phenolics at 3 to 6 and 6 to 9 mm behind the root tip were detected by comparing Fourier transform infrared spectra and UV-fluorescence images of isolated cell walls from water deficit and control roots. Increased UV fluorescence and lignin staining colocated to vascular tissues in the stele. Longitudinal bisection of the elongation zone resulted in inward curvature, suggesting that inner, stelar tissues were also rate limiting for root growth. We suggest that spatially localized changes in wall-phenolic metabolism are involved in the progressive inhibition of wall extensibility and root growth and may facilitate root acclimation to drying environments. PMID:16384904

Effect of residence time on two-step liquefaction of rice straw in a CO2 atmosphere: Differences between subcritical water and supercritical ethanol.

PubMed

Yang, Tianhua; Wang, Jian; Li, Bingshuo; Kai, Xingping; Li, Rundong

2017-04-01

This study investigated the influence of temperature and residence time on liquefaction of rice straw in subcritical CO 2 -subcritical water (subCO 2 -subH 2 O) and in subcritical CO 2 -supercritical ethanol (subCO 2 -scEtOH), considering the final reaction temperatures (270-345°C) and residence times (15 and 30min). Residence time was identified as a crucial parameter in the subCO 2 -subH 2 O liquefaction, whereas residence time had a marginal influence on subCO 2 -scEtOH liquefaction. When reaction conditions were 320°C and 15min, solvents have weak impact on the quality of bio-oil, HHV 28.57MJ/kg and 28.62MJ/kg, respectively. There was an obvious difference between the subCO 2 -subH 2 O and subCO 2 -scEtOH liquefaction mechanisms. In subCO 2 -subH 2 O, CO 2 promoted the carbonyl reaction. In subCO 2 -scEtOH, supercritical ethanol have the function of donating hydrogen and promoting the reaction of hydroxyl-alkylation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemical Reactions in Supercritical Carbon Dioxide

NASA Astrophysics Data System (ADS)

Wai, Chien M.; Hunt, Fred; Ji, Min; Chen, Xiaoyuan

1998-12-01

Utilizing supercritical fluids as environmentally benign solvents for chemical synthesis is one of the new approaches in the "greening" of chemistry. Carbon dioxide is the most widely used gas for supercritical fluid studies because of its moderate critical constants, nontoxic nature, and availability in pure form. One unique property of supercritical carbon dioxide (sc-CO2) is its high solubility for fluorinated compounds. Thus sc-CO2 can be used to replace Freons that are conventionally used as solvents for synthesis of perfluoro-polymers. Another property of sc-CO2 is its miscibility with gases such as H2. Heterogeneous reactions involving these gases may become homogeneous reactions in sc-CO2. Reactions in sc-CO2 may offer several advantages including controlling phase behavior and products, increasing speed of reactions, and obtaining specific reaction channels. This paper describes the following nine types of chemical reactions reported in the literature utilizing sc-CO2 as a solvent to illustrate the unique properties of the supercritical fluid reaction systems: (i) hydrogenation and hydroformylation, (ii) synthesis of organometallic compounds, (iii) metal chelation and extraction, (iv) preparation of inorganic nanoparticles, (v) stereo-selectivity of lipase-catalyzed reactions, (vi) asymmetric catalytic hydrogenation, (vii) polymerization, (viii) Diels-Alder reaction, and (ix) free radical reactions.

Production of pure indinavir free base nanoparticles by a supercritical anti-solvent (SAS) method.

PubMed

Imperiale, Julieta C; Bevilacqua, Gabriela; Rosa, Paulo de Tarso Vieira E; Sosnik, Alejandro

2014-12-01

This work investigated the production of pure indinavir free base nanoparticles by a supercritical anti-solvent method to improve the drug dissolution in intestine-like medium. To increase the dissolution of the drug by means of a supercritical fluid processing method. Acetone was used as solvent and supercritical CO2 as antisolvent. Products were characterized by dynamic light scattering (size, size distribution), scanning electron microscopy (morphology), differential scanning calorimetry (thermal behaviour) and X-rays diffraction (crystallinity). Processed indinavir resulted in particles of significantly smaller size than the original drug. Particles showed at least one dimension at the nanometer scale with needle or rod-like morphology. Results of X-rays powder diffraction suggested the formation of a mixture of polymorphs. Differential scanning calorimetry analysis showed a main melting endotherm at 152 °C. Less prominent transitions due to the presence of small amounts of bound water (in the raw drug) or an unstable polymorph (in processed IDV) were also visible. Finally, drug particle size reduction significantly increased the dissolution rate with respect to the raw drug. Conversely, the slight increase of the intrinsic solubility of the nanoparticles was not significant. A supercritical anti-solvent method enabled the nanonization of indinavir free base in one single step with high yield. The processing led to faster dissolution that would improve the oral bioavailability of the drug.

Chitosan impregnation with biologically active tryaryl imidazoles in supercritical carbon dioxide.

PubMed

Cherkasova, Anastasia V; Glagolev, Nikolay N; Shienok, Andrey I; Demina, Tatiana S; Kotova, Svetlana L; Zaichenko, Natalia L; Akopova, Tatiana A; Timashev, Peter S; Bagratashvili, Victor N; Solovieva, Anna B

2016-09-01

The presented paper is focused on impregnation of chitosan and its derivatives with a biologically active triaryl imidazole model compound ((2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole) in the supercritical carbon dioxide medium. Since initial chitosan represents a polycation-exchange resin and does not swell in supercritical carbon dioxide, the impregnation was carried out in the presence of water (0.15-3.0 vol%). The maximum 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole concentration in a chitosan film was achieved at the ~5 × 10(-3) g/cm(3) water content in the reactor. We also used hydroxy carboxylic acid derivatives of chitosan and its copolymer with polylactide as matrices for introduction of hydrophobic 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole. We have shown that unmodified chitosan contains the greatest amount of 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole, as compared with its hydrophobic derivatives. The kinetics of 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole diffusion from a chitosan matrix was studied in acidified water with pH 1.6. We found that the complete release of 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole into the aqueous phase from unmodified chitosan films occurred in 48 h, while its complete release from chitosan modified with hydroxy carboxylic acids occurred in 5 min or less.

Sterilizing Bacillus pumilus spores using supercritical carbon dioxide.

PubMed

Zhang, Jian; Burrows, Sarah; Gleason, Courtney; Matthews, Michael A; Drews, Michael J; Laberge, Martine; An, Yuehuei H

2006-09-01

Supercritical carbon dioxide (SC CO(2)) has been evaluated as a new sterilization technology. Results are presented on killing of B. pumilus spores using SC CO(2) containing trace levels of additives. Complete killing was achieved with 200 part per million (ppm) hydrogen peroxide in SC CO(2) at 60 degrees C, 27.5 MPa. Addition of water to SC CO(2) resulted in greater than three-log killing, but this is insufficient to claim sterilization. Neither ethanol nor isopropanol when added to SC CO(2) affected killing.

Supercritical Fluid Processing of Propellant Polymers

DTIC Science & Technology

1991-01-01

coffee decaffeination , spice extraction, and lipids purification. The processing principles have also long been well known and practiced in the...rn PL-TR-91 -3003 AD: AD-A234 285 Final Report Supercritical Fluid Processing for the period of Propellant Polymers September 1989 to September 1990...PROJECT TASK I’Ac K UNIT ELEMENT NO. NO. P:~53Co O 62302F 5730 0055 3𔃻U-- 11. TITLE (Include Security Classification) Supercritical Fluid Processing

Wall extensibility and cell hydraulic conductivity decrease in enlarging stem tissues at low water potentials. [Glycine max L. Merr

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nonami, Hiroshi; Boyer, J.S.

1990-08-01

Measurements with a guillotine psychrometer indicate that the inhibition of stem growth at low water potentials (low {psi}{sub w}) is accompanied by decreases in cell wall extensibility and tissue hydraulic conductance to water that eventually limit growth rate in soybean (Glycine max L. Merr.). To check this conclusion, we measured cell wall properties and cell hydraulic conductivities with independent techniques in soybean seedlings grown and treated the same way, i.e. grown in the dark and exposed to low {psi}{sub w} by transplanting dark grown seedlings to vermiculite of low water content. Results suggest that the plastic properties of the cellmore » walls and the conductance of the cells to water were decreased at low {psi}{sub w} but that the elastic properties of the walls were of little consequence in this response.« less

Supercritical Fluid Infusion of Iron Additives in Polymeric Matrices

NASA Technical Reports Server (NTRS)

Nazem, Negin; Taylor, Larry T.

1999-01-01

The objective of this project was the experimentation to measure preparation of iron nanophases within polymeric matrices via supercritical fluid infusion of iron precursors followed by thermal reduction. Another objective was to determine if supercritical CO2 could infuse into the polymer. The experiment is described along with the materials, and the supercritical fluid infusion and cure procedures. X-ray photoelectron spectra and transmission electron micrographs were obtained. The results are summarized in charts, and tables.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zheming; Felmy, Andrew R.; Thompson, Christopher J.

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 themore » 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.« less

Supercritical and Transcritical Real-Fluid Mixing in Diesel Engine Applications

DTIC Science & Technology

2015-09-01

ARL-RP-0551 ● SEP 2015 US Army Research Laboratory Supercritical and Transcritical Real-Fluid Mixing in Diesel Engine...ARL-RP-0551 ● SEP 2015 US Army Research Laboratory Supercritical and Transcritical Real-Fluid Mixing in Diesel Engine Applications by...COVERED (From - To) 1 January 2014–30 September 2014 4. TITLE AND SUBTITLE Supercritical and Transcritical Real-Fluid Mixing in Diesel Engine

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.

Wet in situ transesterification of spent coffee grounds with supercritical methanol for the production of biodiesel.

PubMed

Son, Jeesung; Kim, Bora; Park, Jeongseok; Yang, Jeongwoo; Lee, Jae W

2018-07-01

This work introduces biodiesel production from wet spent coffee grounds (SCGs) with supercritical methanol without any pre-drying process. Supercritical methanol and subcritical water effectively produced biodiesel via in situ transesterification by inducing more porous SCG and enhancing the efficiency of lipid extraction and conversion. It was also found that space loading was one of the critical factors for biodiesel production. An optimal biodiesel yield of 10.17 wt% of dry SCG mass (86.33 w/w% of esterifiable lipids in SCG) was obtained at reaction conditions of 270 °C, 90 bars, methanol to wet SCG ratio 5:1, space loading 58.4 ml/g and reaction time 20 min. Direct use of wet SCG waste as feedstock for supercritical biodiesel production eliminates the conventional dying process and the need of catalyst and also reduces environmental problems caused by landfill accumulation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Widom Lines in Binary Mixtures of Supercritical Fluids.

PubMed

Raju, Muralikrishna; Banuti, Daniel T; Ma, Peter C; Ihme, Matthias

2017-06-08

Recent experiments on pure fluids have identified distinct liquid-like and gas-like regimes even under supercritical conditions. The supercritical liquid-gas transition is marked by maxima in response functions that define a line emanating from the critical point, referred to as Widom line. However, the structure of analogous state transitions in mixtures of supercritical fluids has not been determined, and it is not clear whether a Widom line can be identified for binary mixtures. Here, we present first evidence for the existence of multiple Widom lines in binary mixtures from molecular dynamics simulations. By considering mixtures of noble gases, we show that, depending on the phase behavior, mixtures transition from a liquid-like to a gas-like regime via distinctly different pathways, leading to phase relationships of surprising complexity and variety. Specifically, we show that miscible binary mixtures have behavior analogous to a pure fluid and the supercritical state space is characterized by a single liquid-gas transition. In contrast, immiscible binary mixture undergo a phase separation in which the clusters transition separately at different temperatures, resulting in multiple distinct Widom lines. The presence of this unique transition behavior emphasizes the complexity of the supercritical state to be expected in high-order mixtures of practical relevance.

Determination of major aromatic constituents in vanilla using an on-line supercritical fluid extraction coupled with supercritical fluid chromatography.

PubMed

Liang, Yanshan; Liu, Jiaqi; Zhong, Qisheng; Shen, Lingling; Yao, Jinting; Huang, Taohong; Zhou, Ting

2018-04-01

An on-line supercritical fluid extraction coupled with supercritical fluid chromatography method was developed for the determination of four major aromatic constituents in vanilla. The parameters of supercritical fluid extraction were systematically investigated using single factor optimization experiments and response surface methodology by a Box-Behnken design. The modifier ratio, split ratio, and the extraction temperature and pressure were the major parameters which have significant effects on the extraction. While the static extraction time, dynamic extraction time, and recycle time had little influence on the compounds with low polarity. Under the optimized conditions, the relative extraction efficiencies of all the constituents reached 89.0-95.1%. The limits of quantification were in the range of 1.123-4.747 μg. The limits of detection were in the range of 0.3368-1.424 μg. The recoveries of the four analytes were in the range of 76.1-88.9%. The relative standard deviations of intra- and interday precision ranged from 4.2 to 7.6%. Compared with other off-line methods, the present method obtained higher extraction yields for all four aromatic constituents. Finally, this method has been applied to the analysis of vanilla from different sources. On the basis of the results, the on-line supercritical fluid extraction-supercritical fluid chromatography method shows great promise in the analysis of aromatic constituents in natural products. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transport relaxation processes in supercritical fluids

NASA Astrophysics Data System (ADS)

Jonas, J.

The technique for solubility measurements of solids in compressed supercritical fluids using NMR and theoretical analysis of experimental data on collision induced scattering were examined. Initial tests for a determination of solid solubilities in supercritical fluids without mixing were previously described and these preparations have continued. Super critical carbon dioxide dissolving naphthalene, for which solubility data is already available (M. McHugh, M.E. Paulaitis, J. Chem. Eng. Data, Vol. 25 (4), 1980) is being studied. This initial testing of the NMR technique for measuring solubilities in a well characterized system should prove very valuable for our later determinations with the proposed mixing probe. Systematic experimental studies of collision induced spectra in several supercritical fluids using both Raman and Rayleigh scattering are continued. The experimental work on SF6 and CH4 was finished and the experimental data testing of the various theoretical models for collision induced scattering is being analyzed.

Fabrication of water-repellent cellulose fiber coated with magnetic nanoparticles under supercritical carbon dioxide

NASA Astrophysics Data System (ADS)

Xu, Shengjie; Shen, Danping; Wu, Peiyi

2013-04-01

Hematite nanoparticle-coated magnetic composite fiber was prepared in supercritical carbon dioxide (scCO2). With the help of scCO2, cellulose did not need to be dissolved and regenerated and it could be in any form (e.g., cotton wool, filter paper, textile, etc.). The penetrating and swelling effect of scCO2, the slowing reaction rate of weak alkalis, and the template effect of cellulose fibers were discovered to be the key factors for the fabrication of ordered cellulose/Fe2O3 composite fibers. The structures of the composite fibers as well as the layers of Fe2O3 particles were characterized by means of scanning/transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman investigation. It was found that α-Fe2O3 granules which ranged from 30 to 85 nm with average diameter around 55 nm would be generated on the surface of cellulose fibers via potassium acetate, while irregular square prisms (ranged from 200 to 600 nm) which were composed of smaller nanoparticles ( 10 nm) would be fabricated via urea. And, the obtained composite was highly water repellent with superparamagnetic or ferromagnetic properties.

Influence of supercritical water treatment on heavy metals in medical waste incinerator fly ash.

PubMed

Bo, Da; Zhang, Fu-Shen; Zhao, Lijuan

2009-10-15

In this work, medical waste (MW) incinerator fly ashes from different types of incinerators were subjected to supercritical water (SCW) and SCW+H(2)O(2) (SCWH) treatments. Sequential extraction experiments showed that, after SCW treatment, heavy metals in exchangeable and carbonate forms in the ashes could be transferred into other relatively stable forms, e.g., Ba and Cr into residual fraction, Cu and Pb into organic matter fraction. SCWH treatment could stabilize heavy metals in Fe-Mn oxides and residual fractions. However, the behavior of As was quite different from heavy metals, which could be leached out from residue fraction after SCW and SWCH treatments. The leached As tended to absorb onto Fe-Mn oxides and organic matters under near neutral environment, but it could react with Ca(2+) at lower pH, increasing the mobility of this element. Therefore, it is necessary to neutralize acidic ash to near neutral condition before subjecting it to SCW and SCWH treatments so as to effectively stabilize hazardous elements in the ash. Consequently, it is believed that SCWH treatment is an effective alternative for hazardous elements detoxification in MW fly ash.

The NASA supercritical-wing technology

NASA Technical Reports Server (NTRS)

Bartlett, D. W.; Patterson, J. C., Jr.

1978-01-01

A number of high aspect ratio supercritical wings in combination with a representative wide body type fuselage were tested in the Langley 8 foot transonic pressure tunnel. The wing parameters investigated include aspect ratio, sweep, thickness to chord ratio, and camber. Subsequent to these initial series of tests, a particular wing configuration was selected for further study and development. Tests on the selected wing involved the incorporation of a larger inboard trailing edge extension, an inboard leading edge extension, and flow through nacelles. Range factors for the various supercritical wing configurations are compared with those for a reference wide body transport configuration.

Optimizing supercritical carbon dioxide in the inactivation of bacteria in clinical solid waste by using response surface methodology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hossain, Md. Sohrab; Nik Ab Rahman, Nik Norulaini; Balakrishnan, Venugopal

2015-04-15

Highlights: • Supercritical carbon dioxide sterilization of clinical solid waste. • Inactivation of bacteria in clinical solid waste using supercritical carbon dioxide. • Reduction of the hazardous exposure of clinical solid waste. • Optimization of the supercritical carbon dioxide experimental conditions. - Abstract: Clinical solid waste (CSW) poses a challenge to health care facilities because of the presence of pathogenic microorganisms, leading to concerns in the effective sterilization of the CSW for safe handling and elimination of infectious disease transmission. In the present study, supercritical carbon dioxide (SC-CO{sub 2}) was applied to inactivate gram-positive Staphylococcus aureus, Enterococcus faecalis, Bacillus subtilis,more » and gram-negative Escherichia coli in CSW. The effects of SC-CO{sub 2} sterilization parameters such as pressure, temperature, and time were investigated and optimized by response surface methodology (RSM). Results showed that the data were adequately fitted into the second-order polynomial model. The linear quadratic terms and interaction between pressure and temperature had significant effects on the inactivation of S. aureus, E. coli, E. faecalis, and B. subtilis in CSW. Optimum conditions for the complete inactivation of bacteria within the experimental range of the studied variables were 20 MPa, 60 °C, and 60 min. The SC-CO{sub 2}-treated bacterial cells, observed under a scanning electron microscope, showed morphological changes, including cell breakage and dislodged cell walls, which could have caused the inactivation. This espouses the inference that SC-CO{sub 2} exerts strong inactivating effects on the bacteria present in CSW, and has the potential to be used in CSW management for the safe handling and recycling-reuse of CSW materials.« less

LOX droplet vaporization in a supercritical forced convective environment

NASA Technical Reports Server (NTRS)

Hsiao, Chia-Chun; Yang, Vigor

1993-01-01

Modern liquid rocket engines often use liquid oxygen (LOX) and liquid hydrogen (LH2) as propellants to achieve high performance, with the engine operational conditions in the supercritical regimes of the propellants. Once the propellant exceeds its critical state, it essentially becomes a puff of dense fluid. The entire field becomes a continuous medium, and no distinct interfacial boundary between the liquid and gas exists. Although several studies have been undertaken to investigate the supercritical droplet behavior at quiescent conditions, very little effort has been made to address the fundamental mechanisms associated with LOX droplet vaporization in a supercritical, forced convective environment. The purpose is to establish a theoretical framework within which supercritical droplet dynamics and vaporization can be studied systematically by means of an efficient and robust numerical algorithm.

Electrodeposition of germanium from supercritical fluids.

PubMed

Ke, Jie; Bartlett, Philip N; Cook, David; Easun, Timothy L; George, Michael W; Levason, William; Reid, Gillian; Smith, David; Su, Wenta; Zhang, Wenjian

2012-01-28

Several Ge(II) and Ge(IV) compounds were investigated as possible reagents for the electrodeposition of Ge from liquid CH(3)CN and CH(2)F(2) and supercritical CO(2) containing as a co-solvent CH(3)CN (scCO(2)) and supercritical CH(2)F(2) (scCH(2)F(2)). For Ge(II) reagents the most promising results were obtained using [NBu(n)(4)][GeCl(3)]. However the reproducibility was poor and the reduction currents were significantly less than the estimated mass transport limited values. Deposition of Ge containing films was possible at high cathodic potential from [NBu(n)(4)][GeCl(3)] in liquid CH(3)CN and supercritical CO(2) containing CH(3)CN but in all cases they were heavily contaminated by C, O, F and Cl. Much more promising results were obtained using GeCl(4) in liquid CH(2)F(2) and supercritical CH(2)F(2). In this case the reduction currents were consistent with mass transport limited reduction and bulk electrodeposition produced amorphous films of Ge. Characterisation by XPS showed the presence of low levels of O, F and C, XPS confirmed the presence of Ge together with germanium oxides, and Raman spectroscopy showed that the as deposited amorphous Ge could be crystallised by the laser used in obtaining the Raman measurements.

Enhancement of the dissolution rate and bioavailability of fenofibrate by a melt-adsorption method using supercritical carbon dioxide

PubMed Central

Cha, Kwang-Ho; Cho, Kyung-Jin; Kim, Min-Soo; Kim, Jeong-Soo; Park, Hee Jun; Park, Junsung; Cho, Wonkyung; Park, Jeong-Sook; Hwang, Sung-Joo

2012-01-01

Background: The aim of this study was to enhance the bioavailability of fenofibrate, a poorly water-soluble drug, using a melt-adsorption method with supercritical CO2. Methods: Fenofibrate was loaded onto Neusilin® UFL2 at different weight ratios of fenofibrate to Neusilin UFL2 by melt-adsorption using supercritical CO2. For comparison, fenofibrate-loaded Neusilin UFL2 was prepared by solvent evaporation and hot melt-adsorption methods. The fenofibrate formulations prepared were characterized by differential scanning calorimetry, powder x-ray diffractometry, specific surface area, pore size distribution, scanning electron microscopy, and energy-dispersive x-ray spectrometry. In vitro dissolution and in vivo bioavailability were also investigated. Results: Fenofibrate was distributed into the pores of Neusilin UFL2 and showed reduced crystal formation following adsorption. Supercritical CO2 facilitated the introduction of fenofibrate into the pores of Neusilin UFL2. Compared with raw fenofibrate, fenofibrate from the prepared powders showed a significantly increased dissolution rate and better bioavailability. In particular, the area under the drug concentration-time curve and maximal serum concentration of the powders prepared using supercritical CO2 were 4.62-fold and 4.52-fold greater than the corresponding values for raw fenofibrate. Conclusion: The results of this study highlight the usefulness of the melt-adsorption method using supercritical CO2 for improving the bioavailability of fenofibrate. PMID:23118538

Efficient separation of curcumin, demethoxycurcumin, and bisdemethoxycurcumin from turmeric using supercritical fluid chromatography: From analytical to preparative scale.

PubMed

Song, Wei; Qiao, Xue; Liang, Wen-fei; Ji, Shuai; Yang, Lu; Wang, Yuan; Xu, Yong-wei; Yang, Ying; Guo, De-an; Ye, Min

2015-10-01

Curcumin is the major constituent of turmeric (Curcuma longa L.). It has attracted widespread attention for its anticancer and anti-inflammatory activities. The separation of curcumin and its two close analogs, demethoxycurcumin and bisdemethoxycurcumin, has been challenging by conventional techniques. In this study, an environmentally friendly method based on supercritical fluid chromatography was established for the rapid and facile separation of the three curcuminoids directly from the methanol extract of turmeric. The method was first developed and optimized by ultra performance convergence chromatography, and was then scaled up to preparative supercritical fluid chromatography. Eluted with supercritical fluid CO2 containing 8-15% methanol (containing 10 mM oxalic acid) at a flow rate of 80 mL/min, curcumin, demethoxycurcumin and bisdemethoxycurcumin could be well separated on a Viridis BEH OBD column (Waters, 250 mm × 19 mm, 5 μm) within 6.5 min. As a result, 20.8 mg of curcumin (97.9% purity), 7.0 mg of demethoxycurcumin (91.1%), and 4.6 mg of bisdemethoxycurcumin (94.8%) were obtained after a single step of supercritical fluid chromatography separation with a mean recovery of 76.6%. Showing obvious advantages in low solvent consumption, large sample loading, and easy solvent removal, supercritical fluid chromatography was proved to be a superior technique for the efficient separation of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical deposition methods using supercritical fluid solutions

DOEpatents

Sievers, Robert E.; Hansen, Brian N.

1990-01-01

A method for depositing a film of a desired material on a substrate comprises dissolving at least one reagent in a supercritical fluid comprising at least one solvent. Either the reagent is capable of reacting with or is a precursor of a compound capable of reacting with the solvent to form the desired product, or at least one additional reagent is included in the supercritical solution and is capable of reacting with or is a precursor of a compound capable of reacting with the first reagent or with a compound derived from the first reagent to form the desired material. The supercritical solution is expanded to produce a vapor or aerosol and a chemical reaction is induced in the vapor or aerosol so that a film of the desired material resulting from the chemical reaction is deposited on the substrate surface. In an alternate embodiment, the supercritical solution containing at least one reagent is expanded to produce a vapor or aerosol which is then mixed with a gas containing at least one additional reagent. A chemical reaction is induced in the resulting mixture so that a film of the desired material is deposited.

Compositional analysis of Chinese water chestnut (Eleocharis dulcis) cell-wall material from parenchyma, epidermis, and subepidermal tissues.

PubMed

Grassby, Terri; Jay, Andrew J; Merali, Zara; Parker, Mary L; Parr, Adrian J; Faulds, Craig B; Waldron, Keith W

2013-10-09

Chinese water chestnut (Eleocharis dulcis (Burman f.) Trin ex Henschel) is a corm consumed globally in Oriental-style cuisine. The corm consists of three main tissues, the epidermis, subepidermis, and parenchyma; the cell walls of which were analyzed for sugar, phenolic, and lignin content. Sugar content, measured by gas chromatography, was higher in the parenchyma cell walls (931 μg/mg) than in the subepidermis (775 μg/mg) or epidermis (685 μg/mg). The alkali-extractable phenolic content, measured by high-performance liquid chromatography, was greater in the epidermal (32.4 μg/mg) and subepidermal cell walls (21.7 μg/mg) than in the cell walls of the parenchyma (12.3 μg/mg). The proportion of diferulic acids was higher in the parenchyma. The Klason lignin content of epidermal and subepidermal cell walls was ~15%. Methylation analysis of Chinese water chestnut cell-wall polysaccharides identified xyloglucan as the predominant hemicellulose in the parenchyma for the first time, and also a significant pectin component, similar to other nongraminaceous monocots.

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Selective free radical reactions using supercritical carbon dioxide.

PubMed

Cormier, Philip J; Clarke, Ryan M; McFadden, Ryan M L; Ghandi, Khashayar

2014-02-12

We report herein a means to modify the reactivity of alkenes, and particularly to modify their selectivity toward reactions with nonpolar reactants (e.g., nonpolar free radicals) in supercritical carbon dioxide near the critical point. Rate constants for free radical addition of the light hydrogen isotope muonium to ethylene, vinylidene fluoride, and vinylidene chloride in supercritical carbon dioxide are compared over a range of pressures and temperatures. Near carbon dioxide's critical point, the addition to ethylene exhibits critical speeding up, while the halogenated analogues display critical slowing. This suggests that supercritical carbon dioxide as a solvent may be used to tune alkene chemistry in near-critical conditions.

Prospects of Supercritical Fluids in Realizing Graphene-Based Functional Materials.

PubMed

Padmajan Sasikala, Suchithra; Poulin, Philippe; Aymonier, Cyril

2016-04-13

Supercritical-fluids science and technology predate all the approaches that are currently established for graphene production by several decades in advanced materials design. However, it has only recently been proposed as a plausible approach for graphene processing. Since then, supercritical fluids have emerged into contention as an alternative to existing technologies because of their scalability and versatility in processing graphene materials, which include composites, aerogels, and foams. Here, an overview is presented of such materials prepared through supercritical fluids from an advanced materials science standpoint, with a discussion on their fundamental properties and technological applications. The benefits of supercritical-fluid processing over conventional liquid-phase processing are presented. The benefits include not only better performances for advanced applications but also environmental issues associated with the synthesis process. Nevertheless, the limitations of supercritical-fluid processing are also stressed, along with challenges that are still faced toward the achievement of the great expectations from graphene materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 andmore » pressure conditions in magmatic geothermal systems.« less

DNS of High Pressure Supercritical Combustion

NASA Astrophysics Data System (ADS)

Chong, Shao Teng; Raman, Venkatramanan

2016-11-01

Supercritical flows have always been important to rocket motors, and more recently to aircraft engines and stationary gas turbines. The purpose of the present study is to understand effects of differential diffusion on reacting scalars using supercritical isotropic turbulence. Focus is on fuel and oxidant reacting in the transcritical region where density, heat capacity and transport properties are highly sensitive to variations in temperature and pressure. Reynolds and Damkohler number vary as a result and although it is common to neglect differential diffusion effects if Re is sufficiently large, this large variation in temperature with heat release can accentuate molecular transport differences. Direct numerical simulations (DNS) for one step chemistry reaction between fuel and oxidizer are used to examine the differential diffusion effects. A key issue investigated in this paper is if the flamelet progress variable approach, where the Lewis number is usually assumed to be unity and constant for all species, can be accurately applied to simulate supercritical combustion.

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

PubMed

Eller, F J; King, J W

2001-10-01

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

Synthesis of a proline-modified acrylic acid copolymer in supercritical CO2 for glass-ionomer dental cement applications.

PubMed

Moshaverinia, Alireza; Roohpour, Nima; Darr, Jawwad A; Rehman, Ihtesham U

2009-06-01

Supercritical (sc-) fluids (such as sc-CO(2)) represent interesting media for the synthesis of polymers in dental and biomedical applications. Sc-CO(2) has several advantages for polymerization reactions in comparison to conventional organic solvents. It has several advantages in comparison to conventional polymerization solvents, such as enhanced kinetics, being less harmful to the environment and simplified solvent removal process. In our previous work, we synthesized poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone) (PAA-IA-NVP) terpolymers in a supercritical CO(2)/methanol mixture for applications in glass-ionomer dental cements. In this study, proline-containing acrylic acid copolymers were synthesized, in a supercritical CO(2) mixture or in water. Subsequently, the synthesized polymers were used in commercially available glass-ionomer cement formulations (Fuji IX commercial GIC). Mechanical strength (compressive strength (CS), diametral tensile strength (DTS) and biaxial flexural strength (BFS)) and handling properties (working and setting time) of the resulting modified cements were evaluated. It was found that the polymerization reaction in an sc-CO(2)/methanol mixture was significantly faster than the corresponding polymerization reaction in water and the purification procedures were simpler for the former. Furthermore, glass-ionomer cement samples made from the terpolymer prepared in sc-CO(2)/methanol exhibited higher CS and DTS and comparable BFS compared to the same polymer synthesized in water. The working properties of glass-ionomer formulations made in sc-CO(2)/methanol were comparable and better than the values of those for polymers synthesized in water.

Supercritical Fluid Extraction of Bioactive Compounds from Plant Materials.

PubMed

Wrona, Olga; Rafińska, Katarzyna; Możeński, Cezary; Buszewski, Bogusław

2017-11-01

There has been growing interest in the application of supercritical solvents over the last several years, many of the applications industrial in nature. The purpose of plant material extraction is to obtain large amounts of extract rich in the desired active compounds in a time-sensitive and cost-effective manner. The productivity and profitability of a supercritical fluid extraction (SFE) process largely depends on the selection of process parameters, which are elaborated upon in this paper. Carbon dioxide (CO2) is the most desirable solvent for the supercritical extraction of natural products. Its near-ambient critical temperature makes it suitable for the extraction of thermolabile components without degradation. A new approach has been adopted for SFE in which the solubility of nonpolar supercritical CO2 can be enhanced by the addition of small amounts of cosolvent.

Reactivity of dissolved- vs. supercritical-CO2 phase toward muscovite basal surfaces

NASA Astrophysics Data System (ADS)

Wan, J.; Tokunaga, T. K.; Kim, Y.; Wang, S.; Altoe, M. V. P.; Ashby, P. D.; DePaolo, D.

2015-12-01

The current understanding of geochemical reactions in reservoirs for geological carbon sequestration (GCS) is largely based on aqueous chemistry (CO2 dissolves in reservoir brine and brine reacts with rocks). However, only a portion of the injected supercritical (sc) CO2 dissolves before the buoyant plume contacts caprock, where it is expected to reside for a long time. Although numerous studies have addressed scCO2-mineral reactions occurring within adsorbed aqueous films, possible reactions resulting from direct CO2-rock contact remain less understood. Does CO2 as a supercritical phase react with reservoir rocks? Do mineral react differently with scCO2 than with dissolved CO2? We selected muscovite, one of the more stable and common rock-forming silicate minerals, to react with scCO2 phase (both water-saturated and water-free) and compared with CO2-saturated-brine. The reacted basal surfaces were analyzed using atomic force microscopy and X-ray photoelectron spectroscopy for examining the changes in surface morphology and chemistry. The results show that scCO2 (regardless of its water content) altered muscovite considerably more than CO2-saturated brine; suggest CO2 diffusion into mica interlayers and localized mica dissolution into scCO2 phase. The mechanisms underlying these observations and their implications for GCS need further exploration.

Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Hata, Kenji; Futaba, Don N.; Mizuno, Kohei; Namai, Tatsunori; Yumura, Motoo; Iijima, Sumio

2004-11-01

We demonstrate the efficient chemical vapor deposition synthesis of single-walled carbon nanotubes where the activity and lifetime of the catalysts are enhanced by water. Water-stimulated enhanced catalytic activity results in massive growth of superdense and vertically aligned nanotube forests with heights up to 2.5 millimeters that can be easily separated from the catalysts, providing nanotube material with carbon purity above 99.98%. Moreover, patterned, highly organized intrinsic nanotube structures were successfully fabricated. The water-assisted synthesis method addresses many critical problems that currently plague carbon nanotube synthesis.

METHOD FOR THE SUPERCRITICAL FLUID EXTRACTION OF SOILS/SEDIMENTS

EPA Science Inventory

Supercritical fluid extraction has been publicized as an extraction method which has several advantages over conventional methods, and it is expected to result in substantial cost and labor savings. This study was designed to evaluate the feasibility of using supercritical fluid ...

Supercritical fluids as a green technology for the pretreatment of lignocellulosic biomass.

PubMed

Daza Serna, L V; Orrego Alzate, C E; Cardona Alzate, C A

2016-01-01

One of the main drawbacks for using lignocellulosic biomass is related to its recalcitrance. The pretreatment of lignocellulosic biomass plays an important role for delignification and crystallinity reduction purposes. In this work rice husk (RH) was submitted to supercritical pretreatment at 80°C and 270 bar with the aim to determine the effect on lignin content, crystallinity as well as enzymatic digestibility. The yields obtained were compared with dilute sulfuric acid pretreatment as base case. Additionally a techno-economic and environmental comparison of the both pretreatment technologies was performed. The results show a lignin content reduction up to 90.6% for the sample with 75% moisture content using a water-ethanol mixture. The results for crystallinity and enzymatic digestibility demonstrated that no reductions were reached. Supercritical pretreatment presents the best economical and environmental performance considering the solvents and carbon dioxide recycling. Copyright © 2015 Elsevier Ltd. All rights reserved.

Supercritical-Fluid Extraction of Oil From Tar Sands

NASA Technical Reports Server (NTRS)

Compton, L. E.

1982-01-01

New supercritical solvent mixtures have been laboratory-tested for extraction of oil from tar sands. Mixture is circulated through sand at high pressure and at a temperature above critical point, dissolving organic matter into the compressed gas. Extract is recovered from sand residues. Low-temperature super-critical solvents reduce energy consumption and waste-disposal problems.

Supercritical bedforms and sedimentary structures from field and core studies, Middle Eocene deep-marine base-of-slope environment, Ainsa Basin, Spanish Pyrenees

NASA Astrophysics Data System (ADS)

Cornard, Pauline; Pickering, Kevin

2017-04-01

In recent years, many researchers have focussed on supercritical- and subcritical-flow deposits using flume-tank experiments (e.g., Cartigny el al., 2011; Postma et al., 2014; Postma and Cartigny, 2014), or from direct observations on presently active deep-water systems (e.g., Hughes et al., 2012). Using outcrop and core examples from a base-of-slope environment in the Middle Eocene Ainsa Basin, Spanish Pyrenees, and with published experimental work, a range of deposits are interpreted as upper-flow regime sedimentary structures. This contribution focusses on the interpretation of several supercritical bedforms (antidunes and chutes-and-pools) observed on the field and upper-flow regime sedimentary structures recognized in cores. The spatial distribution of supercritical-flow deposits obtained from an analysis of field outcrops and core sedimentary logs are evaluated in relation to the depositional environment (channel axis, off-axis, margin and interfan). The frequency distributions of the bed thicknesses are also analysed in relation to supercritical versus subcritical bed-thickness distributions.

Relationship between Pipeline Wall Thickness (Gr. X60) and Water Depth towards Avoiding Failure during Installation

NASA Astrophysics Data System (ADS)

Razak, K. Abdul; Othman, M. I. H.; Mat Yusuf, S.; Fuad, M. F. I. Ahmad; yahaya, Effah

2018-05-01

Oil and gas today being developed at different water depth characterized as shallow, deep and ultra-deep waters. Among the major components involved during the offshore installation is pipelines. Pipelines are a transportation method of material through a pipe. In oil and gas industry, pipeline come from a bunch of line pipe that welded together to become a long pipeline and can be divided into two which is gas pipeline and oil pipeline. In order to perform pipeline installation, we need pipe laying barge or pipe laying vessel. However, pipe laying vessel can be divided into two types: S-lay vessel and J-lay vessel. The function of pipe lay vessel is not only to perform pipeline installation. It also performed installation of umbilical or electrical cables. In the simple words, pipe lay vessel is performing the installation of subsea in all the connecting infrastructures. Besides that, the installation processes of pipelines require special focus to make the installation succeed. For instance, the heavy pipelines may exceed the lay vessel’s tension capacities in certain kind of water depth. Pipeline have their own characteristic and we can group it or differentiate it by certain parameters such as grade of material, type of material, size of diameter, size of wall thickness and the strength. For instances, wall thickness parameter studies indicate that if use the higher steel grade of the pipelines will have a significant contribution in pipeline wall thickness reduction. When running the process of pipe lay, water depth is the most critical thing that we need to monitor and concern about because of course we cannot control the water depth but we can control the characteristic of the pipe like apply line pipe that have wall thickness suitable with current water depth in order to avoid failure during the installation. This research will analyse whether the pipeline parameter meet the requirements limit and minimum yield stress. It will overlook to simulate pipe

Supercritical fluid chromatography for lipid analysis in foodstuffs.

PubMed

Donato, Paola; Inferrera, Veronica; Sciarrone, Danilo; Mondello, Luigi

2017-01-01

The task of lipid analysis has always challenged separation scientists, and new techniques in chromatography were often developed for the separation of lipids; however, no single technique or methodology is yet capable of affording a comprehensive screening of all lipid species and classes. This review acquaints the role of supercritical fluid chromatography within the field of lipid analysis, from the early developed capillary separations based on pure CO 2 , to the most recent techniques employing packed columns under subcritical conditions, including the niche multidimensional techniques using supercritical fluids in at least one of the separation dimensions. A short history of supercritical fluid chromatography will be introduced first, from its early popularity in the late 1980s, to the sudden fall and oblivion until the last decade, experiencing a regain of interest within the chromatographic community. Afterwards, the subject of lipid nomenclature and classification will be briefly dealt with, before discussing the main applications of supercritical fluid chromatography for food analysis, according to the specific class of lipids. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Technical Note: The determination of enclosed water volume in large flexible-wall mesocosms "KOSMOS"

NASA Astrophysics Data System (ADS)

Czerny, J.; Schulz, K. G.; Krug, S. A.; Ludwig, A.; Riebesell, U.

2013-03-01

The volume of water enclosed inside flexible-wall mesocosm bags is hard to estimate using geometrical calculations and can be strongly variable among bags of the same dimensions. Here we present a method for precise water volume determination in mesocosms using salinity as a tracer. Knowledge of the precise volume of water enclosed allows establishment of exactly planned treatment concentrations and calculation of elemental budgets.

Supercritical Anomalies and the Widom Line for the Isostructural Phase Transition in Solids

NASA Astrophysics Data System (ADS)

Tareyeva, E. E.; Fomin, Yu. D.; Tsiok, E. N.; Ryzhov, V. N.

2018-01-01

The representation of the Widom line as a line of maximums of the correlation length and a whole set of thermodynamic response functions above the critical point were introduced to describe anomalies observed in water above the hypothetical critical point of the liquid-liquid transition. The supercritical region for the gas-liquid transition was also described later in terms of the Widom line. It is natural to assume that an analogue of the Widom line also exists in the supercritical region for the first-order isostructural transition in crystals, which ends at a critical point. We use a simple semiphenomenological model, close in spirit the van der Waals theory, to study the properties of the new Widom line. We calculate the thermodynamic response functions above the critical point of the isostructural transition and find their maximums determining the Widom line position.

Physical properties of the benchmark models program supercritical wing

NASA Technical Reports Server (NTRS)

Dansberry, Bryan E.; Durham, Michael H.; Bennett, Robert M.; Turnock, David L.; Silva, Walter A.; Rivera, Jose A., Jr.

1993-01-01

The goal of the Benchmark Models Program is to provide data useful in the development and evaluation of aeroelastic computational fluid dynamics (CFD) codes. To that end, a series of three similar wing models are being flutter tested in the Langley Transonic Dynamics Tunnel. These models are designed to simultaneously acquire model response data and unsteady surface pressure data during wing flutter conditions. The supercritical wing is the second model of this series. It is a rigid semispan model with a rectangular planform and a NASA SC(2)-0414 supercritical airfoil shape. The supercritical wing model was flutter tested on a flexible mount, called the Pitch and Plunge Apparatus, that provides a well-defined, two-degree-of-freedom dynamic system. The supercritical wing model and associated flutter test apparatus is described and experimentally determined wind-off structural dynamic characteristics of the combined rigid model and flexible mount system are included.

Bacterial community radial-spatial distribution in biofilms along pipe wall in chlorinated drinking water distribution system of East China.

PubMed

Liu, Jingqing; Ren, Hongxing; Ye, Xianbei; Wang, Wei; Liu, Yan; Lou, Liping; Cheng, Dongqing; He, Xiaofang; Zhou, Xiaoyan; Qiu, Shangde; Fu, Liusong; Hu, Baolan

2017-01-01

Biofilms in the pipe wall may lead to water quality deterioration and biological instability in drinking water distribution systems (DWDSs). In this study, bacterial community radial-spatial distribution in biofilms along the pipe wall in a chlorinated DWDS of East China was investigated. Three pipes of large diameter (300, 600, and 600 mm) were sampled in this DWDS, including a ductile cast iron pipe (DCIP) with pipe age of 11 years and two gray cast iron pipes (GCIP) with pipe ages of 17 and 19 years, and biofilms in the upper, middle, and lower parts of each pipe wall were collected. Real-time quantitative polymerase chain reaction (qPCR) and culture-based method were used to quantify bacteria. 454 pyrosequencing was used for bacterial community analysis. The results showed that the biofilm density and total solid (TS) and volatile solid (VS) contents increased gradually from the top to the bottom along the pipe wall. Microorganisms were concentrated in the upper and lower parts of the pipe wall, together accounting for more than 80 % of the total biomass in the biofilms. The bacterial communities in biofilms were significantly different in different areas of the pipe wall and had no strong interaction. Compared with the upper and lower parts of the pipe wall, the bacterial community in the middle of the pipe wall was distributed evenly and had the highest diversity. The 16S rRNA genes of various possible pathogens, including Escherichia coli, Staphylococcus epidermidis, Pseudomonas aeruginosa, and Salmonella enterica, were detected in the biofilms, and the abundances of these possible pathogens were highest in the middle of the pipe wall among three areas. The detachment of the biofilms is the main reason for the deterioration of the water quality in DWDSs. The results of this study suggest that the biofilms in the middle of the pipe wall have highly potential risk for drinking water safety, which provides new ideas for the study of the microbial ecology in

The design and operational development of self-streamlining 2-dimensional flexible walled test sections. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Wolf, S. W. D.

1984-01-01

Self streamlining two dimensional flexible walled test sections eliminate the uncertainties found in data from conventional test sections particularly at transonic speeds. The test section sidewalls are rigid, while the floor and ceiling are flexible and are positioned to streamline shapes by a system of jacks, without reference to the model. The walls are therefore self streamlining. Data are taken from the model when the walls are good streamlines such that the inevitable residual wall induced interference is acceptably small and correctable. Successful two dimensional validation testing at low speeds has led to the development of a new transonic flexible walled test section. Tunnel setting times are minimized by the development of a rapid wall setting strategy coupled with on line computer control of wall shapes using motorized jacks. Two dimensional validation testing using symmetric and cambered aerofoils in the Mach number range up to about 0.85 where the walls are just supercritical, shows good agreement with reference data using small height-chord ratios between 1.5 and unity.

A Multi-Walled Carbon Nanotube-based Biosensor for Monitoring Microcystin-LR in Sources of Drinking Water Supplies

EPA Science Inventory

A multi-walled carbon nanotube-based electrochemical biosensor is developed for monitoring microcystin-LR (MC-LR), a toxic cyanobacterial toxin, in sources of drinking water supplies. The biosensor electrodes are fabricated using dense, mm-long multi-walled CNT (MWCNT) arrays gro...

Synthesis and characterization of nanocrystalline mesoporous zirconia using supercritical drying.

PubMed

Tyagi, Beena; Sidhpuria, Kalpesh; Shaik, Basha; Jasra, Raksh Vir

2006-06-01

Synthesis of nano-crystalline zirconia aerogel was done by sol-gel technique and supercritical drying using n-propanol solvent at and above supercritical temperature (235-280 degrees C) and pressure (48-52 bar) of n-propanol. Zirconia xerogel samples have also been prepared by conventional thermal drying method to compare with the super critically dried samples. Crystalline phase, crystallite size, surface area, pore volume, and pore size distribution were determined for all the samples in detail to understand the effect of gel drying methods on these properties. Supercritical drying of zirconia gel was observed to give thermally stable, nano-crystalline, tetragonal zirconia aerogels having high specific surface area and porosity with narrow and uniform pore size distribution as compared to thermally dried zirconia. With supercritical drying, zirconia samples show the formation of only mesopores whereas in thermally dried samples, substantial amount of micropores are observed along with mesopores. The samples prepared using supercritical drying yield nano-crystalline zirconia with smaller crystallite size (4-6 nm) as compared to higher crystallite size (13-20 nm) observed with thermally dried zirconia.

Supercritical solvent extraction of oil sand bitumen

NASA Astrophysics Data System (ADS)

Imanbayev, Ye. I.; Ongarbayev, Ye. K.; Tileuberdi, Ye.; Mansurov, Z. A.; Golovko, A. K.; Rudyk, S.

2017-08-01

The supercritical solvent extraction of bitumen from oil sand studied with organic solvents. The experiments were performed in autoclave reactor at temperature above 255 °C and pressure 29 atm with stirring for 6 h. The reaction resulted in the formation of coke products with mineral part of oil sands. The remaining products separated into SARA fractions. The properties of the obtained products were studied. The supercritical solvent extraction significantly upgraded extracted natural bitumen.

Advanced Stimulated Scattering Measurements in Supercritical Fluids

DTIC Science & Technology

2006-09-01

supercritical fluid measurement techniques. Ajay Agrawal, optical diagnostics. Mel Roquemore, turbine engines. Fred Schauer, pulse detonation propulsion...Lett. 87, 233902 (2001). 11. R. W. Gammon, H. L. Swinney, and H. Z. Cummins, "Brillouin scattering in carbon dioxide in the critical region," Phys. Rev...Stimulated Scattering Measurements in Supercritical F49620-03-C-0015 Fluids 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) 5d

Supercritical carbon dioxide processing of active pharmaceutical ingredients for polymorphic control and for complex formation.

PubMed

Moribe, Kunikazu; Tozuka, Yuichi; Yamamoto, Keiji

2008-02-14

Supercritical fluid technique have been exploited in extraction, separation and crystallization processes. In the field of pharmaceutics, supercritical carbon dioxide (scCO(2)) has been used for the purpose of micronization, polymorphic control, and preparation of solid dispersion and complexes. Particle design of active pharmaceutical ingredients is important to make the solid dosage forms with suitable physicochemical properties. Control of the characteristic properties of particles, such as size, shape, crystal structure and morphology is required to optimize the formulation. For solubility enhancement of poorly water-soluble drugs, preparation of the solid dispersion or the complexation with proper drugs or excipients should be a promising approach. This review focuses on aspects of polymorphic control and complexation behavior of active pharmaceutical ingredients by scCO(2) processing.

Supercritical extraction of lycopene from tomato industrial wastes with ethane.

PubMed

Nobre, Beatriz P; Gouveia, Luisa; Matos, Patricia G S; Cristino, Ana F; Palavra, António F; Mendes, Rui L

2012-07-11

Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO₂ and a near critical mixture of ethane and propane). The recovery of all-E-lycopene increased with pressure, decreased with the increase of the particle size in the initial stages of the extraction and was not practically affected by the solvent superficial velocity. The effect of the temperature was more complex. When the temperature increased from 40 to 60 °C the recovery of all-E-lycopene increased from 80 to 90%. However, for a further increase to 80 °C, the recovery remained almost the same, indicating that some E-Z isomerization could have occurred, as well as some degradation of lycopene. The recovery of all-E-lycopene was almost the same for feed samples with different all-E-lycopene content. Furthermore, when a batch with a higher all-E-lycopene content was used, supercritical ethane and a near critical mixture of ethane and propane showed to be better solvents than supercritical CO₂ leading to a faster extraction with a higher recovery of the carotenoid.

Carotenoids microencapsulation by spray drying method and supercritical micronization.

PubMed

Janiszewska-Turak, Emilia

2017-09-01

Carotenoids are used as natural food colourants in the food industry. As unstable natural pigments they need protection. This protection can involve the microencapsulation process. There are numerous techniques that can be used for carotenoid protection, but two of them -spray drying and supercritical micronization - are currently the most commonly used. The objective of this paper is to describe these two techniques for carotenoid microencapsulation. In this review information from articles from the last five years was taken into consideration. Pigments described in the review are all carotenoids. Short summary of carotenoids sources was presented. For the spray drying technique, a review of carrier material and process conditions was made. Moreover, a short description of some of the most suitable processes involving supercritical fluids for carotenoids (astaxanthin, β-carotene, lutein and lycopene) encapsulation was given. These include the Supercritical Antisolvent process (SAS), Particles from Gas-Saturated Solutions (PGSS), Supercritical Fluid Extraction From an Emulsion (SFEE) and Solution Enhanced Dispersion by Supercritical fluids (SEDS). In most cases the studies, independently of the described method, were conducted on the laboratory scale. In some a scale-up was also tested. In the review a critical assessment of the used methods was made. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterizing the effect of creep on stress corrosion cracking of cold worked Alloy 690 in supercritical water environment

NASA Astrophysics Data System (ADS)

Zhang, Lefu; Chen, Kai; Du, Donghai; Gao, Wenhua; Andresen, Peter L.; Guo, Xianglong

2017-08-01

The effect of creep on stress corrosion cracking (SCC) was studied by measuring crack growth rates (CGRs) of 30% cold worked (CW) Alloy 690 in supercritical water (SCW) and inert gas environments at temperatures ranging from 450 °C to 550 °C. The SCC crack growth rate under SCW environments can be regarded as the cracking induced by the combined effect of corrosion and creep, while the CGR in inert gas environment can be taken as the portion of creep induced cracking. Results showed that the CW Alloy 690 sustained high susceptibility to intergranular (IG) cracking, and creep played a dominant role in the SCC crack growth behavior, contributing more than 80% of the total crack growth rate at each testing temperature. The temperature dependence of creep induced CGRs follows an Arrhenius dependency, with an apparent activation energy (QE) of about 225 kJ/mol.

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.

New Linear Partitioning Models Based on Experimental Water: Supercritical CO 2 Partitioning Data of Selected Organic Compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burant, Aniela; Thompson, Christopher; Lowry, Gregory V.

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 inmore » 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. 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 the model built for the entire dataset.« less

Examination of water phase transitions in Loblolly pine and cell wall components by differential scanning calorimetry

Treesearch

Samuel L. Zelinka; Michael J. Lambrecht; Samuel V. Glass; Alex C. Wiedenhoeft; Daniel J. Yelle

2012-01-01

This paper examines phase transformations of water in wood and isolated wood cell wall components using differential scanning calorimetry with the purpose of better understanding "Type II water" or "freezable bound water" that has been reported for cellulose and other hydrophilic polymers. Solid loblolly pine (Pinus taeda...

New large volume hydrothermal reaction cell for studying chemical processes under supercritical hydrothermal conditions using time-resolved in situ neutron diffraction.

PubMed

Ok, Kang Min; O'Hare, Dermot; Smith, Ronald I; Chowdhury, Mohammed; Fikremariam, Hanna

2010-12-01

The design and testing of a new large volume Inconel pressure cell for the in situ study of supercritical hydrothermal syntheses using time-resolved neutron diffraction is introduced for the first time. The commissioning of this new cell is demonstrated by the measurement of the time-of-flight neutron diffraction pattern for TiO(2) (Anatase) in supercritical D(2)O on the POLARIS diffractometer at the United Kingdom's pulsed spallation neutron source, ISIS, Rutherford Appleton Laboratory. The sample can be studied over a wide range of temperatures (25-450 °C) and pressures (1-355 bar). This novel apparatus will now enable us to study the kinetics and mechanisms of chemical syntheses under extreme environments such as supercritical water, and in particular to study the crystallization of a variety of technologically important inorganic materials.

A novel strategy to design sustained-release poorly water-soluble drug mesoporous silica microparticles based on supercritical fluid technique.

PubMed

Li-Hong, Wang; Xin, Che; Hui, Xu; Li-Li, Zhou; Jing, Han; Mei-Juan, Zou; Jie, Liu; Yi, Liu; Jin-Wen, Liu; Wei, Zhang; Gang, Cheng

2013-09-15

The organic solvent solution immersion method was often used to achieve the loading of the drugs into mesoporous silica, but the drugs that have loaded into the pores of the mesoporous silica would inevitable migrate from the inside to the external surface or near the outside surface during the process of drying. Hence, it often leads to the pores of mesoporous materials not be fully utilized, and results in a low drug loading efficiency and a fast releasing rate. The purpose of this study was to develop a novel drug loading strategy to avoid soluble component migration during the process of drying, then, to prepare poorly water-soluble drug mesoporous silica microparticles with higher drug loading efficiency and longer sustained-release time. Ibuprofen was used as model drug. The microparticles were prepared by a novel method based on mesoporous silica and supercritical fluid (SCF) technique. The drug-loaded mesoporous silica microparticles prepared by SCF technique were analyzed by thermogravimetric analysis (TGA), N2 adsorption/desorption, scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC). In vitro releasing study was used to evaluate the sustained-release effect of the drug-loaded microparticles. By virtue of the high diffusibility and the high dissolving capacity of the supercritical carbon dioxide (SCF-CO2), the poorly water-soluble drugs, ibuprofen, entered the pores of the mesoporous silica. The amount and the depth of ibuprofen entered the pores of the mesoporous silica by SCF technique were both larger than those by the solution immersion method. It was found that ibuprofen loaded into the mesoporous silica by SCF technique was amorphous and the largest amount of the ibuprofen loaded into the mesoporous silica by SCF technique could reach 386 mg/g (w/w, ibuprofen/SiO2), it was more than that by the solution immersion method. In vitro releasing study showed that the sustained-release effect of

Supercritical Fluid Facilitated Growth of Copper and Aluminum Oxide Nanoparticles

ERIC Educational Resources Information Center

Williams, Geoffrey L.; Vohs, Jason K.; Brege, Jonathan J.; Fahlman, Bradley D.

2005-01-01

Supercritical fluids (SCFs) possess properties that are intermediate between liquids and gases. The combination of supercritical fluid technology with advanced characterization techniques such as electron microscopy provided a practical and rewarding undergraduate laboratory experiment.

Supercritical fluid technology: a promising approach in pharmaceutical research.

PubMed

Girotra, Priti; Singh, Shailendra Kumar; Nagpal, Kalpana

2013-02-01

Supercritical fluids possess the unique properties of behaving like liquids and gases, above their critical point. Supercritical fluid technology has recently emerged as a green and novel technique for various processes such as solubility enhancement of poorly soluble drugs, plasticization of polymers, surface modification, nanosizing and nanocrystal modification, and chromatographic extraction. Research interest in this area has been fuelled because of the numerous advantages that the technology offers over the conventional methods. This work aims to review the merits, demerits, and various processes such as rapid expansion of supercritical solutions (RESS), particles from gas saturated solutions (PGSS), gas antisolvent process (GAS), supercritical antisolvent process (SAS) and polymerization induced phase separation (PIPS), that have enabled this technology to considerably raise the interest of researchers over the past two decades. An insight has been given into the numerous applications of this technology in pharmaceutical industry and the future challenges which must be appropriately dealt with to make it effective on a commercial scale.

Simultaneous Graphite Exfoliation and N Doping in Supercritical Ammonia.

PubMed

Sasikala, Suchithra Padmajan; Huang, Kai; Giroire, Baptiste; Prabhakaran, Prem; Henry, Lucile; Penicaud, Alain; Poulin, Philippe; Aymonier, Cyril

2016-11-16

We report the exfoliation of graphite and simultaneous N doping of graphene by two methods: supercritical ammonia treatment and liquid-phase exfoliation with NH 4 OH. While the supercritical ammonia allowed N doping at a level of 6.4 atom % in 2 h, the liquid-phase exfoliation with NH 4 OH allowed N doping at a level of 2.7 atom % in 6 h. The N doped graphene obtained via the supercritical ammonia route had few layers (<5) and showed large lateral flake size (∼8 μm) and low defect density (I D /I G < 0.6) in spite of their high level of N doping. This work is the first demonstration of supercritical ammonia as an exfoliation agent and N doping precursor for graphene. Notably, the N doped graphene showed electrocatalytic activity toward oxygen reduction reaction with high durability and good methanol tolerance compared to those of commercial Pt/C catalyst.

Design of experimental system for supercritical CO2 fracturing under confining pressure conditions

NASA Astrophysics Data System (ADS)

Wang, H.; Lu, Q.; Li, X.; Yang, B.; Zheng, Y.; Shi, L.; Shi, X.

2018-03-01

Supercritical CO2 has the characteristics of low viscosity, high diffusion and zero surface tension, and it is considered as a new fluid for non-polluting and non-aqueous fracturing which can be used for shale gas development. Fracturing refers to a method of utilizing the high-pressure fluid to generate fractures in the rock formation so as to improve the oil and gas flow conditions and increase the oil and gas production. In this article, a new type of experimental system for supercritical CO2 fracturing under confining pressure conditions is designed, which is based on characteristics of supercritical CO2, shale reservoir and down-hole environment. The experimental system consists of three sub-systems, including supercritical CO2 generation system, supercritical CO2 fracturing system and data analysis system. It can be used to simulate supercritical CO2 fracturing under geo-stress conditions, thus to study the rock initiation pressure, the formation of the rock fractures, fractured surface morphology and so on. The experimental system has successfully carried out a series of supercritical CO2 fracturing experiments. The experimental results confirm the feasibility of the experimental system and the high efficiency of supercritical CO2 in fracturing tight rocks.

Simultaneous production and co-mixing of microparticles of nevirapine with excipients by supercritical antisolvent method for dissolution enhancement.

PubMed

Sanganwar, Ganesh P; Sathigari, Sateeshkumar; Babu, R Jayachandra; Gupta, Ram B

2010-01-31

Microparticles of a poorly water-soluble model drug, nevirapine (NEV) were prepared by supercritical antisolvent (SAS) method and simultaneously deposited on the surface of excipients such as lactose and microcrystalline cellulose in a single step to reduce drug-drug particle aggregation. In the proposed method, termed supercritical antisolvent-drug excipient mixing (SAS-DEM), drug particles were precipitated in supercritical CO(2) vessel containing excipient particles in suspended state. Drug/excipient mixtures were characterized for surface morphology, crystallinity, drug-excipient physico-chemical interactions, and molecular state of drug. In addition, the drug content uniformity and dissolution rate were determined. A highly ordered NEV-excipient mixture was produced. The SAS-DEM treatment was effective in overcoming drug-drug particle aggregation and did not affect the crystallinity or physico-chemical properties of NEV. The produced drug/excipient mixture has a significantly faster dissolution rate as compared to SAS drug microparticles alone or when physically mixed with the excipients. Copyright 2009 Elsevier B.V. All rights reserved.

Lessons Learned in the Selection and Development of Test Cases for the Aeroelastic Prediction Workshop: Rectangular Supercritical Wing

NASA Technical Reports Server (NTRS)

Heeg, Jennifer; Chwalowski, Pawel; Wieseman, Carol D.; Florance, Jennifer P.; Schuster, David M.

2013-01-01

The Aeroelastic Prediction Workshop brought together an international community of computational fluid dynamicists as a step in defining the state of the art in computational aeroelasticity. The Rectangular Supercritical Wing (RSW) was chosen as the first configuration to study due to its geometric simplicity, perceived simple flow field at transonic conditions and availability of an experimental data set containing forced oscillation response data. Six teams performed analyses of the RSW; they used Reynolds-Averaged Navier-Stokes flow solvers exercised assuming that the wing had a rigid structure. Both steady-state and forced oscillation computations were performed by each team. The results of these calculations were compared with each other and with the experimental data. The steady-state results from the computations capture many of the flow features of a classical supercritical airfoil pressure distribution. The most dominant feature of the oscillatory results is the upper surface shock dynamics. Substantial variations were observed among the computational solutions as well as differences relative to the experimental data. Contributing issues to these differences include substantial wind tunnel wall effects and diverse choices in the analysis parameters.

Charting the landscape of supercritical string theory.

PubMed

Hellerman, Simeon; Swanson, Ian

2007-10-26

Special solutions of string theory in supercritical dimensions can interpolate in time between theories with different numbers of spacetime dimensions and different amounts of world sheet supersymmetry. These solutions connect supercritical string theories to the more familiar string duality web in ten dimensions and provide a precise link between supersymmetric and purely bosonic string theories. Dimension quenching and c duality appear to be natural concepts in string theory, giving rise to large networks of interconnected theories.

Hydroetching of high surface area ceramics using moist supercritical fluids

DOEpatents

Fryxell, Glen; Zemanian, Thomas S.

2004-11-02

Aerogels having a high density of hydroxyl groups and a more uniform pore size with fewer bottlenecks are described. The aerogel is exposed to a mixture of a supercritical fluid and water, whereupon the aerogel forms a high density of hydroxyl groups. The process also relaxes the aerogel into a more open uniform internal structure, in a process referred to as hydroetching. The hydroetching process removes bottlenecks from the aerogels, and forms the hydrogels into more standard pore sizes while preserving their high surface area.

Analytical method development for the determination of emerging contaminants in water using supercritical-fluid chromatography coupled with diode-array detection.

PubMed

Del Carmen Salvatierra-Stamp, Vilma; Ceballos-Magaña, Silvia G; Gonzalez, Jorge; Ibarra-Galván, Valentin; Muñiz-Valencia, Roberto

2015-05-01

An analytical method using supercritical-fluid chromatography coupled with diode-array detection for the determination of seven emerging contaminants-two pharmaceuticals (carbamazepine and glyburide), three endocrine disruptors (17α-ethinyl estradiol, bisphenol A, and 17β-estradiol), one bactericide (triclosan), and one pesticide (diuron)-was developed and validated. These contaminants were chosen because of their frequency of use and their toxic effects on both humans and the environment. The optimized chromatographic separation on a Viridis BEH 2-EP column achieved baseline resolution for all compounds in less than 10 min. This separation was applied to environmental water samples after sample preparation. The optimized sample treatment involved a preconcentration step by means of solid-phase extraction using C18-OH cartridges. The proposed method was validated, finding recoveries higher than 94 % and limits of detection and limits of quantification in the range of 0.10-1.59 μg L(-1) and 0.31-4.83 μg L(-1), respectively. Method validation established the proposed method to be selective, linear, accurate, and precise. Finally, the method was successfully applied to environmental water samples.

Thermographic Imaging of Material Loss in Boiler Water-Wall Tubing by Application of Scanning Line Source

NASA Technical Reports Server (NTRS)

Cramer, K. Elliott; Winfree, William P.

2000-01-01

Localized wall thinning due to corrosion in utility boiler water-wall tubing is a significant inspection concern for boiler operators. Historically, conventional ultrasonics has been used for inspection of these tubes. This technique has proven to be very manpower and time intensive. This has resulted in a spot check approach to inspections, documenting thickness measurements over a relatively small percentage of the total boiler wall area. NASA Langley Research Center has developed a thermal NDE technique designed to image and quantitatively characterize the amount of material thinning present in steel tubing. The technique involves the movement of a thermal line source across the outer surface of the tubing followed by an infrared imager at a fixed distance behind the line source. Quantitative images of the material loss due to corrosion are reconstructed from measurements of the induced surface temperature variations. This paper will present a discussion of the development of the thermal imaging system as well as the techniques used to reconstruct images of flaws. The application of the thermal line source coupled with the analysis technique represents a significant improvement in the inspection speed for large structures such as boiler water-walls. A theoretical basis for the technique will be presented which explains the quantitative nature of the technique. Further, a dynamic calibration system will be presented for the technique that allows the extraction of thickness information from the temperature data. Additionally, the results of applying this technology to actual water-wall tubing samples and in situ inspections will be presented.

The influence of dissolved H2O content in supercritical carbon dioxide to the inclusion complexes formation of ketoprofen/β-cyclodextrin

NASA Astrophysics Data System (ADS)

Goenawan, Joshua; Trisanti, P. N.; Sumarno

2015-12-01

This work studies the relation between dissolved H2O content in supercritical carbon dioxide (SC-CO2) with the formation of ketoprofen (KP)/β-cyclodextrin(CD) inclusion complexes. The process involves a physical mixture of these two compounds into contact with the supercritical carbon dioxide which had been previously saturated with H2O over a certain duration. The pressure used for saturation process is 130 bar and saturation temperature was ranged between 30 °C to 50 °C. The inclusion process was achieved by keeping it for 2 hours at 160 bar and 200 bar with inclusion temperature of 50 °C. The results enable us to suggest explanations for the inclusion formation. The inclusion complexes can be formed by contacting the dissolved H2O in SC-CO2 to the physical mixture of KP and CD. An increase in the temperature of saturation process resulted in an increase of dissolved H2O content in the supercritical carbon dioxide. The increasing levels of this water soluble resulted an increase in the inclusion complexes that has been formed. The formation of inclusion complexes includes the water molecules enhancing the emptying of the CD cavities and being replaced by KP, towards a more stable energy state. The drug release used for analyzing the dissolution rate of the KP/CD complexes. The results vary from 79,85% to 99,98% after 45 minutes which is above the rate that has been assigned by Farmakope Indonesia at 70% dissolution rate for KP. The use of SC-CO2 offers a new methods for increasing the rate of dissolution of drugs that are hydrophobic such as KP. CO2 used as a supercritical fluid because of its relatively low cost, easily obtainable supercritical conditions, and lack of toxicity. The material samples were characterized by DSC and Spectrophotometer UV-vis technique.

Persistence and distribution of 4-nonylphenol in water, sediment, macrophytes, and wall material of littoral enclosures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heinis, L.J.; Tunell, R.; Liber, K.

1994-12-31

Eighteen enclosures (5 m x 10 m) were constructed in the littoral zone of a 2-ha pond near Duluth, MN. Each enclosure consisted of 5 m of natural shoreline and three walls of an inert plastic. The enclosures had an average surface area of 31.9 m{sup 2} , an average depth of 0.6 m and an average water volume of 33.1 m{sup 3}. The enclosure waters were treated with the alkyl phenol ethoxylate precursor and degradation product 4-nonylphenol. Application was accomplished by sub-surface injection over a 20-day period with a 2 day frequency. Nominal aqueous concentrations were 0, 3, 30,more » 100 and 300 {mu}g/L. Concentrations of 4-nonylphenol were monitored during and after application in the water, sediment, macrophytes, and enclosure wall material. Average maximum water concentrations ranged from 96.5% of nominal to 62.0% of nominal and average minimum water concentrations ranged from 33.3% of nominal to 29.5% of nominal during the application period. Water concentrations decreased exponentially after application ended. Sediment concentrations during the application period were constant from 8 to 20 d and peak concentrations occurred 48 d after application began. Macrophyte concentrations peaked 21 d after initial application with a steady decline through 76 d. Enclosure wall material concentrations reached a peak 3 h before the final application. A gradual decline occurred until 34 d after initial application followed by a more rapid dissipation.« less

Application of supercritical fluid carbon dioxide to the extraction and analysis of lipids.

PubMed

Lee, Jae Won; Fukusaki, Eiichiro; Bamba, Takeshi

2012-10-01

Supercritical carbon dioxide (SCCO(2)) is an ecofriendly supercritical fluid that is chemically inert, nontoxic, noninflammable and nonpolluting. As a green material, SCCO(2) has desirable properties such as high density, low viscosity and high diffusivity that make it suitable for use as a solvent in supercritical fluid extraction, an effective and environment-friendly analytical method, and as a mobile phase for supercritical fluid chromatography, which facilitates high-throughput, high-resolution analysis. Furthermore, the low polarity of SCCO(2) is suitable for the extraction and analysis of hydrophobic compounds. The growing concern surrounding environmental pollution has triggered the development of green analysis methods based on the use of SCCO(2) in various laboratories and industries. SCCO(2) is becoming an effective alternative to conventional organic solvents. In this review, the usefulness of SCCO(2) in supercritical fluid extraction and supercritical fluid chromatography for the extraction and analysis of lipids is described.

Organic syntheses employing supercritical carbon dioxide as a reaction solvent

NASA Technical Reports Server (NTRS)

Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

1993-01-01

Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

Organic syntheses employing supercritical carbon dioxide as a reaction solvent

NASA Technical Reports Server (NTRS)

Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

1991-01-01

Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

Extraction of metals using supercritical fluid and chelate forming legand

DOEpatents

Wai, Chien M.; Laintz, Kenneth E.

1998-01-01

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 is described. 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 .beta.-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated .beta.-diketone and a trialkyl phosphate, or a fluorinated .beta.-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated .beta.-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

Extraction of metals using supercritical fluid and chelate forming ligand

DOEpatents

Wai, C.M.; Laintz, K.E.

1998-03-24

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 is described. 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 {beta}-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated {beta}-diketone and a trialkyl phosphate, or a fluorinated {beta}-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated {beta}-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs.

Supercritical fluid processing: opportunities for new resist materials and processes

NASA Astrophysics Data System (ADS)

Gallagher-Wetmore, Paula M.; Ober, Christopher K.; Gabor, Allen H.; Allen, Robert D.

1996-05-01

Over the past two decades supercritical fluids have been utilized as solvents for carrying out separations of materials as diverse as foods, polymers, pharmaceuticals, petrochemicals, natural products, and explosives. More recently they have been used for non-extractive applications such as recrystallization, deposition, impregnation, surface modification, and as a solvent alternative for precision parts cleaning. Today, supercritical fluid extraction is being practiced in the foods and beverage industries; there are commercial plants for decaffeinating coffee and tea, extracting beer flavoring agents from hops, and separating oils and oleoresins from spices. Interest in supercritical fluid processing of polymers has grown over the last ten years, and many new purification, fractionation, and even polymerization techniques have emerged. One of the most significant motivations for applying this technology to polymers has been increased performance demands. More recently, with increasing scrutiny of traditional solvents, supercritical fluids, and in particular carbon dioxide, are receiving widespread attention as 'environmentally conscious' solvents. This paper describes several examples of polymers applications, including a few involving photoresists, which demonstrate that as next- generation advanced polymer systems emerge, supercritical fluids are certain to offer advantages as cutting edge processing tools.

Wall interference and boundary simulation in a transonic wind tunnel with a discretely slotted test section

NASA Technical Reports Server (NTRS)

Al-Saadi, Jassim A.

1993-01-01

A computational simulation of a transonic wind tunnel test section with longitudinally slotted walls is developed and described herein. The nonlinear slot model includes dynamic pressure effects and a plenum pressure constraint, and each slot is treated individually. The solution is performed using a finite-difference method that solves an extended transonic small disturbance equation. The walls serve as the outer boundary conditions in the relaxation technique, and an interaction procedure is used at the slotted walls. Measured boundary pressures are not required to establish the wall conditions but are currently used to assess the accuracy of the simulation. This method can also calculate a free-air solution as well as solutions that employ the classical homogeneous wall conditions. The simulation is used to examine two commercial transport aircraft models at a supercritical Mach number for zero-lift and cruise conditions. Good agreement between measured and calculated wall pressures is obtained for the model geometries and flow conditions examined herein. Some localized disagreement is noted, which is attributed to improper simulation of viscous effects in the slots.

Water uptake by growing cells: an assessment of the controlling roles of wall relaxation, solute uptake, and hydraulic conductance

NASA Technical Reports Server (NTRS)

Cosgrove, D. J.

1993-01-01

Growing plant cells increase in volume principally by water uptake into the vacuole. There are only three general mechanisms by which a cell can modulate the process of water uptake: (a) by relaxing wall stress to reduce cell turgor pressure (thereby reducing cell water potential), (b) by modifying the solute content of the cell or its surroundings (likewise affecting water potential), and (c) by changing the hydraulic conductance of the water uptake pathway (this works only for cells remote from water potential equilibrium). Recent studies supporting each of these potential mechanisms are reviewed and critically assessed. The importance of solute uptake and hydraulic conductance is advocated by some recent studies, but the evidence is indirect and conclusions remain controversial. For most growing plant cells with substantial turgor pressure, it appears that reduction in cell turgor pressure, as a consequence of wall relaxation, serves as the major initiator and control point for plant cell enlargement. Two views of wall relaxation as a viscoelastic or a chemorheological process are compared and distinguished.

Continuous production of biodiesel under supercritical methyl acetate conditions: Experimental investigation and kinetic model.

PubMed

Farobie, Obie; Matsumura, Yukihiko

2017-10-01

In this study, biodiesel production by using supercritical methyl acetate in a continuous flow reactor was investigated for the first time. The aim of this study was to elucidate the reaction kinetics of biodiesel production by using supercritical methyl. Experiments were conducted at various reaction temperatures (300-400°C), residence times (5-30min), oil-to-methyl acetate molar ratio of 1:40, and a fixed pressure of 20MPa. Reaction kinetics of biodiesel production with supercritical methyl acetate was determined. Finally, biodiesel yield obtained from this method was compared to that obtained with supercritical methanol, ethanol, and MTBE (methyl tertiary-butyl ether). The results showed that biodiesel yield with supercritical methyl acetate increased with temperature and time. The developed kinetic model was found to fit the experimental data well. The reactivity of supercritical methyl acetate was the lowest, followed by that of supercritical MTBE, ethanol, and methanol, under the same conditions. Copyright © 2017. Published by Elsevier Ltd.

Preparation of Chitosan-Based Hemostatic Sponges by Supercritical Fluid Technology

PubMed Central

Song, Hu-Fan; Chen, Ai-Zheng; Wang, Shi-Bin; Kang, Yong-Qiang; Ye, Shi-Fu; Liu, Yuan-Gang; Wu, Wen-Guo

2014-01-01

Using ammonium bicarbonate (AB) particles as a porogen, chitosan (CS)-based hemostatic porous sponges were prepared in supercritical carbon dioxide due to its low viscosity, small surface tension, and good compatibility with organic solvent. Fourier transform infrared spectroscopy (FTIR) spectra demonstrated that the chemical compositions of CS and poly-(methyl vinyl ether-co-maleic anhydride) (PVM/MA) were not altered during the phase inversion process. The morphology and structure of the sponge after the supercritical fluid (SCF) process were observed by scanning electron microscopy (SEM). The resulting hemostatic sponges showed a relatively high porosity (about 80%) with a controllable pore size ranging from 0.1 to 200 μm. The concentration of PVM/MA had no significant influence on the porosity of the sponges. Comparative experiments on biological assessment and hemostatic effect between the resulting sponges and Avitene® were also carried out. With the incorporation of PVM/MA into the CS-based sponges, the water absorption rate of the sponges increased significantly, and the CS-PVM/MA sponges showed a similar water absorption rate (about 90%) to that of Avitene®. The results of the whole blood clotting experiment and animal experiment also demonstrated that the clotting ability of the CS-PVM/MA sponges was similar to that of Avitene®. All these results elementarily verified that the sponges prepared in this study were suitable for hemostasis and demonstrated the feasibility of using SCF-assisted phase inversion technology to produce hemostatic porous sponges. PMID:28788577

Place Atrium to Water Seal (PAWS): Assessing Wall Suction Versus No Suction for Chest Tubes After Open Heart Surgery.

PubMed

Kruse, Tamara; Wahl, Sharon; Guthrie, Patricia Finch; Sendelbach, Sue

2017-08-01

Traditionally chest tubes are set to -20 cm H 2 O wall suctioning until removal to facilitate drainage of blood, fluid, and air from the pleural or mediastinal space in patients after open heart surgery. However, no clear evidence supports using wall suction in these patients. Some studies in patients after pulmonary surgery indicate that using chest tubes with a water seal is safer, because this practice decreases duration of chest tube placement and eliminates air leaks. To show that changing chest tubes to a water seal after 12 hours of wall suction (intervention) is a safe alternative to using chest tubes with wall suction until removal of the tubes (usual care) in patients after open heart surgery. A before-and-after quality improvement design was used to evaluate the differences between the 2 chest tube management approaches in chest tube complications, output, and duration of placement. A total of 48 patients received the intervention; 52 received usual care. The 2 groups (intervention vs usual care) did not differ significantly in complications (0 vs 2 events; P = .23), chest tube output (H 1 = 0.001, P = .97), or duration of placement (median, 47 hours for both groups). Changing chest tubes from wall suction to water seal after 12 hours of wall suction is a safe alternative to using wall suctioning until removal of the tubes. ©2017 American Association of Critical-Care Nurses.

Investigation on heat transfer characteristics and flow performance of Methane at supercritical pressures

NASA Astrophysics Data System (ADS)

Xian, Hong Wei; Oumer, A. N.; Basrawi, F.; Mamat, Rizalman; Abdullah, A. A.

2018-04-01

The aim of this study is to investigate the heat transfer and flow characteristic of cryogenic methane in regenerative cooling system at supercritical pressures. The thermo-physical properties of supercritical methane were obtained from the National institute of Standards and Technology (NIST) webbook. The numerical model was developed based on the assumptions of steady, turbulent and Newtonian flow. For mesh independence test and model validation, the simulation results were compared with published experimental results. The effect of four different performance parameter ranges namely inlet pressure (5 to 8 MPa), inlet temperature (120 to 150 K), heat flux (2 to 5 MW/m2) and mass flux (7000 to 15000 kg/m2s) on heat transfer and flow performances were investigated. It was found that the simulation results showed good agreement with experimental data with maximum deviation of 10 % which indicates the validity of the developed model. At low inlet temperature, the change of specific heat capacity at near-wall region along the tube length was not significant while the pressure drop registered was high. However, significant variation was observed for the case of higher inlet temperature. It was also observed that the heat transfer performance and pressure drop penalty increased when the mass flux was increased. Regarding the effect of inlet pressure, the heat transfer performance and pressure drop results decreased when the inlet pressure is increased.

NASA supercritical airfoils: A matrix of family-related airfoils

NASA Technical Reports Server (NTRS)

Harris, Charles D.

1990-01-01

The NASA supercritical airfoil development program is summarized in a chronological fashion. Some of the airfoil design guidelines are discussed, and coordinates of a matrix of family related supercritical airfoils ranging from thicknesses of 2 to 18 percent and over a design lift coefficient range from 0 to 1.0 are presented.

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

On the correlation of buoyancy-influenced turbulent convective heat transfer to fluids at supercritical pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jackson, J. D.; Jiang, P. X.; Liu, B.

2012-07-01

This paper is concerned with buoyancy-influenced turbulent convective heat transfer in vertical tubes for conditions where the physical properties vary strongly with temperature as in fluids at supercritical pressure in the pseudocritical temperature region. An extended physically-based, semi-empirical model is described which has been developed to account for the extreme non-uniformity of properties which can be present in such fluids and lead to strong influences of buoyancy which cause the mean flow and turbulence fields to be modified in such a manner that has a very profound effect on heat transfer. Data for both upward and downward flow from experimentsmore » using carbon dioxide at supercritical pressure (8.80, MPa, p/pc=1.19) in a uniformly heated tube of internal diameter 2 mm and length 290 mm, obtained under conditions of strong non-uniformity of fluid properties, are being correlated and fitted using an approach based on the model. It provides a framework for describing the complex heat transfer behaviour which can be encountered in such experiments by means of an equation of simple form. Buoyancy-induced impairment and enhancement of heat transfer is successfully reproduced by the model. Similar studies are in progress using experimental data for both carbon dioxide and water from other sources. The aim is to obtain an in-depth understanding of the mechanisms by which deterioration of heat transfer might arise in sensitive applications involving supercritical pressure fluids, such as high pressure, water-cooled reactors operating above the critical pressure. (authors)« less

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).

Study on Trailing Edge Ramp of Supercritical Airfoil

DTIC Science & Technology

2016-03-30

7 th Asia-Pacific International Symposium on Aerospace Technology, 25 – 27 November 2015, Cairns Study on Trailing Edge Ramp of Supercritical...China Abstract Trailing edge flow control method could improve the performance of supercritical airfoil with a small modification on the original...airfoil. In this paper, a ramp of 2%~7% chord length is sliced near the trailing edge to improve airfoil performance. The trailing edge ramp is

Scour in supercritical flow

DOT National Transportation Integrated Search

1988-10-01

Scour in supercritical flow is one extreme aspect of the effects of velocity on scour. Analysis of the case of scour in a long contraction shows that if all other independent variables are kept constant (1) some finite velocity is necessary to have a...

A study on post impingement effects of urea-water solution spray on the heated wall of automotive SCR systems

NASA Astrophysics Data System (ADS)

Shahariar, G. M. H.; Wardana, M. K. A.; Lim, O. T.

2018-04-01

The post impingement effects of urea-water solution spray on the heated wall of automotive SCR systems was numerically investigated in a constant volume chamber using STAR CCM+ CFD code. The turbulence flow was modelled by realizable k-ε two-layer model together with standard wall function and all y+ treatment was applied along with two-layer approach. The Eulerian-Lagrangian approach was used for the modelling of multi phase flow. Urea water solution (UWS) was injected onto the heated wall for the wall temperature of 338, 413, 473, 503 & 573 K. Spray development after impinging on the heated wall was visualized and measured. Droplet size distribution and droplet evaporation rates were also measured, which are vital parameters for the system performance but still not well researched. Specially developed user defined functions (UDF) are implemented to simulate the desired conditions and parameters. The investigation reveals that wall temperature has a great impact on spray development after impingement, droplet size distribution and evaporation. Increasing the wall temperature leads to longer spray front projection length, smaller droplet size and faster droplet evaporation which are preconditions for urea crystallization reduction. The numerical model and parameters are validated comparing with experimental data.

Supercritical carbon dioxide and sulfur in the Madison Limestone: A natural analog in southwest Wyoming for geologic carbon-sulfur co-sequestration

NASA Astrophysics Data System (ADS)

Kaszuba, John P.; Navarre-Sitchler, Alexis; Thyne, Geoffrey; Chopping, Curtis; Meuzelaar, Tom

2011-09-01

The Madison Limestone on the Moxa Arch, southwest Wyoming, USA contains large volumes (65-95%) of supercritical CO 2 that it has stored naturally for 50 million years. This reservoir also contains supercritical H 2S, aqueous sulfur complexes (SO 42- and HS -), and sulfur-bearing minerals (anhydrite and pyrite). Although SO 2 is not present, these sulfur-bearing phases are known products of SO 2 disproportionation in other water-rock systems. The natural co-occurrence of SO 42-, S 2-, supercritical CO 2 and brine affords the opportunity to evaluate the fate of a carbon-sulfur co-sequestration scenario. Mineralogic data was obtained from drill core and aqueous geochemical data from wells outside and within the current supercritical CO 2-sulfur-brine-rock system. In addition to dolomite, calcite, and accessory sulfur-bearing minerals, the Madison Limestone contains accessory quartz and the aluminum-bearing minerals feldspar, illite, and analcime. Dawsonite (NaAlCO 3(OH) 2), predicted as an important carbon sink in sequestration modeling studies, is not present. After confirming equilibrium conditions for the Madison Limestone system, reaction path models were constructed with initial conditions based on data from outside the reservoir. Addition of supercritical CO 2 to the Madison Limestone was simulated and the results compared to data from inside the reservoir. The model accurately predicts the observed mineralogy and captures the fundamental changes expected in a Madison Limestone-brine system into which CO 2 is added. pH decreases from 5.7 to 4.5 at 90 °C and to 4.0 at 110 °C, as expected from dissolution of supercritical CO 2, creation of carbonic acid, and buffering by the carbonate rock. The calculated redox potential increases by 0.1 V at 90 °C and 0.15 V at 110 °C due to equilibrium among CO 2, anhydrite, and pyrite. Final calculated Eh and pH match conditions for the co-existing sulfur phases present in produced waters and core from within the reservoir

Comparison of conventional and adaptive wall wind tunnel results with regard to Reynolds number effects

NASA Technical Reports Server (NTRS)

Stanewsky, E.; Freimuth, P.

1989-01-01

A comparison of results from conventional and adaptive wall wind tunnels with regard to Reynolds number effects was carried out. The special objective of this comparison was to confirm or reject earlier conclusions, soley based on conventional wind tunnel results, concerning the influence of viscous effects on the characteristics of partially open wind tunnel walls, hence wall interference. The following postulations could be confirmed: (1) certain classes of supercritical airfoils exhibit a non-linear increase in lift which is, at least in part, related to viscous-inviscid interactions on the airfoil. This non-linear lift characteristic can erroneously be suppressed by sidewall interference effects in addition to being affected by changes in Reynolds number. Adaptive walls seem to relieve the influence of sidewall interference; (2) the degree of (horizontal) wall interference effects can be significantly affected by changes in Reynolds number, thus appearing as true Reynolds number effects; (3) perforated wall characteristics seem much more susceptible to viscous changes than the characteristics of slotted walls; here, blockage interference may be most severely influenced by viscous changes; and (4) real Reynolds number effects are present on the CAST 10-2/DOA 2 airfoil; they were shown to be appreciable also by the adaptive wall wind tunnel tests.

Use and practice of achiral and chiral supercritical fluid chromatography in pharmaceutical analysis and purification.

PubMed

Lemasson, Elise; Bertin, Sophie; West, Caroline

2016-01-01

The interest of pharmaceutical companies for complementary high-performance chromatographic tools to assess a product's purity or enhance this purity is on the rise. The high-throughput capability and economic benefits of supercritical fluid chromatography, but also the "green" aspect of CO2 as the principal solvent, render supercritical fluid chromatography very attractive for a wide range of pharmaceutical applications. The recent reintroduction of new robust instruments dedicated to supercritical fluid chromatography and the progress in stationary phase technology have also greatly benefited supercritical fluid chromatography. Additionally, it was shown several times that supercritical fluid chromatography could be orthogonal to reversed-phase high-performance liquid chromatography and could efficiently compete with it. Supercritical fluid chromatography is an adequate tool for small molecules of pharmaceutical interest: synthetic intermediates, active pharmaceutical ingredients, impurities, or degradation products. In this review, we first discuss about general chromatographic conditions for supercritical fluid chromatography analysis to better suit compounds of pharmaceutical interest. We also discuss about the use of achiral and chiral supercritical fluid chromatography for analytical purposes and the recent applications in these areas. The use of preparative supercritical fluid chromatography by pharmaceutical companies is also covered. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Material Property Variations at Near Critical Thermodynamic Conditions on Pipe Flow Heat Transfer

NASA Astrophysics Data System (ADS)

Barney, Rebecca; Nourgaliev, Robert; Delplanque, Jean-Pierre; McCallen, Rose

2017-11-01

Heat transfer is quantified and contrasted for the Poiseuille flow of a fluid at both subcritical and supercritical thermodynamic conditions in a circular pipe subject to a uniform wall heat flux. The conditions considered are relevant to Supercritical Water Reactor (SCWR) applications. In the supercritical thermodynamic regime, a fluid can exhibit large density variations of density, thermal conductivity, and viscosity, which will affect flow and heat transfer characteristics significantly. An advanced equation of state for supercritical water was implemented in a 2D and 3D Arbitrary Lagrangian-Eurlerian multi-physics simulation tool called ALE3D developed at Lawrence Livermore National Laboratory. A newly developed, robust, high-order in space and time, fully implicit reconstructed discontinuous Galerkin (rDG) method is used to enable the numerical simulation of convective heat transfer with supercritical water. Results demonstrate the capability of this approach to accurately capture the non-linear behavior and enhanced heat transfer with supercritical water. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Information management release number LLNL-ABS-736004. Work is supported by the Integrated University Program Graduate Fellowship. Opinions, findings, conclusions or recommendations expressed are of the authors and do not necessarily reflect the views of DOE office of NE.

Supercritical water treatment of heavy metal and arsenic metalloid-bioaccumulating-biomass.

PubMed

Li, Jianxin; Chen, Jinbo; Chen, Shan

2018-08-15

Hyperaccumulator biomass, as a promising resource for renewable energy that can be converted into valuable fuel productions with high conversion efficiency, must be considered as hazardous materials and be carefully treated before further reuse due to the high contents of heavy metals. In this study, Pteris vittata L., an As-hyperaccumulator biomass was treated by an effective and environmental friendly method-supercritical water gasification (SCWG) using a bench-scale batch reactor. The contents of heavy metals (Cd, Pb and Zn) and arsenic metalloid in solid, liquid and gaseous products during SCWG process were thoroughly investigated. The speciation fractions including exchangeable, reducible, oxidizable and residual fractions of each heavy metal as the proportion of the total contents in solid residue were presented and the transformations trend of these heavy metals during the SCWG process was especially demonstrated. The significant operating parameters, including reaction temperature (395-445 °C), pressure (21-27 MPa) and residence time (0-40 min) were varied to explore their effects on the contents and forms. Moreover, the environmental risks of heavy metals in solid residues were evaluated based on risk assessment code, taking into consideration the speciation fractions and bioavailability. It was highlighted that although heavy metals particularly Pb and Zn tended to accumulate in solid residues with a maximum increment of about 50% in the total content, they were mostly converted to more stable oxidizable and residual fractions, and thus the ecotoxicity and bioavailability were greatly mitigated with no obvious increase in direct toxicity fractions. Each tested heavy metal presented no or low risk to the environments after SCWG treatments, meaning that the environmental pollution levels were markedly reduced with no or low risk to the environment. This study highlights the remarkable ability of SCWG for the heavy metal stabilization. Copyright �

Supercritical fluid technology for enhanced drug delivery and heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Pathak, Pankaj

In recent years there has been great interest in the properties of supercritical fluids (SCFs) and applications of supercritical fluid technology in chemistry, material sciences and many other areas. In our laboratory, we have applied supercritical fluid namely CO2, as a medium for pharmaceutical processing and also for heterogeneous catalysis. The method used for pharmaceutical processing is based on the Rapid Expansion of supercritical solutions into a liquid SOLVent (RESOLV). We have used this method for the preparation of nanoparticles from various anti-inflammatory (Ibuprofen and Naproxen), anti-fungal (Amphotericin B) and anti-cancer (Paclitaxel) drugs. The anticancer drug nanoparticle formulations were further used for in vitro biological evaluation. In this dissertation, results from the preparation, characterization and biological evaluation of nanoscale drug particles are reported. The effect of experimental conditions on the properties of the nanoparticles prepared via our RESOLV method is discussed. In addition we have used supercritical CO2 as a medium for photoreduction of CO2 using dispersed TiO 2 or metal coated-TiO2 nanoparticles encapsulated in nanoscale cavities of perfluorinated ionomer membranes. These catalytic films are also stable chemically and photochemically, reusable in repeated reactions. The results from the characterization of the nanoparticles and the use of films using different catalysts are presented and discussed.

Geological model of supercritical geothermal reservoir related to subduction system

NASA Astrophysics Data System (ADS)

Tsuchiya, Noriyoshi

2017-04-01

Following the Great East Japan Earthquake and the accident at the Fukushima Daiichi Nuclear power station on 3.11 (11th March) 2011, geothermal energy came to be considered one of the most promising sources of renewable energy for the future in Japan. The temperatures of geothermal fields operating in Japan range from 200 to 300 °C (average 250 °C), and the depths range from 1000 to 2000 m (average 1500 m). In conventional geothermal reservoirs, the mechanical behavior of the rocks is presumed to be brittle, and convection of the hydrothermal fluid through existing network is the main method of circulation in the reservoir. In order to minimize induced seismicity, a rock mass that is "beyond brittle" is one possible candidate, because the rock mechanics of "beyond brittle" material is one of plastic deformation rather than brittle failure. Supercritical geothermal resources could be evaluated in terms of present volcanic activities, thermal structure, dimension of hydrothermal circulation, properties of fracture system, depth of heat source, depth of brittle factures zone, dimension of geothermal reservoir. On the basis of the GIS, potential of supercritical geothermal resources could be characterized into the following four categories. 1. Promising: surface manifestation d shallow high temperature, 2 Probability: high geothermal gradient, 3 Possibility: Aseismic zone which indicates an existence of melt, 4 Potential : low velocity zone which indicates magma input. Base on geophysical data for geothermal reservoirs, we have propose adequate tectonic model of development of the supercritical geothermal reservoirs. To understand the geological model of a supercritical geothermal reservoir, granite-porphyry system, which had been formed in subduction zone, was investigated as a natural analog of the supercritical geothermal energy system. Quartz veins, hydrothermal breccia veins, and glassy veins are observed in a granitic body. The glassy veins formed at 500-550 �

Chemical Composition Analysis of Extracts from Ficus Hirta Using Supercritical Fluid

NASA Astrophysics Data System (ADS)

Deng, S. B.; Chen, J. P.; Chen, Y. Z.; Yu, C. Q.; Yang, Y.; Wu, S. H.; Chen, C. Z.

2018-05-01

Ficus hirta was extracted by supercritical carbon dioxide. The volatile chemical components of extracts were analyzed using gas chromatography-mass spectrometry (GC-MS). The percentage of products extracted by Supercritical Fluid Extraction(SFE) was 2.5%. Nineteen volatile compounds were identified. The main volatile components were Elemicin, Psoralen, Palmitic acid, Bergapten, α-Linolenic acid, Medicarpin, Retinoic Acid, Maackiain, and Squalene. The method is simple and quick, and can be used for the preliminary analysis of chemical constituents of supercritical extracts of Ficus hirta.

Interfacial enhancement of carbon fiber composites by growing TiO2 nanowires onto amine-based functionalized carbon fiber surface in supercritical water

NASA Astrophysics Data System (ADS)

Ma, Lichun; Li, Nan; Wu, Guangshun; Song, Guojun; Li, Xiaoru; Han, Ping; Wang, Gang; Huang, Yudong

2018-03-01

A novel amine-based functionalization method was developed to improve the interfacial adhesion between TiO2 NWs and CFs in supercritical water. The microstructure, morphology and mechanical properties of CFs were investigated. It was found that introducing hexamethylenetetramine (HMTA) dendrimers and branched polyethyleneimine (PEI) on CF could increase significantly the adhesion strength between CF and TiO2 NWs and their interfacial shear strength with epoxy resin, and the order is CF-PEI-TiO2 NWs > CF-HMTA-TiO2 NWs > CF-COOH-TiO2 NWs > CF-TiO2 NW. Meanwhile, the reinforcing mechanisms and interfacial failure modes have also been discussed. We believe that these effective methods may provide theoretical foundation for the preparation of high performance composite materials.

Salinity-dependent toxicity of water-dispersible, single-walled carbon nanotubes to Japanese medaka embryos.

PubMed

Kataoka, Chisato; Nakahara, Kousuke; Shimizu, Kaori; Kowase, Shinsuke; Nagasaka, Seiji; Ifuku, Shinsuke; Kashiwada, Shosaku

2017-04-01

To investigate the effects of salinity on the behavior and toxicity of functionalized single-walled carbon nanotubes (SWCNTs), which are chemical modified nanotube to increase dispersibility, medaka embryos were exposed to non-functionalized single-walled carbon nanotubes (N-SWCNTs), water-dispersible, cationic, plastic-polymer-coated, single-walled carbon nanotubes (W-SWCNTs), or hydrophobic polyethylene glycol-functionalized, single-walled carbon nanotubes (PEG-SWCNTs) at different salinities, from freshwater to seawater. As reference nanomaterials, we tested dispersible chitin nanofiber (CNF), chitosan-chitin nanofiber (CCNF) and chitin nanocrystal (CNC, i.e. shortened CNF). Under freshwater conditions, with exposure to 10 mg l -1  W-SWCNTs, the yolk sacks of 57.8% of embryos shrank, and the remaining embryos had a reduced heart rate, eye diameter and hatching rate. Larvae had severe defects of the spinal cord, membranous fin and tail formation. These toxic effects increased with increasing salinity. Survival rates declined with increasing salinity and reached 0.0% in seawater. In scanning electron microscope images, W-SWCNTs, CNF, CCNF and CNC were adsorbed densely over the egg chorion surface; however, because of chitin's biologically harmless properties, only W-SWCNTs had toxic effects on the medaka eggs. No toxicity was observed from N-SWCNT and PEG-SWCNT exposure. We demonstrated that water dispersibility, surface chemistry, biomedical properties and salinity were important factors in assessing the aquatic toxicity of nanomaterials. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Supercritical Fluid Chromatography/Fourier Transform Infrared Spectroscopy Of Food Components

NASA Astrophysics Data System (ADS)

Calvey, Elizabeth M.; Page, Samuel W.; Taylor, Larry T.

1989-12-01

Supercritical fluid (SF) technologies are being investigated extensively for applications in food processing. The number of SF-related patents issued testifies to the level of interest. Among the properties of materials at temperatures and pressures above their critical points (supercritical fluids) is density-dependent solvating power. Supercritical CO2 is of particular interest to the food industry because of its low critical temperature (31.3°C) and low toxicity. Many of the components in food matrices react or degrade at elevated temperatures and may be adversely affected by high temperature extractions. Likewise, these components may not be amenable to GC analyses. Our SF research has been in the development of methods employing supercritical fluid chromatography (SFC) and extraction (SFE) coupled to a Fourier transform infrared (FT-IR) spectrometer to investigate food composition. The effects of processing techniques on the isomeric fatty acid content of edible oils and the analysis of lipid oxidation products using SFC/FT-IR with a flow-cell interface are described.

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

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.

Corrosion behavior of pre-oxidized HR-224 superalloy in supercritical water environment at 700 °C

NASA Astrophysics Data System (ADS)

Liu, Yu-Chen; Chen, Shih-Ming; Ouyang, Fan-Yi; Kai, Ji-Jung

2018-07-01

Corrosion of cladding materials in supercritical water (SCW) environment is a key reliability issue for the safety of nuclear power plant. In this study, we propose to use the pre-oxidized treatment to provide better corrosion resistance of cladding materials in the SCW environment. The nickel-based superalloy HR-224 was first pre-oxidized in flowing air at 982 °C for 100 h to establish a continuous and dense scales and then exposed in the SCW environment with high oxygen content (8.3 ppm) at 700 °C and 24.8 MPa for cyclic oxidation testing up to 1300 h. The pre-oxidized samples exhibit better corrosion resistance than as-received samples in the SCW environment. After pre-oxidizing process, triple scales, Ni(Cr, Fe)2O4 spinel/Cr2O3/α-Al2O3 were observed, and the growth of inner α-Al2O3 layer is predominant in the SCW environment. The α-Al2O3 layer in pre-oxidized samples was found to effectively decrease outward migration of metal ions in Alloy HR-224 and thus provides better corrosion resistance than as-received samples in SCW environment.

Effect of dewatering on seismic performance of multi-anchor wall due to high ground water level

NASA Astrophysics Data System (ADS)

Kobayashi, Makoto; Miura, Kinya; Konami, Takeharu; Hayashi, Taketo; Sato, Hiroki

2017-10-01

Previous research reported that the ground water in the backfill of reinforced soil wall made it deteriorate. According to the damage investigation of Great East Earthquake 2011, the reinforced soil structure due to high ground water level by seismic wave were deformed remarkably. Some of them classified ultimate limit state or restorability limit state. However, more than 90% of reinforced soil structure, which suffered from this earthquake, were classified into no damage condition. Therefore, it is necessary that the seismic behaviors of multi-anchor wall due to seepage flow should be clarified in order to adopt the performance-based design in such reinforced soil structure. In this study, a series of centrifugal shaking table tests were conducted to investigate the seismic behavior of multi-anchor wall due to high ground water level. The reinforced drainage pipes were installed into the backfill in order to verify the dewatering effect and additional reinforcement. Furthermore, to check only the dewatering effect, the model tests was carried out with several ground water table that was modeled the case reinforced drainage pipes installed. The test results show unique behavior of reinforced region that moved integrally. This implies that the reinforced region has been behaved as if it became one mass, and this behavior make this structure increase seismic performance. Thus, the effectiveness of dewatering was observed remarkably because of decreasing the inertial force during earthquake.

Vessel-wall imaging and quantification of flow-mediated dilation using water-selective 3D SSFP-echo.

PubMed

Langham, Michael C; Li, Cheng; Englund, Erin K; Chirico, Erica N; Mohler, Emile R; Floyd, Thomas F; Wehrli, Felix W

2013-10-30

To introduce a new, efficient method for vessel-wall imaging of carotid and peripheral arteries by means of a flow-sensitive 3D water-selective SSFP-echo pulse sequence. Periodic applications of RF pulses will generate two transverse steady states, immediately after and before an RF pulse; the latter being referred to as the SSFP-echo. The SSFP-echo signal for water protons in blood is spoiled as a result of moving spins losing phase coherence in the presence of a gradient pulse along the flow direction. Bloch equation simulations were performed over a wide range of velocities to evaluate the flow sensitivity of the SSFP-echo signal. Vessel walls of carotid and femoral and popliteal arteries were imaged at 3 T. In two patients with peripheral artery disease the femoral arteries were imaged bilaterally to demonstrate method's potential to visualize atherosclerotic plaques. The method was also evaluated as a means to measure femoral artery flow-mediated dilation (FMD) in response to cuff-induced ischemia in four subjects. The SSFP-echo pulse sequence, which does not have a dedicated blood signal suppression preparation, achieved low blood signal permitting discrimination of the carotid and peripheral arterial walls with in-plane spatial resolution ranging from 0.5 to 0.69 mm and slice thickness of 2 to 3 mm, i.e. comparable to conventional 2D vessel-wall imaging techniques. The results of the simulations were in good agreement with analytical solution and observations for both vascular territories examined. Scan time ranged from 2.5 to 5 s per slice yielding a contrast-to-noise ratio between the vessel wall and lumen from 3.5 to 17. Mean femoral FMD in the four subjects was 9%, in good qualitative agreement with literature values. Water-selective 3D SSFP-echo pulse sequence is a potential alternative to 2D vessel-wall imaging. The proposed method is fast, robust, applicable to a wide range of flow velocities, and straightforward to implement.

Capillary pressure heterogeneity and hysteresis for the supercritical CO2/water system in a sandstone

NASA Astrophysics Data System (ADS)

Pini, Ronny; Benson, Sally M.

2017-10-01

We report results from an experimental investigation on the hysteretic behaviour of the capillary pressure curve for the supercritical CO2-water system in a Berea Sandstone core. Previous observations have highlighted the importance of subcore-scale capillary heterogeneity in developing local saturations during drainage; we show in this study that the same is true for the imbibition process. Spatially distributed drainage and imbibition scanning curves were obtained for mm-scale subsets of the rock sample non-invasively using X-ray CT imagery. Core- and subcore-scale measurements are well described using the Brooks-Corey formalism, which uses a linear trapping model to compute mobile saturations during imbibition. Capillary scaling yields two separate universal drainage and imbibition curves that are representative of the full subcore-scale data set. This enables accurate parameterisation of rock properties at the subcore-scale in terms of capillary scaling factors and permeability, which in turn serve as effective indicators of heterogeneity at the same scale even when hysteresis is a factor. As such, the proposed core-analysis workflow is quite general and provides the required information to populate numerical models that can be used to extend core-flooding experiments to conditions prevalent in the subsurface, which would be otherwise not attainable in the laboratory.

Supercritical sedimentary structures and bedforms and criteria for recognition in the field: insights from the Middle Eocene deep-marine Morillo and Guaso systems, Ainsa Basin, Spanish Pyrenees

NASA Astrophysics Data System (ADS)

Torley, John; Pickering, Kevin

2017-04-01

It has long been acknowledged that for most submarine slopes with gradients > 0.5, common to many deep-water environments, they should contain abundant evidence of supercritical flows and their deposits. However, it is common for deep-marine sands/sandstones to be routinely modelled using the Bouma (1962) sequence for turbidites. Recently, the importance of supercritical flows has been highlighted from seafloor observations, with numerical and physical experiments. Such experiments have produced previously unrecognised bedforms which fail to be interpreted adequately by Bouma's model, including antidunes, chutes-and-pools, and cyclic steps. Fieldwork in the Middle Eocene Ainsa Basin, Spanish Pyrenees, has been undertaken in the Morillo and Guaso systems of the Upper Hecho Group. Approximately 5,000 beds were measured and documented in detail, e.g., grain size, sedimentary structures, bedforms and facies. Collectively, this data can be used to understand supercritical versus subcritical flow. The relative importance of supercritical flow can then be compared and contrasted within individual ancient deep-marine systems. The Morillo System is relatively coarse-grained, compared with the Guaso System. The results of this research contribute to an improved understanding of the processes in deep-marine systems, and directly benefit the hydrocarbon industry by providing better constraints to predict deep-water reservoir composition and architecture.

Production of cromolyn sodium microparticles for aerosol delivery by supercritical assisted atomization.

PubMed

Reverchon, Ernesto; Adami, Renata; Caputo, Giuseppe

2007-12-21

The purpose of this study was to produce cromolyn sodium (CS) micrometric particles with controlled particle size (PS) and PS distribution (PSD) suitable for aerosol delivery, using a supercritical fluids-based process. CS was micronized using the supercritical assisted atomization (SAA) technique at different solute concentrations in water and different precipitation temperatures. Two techniques were used to measure PS and PSD of produced particles: scanning electron microscopy image analysis and laser scattering analysis. The 2 techniques were compared to provide a complete description of the powder obtained. High-performance liquid chromatography analysis was used to verify the absence of degradation of CS after micronization; differential scanning calorimetry, thermogravimetric analysis (TGA), and X-ray analysis were performed to study the effect of operative conditions on the crystalline structure and on the water content of SAA micronized particles. The CS particles obtained were spherical, with a volumetric percentage of particles with a diameter ranging between 1 and 5 microm of 50% to 66%. The precipitation temperature had no significant effect on PSD, but high drying temperatures led to product degradation. Increasing the concentration of CS in water solution produced an increase in PS of the micronized particles. TGA showed that the micronized CS had a different hydration state than the untreated CS did. The micronized product was stable after 12 months of storage, and no modifications in structure, morphology, or crystallinity were detected. In conclusion, SAA is an efficient technique for micronization of CS, and stable spherical amorphous particles suitable for aerosol delivery can be produced.

IMAGE Project: Results of Laboratory Tests on Tracers for Supercritical Conditions.

NASA Astrophysics Data System (ADS)

Brandvoll, Øyvind; Opsahl Viig, Sissel; Nardini, Isabella; Muller, Jiri

2016-04-01

The use of tracers is a well-established technique for monitoring dynamic behaviour of water and gas through a reservoir. In geothermal reservoirs special challenges are encountered due to high temperatures and pressures. In this work, tracer candidates for monitoring water at supercritical conditions (temperature > 374°C, pressure ca 218 bar), are tested in laboratory experiments. Testing of tracers at supercritical water conditions requires experimental set-ups which tolerate harsh conditions with respect to high temperature and pressure. In addition stringent HES (health, environment and safety) factors have to be taken into consideration when designing and performing the experiments. The setup constructed in this project consists of a pressure vessel, high pressure pump, instrumentation for pressure and temperature control and instrumentation required for accurate sampling of tracers. In order to achieve accurate results, a special focus has been paid to the development of the tracer sampling technique. Perfluorinated cyclic hydrocarbons (PFCs) have been selected as tracer candidates. This group of compounds is today commonly used as gas tracers in oil reservoirs. According to the literature they are stable at temperatures up to 400°C. To start with, five PFCs have been tested for thermal stability in static experiments at 375°C and 108 bar in the experimental setup described above. The tracer candidates will be further tested for several months at the relevant conditions. Preliminary results indicate that some of the PFC compounds show stability after three months. However, in order to arrive at conclusive results, the experiments have to be repeated over a longer period and paying special attention to more accurate sampling procedures.

Particle Formation and Product Formulation Using Supercritical Fluids.

PubMed

Knez, Željko; Knez Hrnčič, Maša; Škerget, Mojca

2015-01-01

Traditional methods for solids processing involve either high temperatures, necessary for melting or viscosity reduction, or hazardous organic solvents. Owing to the negative impact of the solvents on the environment, especially on living organisms, intensive research has focused on new, sustainable methods for the processing of these substances. Applying supercritical fluids for particle formation may produce powders and composites with special characteristics. Several processes for formation and design of solid particles using dense gases have been studied intensively. The unique thermodynamic and fluid-dynamic properties of supercritical fluids can be used also for impregnation of solid particles or for the formation of solid powderous emulsions and particle coating, e.g., for formation of solids with unique properties for use in different applications. We give an overview of the application of sub- and supercritical fluids as green processing media for particle formation processes and present recent advances and trends in development.

Experimental study on the liquefaction of cellulose in supercritical ethanol

NASA Astrophysics Data System (ADS)

Peng, Jinxing; Liu, Xinyuan; Bao, Zhenbo

2018-03-01

Cellulose is the major composition of solid waste for producing biofuel; cellulose liquefaction is helpful for realizing biomass supercritical liquefaction process. This paper is taking supercritical ethanol as the medium, liquefied cellulose with the intermittence installation of high press cauldron. Experiments have studied technical condition and the technology parameter of cellulose liquefaction in supercritical ethanol, and the pyrolysis mechanism was analysed based on the pyrolysis product. Results show that cellulose can be liquefied, can get good effect through appropriate technology condition. Under not catalyst, highest liquefaction rate of cellulose can reach 73.5%. The composition of the pyrolysis product was determined by GC-MS.

Large Eddy Simulation of a Supercritical Turbulent Mixing Layer

NASA Astrophysics Data System (ADS)

Sheikhi, Reza; Hadi, Fatemeh; Safari, Mehdi

2017-11-01

Supercritical turbulent flows are relevant to a wide range of applications such as supercritical power cycles, gas turbine combustors, rocket propulsion and internal combustion engines. Large eddy simulation (LES) analysis of such flows involves solving mass, momentum, energy and scalar transport equations with inclusion of generalized diffusion fluxes. These equations are combined with a real gas equation of state and the corresponding thermodynamic mixture variables. Subgrid scale models are needed for not only the conventional convective terms but also the additional high pressure effects arising due to the nonlinearity associated with generalized diffusion fluxes and real gas equation of state. In this study, LES is carried out to study the high pressure turbulent mixing of methane with carbon dioxide in a temporally developing mixing layer under supercritical condition. LES results are assessed by comparing with data obtained from direct numerical simulation (DNS) of the same layer. LES predictions agree favorably with DNS data and represent several key supercritical turbulent flow features such as high density gradient regions. Supported by DOE Grant SC0017097; computational support is provided by DOE National Energy Research Scientific Computing Center.

Extraction of curcumin from Curcuma longa L. using ultrasound assisted supercritical carbon dioxide

NASA Astrophysics Data System (ADS)

Kimthet, Chhouk; Wahyudiono, Kanda, Hideki; Goto, Motonobu

2017-05-01

Curcumin is one of phenolic compounds, which has been recently shown to have useful pharmacological properties such as anti-inflammatory, anti-bacterial, anti-carcinogenic, antifungal, and antimicrobial activities. The objective of this research is to extract the curcumin from Curcuma longa L. using ultrasound assisted supercritical carbon dioxide extraction (USC-CO2). The extraction was performed at 50°C, 25 MPa, CO2 flow rate of 3 mL/min with 10% cosolvent. The result of extraction, thermogravimetry (TG), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) showed that ultrasound power could disrupt cell wall and release the target compounds from Curcuma longa L. USC-CO2 could provide higher curcumin content in the extracts and faster extraction compared to SC-CO2 extraction without ultrasound.

Uncertainty Analysis of Heat Transfer to Supercritical Hydrogen in Cooling Channels

NASA Technical Reports Server (NTRS)

Locke, Justin M.; Landrum, D. Brian

2005-01-01

Sound understanding of the cooling efficiency of supercritical hydrogen is crucial to the development of high pressure thrust chambers for regeneratively cooled LOX/LH2 rocket engines. This paper examines historical heat transfer correlations for supercritical hydrogen and the effects of uncertainties in hydrogen property data. It is shown that uncertainty due to property data alone can be as high as 10%. Previous heated tube experiments with supercritical hydrogen are summarized, and data from a number of heated tube experiments are analyzed to evaluate conditions for which the available correlations are valid.

Direct visualization of the arterial wall water permeability barrier using CARS microscopy

PubMed Central

Lucotte, Bertrand M.; Powell, Chloe; Knutson, Jay R.; Combs, Christian A.; Malide, Daniela; Yu, Zu-Xi; Knepper, Mark; Patel, Keval D.; Pielach, Anna; Johnson, Errin; Borysova, Lyudmyla; Balaban, Robert S.

2017-01-01

The artery wall is equipped with a water permeation barrier that allows blood to flow at high pressure without significant water leak. The precise location of this barrier is unknown despite its importance in vascular function and its contribution to many vascular complications when it is compromised. Herein we map the water permeability in intact arteries, using coherent anti-Stokes Raman scattering (CARS) microscopy and isotopic perfusion experiments. Generation of the CARS signal is optimized for water imaging with broadband excitation. We identify the water permeation barrier as the endothelial basolateral membrane and show that the apical membrane is highly permeable. This is confirmed by the distribution of the AQP1 water channel within endothelial membranes. These results indicate that arterial pressure equilibrates within the endothelium and is transmitted to the supporting basement membrane and internal elastic lamina macromolecules with minimal deformation of the sensitive endothelial cell. Disruption of this pressure transmission could contribute to endothelial cell dysfunction in various pathologies. PMID:28373558

Using ground and intact coal Samples to evaluate hydrocarbon fate during supercritical CO2 injection into coal beds: effects of particle size and coal moisture

USGS Publications Warehouse

Kolak, Jon; Hackley, Paul C.; Ruppert, Leslie F.; Warwick, Peter D.; Burruss, Robert

2015-01-01

To investigate the potential for mobilizing organic compounds from coal beds during geologic carbon dioxide (CO2) storage (sequestration), a series of solvent extractions using dichloromethane (DCM) and using supercritical CO2 (40 °C and 10 MPa) were conducted on a set of coal samples collected from Louisiana and Ohio. The coal samples studied range in rank from lignite A to high volatile A bituminous, and were characterized using proximate, ultimate, organic petrography, and sorption isotherm analyses. Sorption isotherm analyses of gaseous CO2 and methane show a general increase in gas storage capacity with coal rank, consistent with findings from previous studies. In the solvent extractions, both dry, ground coal samples and moist, intact core plug samples were used to evaluate effects of variations in particle size and moisture content. Samples were spiked with perdeuterated surrogate compounds prior to extraction, and extracts were analyzed via gas chromatography–mass spectrometry. The DCM extracts generally contained the highest concentrations of organic compounds, indicating the existence of additional hydrocarbons within the coal matrix that were not mobilized during supercritical CO2 extractions. Concentrations of aliphatic and aromatic compounds measured in supercritical CO2 extracts of core plug samples generally are lower than concentrations in corresponding extracts of dry, ground coal samples, due to differences in particle size and moisture content. Changes in the amount of extracted compounds and in surrogate recovery measured during consecutive supercritical CO2extractions of core plug samples appear to reflect the transition from a water-wet to a CO2-wet system. Changes in coal core plug mass during supercritical CO2 extraction range from 3.4% to 14%, indicating that a substantial portion of coal moisture is retained in the low-rank coal samples. Moisture retention within core plug samples, especially in low-rank coals, appears to inhibit

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

Step-wise supercritical extraction of carbonaceous residua

DOEpatents

Warzinski, Robert P.

1987-01-01

A method of fractionating a mixture containing high boiling carbonaceous material and normally solid mineral matter includes processing with a plurality of different supercritical solvents. The mixture is treated with a first solvent of high critical temperature and solvent capacity to extract a large fraction as solute. The solute is released as liquid from solvent and successively treated with other supercritical solvents of different critical values to extract fractions of differing properties. Fractionation can be supplemented by solute reflux over a temperature gradient, pressure let down in steps and extractions at varying temperature and pressure values.

Fabrication of through-silicon via arrays by photo-assisted electrochemical etching and supercritical electroplating

NASA Astrophysics Data System (ADS)

Chuang, Ho-Chiao; Yang, Hsi-Min; Wu, Cheng-Xiang; Sanchez, Jorge; Shyu, Jenq-Huey

2017-01-01

This paper aims to fabricate high aspect ratio through silicon via (TSV) by photo-assisted electrochemical etching (PAECE) and supercritical CO2 copper electroplating. A blind-holed silicon array was first fabricated by PAECE. By studying the etching parameters, including hydrofluoric acid concentration, etchant temperature, stirring speed, tetrabutylammonium perchlorate (TBAP) content, and Ohmic contact thickness, an array of pores with a 1∶45 aspect ratio (height=250 μm and diameter=5.5 μm) was obtained successfully. Moreover, TBAP and Kodak Photo-Flo (PF) solution were added into the etchant to acquire smooth sidewalls for the first time. TBAP was added for the first time to serve as an antistatic agent in deionized water-based etchant to prevent side-branch etching, and PF was used to degasify hydrogen bubbles in the etchant. The effect of gold thickness over Ohmic contact was investigated. Randomized etching was observed with an Au thickness of 200 Å, but it can be improved by increasing the etching voltage. The silicon mold of through-holes was filled with metal using supercritical CO2 copper electroplating, which features high diffusivity, permeability, and density. The TSV structure (aspect ratio=1∶35) was obtained at a supercritical pressure of 2000 psi, temperature of 50°C, and current density of 30 mA/cm2 in 2.5 h.

Multi-walled Carbon Nanotubes Reduce Toxicity of Diphenhydramine to Ceriodaphnia dubia in Water and Sediment Exposures.

PubMed

Myer, Mark H; Black, Marsha C

2017-09-01

Multi-walled carbon nanotubes are adsorptive materials that have potential for remediation of organic contaminants in water. Sediment elutriate exposures were undertaken with Ceriodaphnia dubia to compare the toxic effects of diphenhydramine in the presence and absence of sediment and multi-walled carbon nanotubes. In both sediment and solution-only treatments, addition of 0.318 mg/g of carbon nanotubes significantly decreased 48-h mortality relative to control, with a 78.7%-90.1% reduction in treatments with nanotube-amended sediment and 40.7%-53.3% reduction in nanotube-amended water exposures. The greatest degree of relative mortality reduction occurred in sediments containing higher levels of natural organic matter, indicating a potential additive effect.

Experimental insights into the geochemistry and mineralogy of a granite-hosted geothermal system injected with supercritical CO2

NASA Astrophysics Data System (ADS)

Lo Re, C.; Kaszuba, J. P.; Moore, J.; McPherson, B. J.

2011-12-01

Supercritical CO2 may be a viable working fluid in enhanced geothermal systems (EGS) due to its large expansivity, low viscosity, and reduced reactivity with rock as compared to water. Hydrothermal experiments are underway to evaluate the geochemical impact of using supercritical CO2 as a working fluid in granite-hosted geothermal systems. Synthetic aqueous fluid and a model granite are reacted at 250 °C and 250 bars in a rocking autoclave and Au-Ti reaction cell for a minimum of 28 days (water:rock ratio of approximately 20:1). Subsequent injection of supercritical CO2 increases pressure, which decays over time as the CO2 dissolves into the aqueous fluid. Initial experiments decreased to a steady state pressure of 450 bars approximately 14 hours after injection of supercritical CO2. Post-injection reaction is allowed to continue for at least an additional 28 days. Excess CO2 is injected to produce a separate supercritical fluid phase (between 1.7 and 3.1 molal), ensuring aqueous CO2 saturation for the duration of each experiment. The granite was created using mineral separates and consists of ground (75 wt%, <45 microns) and chipped (25 wt%, 0.5-1.0 cm), sub-equal portions of quartz, perthitic potassium feldspar (~ 25 wt% albite and 75 wt% potassium feldspar), oligoclase, and a minor (4 wt%) component of Fe-rich biotite. The synthetic saline water (I = 0.12 m) contains molal quantities of Na, Cl, and HCO3 and millimolal quantities of K, SiO2, SO4, Ca, Al, and Mg, in order of decreasing molality. Aqueous fluids are sampled approximately 10 times over the course of each experiment and analyzed for total dissolved carbon and sulfide by coulometric titration, anions by ion chromatography, and major, minor, and trace cations by ICP-OES and -MS. Bench pH measurements are paired with aqueous analyses to calculate in-situ pH. Solid reactants are evaluated by SEM-EDS, XRD, and/or bulk chemical analysis before and after each experiment. Analytical data are reviewed

Effects of Natural Osmolytes on the Protein Structure in Supercritical CO2: Molecular Level Evidence.

PubMed

Monhemi, Hassan; Housaindokht, Mohammad Reza; Nakhaei Pour, Ali

2015-08-20

Protein instability in supercritical CO2 limits the application of this green solvent in enzyme-catalyzed reactions. CO2 molecules act as a protein denaturant at high pressure under supercritical conditions. Here, for the first time, we show that natural osmolytes could stabilize protein conformation in supercritical CO2. Molecular dynamics simulation is used to monitor the effects of adding different natural osmolytes on the conformation and dynamics of chymotrypsin inhibitor 2 (CI2) in supercritical CO2. Simulations showed that CI2 is denatured at 200 bar in supercritical CO2, which is in agreement with experimental observations. Interestingly, the protein conformation remains native after addition of ∼1 M amino acid- and sugar-based osmolyte models. These molecules stabilize protein through the formation of supramolecular self-assemblies resulting from macromolecule-osmolyte hydrogen bonds. Nevertheless, trimethylamine N-oxide, which is known as a potent osmolyte for protein stabilization in aqueous solutions, amplifies protein denaturation in supercritical CO2. On the basis of our structural analysis, we introduce a new mechanism for the osmolyte effect in supercritical CO2, an "inclusion mechanism". To the best of our knowledge, this is the first study that introduces the application of natural osmolytes in a supercritical fluid and describes mechanistic insights into osmolyte action in nonaqueous media.

Turbulent properties under sloping Ice-wall in polar water

NASA Astrophysics Data System (ADS)

Mondal, Mainak; Gayen, Bishakhdatta; Griffiths, Ross W.; Kerr, Ross C.

2017-11-01

Ice-shelves around West Antarctic basins are the most vulnerable to melting in the presence of warmer continental shelf water. A large extent of slope exists under these ice-shelves, where turbulent transport of salt and heat into the ice wall drives a convective melt-water plume against it. Large scale ice-ocean models neglect the effect of convection which can lead to a wrong estimation of melt rate. We perform direct numerical simulations under sloping ice-shelves with realistic ambient conditions. We estimated the melt rates, boundary layer thicknesses and entrainment coefficients as a function of slope angle. The numerical results are further supported by theoretical predictions. Over the range of slope angles, different mechanisms are active for sustaining turbulence. For near vertical case, buoyancy production is the primary source of turbulent kinetic energy whereas for shallower angles turbulence is produced by velocity shear in the meltwater plume. Australian Research Council.

In-vitro and in-vivo study of amorphous spironolactone prepared by adsorption method using supercritical CO2.

PubMed

Jiang, Qikun; Li, Yuanyuan; Fu, Qiang; Geng, Yajie; Zhao, Juanhang; Ma, Panqin; Zhang, Tianhong

2015-02-01

The aim of this study was to improve the oral bioavailability of spironolactone (SP). SP was adsorbed on the fumed silica using supercritical CO2 (scCO2) technology and further compressed into tablets. The morphology was observed by scanning electron microscopy (SEM), and the crystalline form was investigated by differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD). The dissolution test was performed in water, 0.1 M HCl solution, pH 4.5 acetate buffers and pH 6.8 phosphate buffers using the paddle method. The pharmacokinetics was undertaken in six dogs in a crossover fashion. SP was successfully prepared into tablets and presented in amorphous state. SP-silica scCO2 tablets displayed higher dissolution profiles than SP-silica physical mixtures tablets in different media. The AUC0-t and Cmax of SP-silica supercritical CO2 was 1.61- and 1.52-fold greater than those of SP-silica physical mixtures (p < 0.05), respectively. It is a promising method in improving dissolution and bioavailability by adsorbing SP, a poorly soluble drug, on the fumed silica using rapid expansion of supercritical solutions.

Simultaneous destraction and desulfurization of Illinois coals with supercritical ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, B.C.

1983-01-01

Various Illinois coals (with Illinois number6 being the main one) are liquefied with various supercritical solvents (ethanol being the main solvent) at 543-598 K, system pressures of 6.99-24.23 MPa, flow rates of 3.0-7.5 ml/min, reaction time of 0-180 minutes, and coal particle sizes of 0.36-0.85 mm to 1.00-2.36 mm to systematically investigate the effects of flow rates, reaction time, coal particle size, temperature, pressure, coal characteristics (by using different Illinois coals), supercritical medium (by using different solvents), and the addition of potassium hydroxide. The % weight loss of coal and the % sulfur removal during destraction and desulfurization of coalmore » are functions of the flow rate, the reaction time, the coal particle size, temperature, pressure and the supercritical solvent. Temperature, pressure and the supercritical medium are the most important parameters in controlling the % weight loss of coal and the % sulfur removal. The % weight loss of coal can be related to a power law and fits quite nicely into a second order kinetic model. The % sulfur removal also follows a second order kinetic model. A secondary reaction is observed during the destraction process, which implies that destraction, and possibly desulfurization, of coal is a multistep reaction including a physical extraction step where the major portion of the coal and sulfur was removed and then followed by a chemical reaction. Supercritical ethanol definitely enhances the removal of sulfur compounds from coal. The enhanced selectivity by supercritical ethanol is greatest at a pressure just above the critical pressure of ethanol. Finally, addition of a base such as potassium hydroxide enhances both % weight loss of coal and the % sulfur removal.« less

Supercritical Fluid Chromatography--Theoretical Background and Applications on Natural Products.

PubMed

Hartmann, Anja; Ganzera, Markus

2015-11-01

The use of supercritical fluid chromatography for natural product analysis as well as underlying theoretical mechanisms and instrumental requirements are summarized in this review. A short introduction focusing on the historical development of this interesting separation technique is followed by remarks on the current instrumental design, also describing possible detection modes and useable stationary phases. The overview on relevant applications is grouped based on their basic intention, may it be (semi)preparative or purely analytical. They indicate that supercritical fluid chromatography is still primarily considered for the analysis of nonpolar analytes like carotenoids, fatty acids, or terpenes. The low polarity of supercritical carbon dioxide, which is used with modifiers almost exclusively as a mobile phase today, combined with high efficiency and fast separations might explain the popularity of supercritical fluid chromatography for the analysis of these compounds. Yet, it has been shown that more polar natural products (e.g., xanthones, flavonoids, alkaloids) are separable too, with the same (if not superior) selectivity and reproducibility than established approaches like HPLC or GC. Georg Thieme Verlag KG Stuttgart · New York.

Isoprene/methyl acrylate Diels-Alder reaction in supercritical carbon dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, B.; Akgerman, A.

1999-12-01

The Diels-Alder reaction between isoprene and methyl acrylate was carried out in supercritical carbon dioxide in the temperature range 110--140 C and the pressure range 95.2--176.9 atm in a 300 cm{sup 3} autoclave. The high-pressure phase behavior of the reaction mixture in the vicinity of its critical region was determined in a mixed vessel with a sight window to ensure that all the experiments were performed in the supercritical single-phase region. Kinetic data were obtained at different temperatures, pressures, and reaction times. It was observed that in the vicinity of the critical point the reaction rate constant decreases with increasingmore » pressure. It was also determined that the reaction selectivity does not change with operating conditions. Transition-state theory was used to explain the effect of pressure on reaction rate and product selectivity. Additional experiments were conducted at constant temperature but different phase behaviors (two-phase region, liquid phase, supercritical phase) by adjusting the initial composition and pressure. It was shown that the highest reaction rate is in the supercritical region.« less

Solubility and conversion of carbamazepine polymorphs in supercritical carbon dioxide.

PubMed

Bettini, R; Bonassi, L; Castoro, V; Rossi, A; Zema, L; Gazzaniga, A; Giordano, F

2001-06-01

The aim of this work was to investigate whether mixtures of carbamazepine polymorphs could be processed in supercritical (SC) CO(2) in order to obtain the pure stable crystalline phase. To accomplish this goal the solubility of carbamazepine polymorphs I and III in supercritical CO(2) was first assessed using a low solvent flux dynamic method. Mixtures of Form I and Form III were processed in dynamic or static conditions in SC-CO(2). Differential scanning calorimetry, Fourier transformed infrared spectroscopy, and powder X-ray diffractometry were used to analyse solid samples in terms of polymorph composition. It was found that Form I and Form III of carbamazepine have different solubility in supercritical CO(2) at 55 degrees C above 300 bar. Due to the transformation of the metastable form, conversion of Form I into Form III can be carried out on a binary mixture of the two polymorphs by treating the mixture at 55 degrees C and 350 bar, under both static and dynamic conditions, via its solubilization in supercritical CO(2).

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

2015-01-06

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.

Impregnation of cinnamaldehyde into cassava starch biocomposite films using supercritical fluid technology for the development of food active packaging.

PubMed

de Souza, Ana Cristina; Dias, Ana M A; Sousa, Hermínio C; Tadini, Carmen C

2014-02-15

In this work, supercritical solvent impregnation (SSI) has been tested for the incorporation of natural compounds into biocomposite materials for food packaging. Cinnamaldehyde, with proved antimicrobial activity against fungi commonly found in bread products, was successfully impregnated on biocomposite cassava starch based materials using supercritical carbon dioxide as solvent. Different process experimental conditions were tested (pressure, impregnation time and depressurization rate) at a fixed temperature (35 °C) in order to study their influence on the amount of impregnated cinnamaldehyde as well as on the morphology of the films. Results showed that all conditions permitted to impregnate antimicrobial active amounts superior to those previously obtained using conventional incorporation methods. Moreover, a significant decrease of the equilibrium water vapor sorption capacity and water vapor permeability of the films was observed after SSI processing which is a clear advantage of the process, considering the envisaged applications. Copyright © 2013 Elsevier Ltd. All rights reserved.

Supercritical Fluid Spray Application Process for Adhesives and Primers

DTIC Science & Technology

2003-03-01

The basic scheme of SFE process consists of three steps. A solvent, typically carbon dioxide, first is heated and pressurized to a supercritical...passivation step to remove contaminants and to prevent recontamination. Bok et al. (25) describe a pressure pulsation mechanism to stimulate improved...in as a liquid, and then it is heated to above its critical temperature to become a supercritical fluid. The sample is injected and dissolved into

Hydrogel Nanoparticles from Supercritical Technology for Pharmaceutical and Seismological Applications

NASA Astrophysics Data System (ADS)

Hemingway, Melinda Graham

This research focuses on hydrogel nanoparticle formation using miniemulsion polymerization and supercritical carbon dioxide. Hydrogel nanopowder is produced by a novel combination of inverse miniemulsion polymerization and supercritical drying (MPSD) methods. Three drying methods of miniemulsions are examined: (1) a conventional freeze drying technique, and (2) two supercritical drying techniques: (2a) supercritical fluid injection into miniemulsions, and (2b) the polymerized miniemulsion injection into supercritical fluid. Method 2b can produce non-agglomerated hydrogel nanoparticles that are free of solvent or surfactant (Chapter 2). The optimized MPSD method was applied for producing an extended release drug formulation with mucoadhesive properties. Drug nanoparticles of mesalamine, were produced using supercritical antisolvent technology and encapsulation within two hydrogels, polyacrylamide and poly(acrylic acid-co-acrylamide). The encapsulation efficiency and release profile of drug nanoparticles is compared with commercial ground mesalamine particles. The loading efficiency is influenced by morphological compatibility (Chapter 3). The MPSD method was extended for encapsulation of zinc oxide nanoparticles for UV protection in sunscreens (Chapter 4). ZnO was incorporated into the inverse miniemulsion during polymerization. The effect of process parameters are examined on absorbency of ultraviolet light and transparency of visible light. For use of hydrogel nanoparticles in a seismological application, delayed hydration is needed. Supercritical methods extend MPSD so that a hydrophobic coating can be applied on the particle surface (Chapter 5). Multiple analysis methods and coating materials were investigated to elucidate compatibility of coating material to polyacrylamide hydrogel. Coating materials of poly(lactide), poly(sulphone), poly(vinyl acetate), poly(hydroxybutyrate), Geluice 50-13, Span 80, octadecyltrichlorosilane, and perfluorobutane sulfate (PFBS

Topics in Chemical Instrumentation--An Introduction to Supercritical Fluid Chromatography: Part 1: Principles and Instrumentation.

ERIC Educational Resources Information Center

Palmieri, Margo D.

1988-01-01

Identifies the properties and characteristics of supercritical fluids. Discusses the methodology for supercritical fluid chromatography including flow rate, plate height, column efficiency, viscosity, and other factors. Reviews instruments, column types, and elution conditions. Lists supercritical fluid data for 22 compounds, mostly organic. (MVL)

Modeling Solvation in Supercritical CO2.

PubMed

Ingrosso, Francesca; Ruiz-López, Manuel F

2017-10-06

In recent decades, a microscopic understanding of solute-solvent intermolecular interactions has been key to advances in technologies based on supercritical carbon dioxide. In many cases, computational work has provided the impetus for new discoveries, shedding new light on important concepts such as the local structure around the solute in the supercritical medium, the influence of the peculiar properties of the latter on the molecular behavior of dissolved substances and, importantly, CO 2 -philicity. In this Review, the theoretical work that has been relevant to these developments is surveyed and, by presenting some crucial open questions, the possible routes to achieving further progress based on the interplay between theory and experiments is discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancing Phenolic Contents and Antioxidant Potentials of Antidesma thwaitesianum by Supercritical Carbon Dioxide Extraction

PubMed Central

Poontawee, Warut; Natakankitkul, Surapol; Wongmekiat, Orawan

2015-01-01

Supercritical fluid extraction (SFE) has increasingly gained attention as an alternative technique for extraction of natural products without leaving toxic residues in extracts. Antidesma thwaitesianum Muell. Arg. (Phyllanthaceae), or ma mao, has been reported to exhibit antioxidant health benefits due to its phenolic constituents. To determine whether SFE technique could impact on phenolic contents and associated antioxidant potentials, ripe fruits of Antidesma thwaitesianum (Phyllanthaceae) were extracted using supercritical carbon dioxide (SC-CO2) and conventional solvents (ethanol, water). The results showed that the SC-CO2 extract contained significantly higher yield, total phenolic, flavonoid, and proanthocyanidin contents than those obtained from ethanol and water. It also demonstrated the greatest antioxidant activities as assessed by ABTS radical cation decolorization, DPPH radical scavenging, and ferric reducing antioxidant power (FRAP) assays. Further analysis using high-performance liquid chromatography with diode array and mass spectrometry detectors (HPLC-DAD/MSD) revealed the presence of catechin as a major phenolic compound of Antidesma thwaitesianum (Phyllanthaceae), with the maximum amount detected in the SC-CO2 extract. These data indicate that SFE technology improves both quantity and quality of Antidesma thwaitesianum fruit extract. The findings added more reliability of using this technique to produce high added value products from this medicinal plant. PMID:25977832

Experimental study of elliptical jet from sub to supercritical conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muthukumaran, C. K.; Vaidyanathan, Aravind, E-mail: aravind7@iist.ac.in

2014-04-15

The jet mixing at supercritical conditions involves fluid dynamics as well as thermodynamic phenomena. All the jet mixing studies at critical conditions to the present date have focused only on axisymmetric jets. When the liquid jet is injected into supercritical environment, the thermodynamic transition could be well understood by considering one of the important fluid properties such as surface tension since it decides the existence of distinct boundary between the liquid and gaseous phase. It is well known that an elliptical liquid jet undergoes axis-switching phenomena under atmospheric conditions due to the presence of surface tension. The experimental investigations weremore » carried out with low speed elliptical jet under supercritical condition. Investigation of the binary component system with fluoroketone jet and N{sub 2} gas as environment shows that the surface tension force dominates for a large downstream distance, indicating delayed thermodynamic transition. The increase in pressure to critical state at supercritical temperature is found to expedite the thermodynamic transition. The ligament like structures has been observed rather than droplets for supercritical pressures. However, for the single component system with fluoroketone jet and fluoroketone environment shows that the jet disintegrates into droplets as it is subjected to the chamber conditions even for the subcritical pressures and no axis switching phenomenon is observed. For a single component system, as the pressure is increased to critical state, the liquid jet exhibits gas-gas like mixing behavior and that too without exhibiting axis-switching behavior.« less

Research activities on supercritical fluid science in food biotechnology.

PubMed

Khosravi-Darani, Kianoush

2010-06-01

This article serves as an overview, introducing the currently popular area of supercritical fluids and their uses in food biotechnology. Within each application, and wherever possible, the basic principles of the technique, as well as a description of the history, instrumentation, methodology, uses, problems encountered, and advantages over the traditional, non-supercritical methods are given. Most current commercial application of the supercritical extraction involve biologically-produced materials; the technique may be particularly relevant to the extraction of biological compounds in cases where there is a requirement for low-temperature processing, high mass-transfer rates, and negligible carrying over of the solvent into the final product. Special applications to food processing include the decaffeination of green coffee beans, the production of hops extracts, the recovery of aromas and flavors from herbs and spices, the extraction and fractionation of edible oils, and the removal of contaminants, among others. New advances, in which the extraction is combined with reaction or crystallization steps, may further increase the attractiveness of supercritical fluids in the bioprocess industries. To develop and establish a novel and effective alternative to heating treatment, the lethal action of high hydrostatic pressure CO(2) on microorganisms, with none or only a minimal heating process, has recently received a great deal of attention.

Lipidomics by Supercritical Fluid Chromatography

PubMed Central

Laboureur, Laurent; Ollero, Mario; Touboul, David

2015-01-01

This review enlightens the role of supercritical fluid chromatography (SFC) in the field of lipid analysis. SFC has been popular in the late 1980s and 1990s before almost disappearing due to the commercial success of liquid chromatography (LC). It is only 20 years later that a regain of interest appeared when new commercial instruments were introduced. As SFC is fully compatible with the injection of extracts in pure organic solvent, this technique is perfectly suitable for lipid analysis and can be coupled with either highly universal (UV or evaporative light scattering) or highly specific (mass spectrometry) detection methods. A short history of the use of supercritical fluids as mobile phase for the separation oflipids will be introduced first. Then, the advantages and drawbacks of SFC are discussed for each class of lipids (fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, sterols, prenols, polyketides) defined by the LIPID MAPS consortium. PMID:26090714

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.

Experimental study of elliptical jet from supercritical to subcritical conditions using planar laser induced fluorescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muthukumaran, C. K.; Vaidyanathan, Aravind, E-mail: aravind7@iist.ac.in

2015-03-15

The study of fluid jet dynamics at supercritical conditions involves strong coupling between fluid dynamic and thermodynamic phenomena. Beyond the critical point, the liquid-vapor coexistence ceases to exist, and the fluid exists as a single phase known as supercritical fluid with its properties that are entirely different from liquids and gases. At the critical point, the liquids do not possess surface tension and latent heat of evaporation. Around the critical point, the fluid undergoes large changes in density and possesses thermodynamic anomaly like enhancement in thermal conductivity and specific heat. In the present work, the transition of the supercritical andmore » near-critical elliptical jet into subcritical as well as supercritical environment is investigated experimentally with nitrogen and helium as the surrounding environment. Under atmospheric condition, a liquid jet injected from the elliptical orifice exhibits axis switching phenomena. As the injection temperature increases, the axis switching length also increases. Beyond the critical temperature, the axis switching is not observed. The investigation also revealed that pressure plays a major role in determining the thermodynamic transition of the elliptical jet only for the case of supercritical jet injected into subcritical chamber conditions. At larger pressures, the supercritical jet undergoes disintegration and formation of droplets in the subcritical environment is observed. However, for supercritical jet injection into supercritical environment, the gas-gas like mixing behavior is observed.« less

Wall relaxation and the driving forces for cell expansive growth

NASA Technical Reports Server (NTRS)

Cosgrove, D. J.

1987-01-01

When water uptake by growing cells is prevented, the turgor pressure and the tensile stress in the cell wall are reduced by continued wall loosening. This process, termed in vivo stress relaxation, provides a new way to study the dynamics of wall loosening and to measure the wall yield threshold and the physiological wall extensibility. Stress relaxation experiments indicate that wall stress supplies the mechanical driving force for wall yielding. Cell expansion also requires water absorption. The driving force for water uptake during growth is created by wall relaxation, which lowers the water potential of the expanding cells. New techniques for measuring this driving force show that it is smaller than believed previously; in elongating stems it is only 0.3 to 0.5 bar. This means that the hydraulic resistance of the water transport pathway is small and that rate of cell expansion is controlled primarily by wall loosening and yielding.

Remediation of Contaminated Soils By Supercritical Carbon Dioxide Extraction

NASA Astrophysics Data System (ADS)

Ferri, A.; Zanetti, M. C.; Banchero, M.; Fiore, S.; Manna, L.

The contaminants that can be found in soils are many, inorganic, like heavy metals, as well as organic. Among the organic contaminants, oil and coal refineries are responsi- ble for several cases of soil contamination with PAHs (Polycyclic Aromatic Hydrocar- bons). Polynuclear aromatic hydrocarbons (PAHs) have toxic, carcinogenic and mu- tagenic effects. Limits have been set on the concentration of most contaminants, and growing concern is focusing on soil contamination issues. USA regulations set the maximum acceptable level of contamination by PAHs equal to 40 ppm at residential sites and 270 ppm at industrial sites. Stricter values are usually adopted in European Countries. Supercritical carbon dioxide extraction is a possible alternative technology to remove volatile organic compounds from contaminated soils. Supercritical fluid extraction (SFE) offers many advantages over conventional solvent extraction. Super- critical fluids combine gaseous properties as a high diffusion coefficient, and liquid properties as a high solvent power. The solvent power is strongly pressure-dependent near supercritical conditions: selective extractions are possible without changing the solvent. Solute can be separate from the solvent depressurising the system; therefore, it is possible to recycle the solvent and recover the contaminant. Carbon dioxide is frequently used as supercritical fluid, because it has moderate critical conditions, it is inert and available in pure form. In this work, supercritical fluid extraction technology has been used to remove a polynuclear aromatic hydrocarbon from contaminated soils. The contaminant choice for the experiment has been naphthalene since several data are available in literature. G. A. Montero et al. [1] studied soil remediation with supercrit- ical carbon dioxide extraction technology; these Authors have found that there was a mass-transfer limitation. In the extraction vessel, the mass transfer coefficient in- creases with the

Cooling beyond the boundary value in supercritical fluids under vibration

NASA Astrophysics Data System (ADS)

Sharma, D.; Erriguible, A.; Amiroudine, S.

2017-12-01

Supercritical fluids when subjected to simultaneous quench and vibration have been known to cause various intriguing flow phenomena and instabilities depending on the relative direction of temperature gradient and vibration. Here we describe a surprising and interesting phenomenon wherein temperature in the fluid falls below the imposed boundary value when the walls are quenched and the direction of vibration is normal to the temperature gradient. We define these regions in the fluid as sink zones, because they act like sink for heat within the fluid domain. The formation of these zones is first explained using a one-dimensional (1D) analysis with acceleration in constant direction. Subsequently, the effect of various boundary conditions and the relative direction of the temperature gradient to acceleration are analyzed, highlighting the necessary conditions for the formation of sink zones. It is found that the effect of high compressibility and the action of self-weight (due to high acceleration) causes the temperature to change in the bulk besides the usual action of piston effect. This subsequently affects the overall temperature profile thereby leading to the formation of sink zones. Though the examined 1D cases differ from the current two-dimensional (2D) cases, owing to the direction of acceleration being normal as compared to parallel in case of former, the explanations pertaining to 1D cases are judiciously utilized to elucidate the formation of sink zones in 2D supercritical fluids subjected to thermal quench and vibrational acceleration. The appearance of sink zones is found to be dependent on several factors such as proximity to the critical point and acceleration. A surface three-dimensional plot illustrating the effect of these parameters on onset time of sink zones is presented to further substantiate these arguments.

Active Control of Separation From the Flap of a Supercritical Airfoil

NASA Technical Reports Server (NTRS)

Melton, LaTunia Pack; Yao, Chung-Sheng; Seifert, Avi

2006-01-01

Zero-mass-flux periodic excitation was applied at several regions on a simplified high-lift system to delay the occurrence of flow separation. The NASA Energy Efficient Transport (EET) supercritical airfoil was equipped with a 15% chord simply hinged leading edge flap and a 25% chord simply hinged trailing edge flap. Detailed flow features were measured in an attempt to identify optimal actuator placement. The measurements included steady and unsteady model and tunnel wall pressures, wake surveys, arrays of surface hot-films, flow visualization, and particle image velocimetry (PIV). The current paper describes the application of active separation control at several locations on the deflected trailing edge flap. High frequency (F(+) approximately equal to 10) and low frequency amplitude modulation (F(+) sub AM approximately equal to 1) of the high frequency excitation were used for control. It was noted that the same performance gains were obtained with amplitude modulation and required only 30% of the momentum input required by pure sine excitation.

Active Control of Separation From the Flap of a Supercritical Airfoil

NASA Technical Reports Server (NTRS)

Melton, La Tunia Pack; Yao, Chung-Sheng; Seifert, Avi

2003-01-01

Active flow control in the form of periodic zero-mass-flux excitation was applied at several regions on the leading edge and trailing edge flaps of a simplified high-lift system t o delay flow separation. The NASA Energy Efficient Transport (EET) supercritical airfoil was equipped with a 15% chord simply hinged leading edge flap and a 25% chord simply hinged trailing edge flap. Detailed flow features were measured in an attempt to identify optimal actuator placement. The measurements included steady and unsteady model and tunnel wall pressures, wake surveys, arrays of surface hot-films, flow visualization, and particle image velocimetry (PIV). The current paper describes the application of active separation control at several locations on the deflected trailing edge flap. High frequency (F(+) approx.= 10) and low frequency amplitude modulation (F(+)AM approx.= 1) of the high frequency excitation were used for control. Preliminary efforts to combine leading and trailing edge flap excitations are also reported.

Supercritical fluids in separation science--the dreams, the reality and the future.

PubMed

Smith, R M

1999-09-24

The last 20 years have seen an intense interest in the use of supercritical fluids in separation science. This started with the introduction of commercial instruments first for packed and then for capillary chromatography and it looked as if this would be a technique to rival gas-liquid chromatography and HPLC. The activity developed quite rapidly into packed column supercritical fluid separations then into supercritical fluid extraction. However, in recent years there has been a decline in publications. These later techniques continue to be used but are now principally applied to a limited group of applications where they offer significant advantages over alternative techniques. This review looks back over this period and analyses how these methods were developed and the fluids, detectors and applications that were examined. It suggests why many of the initial applications have vanished and why the initial apparent promise was not fulfilled. The rise and fall of supercritical fluids represents a lesson in the way analysts approach new techniques and how we might view other new separation developments at the end of this millennium. The review looks forward to the future of supercritical fluids and their role at the end of the first century of separation science. Probably the most important idea that supercritical fluids have brought to separation science is a recognition that there is unity in the separation methods and that a continuum exists from gases to liquids.

Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes-``Super-Growth''

NASA Astrophysics Data System (ADS)

Hata, Kenji

2005-03-01

We demonstrate an extremely efficient chemical vapour deposition synthesis of single-walled carbon nanotubes where the activity and lifetime of the catalysts are enhanced by water [1]. Water-stimulated enhanced catalytic activity results in massive growth of super-dense and vertically-aligned nanotube forests with heights up to 2.5 millimeters that can be easily separated from the catalysts, providing nanotube material with carbon purity above 99.98%. Moreover, patterned highly organized intrinsic nanotube structures were successfully fabricated. The water-assisted synthesis method addresses many critical problems that currently plague carbon nanotube synthesis. [1] K. Hata, et al., Science, 306, 1362 (2004).

High Materials Performance in Supercritical CO2 in Comparison with Atmospheric Pressure CO2 and Supercritical Steam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holcomb, Gordon; Tylczak, Joseph; Carney, Casey

2017-02-26

This presentation covers environments (including advanced ultra-supercritical (A-USC) steam boiler/turbine and sCO2 indirect power cycle), effects of pressure, exposure tests, oxidation results, and mechanical behavior after exposure.

Plasma microreactor in supercritical xenon and its application to diamondoid synthesis

NASA Astrophysics Data System (ADS)

Oshima, F.; Stauss, S.; Ishii, C.; Pai, D. Z.; Terashima, K.

2012-10-01

The generation of plasmas in a microreactor is demonstrated in xenon from atmospheric pressure up to supercritical conditions. Ac high voltage at a frequency of 15 kHz was applied across a 25-µm discharge gap between a tungsten wire and a fused silica micro-capillary tube in a coaxial configuration. Using this continuous flow supercritical fluid microreactor, it was possible to synthesize diamantane and other diamondoids up to nonamantane, using adamantane as a precursor and seed. It is anticipated that plasmas generated in supercritical fluid microreactors may not only allow faster fabrication of diamondoids, but also offer opportunities for the fabrication of other nanomaterials.

Supercritical-fluid extraction and chromatography-mass spectrometry for analysis of mycotoxins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R.D.; Udseth, H.R.

1982-07-01

The use of direct supercritical-fluid injection-mass spectrometry for the rapid analysis of mycotoxins of the tricothecene group is demonstrated. A solution containing diacetoxyscirpenol or T-2 toxin is injected into a fluid consisting primarily of pentane or carbon dioxide and is rapidly brought to supercritical conditions. Direct injection of the fluid stream into a chemical ionization source allows thermally labile compounds to be analyzed. Under these conditions trichothecene mass spectra showing significant (M + 1)/sup +/ ions and distinctive fragmentation patterns are obtained. Detection limits are in the subnanogram range. Direct analysis from complex substrates using selective supercritical-fluid extraction is proposed.more » 4 figures.« less

Solid-state chemistry and particle engineering with supercritical fluids in pharmaceutics.

PubMed

Pasquali, Irene; Bettini, Ruggero; Giordano, Ferdinando

2006-03-01

The present commentary aims to review the modern and innovative strategies in particle engineering by the supercritical fluid technologies and it is principally concerned with the aspects of solid-state chemistry. Supercritical fluids based processes for particle production have been proved suitable for controlling solid-state, morphology and particle size of pharmaceuticals, in some cases on an industrial scale. Supercritical fluids should be considered in a prominent position in the development processes of drug products for the 21st century. In this respect, this innovative technology will help in meeting the more and more stringent requirements of regulatory authorities in terms of solid-state characterisation and purity, and environmental acceptability.

Formation of curcumin nanoparticles via solution-enhanced dispersion by supercritical CO2

PubMed Central

Zhao, Zheng; Xie, Maobin; Li, Yi; Chen, Aizheng; Li, Gang; Zhang, Jing; Hu, Huawen; Wang, Xinyu; Li, Shipu

2015-01-01

In order to enhance the bioavailability of poorly water-soluble curcumin, solution-enhanced dispersion by supercritical carbon dioxide (CO2) (SEDS) was employed to prepare curcumin nanoparticles for the first time. A 24 full factorial experiment was designed to determine optimal processing parameters and their influence on the size of the curcumin nanoparticles. Particle size was demonstrated to increase with increased temperature or flow rate of the solution, or with decreased precipitation pressure, under processing conditions with different parameters considered. The single effect of the concentration of the solution on particle size was not significant. Curcumin nanoparticles with a spherical shape and the smallest mean particle size of 325 nm were obtained when the following optimal processing conditions were adopted: P =20 MPa, T =35°C, flow rate of solution =0.5 mL·min−1, concentration of solution =0.5%. Fourier transform infrared (FTIR) spectroscopy measurement revealed that the chemical composition of curcumin basically remained unchanged. Nevertheless, X-ray powder diffraction (XRPD) and thermal analysis indicated that the crystalline state of the original curcumin decreased after the SEDS process. The solubility and dissolution rate of the curcumin nanoparticles were found to be higher than that of the original curcumin powder (approximately 1.4 μg/mL vs 0.2 μg/mL in 180 minutes). This study revealed that supercritical CO2 technologies had a great potential in fabricating nanoparticles and improving the bioavailability of poorly water-soluble drugs. PMID:25995627

Formation of curcumin nanoparticles via solution-enhanced dispersion by supercritical CO2.

PubMed

Zhao, Zheng; Xie, Maobin; Li, Yi; Chen, Aizheng; Li, Gang; Zhang, Jing; Hu, Huawen; Wang, Xinyu; Li, Shipu

2015-01-01

In order to enhance the bioavailability of poorly water-soluble curcumin, solution-enhanced dispersion by supercritical carbon dioxide (CO2) (SEDS) was employed to prepare curcumin nanoparticles for the first time. A 2(4) full factorial experiment was designed to determine optimal processing parameters and their influence on the size of the curcumin nanoparticles. Particle size was demonstrated to increase with increased temperature or flow rate of the solution, or with decreased precipitation pressure, under processing conditions with different parameters considered. The single effect of the concentration of the solution on particle size was not significant. Curcumin nanoparticles with a spherical shape and the smallest mean particle size of 325 nm were obtained when the following optimal processing conditions were adopted: P = 20 MPa, T = 35°C, flow rate of solution = 0.5 mL·min(-1), concentration of solution = 0.5%. Fourier transform infrared (FTIR) spectroscopy measurement revealed that the chemical composition of curcumin basically remained unchanged. Nevertheless, X-ray powder diffraction (XRPD) and thermal analysis indicated that the crystalline state of the original curcumin decreased after the SEDS process. The solubility and dissolution rate of the curcumin nanoparticles were found to be higher than that of the original curcumin powder (approximately 1.4 μg/mL vs 0.2 μg/mL in 180 minutes). This study revealed that supercritical CO2 technologies had a great potential in fabricating nanoparticles and improving the bioavailability of poorly water-soluble drugs.

Using supercritical fluids to refine hydrocarbons

DOEpatents

Yarbro, Stephen Lee

2014-11-25

This is a method to reactively refine hydrocarbons, such as heavy oils with API gravities of less than 20.degree. and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure using a selected fluid at supercritical conditions. The reaction portion of the method delivers lighter weight, more volatile hydrocarbons to an attached contacting device that operates in mixed subcritical or supercritical modes. This separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques. This method produces valuable products with fewer processing steps, lower costs, increased worker safety due to less processing and handling, allow greater opportunity for new oil field development and subsequent positive economic impact, reduce related carbon dioxide, and wastes typical with conventional refineries.

Supercritical Wing Technology: A Progress Report on Flight Evaluations

NASA Technical Reports Server (NTRS)

1972-01-01

The papers in this compilation were presented at the NASA Symposium on "Supercritical Wing Technology: A Progress Report on Flight Evaluation" held at the NASA Flight Research Center, Edwards, Calif., on February 29, 1972. The purpose of the symposium was to present timely information on flight results obtained with the F-8 and T-2C supercritical wing configurations, discuss comparisons with wind-tunnel predictions, and project [ ] flight programs planned for the F-8 and F-III (TACT) airplanes.

Effect temperature of supercritical CO2 fluid extraction on phytochemical analysis and antioxidant activity of Zingiber officinale Roscoe

NASA Astrophysics Data System (ADS)

Sondari, Dewi; Irawadi, Tun Tedja; Setyaningsih, Dwi; Tursiloadi, Silvester

2017-11-01

Supercritical fluid extraction of Zingiber officinale Roscoe has been carried out at a pressure of 16 MPa, with temperatures between 20-40 °C, during extraction time of 6 hours and the flow rate of CO2 fluid 5.5 ml/min. The result of supercritical method was compared with the extraction maceration using a mixture of water and ethanol (70% v/v) for 24 hours. The main content in ginger that has a main role as an antioxidant is a gingerol compound that can help neutralize the damaging effects caused by free radicals in the body, as anti-coagulant, and inhibit the occurrence of blood clots. This study aims to determine the effect of temperature on chemical components contained in rough extract of Zingiber officinale Roscoe and its antioxidant activity, total phenol and total flavonoid content. To determine the chemical components contained in the crude extract of Zingiber officinale Roscoe extracted by supercritical fluid and maceration extraction, GC-MS analysis was performed. Meanwhile, the antioxidant activity of the extract was evaluated based on a 2.2-diphenyl-1-picrylhydrazyl (DPPH) free radical damping method. The results of the analysis show that the result of ginger extract by using the supercritical CO2 extraction method has high antioxidant activity than by using maceration method. The highest total phenol content and total flavonoids were obtained on ginger extraction using supercritical CO2 fluid extraction, indicating that phenol and flavonoid compounds contribute to antioxidant activity. Chromatographic analysis showed that the chemical profile of ginger extract containing oxygenated monoterpenes, monoterpene hydrocarbons, sesquiterpene hydrocarbons, oxygenated monoterpene gingerol and esters. In supercritical fluid extraction, the compounds that can be identified at a temperature of 20-40 °C contain 27 compounds, and 11 compounds from the result of maceration extract. The main component of Zingiber officinale Roscoe extracted using supercritical fluid

Buffet characteristics of the F-8 supercritical wing airplane

NASA Technical Reports Server (NTRS)

Deangelis, V. M.; Monaghan, R. C.

1977-01-01

The buffet characteristics of the F-8 supercritical wing airplane were investigated. Wing structural response was used to determine the buffet characteristics of the wing and these characteristics are compared with wind tunnel model data and the wing flow characteristics at transonic speeds. The wingtip accelerometer was used to determine the buffet onset boundary and to measure the buffet intensity characteristics of the airplane. The effects of moderate trailing edge flap deflections on the buffet onset boundary are presented. The supercritical wing flow characteristics were determined from wind tunnel and flight static pressure measurements and from a dynamic pressure sensor mounted on the flight test airplane in the vicinity of the shock wave that formed on the upper surface of the wing at transonic speeds. The comparison of the airplane's structural response data to the supercritical flow characteristics includes the effects of a leading edge vortex generator.

Formation of indomethacin-saccharin cocrystals using supercritical fluid technology.

PubMed

Padrela, Luis; Rodrigues, Miguel A; Velaga, Sitaram P; Matos, Henrique A; de Azevedo, Edmundo Gomes

2009-08-12

The main objective of the present work is to check the feasibility of supercritical fluid (SCF) technologies in the screening and design of cocrystals (novel crystalline solids). The cocrystal formation tendencies in three different SCF techniques, focusing on distinct supercritical fluid properties - solvent, anti-solvent and atomization enhancer - were investigated. The effect of processing parameters on the cocrystal formation behaviour and particle properties in these techniques was also studied. A recently reported indomethacin-saccharin (IND-SAC) cocrystalline system was our model system. A 1:1 molar ratio of indomethacin (gamma-form) and saccharin was used as a starting material. The SCF techniques employed in the study include the CSS technique (cocrystallization with supercritical solvent), the SAS technique (supercritical anti-solvent), and the AAS technique (atomization and anti-solvent). The resulting cocrystalline phase was identified using differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier transform-Raman (FT-Raman). The particle morphologies and size distributions were determined using scanning electron microscopy (SEM) and aerosizer, respectively. The pure IND-SAC cocrystals were obtained from SAS and AAS processes, whilst partial to no cocrystal formation occurred in the CSS process. However, no remarkable differences were observed in terms of cocrystal formation at different processing conditions in SAS and AAS processes. Particles from CSS processes were agglomerated and large, whilst needle-to-block-shaped and spherical particles were obtained from SAS and AAS processes, respectively. The particle size distribution of these particles was 0.2-5microm. Particulate IND-SAC cocrystals with different morphologies and sizes (nano-to-micron) were produced using supercritical fluid techniques. This work demonstrates the potential of SCF technologies as screening methods for cocrystals with possibilities for particle

CLD1/SRL1 modulates leaf rolling by affecting cell wall formation, epidermis integrity and water homeostasis in rice.

PubMed

Li, Wen-Qiang; Zhang, Min-Juan; Gan, Peng-Fei; Qiao, Lei; Yang, Shuai-Qi; Miao, Hai; Wang, Gang-Feng; Zhang, Mao-Mao; Liu, Wen-Ting; Li, Hai-Feng; Shi, Chun-Hai; Chen, Kun-Ming

2017-12-01

Leaf rolling is considered as one of the most important agronomic traits in rice breeding. It has been previously reported that SEMI-ROLLED LEAF 1 (SRL1) modulates leaf rolling by regulating the formation of bulliform cells in rice (Oryza sativa); however, the regulatory mechanism underlying SRL1 has yet to be further elucidated. Here, we report the functional characterization of a novel leaf-rolling mutant, curled leaf and dwarf 1 (cld1), with multiple morphological defects. Map-based cloning revealed that CLD1 is allelic with SRL1, and loses function in cld1 through DNA methylation. CLD1/SRL1 encodes a glycophosphatidylinositol (GPI)-anchored membrane protein that modulates leaf rolling and other aspects of rice growth and development. The cld1 mutant exhibits significant decreases in cellulose and lignin contents in secondary cell walls of leaves, indicating that the loss of function of CLD1/SRL1 affects cell wall formation. Furthermore, the loss of CLD1/SRL1 function leads to defective leaf epidermis such as bulliform-like epidermal cells. The defects in leaf epidermis decrease the water-retaining capacity and lead to water deficits in cld1 leaves, which contribute to the main cause of leaf rolling. As a result of the more rapid water loss and lower water content in leaves, cld1 exhibits reduced drought tolerance. Accordingly, the loss of CLD1/SRL1 function causes abnormal expression of genes and proteins associated with cell wall formation, cuticle development and water stress. Taken together, these findings suggest that the functional roles of CLD1/SRL1 in leaf-rolling regulation are closely related to the maintenance of cell wall formation, epidermal integrity and water homeostasis. © 2017 The Authors The Plant Journal © 2017 John Wiley & Sons Ltd.

Numerical study of the effects of lamp configuration and reactor wall roughness in an open channel water disinfection UV reactor.

PubMed

Sultan, Tipu

2016-07-01

This article describes the assessment of a numerical procedure used to determine the UV lamp configuration and surface roughness effects on an open channel water disinfection UV reactor. The performance of the open channel water disinfection UV reactor was numerically analyzed on the basis of the performance indictor reduction equivalent dose (RED). The RED values were calculated as a function of the Reynolds number to monitor the performance. The flow through the open channel UV reactor was modelled using a k-ε model with scalable wall function, a discrete ordinate (DO) model for fluence rate calculation, a volume of fluid (VOF) model to locate the unknown free surface, a discrete phase model (DPM) to track the pathogen transport, and a modified law of the wall to incorporate the reactor wall roughness effects. The performance analysis was carried out using commercial CFD software (ANSYS Fluent 15.0). Four case studies were analyzed based on open channel UV reactor type (horizontal and vertical) and lamp configuration (parallel and staggered). The results show that lamp configuration can play an important role in the performance of an open channel water disinfection UV reactor. The effects of the reactor wall roughness were Reynolds number dependent. The proposed methodology is useful for performance optimization of an open channel water disinfection UV reactor. Copyright © 2016 Elsevier Ltd. All rights reserved.

Helicity in supercritical temporal mixing layers

NASA Technical Reports Server (NTRS)

Bellan, J.; Okong'o, N.

2003-01-01

Databases of transitional states obtained from Direct Numerical Simulations (DNS) of temporal, supercritical mixing layers for two species systems, 02/H2 and C7Hle/N2, are analyzed to elucidate species-specific turbulence aspects.

Historical background and design evolution of the transonic aircraft technology supercritical wing

NASA Technical Reports Server (NTRS)

Ayers, T. G.; Hallissy, J. B.

1981-01-01

Two dimensional wind tunnel test results obtained for supercritical airfoils indicated that substantial improvements in aircraft performance at high subsonic speeds could be achieved by shaping the airfoil to improve the supercritical flow above the upper surface. Significant increases in the drag divergence Mach number, the maximum lift coefficient for buffer onset, and the Mach number for buffet onset at a given lift coefficient were demonstrated for the supercritical airfoil, as compared with a NACA 6 series airfoil of comparable thickness. These trends were corroborated by results from three dimensional wind tunnel and flight tests. Because these indicated extensions of the buffet boundaries could provide significant improvements in the maneuverability of a fighter airplane, an exploratory wind tunnel investigation was initiated which demonstrated that significant aerodynamic improvements could be achieved from the direct substitution of a supercritical airfoil on a variable wing sweep multimission airplane model.

Application of water flowing PVC pipe and EPS foam bead as insulation for wall panel

NASA Astrophysics Data System (ADS)

Ali, Umi Nadiah; Nor, Norazman Mohamad; Yusuf, Mohammed Alias; Othman, Maidiana; Yahya, Muhamad Azani

2018-02-01

Malaysia located in tropical climate which have a typical temperature range between 21 °C to 36 °C. Due to this, air-conditioning system for buildings become a necessity to provide comfort to occupants. In order to reduce the energy consumption of the air-conditioning system, the transmission of heat from outdoor to indoor space should be kept as minimum as possible. This article discuss about a technology to resist heat transfer through concrete wall panel using a hybrid method. In this research, PVC pipe was embedded at the center of concrete wall panel while the EPS foam beads were added about 1% of the cement content in the concrete mix forming the outer layer of the wall panel. Water is regulated in the PVC pipe from the rainwater harvesting system. The aim of this study is to minimize heat transfer from the external environment into the building. Internal building temperature which indicated in BS EN ISO 7730 or ASHRAE Standard 55 where the comfort indoor thermal is below 25°C during the daytime. Study observed that the internal surface temperature of heat resistance wall panel is up to 3°C lower than control wall panel. Therefore, we can conclude that application of heat resistance wall panel can lead to lower interior building temperature.

Preparation and Physicochemical Properties of Vinblastine Microparticles by Supercritical Antisolvent Process

PubMed Central

Zhang, Xiaonan; Zhao, Xiuhua; Zu, Yuangang; Chen, Xiaoqiang; Lu, Qi; Ma, Yuliang; Yang, Lei

2012-01-01

The objective of the study was to prepare vinblastine microparticles by supercritical antisolvent process using N-methyl-2-pyrrolidone as solvent and carbon dioxide as antisolvent and evaluate its physicochemical properties. The effects of four process variables, pressure, temperature, drug concentration and drug solution flow rate, on drug particle formation during the supercritical antisolvent process, were investigated. Particles with a mean particle size of 121 ± 5.3 nm were obtained under the optimized process conditions (precipitation temperature 60 °C, precipitation pressure 25 MPa, vinblastine concentration 2.50 mg/mL and vinblastine solution flow rate 6.7 mL/min). The vinblastine was characterized by scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, mass spectrometry and dissolution test. It was concluded that physicochemical properties of crystalline vinblastine could be improved by physical modification, such as particle size reduction and generation of amorphous state using the supercritical antisolvent process. Furthermore, the supercritical antisolvent process was a powerful methodology for improving the physicochemical properties of vinblastine. PMID:23202916

High-resolution imaging of the supercritical antisolvent process

NASA Astrophysics Data System (ADS)

Bell, Philip W.; Stephens, Amendi P.; Roberts, Christopher B.; Duke, Steve R.

2005-06-01

A high-magnification and high-resolution imaging technique was developed for the supercritical fluid antisolvent (SAS) precipitation process. Visualizations of the jet injection, flow patterns, droplets, and particles were obtained in a high-pressure vessel for polylactic acid and budesonide precipitation in supercritical CO2. The results show two regimes for particle production: one where turbulent mixing occurs in gas-like plumes, and another where distinct droplets were observed in the injection. Images are presented to demonstrate the capabilities of the method for examining particle formation theories and for understanding the underlying fluid mechanics, thermodynamics, and mass transport in the SAS process.

Widom line, dynamical crossover, and percolation transition of supercritical oxygen via molecular dynamics simulations.

PubMed

Raman, Abhinav S; Li, Huiyong; Chiew, Y C

2018-01-07

Supercritical oxygen, a cryogenic fluid, is widely used as an oxidizer in jet propulsion systems and is therefore of paramount importance in gaining physical insights into processes such as transcritical and supercritical vaporization. It is well established in the scientific literature that the supercritical state is not homogeneous but, in fact, can be demarcated into regions with liquid-like and vapor-like properties, separated by the "Widom line." In this study, we identified the Widom line for oxygen, constituted by the loci of the extrema of thermodynamic response functions (heat capacity, volumetric thermal expansion coefficient, and isothermal compressibility) in the supercritical region, via atomistic molecular dynamics simulations. We found that the Widom lines derived from these response functions all coincide near the critical point until about 25 bars and 15-20 K, beyond which the isothermal compressibility line begins to deviate. We also obtained the crossover from liquid-like to vapor-like behavior of the translational diffusion coefficient, shear viscosity, and rotational relaxation time of supercritical oxygen. While the crossover of the translational diffusion coefficient and shear viscosity coincided with the Widom lines, the rotational relaxation time showed a crossover that was largely independent of the Widom line. Further, we characterized the clustering behavior and percolation transition of supercritical oxygen molecules, identified the percolation threshold based on the fractal dimension of the largest cluster and the probability of finding a cluster that spans the system in all three dimensions, and found that the locus of the percolation threshold also coincided with the isothermal compressibility Widom line. It is therefore clear that supercritical oxygen is far more complex than originally perceived and that the Widom line, dynamical crossovers, and percolation transitions serve as useful routes to better our understanding of the

Widom line, dynamical crossover, and percolation transition of supercritical oxygen via molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Raman, Abhinav S.; Li, Huiyong; Chiew, Y. C.

2018-01-01

Supercritical oxygen, a cryogenic fluid, is widely used as an oxidizer in jet propulsion systems and is therefore of paramount importance in gaining physical insights into processes such as transcritical and supercritical vaporization. It is well established in the scientific literature that the supercritical state is not homogeneous but, in fact, can be demarcated into regions with liquid-like and vapor-like properties, separated by the "Widom line." In this study, we identified the Widom line for oxygen, constituted by the loci of the extrema of thermodynamic response functions (heat capacity, volumetric thermal expansion coefficient, and isothermal compressibility) in the supercritical region, via atomistic molecular dynamics simulations. We found that the Widom lines derived from these response functions all coincide near the critical point until about 25 bars and 15-20 K, beyond which the isothermal compressibility line begins to deviate. We also obtained the crossover from liquid-like to vapor-like behavior of the translational diffusion coefficient, shear viscosity, and rotational relaxation time of supercritical oxygen. While the crossover of the translational diffusion coefficient and shear viscosity coincided with the Widom lines, the rotational relaxation time showed a crossover that was largely independent of the Widom line. Further, we characterized the clustering behavior and percolation transition of supercritical oxygen molecules, identified the percolation threshold based on the fractal dimension of the largest cluster and the probability of finding a cluster that spans the system in all three dimensions, and found that the locus of the percolation threshold also coincided with the isothermal compressibility Widom line. It is therefore clear that supercritical oxygen is far more complex than originally perceived and that the Widom line, dynamical crossovers, and percolation transitions serve as useful routes to better our understanding of the

Non-equilibrium condensation of supercritical carbon dioxide in a converging-diverging nozzle