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Sample records for supercritical co2 fluid

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

    SciTech Connect

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

    2013-07-01

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

  2. Supercritical fluid behavior at nanoscale interfaces: implications for CO2 sequestration in geologic formations

    SciTech Connect

    Cole, David R; Chialvo, Ariel A; Rother, Gernot; Vlcek, L.; Cummings, Peter T

    2010-01-01

    Injection of CO2 into subsurface geologic formations has been identified as a key strategy for mitigating the impact of anthropogenic emissions of CO2. A key aspect of this process is the prevention of leakage from the host formation by an effective cap or seal rock which has low porosity and permeability characteristics. Shales comprise the majority of cap rocks encountered in subsurface injection sites with pore sizes typically less than 100 nm and whose surface chemistries are dominated by quartz (SiO2) and clays. We report the behavior of pure CO2 interacting with simple substrates, i.e. SiO2 and mica, that act as proxies for more complex mineralogical systems. Modeling of small-angle neutron scattering (SANS) data taken from CO2- silica aerogel (95% porosity; 6 nm pores) interactions indicates the presence of fluid depletion for conditions above the critical density. A theoretical framework, i.e. integral equation approximation (IEA), is presented that describes the fundamental behavior of near-critical adsorption onto a non-confining substrate that is consistent with SANS experimental results. Structural and dynamic behavior for supercritical CO2 interaction in K-mica slit pores was assessed by classical molecular dynamics (CMD). These results indicate the development of distinct layers of CO2 within slit pores, reduced mobility by one to two orders of magnitudes compared to bulk CO2 depending on pore size and formation of bonds between CO2 oxygens and H from mica hydroxyls. Analysis of simple, well-characterized fluid-substrate systems can provide details on the thermodynamic, structural and dynamic properties of CO2 at conditions relevant to sequestration.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  4. Impacts of organic ligands on forsterite reactivity in supercritical CO2 fluids.

    PubMed

    Miller, Quin R S; Kaszuba, John P; Schaef, Herbert T; Bowden, Mark E; McGrail, Bernard P

    2015-04-01

    Subsurface injection of CO2 for enhanced hydrocarbon recovery, hydraulic fracturing of unconventional reservoirs, and geologic carbon sequestration produces a complex geochemical setting in which CO2-dominated fluids containing dissolved water and organic compounds interact with rocks and minerals. The details of these reactions are relatively unknown and benefit from additional experimentally derived data. In this study, we utilized an in situ X-ray diffraction technique to examine the carbonation reactions of forsterite (Mg2SiO4) during exposure to supercritical CO2 (scCO2) that had been equilibrated with aqueous solutions of acetate, oxalate, malonate, or citrate at 50 °C and 90 bar. The organics affected the relative abundances of the crystalline reaction products, nesquehonite (MgCO3 · 3H2O) and magnesite (MgCO3), likely due to enhanced dehydration of the Mg(2+) cations by the organic ligands. These results also indicate that the scCO2 solvated and transported the organic ligands to the forsterite surface. This phenomenon has profound implications for mineral transformations and mass transfer in the upper crust. PMID:25807011

  5. Impacts of Organic Ligands on Forsterite Reactivity in Supercritical CO2 Fluids

    SciTech Connect

    Miller, Quin R.; Kaszuba, John; Schaef, Herbert T.; Bowden, Mark E.; McGrail, B. Peter

    2015-04-07

    Subsurface injection of CO2 for enhanced hydrocarbon recovery, hydraulic fracturing of unconventional reservoirs, and geologic carbon sequestration produces a complex geochemical setting in which CO2-dominated fluids containing dissolved water and organic compounds interact with rocks and minerals. The details of these reactions are relatively unknown and benefit from additional experimentally derived data. In this study, we utilized an in situ X-ray diffraction technique to examine the carbonation reactions of forsterite (Mg2SiO4) during exposure to supercritical CO2 (scCO2) that had been equilibrated with aqueous solutions of acetate, oxalate, malonate, or citrate at 50 °C and 90 bar. The organics affected the relative abundances of the crystalline reaction products, nesquehonite (MgCO3·3H2O) and magnesite (MgCO3), likely due to enhanced dehydration of the Mg2+ cations by the organic ligands. These results also indicate that the scCO2 solvated and transported the organic ligands to the forsterite surface. This phenomenon has profound implications for mineral transformations and mass transfer in the upper crust.

  6. Modeling of mass transfer of Phospholipids in separation process with supercritical CO2 fluid by RBF artificial neural networks

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An artificial Radial Basis Function (RBF) neural network model was developed for the prediction of mass transfer of the phospholipids from canola meal in supercritical CO2 fluid. The RBF kind of artificial neural networks (ANN) with orthogonal least squares (OLS) learning algorithm were used for mod...

  7. Viability and adaptation potential of indigenous microorganisms from natural gas field fluids in high pressure incubations with supercritical CO2.

    PubMed

    Frerichs, Janin; Rakoczy, Jana; Ostertag-Henning, Christian; Krüger, Martin

    2014-01-21

    Carbon Capture and Storage (CCS) is currently under debate as large-scale solution to globally reduce emissions of the greenhouse gas CO2. Depleted gas or oil reservoirs and saline aquifers are considered as suitable reservoirs providing sufficient storage capacity. We investigated the influence of high CO2 concentrations on the indigenous bacterial population in the saline formation fluids of a natural gas field. Bacterial community changes were closely examined at elevated CO2 concentrations under near in situ pressures and temperatures. Conditions in the high pressure reactor systems simulated reservoir fluids i) close to the CO2 injection point, i.e. saturated with CO2, and ii) at the outer boundaries of the CO2 dissolution gradient. During the incubations with CO2, total cell numbers remained relatively stable, but no microbial sulfate reduction activity was detected. After CO2 release and subsequent transfer of the fluids, an actively sulfate-respiring community was re-established. The predominance of spore-forming Clostridiales provided evidence for the resilience of this taxon against the bactericidal effects of supercritical (sc)CO2. To ensure the long-term safety and injectivity, the viability of fermentative and sulfate-reducing bacteria has to be considered in the selection, design, and operation of CCS sites.

  8. Natural wax constituents of a supercritical fluid CO(2) extract from quince (Cydonia oblonga Mill.) pomace.

    PubMed

    Lorenz, Peter; Berger, Melanie; Bertrams, Julia; Wende, Kristian; Wenzel, Kristin; Lindequist, Ulrike; Meyer, Ulrich; Stintzing, Florian C

    2008-05-01

    The chemical constituents of a lipophilic extract from quince (Cydonia oblonga Mill.), obtained by supercritical fluid CO(2) extraction of the dried fruit pomace were investigated. Solvent partition of quince wax with n-hexane or acetone yielded an insoluble (crystalline) and a soluble (oily) fraction. Both fractions were analyzed separately using gas chromatography/mass spectrometry (GC/MS). The insoluble fraction consisted of saturated n-aldehydes, n-alcohols and free n-alkanoic acids of carbon chain lengths between 22 and 32, with carbon chain lengths of 26 and 28 dominating. Also odd-numbered unbranched hydrocarbons, mainly C27, C29 and C31, were detected particularly in the acetone-insoluble fraction (total, 15.8%). By means of vacuum liquid chromatography, triterpenoic acids were separated from the hexane-insoluble matter and identified as a mixture of ursolic, oleanolic and betulinic acids. The major constituents of the hexane-soluble fraction were glycerides of linoleic [Δ(9,12), 18:2] and oleic [Δ(9), 18:1] acids, accompanied by free linoleic, oleic and palmitic acids (C16). Moreover β-sitosterol, Δ(5)-avenasterol as well as trace amounts of other sterols were assigned. Finally the carotenoids phytoene and phytofluene were identified and quantified by UV/vis and high-performance liquid chromatography/MS techniques, yielding 1.0 and 0.3% of the quince wax, respectively. It is anticipated that the complex of lipid constituents from quince wax may exert interesting biological activities, the elucidation of which awaits further studies.

  9. Electrodeposition from supercritical fluids.

    PubMed

    Bartlett, P N; Cook, D A; George, M W; Hector, A L; Ke, J; Levason, W; Reid, G; Smith, D C; Zhang, W

    2014-05-28

    Recent studies have shown that it is possible to electrodeposit a range of materials, such as Cu, Ag and Ge, from various supercritical fluids, including hydrofluorocarbons and mixtures of CO2 with suitable co-solvents. In this perspective we discuss the relatively new field of electrodeposition from supercritical fluids. The perspective focuses on some of the underlying physical chemistry and covers both practical and scientific aspects of electrodeposition from supercritical fluids. We also discuss possible applications for supercritical fluid electrodeposition and suggest some key developments that are required to take the field to the next stage.

  10. Heat Transfer and Fluid Transport of Supercritical CO2 in Enhanced Geothermal System with Local Thermal Non-equilibrium Model

    DOE PAGES

    Zhang, Le; Luo, Feng; Xu, Ruina; Jiang, Peixue; Liu, Huihai

    2014-12-31

    The heat transfer and fluid transport of supercritical CO2 in enhanced geothermal system (EGS) is studied numerically with local thermal non-equilibrium model, which accounts for the temperature difference between solid matrix and fluid components in porous media and uses two energy equations to describe heat transfer in the solid matrix and in the fluid, respectively. As compared with the previous results of our research group, the effect of local thermal non-equilibrium mainly depends on the volumetric heat transfer coefficient ah, which has a significant effect on the production temperature at reservoir outlet and thermal breakthrough time. The uniformity of volumetricmore » heat transfer coefficient ah has little influence on the thermal breakthrough time, but the temperature difference become more obvious with time after thermal breakthrough with this simulation model. The thermal breakthrough time reduces and the effect of local thermal non-equilibrium becomes significant with decreasing ah.« less

  11. Inhibitory effect of rape pollen supercritical CO2 fluid extract against testosterone-induced benign prostatic hyperplasia in rats.

    PubMed

    Yang, Bi-Cheng; Jin, Li-Li; Yang, Yi-Fang; Li, Kun; Peng, Dan-Ming

    2014-07-01

    Benign prostatic hyperplasia (BPH) can lead to lower urinary tract symptoms. Rape pollen is an apicultural product that is composed of nutritionally valuable and biologically active substances. The aim of the present study was to investigate the protective effect of rape pollen supercritical CO2 fluid extract (SFE-CO2) in BPH development using a testosterone-induced BPH rat model. BPH was induced in the experimental groups by daily subcutaneous injections of testosterone for a period of 30 days. Rape pollen SFE-CO2 was administered daily by oral gavage concurrently with the testosterone injections. Animals were sacrificed at the scheduled termination and the prostates were weighed and subjected to histopathological examination. Testosterone, dihydrotestosterone (DHT), 5α-reductase and cyclooxygenase-2 (COX-2) levels were also measured. BPH-induced animals exhibited an increase in prostate weight with increased testosterone, DHT, 5α-reductase and COX-2 expression levels. However, rape pollen SFE-CO2 treatment resulted in significant reductions in the prostate index and testosterone, DHT, 5α-reductase and COX-2 levels compared with those in BPH-induced animals. Histopathological examination also demonstrated that rape pollen SFE-CO2 treatment suppressed testosterone-induced BPH. These observations indicate that rape pollen SFE-CO2 inhibits the development of BPH in rats and these effects are closely associated with reductions in DHT, 5α-reductase and COX-2 levels. Therefore, the results of the present study clearly indicate that rape pollen SFE-CO2 extract may be a useful agent in BPH treatment.

  12. Inhibitory effect of rape pollen supercritical CO2 fluid extract against testosterone-induced benign prostatic hyperplasia in rats

    PubMed Central

    YANG, BI-CHENG; JIN, LI-LI; YANG, YI-FANG; LI, KUN; PENG, DAN-MING

    2014-01-01

    Benign prostatic hyperplasia (BPH) can lead to lower urinary tract symptoms. Rape pollen is an apicultural product that is composed of nutritionally valuable and biologically active substances. The aim of the present study was to investigate the protective effect of rape pollen supercritical CO2 fluid extract (SFE-CO2) in BPH development using a testosterone-induced BPH rat model. BPH was induced in the experimental groups by daily subcutaneous injections of testosterone for a period of 30 days. Rape pollen SFE-CO2 was administered daily by oral gavage concurrently with the testosterone injections. Animals were sacrificed at the scheduled termination and the prostates were weighed and subjected to histopathological examination. Testosterone, dihydrotestosterone (DHT), 5α-reductase and cyclooxygenase-2 (COX-2) levels were also measured. BPH-induced animals exhibited an increase in prostate weight with increased testosterone, DHT, 5α-reductase and COX-2 expression levels. However, rape pollen SFE-CO2 treatment resulted in significant reductions in the prostate index and testosterone, DHT, 5α-reductase and COX-2 levels compared with those in BPH-induced animals. Histopathological examination also demonstrated that rape pollen SFE-CO2 treatment suppressed testosterone-induced BPH. These observations indicate that rape pollen SFE-CO2 inhibits the development of BPH in rats and these effects are closely associated with reductions in DHT, 5α-reductase and COX-2 levels. Therefore, the results of the present study clearly indicate that rape pollen SFE-CO2 extract may be a useful agent in BPH treatment. PMID:24944593

  13. Dielectric Interactions and the Prediction of Retention Times of Pesticides in Supercritical Fluid Chromatography with CO2

    NASA Astrophysics Data System (ADS)

    Alvarez, Guillermo A.; Baumanna, Wolfram

    2005-02-01

    A thermodynamic model for the partition of a solute (pesticide) between two immiscible phases, such as the stationary and mobile phases of supercritical fluid chromatography with CO2, is developed from first principles. A key ingredient of the model is the result of the calculation made by Liptay of the energy of interaction of a polar molecule with a dielectric continuum, which represents the solvent. The strength of the interaction between the solute and the solvent, which may be considered a measure of the solvent power, is characterized by a function g = (ɛ - 1)/(2ɛ +1), where ɛ is the dielectric constant of the medium, which is a function of the temperature T and the pressure P. Since the interactions between the nonpolar supercritical CO2 solvent and the slightly polar pesticide molecules are considered to be extremely weak, a regular solution model is appropriate from the thermodynamic point of view. At constant temperature, the model predicts a linear dependence of the logarithm of the capacity factor (lnk) of the chromatographic experiment on the function g = g(P), as the pressure is varied, with a slope which depends on the dipole moment of the solute, dispersion interactions and the size of the solute cavity in the solvent. At constant pressure, once the term containing the g (solvent interaction) factor is subtracted from lnk, a plot of the resulting term against the inverse of temperature yields the enthalpy change of transfer of the solute from the mobile (supercritical CO2) phase to the stationary (adsorbent) phase. The increase in temperature with the consequent large volume expansion of the supercritical fluid lowers its solvent strength and hence the capacity factor of the column (or solute retention time) increases. These pressure and temperature effects, predicted by the model, agree excellently with the experimental retention times of seven pesticides. Beyond a temperature of about 393 K, where the liquid solvent densities approach those of

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

    SciTech Connect

    Bryan, Charles R.; Dewers, Thomas A.; Heath, Jason E.; Wang, Yifeng; Matteo, Edward N.; Meserole, Stephen P.; Tallant, David Robert

    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 Spectroscopy 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 for

  15. Reducing Oyster-Associated Bacteria Levels Using Supercritical Fluid CO2 as an Agent of Warm Pasteurization

    PubMed Central

    Meujo, Damaris A.F.; Kevin, Dion; Peng, Jiangnan; Bowling, John J.; Liu, Jianping; Hamann, Mark T.

    2010-01-01

    An innovative approach to Post-Harvest Processing (PHP) of oysters is introduced focusing on the effects of supercritical carbon dioxide (scCO2) on bacterial contaminants trapped in the digestive system of oysters. Oysters were exposed to scCO2 under two conditions: (1) 100 bar and 37 °C for 30 minutes and (2) 172 bar and 60 °C for 60 minutes. Using FDA standard guidelines for food analysis, variations in the Aerobic Plate Count (APC) was assessed. It was established that exposing oysters to CO2 at 100 bar and 37 °C for 30 minutes and at 172 bar and 60°C for 60 minutes induced 2-log and 3-log reductions in the APC respectively. The decrease in the microbial load as a result of treatment with scCO2 was found to be significant (P=0.002). A release of adductor muscles from the shell was noted in oysters treated at 172 bar and 60 °C for 60 minutes; this was not the case for oysters treated at 100 bar and 37 °C for 30 minutes. A blind study allowing sensory analysis of treated vs. untreated oysters was also completed and no significant change in the physical appearance, smell, or texture was recorded. In this paper, we also report the effect of scCO2 on several bacterial isolates, including a referenced ATCC strain of a non pathogenic Vibrio (V. fisherii) as well as several other bacterial isolates cultured from oyster’ tissues and found to share biochemical features common to pathogenic Vibrio strains. A complete inactivation (minimum 7-log reduction) was achieved with these latter bacterial isolates. A 6-log reduction was observed with V. fisherii. PMID:20022650

  16. Microbial Growth under Supercritical CO2

    PubMed Central

    Peet, Kyle C.; Freedman, Adam J. E.; Hernandez, Hector H.; Britto, Vanya; Boreham, Chris; Ajo-Franklin, Jonathan B.

    2015-01-01

    Growth of microorganisms in environments containing CO2 above its critical point is unexpected due to a combination of deleterious effects, including cytoplasmic acidification and membrane destabilization. Thus, supercritical CO2 (scCO2) is generally regarded as a sterilizing agent. We report isolation of bacteria from three sites targeted for geologic carbon dioxide sequestration (GCS) that are capable of growth in pressurized bioreactors containing scCO2. Analysis of 16S rRNA genes from scCO2 enrichment cultures revealed microbial assemblages of varied complexity, including representatives of the genus Bacillus. Propagation of enrichment cultures under scCO2 headspace led to isolation of six strains corresponding to Bacillus cereus, Bacillus subterraneus, Bacillus amyloliquefaciens, Bacillus safensis, and Bacillus megaterium. Isolates are spore-forming, facultative anaerobes and capable of germination and growth under an scCO2 headspace. In addition to these isolates, several Bacillus type strains grew under scCO2, suggesting that this may be a shared feature of spore-forming Bacillus spp. Our results provide direct evidence of microbial activity at the interface between scCO2 and an aqueous phase. Since microbial activity can influence the key mechanisms for permanent storage of sequestered CO2 (i.e., structural, residual, solubility, and mineral trapping), our work suggests that during GCS microorganisms may grow and catalyze biological reactions that influence the fate and transport of CO2 in the deep subsurface. PMID:25681188

  17. Final Report: Development of a Chemical Model to Predict the Interactions between Supercritical CO2, Fluid and Rock in EGS Reservoirs

    SciTech Connect

    McPherson, Brian J.; Pan, Feng

    2014-09-24

    This report summarizes development of a coupled-process reservoir model for simulating enhanced geothermal systems (EGS) that utilize supercritical carbon dioxide as a working fluid. Specifically, the project team developed an advanced chemical kinetic model for evaluating important processes in EGS reservoirs, such as mineral precipitation and dissolution at elevated temperature and pressure, and for evaluating potential impacts on EGS surface facilities by related chemical processes. We assembled a new database for better-calibrated simulation of water/brine/ rock/CO2 interactions in EGS reservoirs. This database utilizes existing kinetic and other chemical data, and we updated those data to reflect corrections for elevated temperature and pressure conditions of EGS reservoirs.

  18. Supercritical fluid chromatography and two-dimensional supercritical fluid chromatography of polar car lubricant additives with neat CO(2) as mobile phase.

    PubMed

    Lavison, Gwenaelle; Bertoncini, Fabrice; Thiébaut, Didier; Beziau, Jean-François; Carrazé, Bernadette; Valette, Pascale; Duteurtre, Xavier

    2007-08-17

    Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. Their total amount in the commercial lubricant varies from a few percents to 20-25%. As they belong to various chemical classes and are added to a very complex medium, the base stock, their detailed chromatographic analysis is very difficult and time consuming as it should involve sample treatment and preparative scale separations in order to simplify the sample. The aim of this work is to determine the feasibility of the separation of low molecular weight lubricant additives using various packed columns with pure CO(2) as a mobile phase to enable implementation of flame ionisation detection as universal detector. This is part of a hypernated system including more sophisticated specific detectors, such as AED, FTIR or MS to obtain detailed structural information of compounds. This paper is devoted to the comparison of some stationary phases supposed to provide hydrocarbon group type separation (silica and normal phase) or separations on alkyl-bonded silica in non-aqueous mode of some selected classes of additives in test mixtures or in base stocks. Adsorption chromatography allows partial separation of additives from the base stocks while the direct elution of test additives can only be obtained on reversed phase supports having a very efficient silanol group protection so the interaction of the more polar compounds is much reduced. A two-dimensional scheme of analysis is also described. It combines adsorption chromatography to separate most of the polar additives from the base stock and alkyl-bonded silica for more detailed separation of the additives. However, overlapping between groups of compounds and the lack of resolution between some additives and the base stock should be addressed by the implementing of selective detectors. PMID:17582427

  19. 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

  20. Identification of volatile components in Angelica species using supercritical-CO2 fluid extraction and solid phase microextraction coupled to gas chromatography-mass spectrometry.

    PubMed

    Kim, Mi Ra; Abd El-Aty, A M; Choi, Jeong-Heui; Lee, Kang Bong; Shim, Jae Han

    2006-11-01

    As a part of our search for environmentally friendly solvents to extract the active components of medicinal plants, two sampling techniques, supercritical fluid extraction (SFE) using CO(2) and solid-phase microextraction (SPME) were compared for their efficacy in the analysis of volatiles rhizome components emitted from the medicinal herbs Angelica gigas NAKAI (Korean danggui), Angelica sinensis (Chinese danggui), and Angelica acutiloba (Japanese danggui). A total of 54 compounds released from all of these varieties of Angelica rhizomes were separated and identified by gas chromatography-mass spectrometry (GC-MS). The composition of supercritical extracts from these plants was very different from the solid-phase microextraction products. More compounds were detected by SPME-GC-MS (41) than by SFE-GC-MS (17). The results of these analyses suggest that SFE may be useful for detecting the main components, decursinol angelate and decursin in Korean danggui, and butylidene dihydro-phthalide in both Chinese and Japanese danggui, whereas the results for SPME did not. The SFE method required specialized instrumentation, required little time to prepare the sample, and had a small sample size and no organic solvent. In sum, these results suggest that SFE is useful for extracting the volatile main components of danggui cultivars. Its simplicity, low cost and speed may allow SPME to increase the recovery of volatile components in general without disturbing the main components of the plant.

  1. 10 MW Supercritical CO2 Turbine Test

    SciTech Connect

    Turchi, Craig

    2014-01-29

    The Supercritical CO2 Turbine Test project was to demonstrate the inherent efficiencies of a supercritical carbon dioxide (s-CO2) power turbine and associated turbomachinery under conditions and at a scale relevant to commercial concentrating solar power (CSP) projects, thereby accelerating the commercial deployment of this new power generation technology. The project involved eight partnering organizations: NREL, Sandia National Laboratories, Echogen Power Systems, Abengoa Solar, University of Wisconsin at Madison, Electric Power Research Institute, Barber-Nichols, and the CSP Program of the U.S. Department of Energy. The multi-year project planned to design, fabricate, and validate an s-CO2 power turbine of nominally 10 MWe that is capable of operation at up to 700°C and operates in a dry-cooled test loop. The project plan consisted of three phases: (1) system design and modeling, (2) fabrication, and (3) testing. The major accomplishments of Phase 1 included: Design of a multistage, axial-flow, s-CO2 power turbine; Design modifications to an existing turbocompressor to provide s-CO2 flow for the test system; Updated equipment and installation costs for the turbomachinery and associated support infrastructure; Development of simulation tools for the test loop itself and for more efficient cycle designs that are of greater commercial interest; Simulation of s-CO2 power cycle integration into molten-nitrate-salt CSP systems indicating a cost benefit of up to 8% in levelized cost of energy; Identification of recuperator cost as a key economic parameter; Corrosion data for multiple alloys at temperatures up to 650ºC in high-pressure CO2 and recommendations for materials-of-construction; and Revised test plan and preliminary operating conditions based on the ongoing tests of related equipment. Phase 1 established that the cost of the facility needed to test the power turbine at its full power and temperature would exceed the planned funding for Phases 2 and 3. Late

  2. Synthesis of germanium nanocrystals in high temperature supercritical CO(2).

    PubMed

    Lu, Xianmao; Korgel, Brian A; Johnston, Keith P

    2005-07-01

    Germanium nanocrystals were synthesized in supercritical (sc) CO(2) by thermolysis of diphenylgermane (DPG) or tetraethylgermane (TEG) with octanol as a capping ligand at 500 °C and 27.6 MPa. The Ge nanocrystals were characterized with high resolution transmission electron microscopy (HRTEM), energy-dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD). On the basis of TEM, the mean diameters of the nanocrystals made from DPG and TEG were 10.1 and 5.6 nm, respectively. The synthesis in sc-CO(2) produced much less organic contamination compared with similar reactions in organic supercritical fluids. When the same reaction of DPG with octanol was performed in the gas phase without CO(2) present, bulk Ge crystals were formed instead of nanocrystals. Thus, the solvation of the hydrocarbon ligands by CO(2) was sufficient to provide steric stabilization. The presence of steric stabilization in CO(2) at a reduced temperature of 2.5, with a reduced solvent density of only 0.4, may be attributed to a reduction in the differences between ligand-ligand interactions and ligand-CO(2) interactions relative to thermal energy.

  3. Supercritical fluid extraction

    DOEpatents

    Wai, Chien M.; Laintz, Kenneth

    1994-01-01

    A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated or lipophilic crown ether or fluorinated dithiocarbamate. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

  4. Towards Overhauser DNP in supercritical CO2

    NASA Astrophysics Data System (ADS)

    van Meerten, S. G. J.; Tayler, M. C. D.; Kentgens, A. P. M.; van Bentum, P. J. M.

    2016-06-01

    Overhauser Dynamic Nuclear Polarization (ODNP) is a well known technique to improve NMR sensitivity in the liquid state, where the large polarization of an electron spin is transferred to a nucleus of interest by cross-relaxation. The efficiency of the Overhauser mechanism for dipolar interactions depends critically on fast local translational dynamics at the timescale of the inverse electron Larmor frequency. The maximum polarization enhancement that can be achieved for 1H at high magnetic fields benefits from a low viscosity solvent. In this paper we investigate the option to use supercritical CO2 as a solvent for Overhauser DNP. We have investigated the diffusion constants and longitudinal nuclear relaxation rates of toluene in high pressure CO2. The change in 1H T1 by addition of TEMPO radical was analyzed to determine the Overhauser cross-relaxation in such a mixture, and is compared with calculations based on the Force Free Hard Sphere (FFHS) model. By analyzing the relaxation data within this model we find translational correlation times in the range of 2-4 ps, depending on temperature, pressure and toluene concentration. Such short correlation times may be instrumental for future Overhauser DNP applications at high magnetic fields, as are commonly used in NMR. Preliminary DNP experiments have been performed at 3.4 T on high pressure superheated water and model systems such as toluene in high pressure CO2.

  5. Towards Overhauser DNP in supercritical CO2.

    PubMed

    van Meerten, S G J; Tayler, M C D; Kentgens, A P M; van Bentum, P J M

    2016-06-01

    Overhauser Dynamic Nuclear Polarization (ODNP) is a well known technique to improve NMR sensitivity in the liquid state, where the large polarization of an electron spin is transferred to a nucleus of interest by cross-relaxation. The efficiency of the Overhauser mechanism for dipolar interactions depends critically on fast local translational dynamics at the timescale of the inverse electron Larmor frequency. The maximum polarization enhancement that can be achieved for (1)H at high magnetic fields benefits from a low viscosity solvent. In this paper we investigate the option to use supercritical CO2 as a solvent for Overhauser DNP. We have investigated the diffusion constants and longitudinal nuclear relaxation rates of toluene in high pressure CO2. The change in (1)H T1 by addition of TEMPO radical was analyzed to determine the Overhauser cross-relaxation in such a mixture, and is compared with calculations based on the Force Free Hard Sphere (FFHS) model. By analyzing the relaxation data within this model we find translational correlation times in the range of 2-4ps, depending on temperature, pressure and toluene concentration. Such short correlation times may be instrumental for future Overhauser DNP applications at high magnetic fields, as are commonly used in NMR. Preliminary DNP experiments have been performed at 3.4T on high pressure superheated water and model systems such as toluene in high pressure CO2.

  6. Supercritical fluid chromatography

    SciTech Connect

    Gere, D.R.

    1983-10-21

    Chromatographic separations with a supercritical fluid as the mobile phase were suggested more than 20 years ago. Availability of commercial hardware makes this technique more widely usable today. Many separations by this method are now carried out with supercritical carbon dioxide as the mobile phase and packed liquid-chromatography columns as the stationary phase. Although carbon dioxide has many practical advantages, including its near-ambient critical temperature and minimal interference with spectrometric detection, the use of other supercritical fluids or addition of modifiers to carbon dioxide may extend the applications of this technique. Some mixtures that are difficult to analyze by other chromatographic methods may be susceptible to separation by supercritical fluid chromatography. Mixtures that have been separated with supercritical carbon dioxide include resin acids with the empirical formula C/sub 20/H/sub 30/O/sub 2/ and ubiquinones from bacterial cell wall extracts of Legionella pneumophila. 60 refs., 8 figs.

  7. Supercritical fluid regeneration of adsorbents

    NASA Astrophysics Data System (ADS)

    Defilippi, R. P.; Robey, R. J.

    1983-05-01

    The results of a program to perform studies supercritical (fluid) carbon dioxide (SCF CO2) regeneration of adsorbents, using samples of industrial wastewaters from manufacturing pesticides and synthetic solution, and to estimate the economics of the specific wastewater treatment regenerations, based on test data are given. Processing costs for regenerating granular activated carbon GAC) for treating industrial wastewaters depend on stream properties and regeneration throughput.

  8. Operation and analysis of a supercritical CO2 Brayton cycle.

    SciTech Connect

    Wright, Steven Alan; Radel, Ross F.; Vernon, Milton E.; Pickard, Paul S.; Rochau, Gary Eugene

    2010-09-01

    Sandia National Laboratories is investigating advanced Brayton cycles using supercritical working fluids for use with solar, nuclear or fossil heat sources. The focus of this work has been on the supercritical CO{sub 2} cycle (S-CO2) which has the potential for high efficiency in the temperature range of interest for these heat sources, and is also very compact, with the potential for lower capital costs. The first step in the development of these advanced cycles was the construction of a small scale Brayton cycle loop, funded by the Laboratory Directed Research & Development program, to study the key issue of compression near the critical point of CO{sub 2}. This document outlines the design of the small scale loop, describes the major components, presents models of system performance, including losses, leakage, windage, compressor performance, and flow map predictions, and finally describes the experimental results that have been generated.

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

    SciTech Connect

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

    2013-02-01

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

  10. Rheology of Supercritical CO2 dispersed Polymer/Clay Nanocomposites

    NASA Astrophysics Data System (ADS)

    Kannan, Rangaramanujam; Horsch, Steven; Subramanium, Ganapathy; Gulari, Esin

    2006-03-01

    Effective dispersion of the fillers in a polymer matrix has been a key challenge in the field of nanocomposites. Supercritical carbon dioxide (scCO2) appears , PS/clay, The nanocomposites are characterized using WAXD, SEM, TEM, Rheology and DSC. The high degree of dispersion achieved through sc-CO2 appears to result in an order of magnitude increase in the rheological properties of PS, associated with an increase in the Tg of around 13 C, at 10% clay loading. These moduli improvements are significant better than those obtained with conventional, chemically-modified intercalated clay nanocomposites. The degree of enhancement in the properties appears to be strongly dependant on the polymer-clay interactions, and how it is promoted by the supercritical fluid. In the case of PDMS nanocomposites, where the clay-polymer interactions were weak, the modulus increase at low frequencies (for sc-CO2 processed system) was only a factor of 2. In the case of PVME- I30P clay nanocomposites, the modulus increase was substantial even at moderate loadings and dispersions, perhaps to be hydrogen-bonding interactions. The clay and the polymer orientation and interactions in these nanocomposites are also being probed using rheo-optical FTIR spectroscopy.

  11. 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

  12. Electrochemistry in supercritical fluids.

    PubMed

    Branch, Jack A; Bartlett, Philip N

    2015-12-28

    A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide-acetonitrile and supercritical HFCs.

  13. 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

  14. Supercritical Fluid Chromatography, Pressurized Liquid Extraction and Supercritical Fluid Extraction

    SciTech Connect

    Henry, Matthew C.; Yonker, Clement R.

    2006-06-15

    are regulated as food supplements but are intended to treat disease or maintain health. Antioxidants and beneficial lipid products are major examples in this category. The final major category consists of environmental applications, both as an extraction technique for environmental analysis, and as a possible remediation strategy for removing contaminants that would otherwise be too expensive to recover. Most of the work in this area has focused on non-polar compounds, such as polyaromatic hydrocarbons (PAHs) and poly-chlorinated biphenyls (PCB’s), where non-polar supercritical (SC) CO2 offers high extraction efficiencies. Co-solvent systems combining CO2 with one or more modifiers extend the utility of SC CO2 to polar and even ionic compounds. Supercritical water can extract polar compounds, and it has the additional advantage of combining extraction and destruction of contaminants via the supercritical water oxidation (SUWOX) process. Supercritical fluids are also useful in various niche applications. Fuel extraction, conversion, and analysis is one such application. Extraction of metals from various matrixes is also an area of continuing interest. The application of supercritical fluid (SCF) technology to production of nano-structured materials is a new area likely to see rapid growth in the next few years.

  15. Supercritical fluids cleaning

    SciTech Connect

    Butner, S.; Hjeresen, D.; Silva, L.; Spall, D.; Stephenson, R.

    1991-01-01

    This paper discusses a proposed multi-party research and development program which seeks to develop supercritical fluid cleaning technology as an alternative to existing solvent cleaning applications. While SCF extraction technology has been in commercial use for several years, the use of these fluids as cleaning agents poses several new technical challenges. Problems inherent in the commercialization of SCF technology include: the cleaning efficacy and compatibility of supercritical working fluids with the parts to be cleaned must be assessed for a variety of materials and components; process parameters and equipment design Have been optimized for extractive applications and must be reconsidered for application to cleaning; and co-solvents and entrainers must be identified to facilitate the removal of polar inorganic and organic contaminants, which are often not well solvated in supercritical systems. The proposed research and development program would address these issues and lead to the development and commercialization of viable SCF-based technology for precision cleaning applications. This paper provides the technical background, program scope, and delineates the responsibilities of each principal participant in the program.

  16. The combined extraction of sage (Salvia officinalis L.): ultrasound followed by supercritical CO2 extraction.

    PubMed

    Glisic, Sandra B; Ristic, Mihajlo; Skala, Dejan U

    2011-01-01

    A wide spectrum of phytochemicals could be isolated from sage (Salvia officinalis L.) using different extraction or distillation technique: the supercritical fluid extraction (SFE), the volatiles compounds (monoterpenes and sesquiterpenes) isolation using hydrodistillation or higher molecular compounds with Soxhlet extraction or ultrasound-assisted extraction. The combination of ultrasound-assisted extraction followed by re-extraction of obtained extract with supercritical CO(2) was performed in this study. The goal of performed investigation was to concentrate diterpenes present in sage extract which are generally considered to be responsible for antioxidant activity of extracted compounds. The fractionation using the supercritical CO(2), and different combination of the ultrasound-assisted solvent extractions (water-ethanol mixture or only water) followed by supercritical CO(2) re-extraction of obtained extract or treated plant material were analyzed and compared. Based on the results of these investigations it could be proposed the best extraction procedure: the ultrasound pretreatment of plant material with distilled water and re-extraction of plant material (residue) using supercritical CO(2). That procedure gives two valuable products: the ultrasound extract which is rich in sugars and possess the immunomodulatory activity and supercritical extract which is rich in diterpenes and sesquiterpenes.

  17. 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.

  18. Corrosion in supercritical fluids

    SciTech Connect

    Propp, W.A.; Carleson, T.E.; Wai, Chen M.; Taylor, P.R.; Daehling, K.W.; Huang, Shaoping; Abdel-Latif, M.

    1996-05-01

    Integrated studies were carried out in the areas of corrosion, thermodynamic modeling, and electrochemistry under pressure and temperature conditions appropriate for potential applications of supercritical fluid (SCF) extractive metallurgy. Carbon dioxide and water were the primary fluids studied. Modifiers were used in some tests; these consisted of 1 wt% water and 10 wt% methanol for carbon dioxide and of sulfuric acid, sodium sulfate, ammonium sulfate, and ammonium nitrate at concentrations ranging from 0.00517 to 0.010 M for the aqueous fluids. The materials studied were Types 304 and 316 (UNS S30400 and S31600) stainless steel, iron, and AISI-SAE 1080 (UNS G10800) carbon steel. The thermodynamic modeling consisted of development of a personal computer-based program for generating Pourbaix diagrams at supercritical conditions in aqueous systems. As part of the model, a general method for extrapolating entropies and related thermodynamic properties from ambient to SCF conditions was developed. The experimental work was used as a tool to evaluate the predictions of the model for these systems. The model predicted a general loss of passivation in iron-based alloys at SCF conditions that was consistent with experimentally measured corrosion rates and open circuit potentials. For carbon-dioxide-based SCFs, measured corrosion rates were low, indicating that carbon steel would be suitable for use with unmodified carbon dioxide, while Type 304 stainless steel would be suitable for use with water or methanol as modifiers.

  19. SOLUBILITY OF ORGANIC BIOCIDES IN SUPERCRITICAL CO2 AND CO2+ COSOLVENT MIXTURES

    EPA Science Inventory

    Solubilities of four organic biocides in supercritical carbon dioxide (Sc-CO2) were measured using a dynamic flowr apparatus over a pressure range of 10 to 30 MPa and temperature of 35-80 degrees C. The biocides studied were: Amical-48 (diiodomethyl p-tolyl sulfone), chlorothalo...

  20. Physical and Chemical Effects of Two-Phase Brine/Supercritical-CO2 Fluid Flow on Clastic Rocks: Real-Time Monitoring and NMR Imaging of Flow-Through Core Experiments

    NASA Astrophysics Data System (ADS)

    Shaw, C. A.; Vogt, S.; Maneval, J. E.; Brox, T.; Skidmore, M. L.; Codd, S. L.; Seymour, J. D.

    2010-12-01

    Sandstone core samples were challenged with a supercritical CO2-saturated brine mixture in a laboratory flow-through core reactor system over a range of temperatures and brine strengths. Cores of quartz arenite from the Berea formation were selected to represent ideal ‘clean’ sandstone These laboratory experiments potentially provide an analog for the acidification of pore fluids near the brine/CO2 interface during CO2 flooding of depleted clastic hydrocarbon reservoirs for carbon sequestration. Flow in the reactor was perpendicular to bedding. Initial experiments were run at 50°C and 100°C with brine concentrations of 1g/L and 10g/L (TDS) to test effects of different temperatures and brine compositions. Real-time monitoring of fluid pH and conductivity provided a measure of reaction rates. Introduction of supercritical CO2 into the brine-saturated cores initiated a reduction in pH accompanied by an increase in conductivity. NMR images of fresh cores were compared with images of challenged cores using a protocol for pixel-by-pixel comparison to determine the effects on bulk pore volume and geometry. Two types of imaging experiments were conducted: multi-slice spin echo and 3-D spin echo images. Multi-slice experiments had a slice thickness of 1.5 mm and an in-plane resolution of 0.27 mm x 0.27 mm, and 3-D experiments had a resolution of 0.47 mm x 0.55 mm x 0.55mm. Imaging results reflected the observed changes in the physical and chemical structure post-challenge. Two-dimensional relaxation correlation experiments were also conducted to probe the pore sizes, connectivity and fluid saturation of the rock cores before and after challenging. Chemical analyses and microscopic examination of the challenged cores will provide a better understanding of alteration in the cores and the changes in the volume, geometry and connectivity of pore space.

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

    SciTech Connect

    Wright, Steven A.

    2012-09-12

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

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

    2012-09-12

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

  3. Supercritical fluid technology

    SciTech Connect

    Penninger, J.M.L.; McHugh, M.A.; Radosz, M.; Krukonis, V.J.

    1985-01-01

    This book presents the state-of-the-art in the science and technology of supercritical fluid (scf) processing. Current research as described in the book, focuses on developments in equations of state for binary and multicomponent mixtures (including polymer solutions), solubility measurements at near-critical conditions, measurements of critical properties of binary mixtures and their correlation with equations of state. Progress in thermodynamics, coupled with advances in the design and construction of high pressure equipment, has opened up a wide avenue of commercial application (e.g. decaffeination of coffee beans, extractions of flavours and spices, purification of pharmaceutical products, separations of polymeric materials, deodorization and deacidification of vegetable oils, fractionation of fatty acids, coal liquefaction, wood delignitication, etc.)

  4. 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

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

    SciTech Connect

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

    2014-01-01

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

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

    PubMed

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

    2004-01-20

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

  7. Acoustic emission monitoring of hydraulic fracturing laboratory experiment with supercritical and liquid CO2

    NASA Astrophysics Data System (ADS)

    Ishida, Tsuyoshi; Aoyagi, Kazuhei; Niwa, Tomoya; Chen, Youqing; Murata, Sumihiko; Chen, Qu; Nakayama, Yoshiki

    2012-08-01

    Carbon dioxide (CO2) is often used for enhanced oil recovery in depleted petroleum reservoirs, and its behavior in rock is also of interest in CO2 capture and storage projects. CO2 usually becomes supercritical (SC-CO2) at depths greater than 1,000 m, while it is liquid (L-CO2) at low temperatures. The viscosity of L-CO2 is one order lower than that of normal liquid water, and that of SC-CO2 is much lower still. To clarify fracture behavior induced with injection of the low viscosity fluids, we conducted hydraulic fracturing experiments using 17 cm cubic granite blocks. The AE sources with the SC- and L-CO2 injections tend to distribute in a larger area than those with water injection, and furthermore, SC-CO2 tended to generate cracks extending more three dimensionally rather than along a flat plane than L-CO2. It was also found that the breakdown pressures for SC- and L-CO2 injections are expected to be considerably lower than for water.

  8. Alteration of bentonite when contacted with supercritical CO2

    NASA Astrophysics Data System (ADS)

    Jinseok, K.; Jo, H. Y.; Yun, S. T.

    2014-12-01

    Deep saline formations overlaid by impermeable caprocks with a high sealing capacity are attractive CO2 storage reservoirs. Shales, which consist of mainly clay minerals, are potential caprocks for the CO2 storage reservoirs. The properties of clay minerals in shales may affect the sealing capacity of shales. In this study, changes in clay minerals' properties when contacted with supercritical (SC) CO2 at various conditions were investigated. Bentonite, whichis composed of primarily montmorillonite, was used as the clay material in this study. Batch reactor tests on wet bentonite samples in the presence of SC CO2 with or without aqueous phases were conducted at high pressure (12 MPa) and moderate temperature (50 oC) conditions for a week. Results show that the bentonite samples obtained from the tests with SC CO2 had less change in porosity than those obtained from the tests without SC CO2 (vacuum-drying) at a given reaction time, indicating that the bentonite samples dried in the presence of SC CO2 maintained their structure. These results suggest that CO2 molecules can diffuse into interlayer of montmorillonite, which is a primary mineral of bentonite, and form a single CO2 molecule layer or double CO2 molecule layers. The CO2 molecules can displace water molecules in the interlayer, resulting in maintaining the interlayer spacing when dehydration occurs. Noticeable changes in reacted bentonite samples obtained from the tests with an aqueous phase (NaCl, CaCl2, or sea water) are decreases in the fraction of plagioclase and pyrite and formation of carbonate minerals (i.e., calcite and dolomite) and halite. In addition, no significant exchanges of Na or Ca on the exchangeable complex of the montmorillonite in the presence of SC CO2 occurred, resulting in no significant changes in the swelling capacity of bentonite samples after reacting with SC CO2 in the presence of aqueous phases. These results might be attributed by the CO2 molecule layer, which prevents

  9. Compositional changes of reservoir rocks through the injection of supercritical CO2

    NASA Astrophysics Data System (ADS)

    Scherf, Ann-Kathrin; Schulz, Hans-Martin; Zetzl, Carsten; Smirnova, Irina; Andersen, Jenica; Vieth, Andrea

    2010-05-01

    The European project CO2SINK is the first project on the on-shore underground storage of carbon dioxide in Europe. CO2SINK is part of the ongoing efforts to understand the impact, problems, and likelihood of using deep saline aquifers for long term storage of CO2. In Ketzin (north-east Germany, 40 km west of Berlin) a saline sandstone aquifer of the younger Triassic (Stuttgart Formation) has been chosen as a reservoir for the long-term storage of carbon dioxide. Our monitoring focuses on the composition and mobility of the organic carbon pools within the saline aquifer and their changes due to the storage of carbon dioxide. Supercritical carbon dioxide is known as an excellent solvent of non- to moderately polar organic compounds, depending on temperature and pressure (Hawthorne, 1990). The extraction of organic matter (OM) from reservoir rock, using multiple extraction methods, allows insight into the composition of the OM and the biomarker inventory of the deep biosphere. The extraction of reservoir rock using supercritical CO2 may additionally simulate the impact of CO2 storage on the deep biosphere by the possible mobilisation of OM. We will present compound specific results from laboratory CO2 extraction experiments on reservoir rocks from the CO2 storage site in Ketzin, Germany. A total of five rock samples (silt and sandstones) from the injection well and two observation wells were applied to supercritical CO2 extraction. In the experimental setup, a supercritical fluid extractor is used to simulate the conditions within the saline aquifer. The results show distinct quantitative and qualitative differences in extraction yields between the rock samples. This may be due to differences in mineralogy and porosity (12 - 27%; Norden et al., 2007a, b, c), which seem to be extraction-controlling key factors. Furthermore, the results illustrate that the amount of extracted materials depends on the length of the time interval in which CO2 flows through the rock

  10. CFD analysis of supercritical CO2 used as HTF in a solar tower receiver

    NASA Astrophysics Data System (ADS)

    Roldán, M. I.; Fernández-Reche, J.

    2016-05-01

    The relative cost of a solar receiver can be minimized by the selection of an appropriate heat transfer fluid capable of achieving high receiver efficiencies. In a conventional central receiver system, the concentrated solar energy is transferred from the receiver tube walls to the heat transfer fluid (HTF), which passes through a heat exchanger to generate steam for a Rankine cycle. Thus, higher working fluid temperature is associated with greater efficiency in receiver and power cycle. Emerging receiver designs that can enable higher efficiencies using advanced power cycles, such as supercritical CO2 (s-CO2) closed-loop Brayton cycles, include direct heating of s-CO2 in tubular receiver designs capable of withstanding high internal fluid pressures (around 20 MPa) and temperatures (900 K). Due to the high pressures required and the presence of moving components installed in pipelines (ball-joints and/or flexible connections), the use of s-CO2 presents many technical challenges due to the compatibility of seal materials and fluid leakages of the moving connections. These problems are solved in solar tower systems because the receiver is fixed. In this regard, a preliminary analysis of a tubular receiver with s-CO2 as HTF has been developed using the design of a molten-salt receiver which was previously tested at Plataforma Solar de Almería (PSA). Therefore, a simplified CFD model has been carried out in this study in order to analyze the feasibility of s-CO2 as HTF in solar towers. Simulation results showed that the heat gained by s-CO2 was around 75% greater than the one captured by molten salts (fluid inlet temperature of 715 K), but at a pressure range of 7.5-9.7 MPa. Thus, the use of s-CO2 as HTF in solar tower receivers appears to be a promising alternative, taking into account both the operating conditions required and their maintenance cost.

  11. Formation of Magnesite at Low Temperature in Mineral:Supercritical CO2 Systems

    NASA Astrophysics Data System (ADS)

    Qafoku, O.; Hu, J.; Arey, B.; Liu, J.; Ilton, E. S.; Felmy, A.

    2013-12-01

    One of the most promising options for mitigating the impacts of greenhouse gases on global warming is storage and sequestration of the anthropogenic CO2 in deep geologic formations. Consequently, evaluating mineral-fluid interaction in aqueous systems saturated with supercritical CO2 (scCO2) has been the focus for subsurface CO2 storage research. An important factor in assessing mineral-fluid interactions is the potential for the formation of stable divalent metal carbonates, principally Ca and Mg, which can immobilize the disposed CO2 as mineral precipitates. The formation of some of these phases, especially the Mg anhydrous phase magnesite (MgCO3), has been hindered by slow precipitation kinetics owing to the strong affinity of Mg2+ ion for the waters of hydration. Understanding conditions that lead to formation of magnesite at temperatures significant to subsurface disposal of CO2 can be substantial in the development of efficient carbon sequestration techniques. Here we present recently obtained experimental data on the formation of magnesite at low temperature (as low as 350C) and microscopy data that can elucidate factors that might contribute to magnesite formation. The experimental studies were conducted over a range of temperature, pressure, pH, and initial Mg(HCO3)2 concentration to map out the specific solution phase conditions which result in nucleation of magnesite in aqueous solution saturated with scCO2.

  12. The Role of H2O in the Carbonation of Forsterite in Supercritical CO2

    SciTech Connect

    Kwak, Ja Hun; Hu, Jian Z.; Turcu, Romulus VF; Rosso, Kevin M.; Ilton, Eugene S.; Wang, Chong M.; Sears, Jesse A.; Engelhard, Mark H.; Felmy, Andrew R.; Hoyt, David W.

    2011-07-01

    The water concentration dependence of forsterite carbonation in supercritical CO2 (scCO2) at 80°C and 76 bars was investigated by a combination of NMR, XRD, TEM and XPS. Reaction products were not detected using scCO2 alone without added H2O. When trace amounts of water were included, limited reaction was observed. Below saturation, reaction products were a mixture of partially hydrated/hydroxylated magnesium carbonates and hydroxylated silica species that were mainly in an amorphous state, forming a non-resolved layer on the forsterite surface. At water concentrations above saturation, where forsterite was in contact with both a CO2-saturated aqueous fluid and a water-saturated scCO2 fluid, solid reaction products were magnesite (MgCO3) and an amorphous polymerized SiO2 dominated by Q4, and to a lesser extent by Q3 silica coordination. Formation of these phases implies H2O initially bound in precursor hydrated/hydroxylated reaction products was liberated, inducing further reaction. Hence, for a given fluid/mineral ratio there is a water threshold above which a significant portion of the water serves in a catalytic role where more extensive carbonation reaction occurs. Defining the role of water, even in low water content environments, is therefore critical to determining the long term impact of CO2 reactivity in the subsurface.

  13. Supercritical or compressed CO2 as a stimulus for tuning surfactant aggregations.

    PubMed

    Zhang, Jianling; Han, Buxing

    2013-02-19

    surfactant aggregation. We can adjust the aggregation behaviors continuously by pressure and can easily remove CO(2) without contaminating the product, and the method is environmentally benign. We can explain the mechanisms for these effects on surfactant aggregation in terms of molecular interactions. These studies expand the areas of colloid and interface science, supercritical fluid science and technology, and chemical thermodynamics. We hope that the work will influence other fundamental and applied research in these areas. PMID:23106121

  14. An investigation of supercritical-CO2 copper electroplating parameters for application in TSV chips

    NASA Astrophysics Data System (ADS)

    Chuang, Ho-Chiao; Lai, Wei-Hong; Sanchez, Jorge

    2015-01-01

    This study uses supercritical electroplating for the filling of through silicon vias (TSVs) in chips. The present study utilizes the inductively coupled plasma reactive ion etching (ICP RIE) process technique to etch the TSVs and discusses different supercritical-CO2 electroplating parameters, such as the supercritical pressure, the electroplating current density’s effect on the TSV Cu pillar filling time, the I-V curve, the electrical resistance and the hermeticity. In addition, the results for all the tests mentioned above have been compared to results from traditional electroplating techniques. For the testing, we will first discuss the hermeticity of the TSV Cu pillars, using a helium leaking test apparatus to assess the vacuum sealing of the fabricated TSV Cu pillars. In addition, this study also conducts tests for the electrical properties, which include the measurement of the electrical resistance of the TSV at both ends in the horizontal direction, followed by the passing of a high current (10 A, due to probe limitations) to check if the TSV can withstand it without burnout. Finally, the TSV is cut in half in cross-section to observe the filling of Cu pillars by the supercritical electroplating and check for voids. The important characteristic of this study is the use of the supercritical electroplating process without the addition of any surfactants to aid the filling of the TSVs, but by taking advantage of the high permeability and low surface tension of supercritical fluids to achieve our goal. The results of this investigation point to a supercritical pressure of 2000 psi and a current density of 3 A dm-2 giving off the best electroplating filling and hermeticity, while also being able to withstand a high current of 10 A, with a relatively short electroplating time of 3 h (when compared to our own traditional dc electroplating).

  15. Preparation and rheology of supercritical CO2-based dispersed polymer-clay nanocomposites

    NASA Astrophysics Data System (ADS)

    Kannan, Rangaramanujam; Horsch, Steven; Gulari, Esin

    2007-03-01

    Effective dispersion of the fillers in a polymer matrix has been a key challenge in the field of nanocomposites. Supercritical carbon dioxide (scCO2) appears , PS/clay, The nanocomposites are characterized using WAXD, SEM, TEM, Rheology and DSC. The high degree of dispersion achieved through sc-CO2 appears to result in an order of magnitude increase in the rheological properties of PS, associated with an increase in the Tg of around 13 C, at 10% clay loading. These moduli improvements are significant better than those obtained with conventional, chemically-modified intercalated clay nanocomposites. The degree of enhancement in the properties appears to be strongly dependant on the polymer-clay interactions, and how it is promoted by the supercritical fluid. In the case of PDMS nanocomposites, where the clay-polymer interactions were weak, the modulus increase at low frequencies (for sc-CO2 processed system) was only a factor of 2. In the case of PVME- I30P clay nanocomposites, the modulus increase was substantial even at moderate loadings and dispersions, perhaps to be hydrogen-bonding interactions. Our results indicate that scCO2 can not only disperse nanoclays in polymers, it can also significantly enhance clay-polymer interactions.

  16. In Situ Infrared Spectroscopic Study of Forsterite Carbonation in Wet Supercritical CO2

    SciTech Connect

    Loring, John S.; Thompson, Christopher J.; Wang, Zheming; Joly, Alan G.; Sklarew, Deborah S.; Schaef, Herbert T.; Ilton, Eugene S.; Rosso, Kevin M.; Felmy, Andrew R.

    2011-07-19

    Carbonation reactions are central to the prospect of CO2 trapping by mineralization in geologic reservoirs. In contrast to the relevant aqueous-mediated reactions, little is known about the propensity for carbonation in the long-term partner fluid: water-containing supercritical carbon dioxide (‘wet’ scCO2). We employed in situ mid-infrared spectroscopy to follow the reaction of a model silicate mineral (forsterite, Mg2SiO4) for 24 hr with wet scCO2 at 50°C and 180 atm, using water concentrations corresponding to 0%, 55%, 95%, and 136% saturation. Results show a dramatic dependence of reactivity on water concentration and the presence of liquid water on the forsterite particles. Exposure to neat scCO2 showed no detectable carbonation reaction. At 55% and 95% water saturation, a liquid-like thin water film was detected on the forsterite particles; less than 1% of the forsterite transformed, mostly within the first 3 hours of exposure to the fluid. At 136% saturation, where an (excess) liquid water film approximately several nanometers thick was intentionally condensed on the forsterite, the carbonation reaction proceeded continuously for 24 hr with 10% to 15% transformation. Our collective results suggest constitutive links between water concentration, water film formation, reaction rate and extent, and reaction products in wet scCO2.

  17. Supercritical CO2 extract of Cinnamomum zeylanicum: chemical characterization and antityrosinase activity.

    PubMed

    Marongiu, Bruno; Piras, Alessandra; Porcedda, Silvia; Tuveri, Enrica; Sanjust, Enrico; Meli, Massimo; Sollai, Francesca; Zucca, Paolo; Rescigno, Antonio

    2007-11-28

    The volatile oil of the bark of Cinnamomum zeylanicum was extracted by means of supercritical CO2 fluid extraction in different conditions of pressure and temperature. Its chemical composition was characterized by GC-MS analysis. Nineteen compounds, which in the supercritical extract represented >95% of the oil, were identified. (E)-Cinnamaldehyde (77.1%), (E)-beta-caryophyllene (6.0%), alpha-terpineol (4.4%), and eugenol (3.0%) were found to be the major constituents. The SFE oil of cinnamon was screened for its biological activity about the formation of melanin in vitro. The extract showed antityrosinase activity and was able to reduce the formation of insoluble flakes of melanin from tyrosine. The oil also delayed the browning effect in apple homogenate. (E)-Cinnamaldehyde and eugenol were found to be mainly responsible of this inhibition effect.

  18. Supercritical fluid reverse micelle separation

    DOEpatents

    Fulton, John L.; Smith, Richard D.

    1993-01-01

    A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W.sub.o that determines the maximum size of the reverse micelles. The maximum ratio W.sub.o of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions.

  19. Supercritical fluid reverse micelle separation

    DOEpatents

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

    1993-11-30

    A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.

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

    NASA Astrophysics Data System (ADS)

    Rod, K. A.; Wang, G.

    2015-12-01

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

  1. Instrumentation for analytical scale supercritical fluid chromatography.

    PubMed

    Berger, Terry A

    2015-11-20

    Analytical scale supercritical fluid chromatography (SFC) is largely a sub-discipline of high performance liquid chromatography (HPLC), in that most of the hardware and software can be used for either technique. The aspects that separate the 2 techniques stem from the use of carbon dioxide (CO2) as the main component of the mobile phase in SFC. The high compressibility and low viscosity of CO2 mean that pumps, and autosamplers designed for HPLC either need to be modified or an alternate means of dealing with compressibility needs to be found. The inclusion of a back pressure regulator and a high pressure flow cell for any UV-Vis detector are also necessary. Details of the various approaches, problems and solutions are described. Characteristics, such as adiabatic vs. isothermal compressibility, thermal gradients, and refractive index issues are dealt with in detail. PMID:26212805

  2. Instrumentation for analytical scale supercritical fluid chromatography.

    PubMed

    Berger, Terry A

    2015-11-20

    Analytical scale supercritical fluid chromatography (SFC) is largely a sub-discipline of high performance liquid chromatography (HPLC), in that most of the hardware and software can be used for either technique. The aspects that separate the 2 techniques stem from the use of carbon dioxide (CO2) as the main component of the mobile phase in SFC. The high compressibility and low viscosity of CO2 mean that pumps, and autosamplers designed for HPLC either need to be modified or an alternate means of dealing with compressibility needs to be found. The inclusion of a back pressure regulator and a high pressure flow cell for any UV-Vis detector are also necessary. Details of the various approaches, problems and solutions are described. Characteristics, such as adiabatic vs. isothermal compressibility, thermal gradients, and refractive index issues are dealt with in detail.

  3. Thermophysical Properties of Pore-confined Supercritical CO2 by Vibrating Tube Densimetry

    SciTech Connect

    Gruszkiewicz, Miroslaw {Mirek} S; Wesolowski, David J; Cole, David R

    2011-01-01

    Properties of fluids confined in pore systems are needed for modeling fluid flow, fluid-rock interactions, and changes in reservoir porosity. The properties of CO2-rich fluids are particularly relevant to geothermal heat mining using carbon dioxide instead of water. While manometric, volumetric, and gravimetric techniques have been used successfully to investigate adsorption of low-density subcritical vapors, the results have not been satisfactory at higher, liquid-like densities of supercritical fluids. Even if the requirements for high experimental accuracy in the neighborhood of the critical region were met, these methods are fundamentally unable to deliver the total adsorption capacity, since the properties (e.g. density) of the adsorbed phase are in general not known. In this work we utilize vibrating tube densimetry for the first time to measure the total amount of fluid contained within a mesoporous solid. The method is first demonstrated using propane at subcritical and supercritical temperatures between 35 C and 97 C confined in silica aerogel (density 0.2 g cm-3, porosity 90%) that was synthesized inside Hastelloy U-tubes. Sorption and desorption of carbon dioxide on the same solid was measured at 35 C at pressures to 120 bar (density to 0.767 g cm-3). The results show total adsorption increasing monotonically with increasing pressure, unlike excess adsorption isotherms which show a maximum close to the critical density.

  4. Solution Effects on Cesium Complexation with Calixarene - Crown Ethers from Liquid to Supercritical Fluids

    SciTech Connect

    Wai, Chien M.; Yonker,Clem

    1999-06-01

    Supercritical fluid CO2 is an alternative solvent for extraction of metals. The solubility parameter of supercritical CO2 varies with density resembling that of liquid hexane at moderate pressures in the supercritical region to those of chlorinated solvents at very high pressures. By changing density of supercritical CO2, the solvation environment of a metal chelate system can vary continuously and resembles over a wide range of solvents. Thus, supercritical CO2 provides a unique system for studying solvation effects on metal chelation. This project is designed to investigate the solvation effects on cesium complexation with macrocyclic compounds including crown ethers and calixarene-crown ethers in CO2 from liquid to supercritical region at high pressures. A powerful spectroscopic technique for studying cesium chelation is nuclear magnetic resonance (NMR). Cesium has only one isotope, 133Cs, with a nuclear spin I = 7/2. Popov et al. used NMR to study cesium complexation with crown ethers and cryptand.

  5. 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

  6. Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

    NASA Astrophysics Data System (ADS)

    Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

    2014-12-01

    Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the

  7. Supercritical CO2 migration in a fractured rock at reservoir conditions

    NASA Astrophysics Data System (ADS)

    Oh, J.; Kim, K.; Han, W.; Kim, T.; Kim, J.; Park, E.

    2012-12-01

    Suitable geological formations should guarantee a long-term safe and reliable storage of the injected supercritical CO2 (scCO2), and thus densely fractured natural reservoirs are reluctant to consider as a candidate formation. Nevertheless, fractures occur in nearly all geological settings and play a major role for fluid flow. A series of core flooding test were performed to investigate the effect of a fracture on supercritical CO2 migration under reservoir conditions. In the experiment, twin samples of Berea sandstone cores were employed which have 20 % porosity and 1.7×10-13 m2 permeability. One of the twin samples was cut through the center in the direction of longitudinal axis in order to induce a single artificial fracture. The other core represents the homogeneous core. During the test, the downstream pressure was maintained at 10 MPa, and the confining pressure was kept at 20 MPa. The temperature was set to be 40 degrees to reflect the 1 km subsurface environment. The CO2-flooding (drainage) tests with brine-saturated core were performed with different injection rates (q) for both the homogeneous and the fractured core. The scCO2 saturation was measured with linear X-ray scanner. While piston-like brine displacement was observed in homogeneous core with minor effects of gravity over-run, the fractured core showed scCO2 displacing brine at fracture zone instantaneously as the injection started. As the injected volume increased, more CO2 intruded the matrix zone. Injection rates lower than a critical value (3ml/min in our conditions) only allowed CO2 displace brine along fractured zone as the built up pressure did not overcome the entry pressure of the matrix zone. In case q = 5 ml/min, the pressure drop across the cores showed 6 kPa and 13 kPa for fractured and homogeneous core, respectively, revealing that fractured reservoir has advantage on injectivity. The storage capacity was estimated by calculating scCO2 mass stored in both the homogeneous and

  8. Geochemical simulations on CO2-fluid-rock interactions in EGS reservoirs

    NASA Astrophysics Data System (ADS)

    Pan, F.; McPherson, B. J.; Lichtner, P. C.; Kaszuba, J. P.; Lo Re, C.; Karra, S.; Lu, C.; Xu, T.

    2012-12-01

    Supercritical CO2 has been suggested as a heat transmission fluid in Enhanced Geothermal Systems (EGS) reservoirs to improve energy extraction. Understanding the geochemical processes of CO2-fluid-rock interactions in EGS reservoirs is significant important to investigate the performance of energy extraction with CO2 instead of water as a working fluid, carbon sequestration and risk assessment. The objectives of this study: (1) to calibrate and evaluate the kinetic rate constants and specific reactive surface areas of minerals based on the batch experimental data conducted by other researchers (collaborators Kaszuba and Lo Ré at the University of Wyoming); (2) to investigate the effects of CO2-fluid-rock geochemical interactions on the energy extraction efficiency, carbon sequestration, and risk assessment. A series of laboratory experiments were conducted (Lo Ré et al., 2012) to investigate the geochemical reactions among water, fractured granite rocks, and injected supercritical CO2 at elevated temperatures of 250 oC, and pressures of 250-450 bars. The batch simulations were firstly conducted to mimic the laboratory experiments with the calibration of mineral reactive surface areas using TOUGHREACT model and parameter estimation software (PEST). Then, we performed 2-D geochemical modeling to simulate the chemical interactions among CO2, fluids, and rocks at high temperatures and pressures of EGS reservoirs. We further investigated the effects of fluid-rock interactions on the energy extraction, carbon sequestration, and risk assessment with CO2 as a heat transmission fluid instead of water for EGS reservoirs. Results of carbonate mineral precipitations suggested that the CO2 as a working fluid instead of water was favorable for EGS reservoirs on the CO2 sequestration. Our simulations also suggested that the energy extraction could be enhanced using CO2 as the transmission fluid compared to water.

  9. High-power ultrasonic system for the enhancement of mass transfer in supercritical CO2 extraction processes

    NASA Astrophysics Data System (ADS)

    Riera, Enrique; Blanco, Alfonso; García, José; Benedito, José; Mulet, Antonio; Gallego-Juárez, Juan A.; Blasco, Miguel

    2010-01-01

    Oil is an important component of almonds and other vegetable substrates that can show an influence on human health. In this work the development and validation of an innovative, robust, stable, reliable and efficient ultrasonic system at pilot scale to assist supercritical CO2 extraction of oils from different substrates is presented. In the extraction procedure ultrasonic energy represents an efficient way of producing deep agitation enhancing mass transfer processes because of some mechanisms (radiation pressure, streaming, agitation, high amplitude vibrations, etc.). A previous work to this research pointed out the feasibility of integrating an ultrasonic field inside a supercritical extractor without losing a significant volume fraction. This pioneer method enabled to accelerate mass transfer and then, improving supercritical extraction times. To commercially develop the new procedure fulfilling industrial requirements, a new configuration device has been designed, implemented, tested and successfully validated for supercritical fluid extraction of oil from different vegetable substrates.

  10. High-power ultrasonic system for the enhancement of mass transfer in supercritical CO2 extraction processes.

    PubMed

    Riera, Enrique; Blanco, Alfonso; García, José; Benedito, José; Mulet, Antonio; Gallego-Juárez, Juan A; Blasco, Miguel

    2010-02-01

    Oil is an important component of almonds and other vegetable substrates that can show an influence on human health. In this work the development and validation of an innovative, robust, stable, reliable and efficient ultrasonic system at pilot scale to assist supercritical CO(2) extraction of oils from different substrates is presented. In the extraction procedure ultrasonic energy represents an efficient way of producing deep agitation enhancing mass transfer processes because of some mechanisms (radiation pressure, streaming, agitation, high amplitude vibrations, etc.). A previous work to this research pointed out the feasibility of integrating an ultrasonic field inside a supercritical extractor without losing a significant volume fraction. This pioneer method enabled to accelerate mass transfer and then, improving supercritical extraction times. To commercially develop the new procedure fulfilling industrial requirements, a new configuration device has been designed, implemented, tested and successfully validated for supercritical fluid extraction of oil from different vegetable substrates.

  11. Supercritical Fluid Reactions for Coal Processing

    SciTech Connect

    Charles A. Eckert

    1997-11-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we developed a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as one model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane. The Diels-Alder reaction of anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) was selected as a second model system, and it was investigated in supercritical carbon dioxide.

  12. Liquidlike Behavior of Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Gorelli, F.; Santoro, M.; Scopigno, T.; Krisch, M.; Ruocco, G.

    2006-12-01

    The high frequency dynamics of fluid oxygen has been investigated by inelastic x-ray scattering, at high pressures and room temperature. In spite of the markedly supercritical conditions (T≈2Tc, P>102Pc), the sound velocity exceeds the hydrodynamic value of about 20%, a feature which is the fingerprint of liquidlike dynamics. The comparison of the present results with literature data obtained in several fluids allow us to identify the extrapolation of the liquid-vapor-coexistence line in the (P/Pc, T/Tc) plane as the relevant edge between liquidlike and gaslike dynamics. More interestingly, this extrapolation is very close to the non-metal-metal transition in hot dense fluids, at pressure and temperature values as obtained by shock wave experiments. This result points to the existence of a connection between structural modifications and transport properties in dense fluids.

  13. Supercritical CO2 fluid-foaming of polymers to increase porosity: a method to improve the mechanical and biocompatibility characteristics for use as a potential alternative to allografts in impaction bone grafting?

    PubMed

    Tayton, Edward; Purcell, M; Aarvold, A; Smith, J O; Kalra, S; Briscoe, A; Shakesheff, K; Howdle, S M; Dunlop, D G; Oreffo, R O C

    2012-05-01

    Disease transmission, availability and cost of allografts have resulted in significant efforts to find an alternative for use in impaction bone grafting (IBG). Recent studies identified two polymers with both structural strength and biocompatibility characteristics as potential replacements. The aim of this study was to assess whether increasing the polymer porosity further enhanced the mechanical and cellular compatibility characteristics for use as an osteogenic biomaterial alternative to allografts in IBG. Solid and porous poly(DL-lactide) (P(DL)LA) and poly(DL-lactide-co-glycolide) (P(DL)LGA) scaffolds were produced via melt processing and supercritical CO(2) foaming, and the differences characterized using scanning electron microscopy (SEM). Mechanical testing included milling and impaction, with comparisons made using a shear testing rig as well as a novel agitation test for cohesion. Cellular compatibility tests for cell number, viability, and osteogenic differentiation using WST-1 assays, fluorostaining, and ALP assays were determined following 14 day culture with skeletal stem cells. SEM showed excellent porosity throughout both of the supercritical-foam-produced polymer scaffolds, with pores between 50 and 200 μm. Shear testing showed that the porous polymers exceeded the shear strength of allograft controls (P<0.001). Agitation testing showed greater cohesion between the particles of the porous polymers (P<0.05). Cellular studies showed increased cell number, viability, and osteogenic differentiation on the porous polymers compared to solid block polymers (P<0.05). The use of supercritical CO(2) to generate porous polymeric biodegradable scaffolds significantly improves the cellular compatibility and cohesion observed compared to non-porous counterparts, without substantial loss of mechanical shear strength. These improved characteristics are critical for clinical translation as a potential osteogenic composite for use in IBG.

  14. Seismic signatures of supercritical CO2 injection/drainage within brine saturated sandstone samples

    NASA Astrophysics Data System (ADS)

    Nakagawa, S.; Kneafsey, T. J.; Rees, E. V.

    2011-12-01

    Successful sequestration of CO2 in geological formations requires high-resolution monitoring of injected CO2 location and accurate determination of CO2 saturation in the pore space, typically using seismic methods. Although understanding of the rock physics (relationship between geophysical properties such as seismic velocities and attenuations and the physical characteristics and environmental parameters of rock including porosity and saturation) of partially saturated rock has advanced significantly in recent years, relationships between heterogeneities of rock (both inherent heterogeneity in the rock fabric and structure and distribution of multiple fluid phases in the rock) and its impact on seismic properties are complex and difficult to understand using existing models. Further, most laboratory experiments to date examining the seismic signatures of fluid substitution involving liquid or supercritical (sc-) CO2 have been conducted at ultrasonic frequencies which could result in very different results from field measurements, and also their interpretations are often made assuming sample homogeneity. We present the results of our recent laboratory measurements on the changes in sonic-frequency seismic properties of initially brine saturated sandstone samples during sc-CO2 injection and drainage. High-permeability reference sandstone sample (Berea, ~680 mD) and a medium-permeability (~15 mD) reservoir sandstone used for sequestration (Tuscaloosa formation from Cranfield, Mississippi) were tested. A modified resonant bar method (the Split Hopkinson Resonant Bar method) was used to measure near-1 kHz seismic velocities and attenuations. This method allows us to use small core samples which are typically available from boreholes. Although our measurement frequency was higher than typical field seismic measurements, it is close to the frequencies which have been used for recent cross-hole seismic monitoring of CO2 injection at several sequestration demonstration

  15. Biocompatibility of supercritical CO2-treated titanium implants in a rat model.

    PubMed

    Hill, C M; Kang, Q K; Wahl, C; Jimenez, A; Laberge, M; Drews, M; Matthews, M A; An, Y H

    2006-04-01

    Supercritical phase CO2 is a promising method for sterilizing implantable devices and tissue grafts. The goal of this study is to evaluate the biocompatibility of titanium implants sterilized by supercritical phase CO2 in a rat subcutaneous implantation model. At 5 weeks post implantation titanium implants sterilized by supercritical phase CO2 produce a soft tissue reaction that is comparable to other methods of sterilization (steam autoclave, ultraviolet light radiation, ethylene oxide gas, and radio-frequency glow-discharge), as indicated by the thickness and density of the foreign body capsule, although there were some differences on the capillary density. Overall the soft tissue response to the implants was similar among all methods of sterilization, indicating supercritical phase CO2 treatment did not compromise the biocompatibility of the titanium implant.

  16. Biocompatibility of supercritical CO2-treated titanium implants in a rat model.

    PubMed

    Hill, C M; Kang, Q K; Wahl, C; Jimenez, A; Laberge, M; Drews, M; Matthews, M A; An, Y H

    2006-04-01

    Supercritical phase CO2 is a promising method for sterilizing implantable devices and tissue grafts. The goal of this study is to evaluate the biocompatibility of titanium implants sterilized by supercritical phase CO2 in a rat subcutaneous implantation model. At 5 weeks post implantation titanium implants sterilized by supercritical phase CO2 produce a soft tissue reaction that is comparable to other methods of sterilization (steam autoclave, ultraviolet light radiation, ethylene oxide gas, and radio-frequency glow-discharge), as indicated by the thickness and density of the foreign body capsule, although there were some differences on the capillary density. Overall the soft tissue response to the implants was similar among all methods of sterilization, indicating supercritical phase CO2 treatment did not compromise the biocompatibility of the titanium implant. PMID:16705612

  17. Applicability of Supercritical CO2 Speleogenesis to Exo-Planetary Karst Systems

    NASA Astrophysics Data System (ADS)

    Decker, D. D.; Polyak, V. J.; Asmerom, Y.

    2015-10-01

    Supercritical CO2 hypogene speleogenesis and its applications to exo-planetary karst features are discussed. What to look for on the planet's surface to find these types of caves and their possible use is also visited.

  18. PULSE RADIOLYSIS IN SUPERCRITICAL RARE GAS FLUIDS

    SciTech Connect

    HOLROYD,R.

    2007-01-01

    Recently, supercritical fluids have become quite popular in chemical and semiconductor industries for applications in chemical synthesis, extraction, separation processes, and surface cleaning. These applications are based on: the high dissolving power due to density build-up around solute molecules, and the ability to tune the conditions of a supercritical fluid, such as density and temperature, that are most suitable for a particular reaction. The rare gases also possess these properties and have the added advantage of being supercritical at room temperature. Information about the density buildup around both charged and neutral species can be obtained from fundamental studies of volume changes in the reactions of charged species in supercritical fluids. Volume changes are much larger in supercritical fluids than in ordinary solvents because of their higher compressibility. Hopefully basic studies, such as discussed here, of the behavior of charged species in supercritical gases will provide information useful for the utilization of these solvents in industrial applications.

  19. Applications of supercritical CO2 in the fabrication of polymer systems for drug delivery and tissue engineering.

    PubMed

    Davies, Owen R; Lewis, Andrew L; Whitaker, Martin J; Tai, Hongyun; Shakesheff, Kevin M; Howdle, Steven M

    2008-02-14

    Supercritical CO(2) has the potential to be an excellent environment within which controlled release polymers and dry composites may be formed. The low temperature and dry conditions within the fluid offer obvious advantages in the processing of water, solvent or heat labile molecules. The low viscosity and high diffusivity of scCO(2) offer the possibility of novel processing routes for polymer drug composites, but there are still technical challenges to overcome. Moreover, the low solubility of most drug molecules in scCO(2) presents both challenges and advantages. This review explores the current methods that use high pressure and scCO(2) for the production of drug delivery systems and the more specialized application of the fluid in the formation of highly porous tissue engineering scaffolds.

  20. Characterization of microbe-mineral interaction under supercritical CO2: Possible roles for bacteria during geologic carbon sequestration

    NASA Astrophysics Data System (ADS)

    Freedman, A. J.; Peet, K. C.; Ajo Franklin, J. B.; Ajo-Franklin, C.; Cappuccio, J. A.; Thompson, J. R.

    2011-12-01

    The injection of CO2 into geological formations at quantities necessary to significantly reduce CO2 emissions will represent an environmental perturbation on a continental scale. Evaluation of potential impacts at and below the surface requires a multifaceted approach that includes accurate prediction of how the CO2 behaves after injection. Microbial activity can significantly catalyze dissolution and nucleation of minerals in subsurface environments. However, the extent to which biogeochemical processes may play a role in the fate and transport of CO2 injected into geological formations has remained an open question due to the fact that at temperatures and pressures associated with reservoirs targeted for sequestration CO2 exists as a supercritical fluid (scCO2), which has generally been regarded as a sterilizing agent. To investigate whether microbial activity may mediate mineral trapping of CO2 on post-injection timescales we have developed a model system for incubating the scCO2 tolerant strain Bacillus MIT0214 (Hernandez, et al.) with minerals under scCO2 using a novel CO2 delivery apparatus. Growth of Bacillus strain MIT0214 under scCO2 (37°C at 120 atm) with a suite of index and accessory minerals associated with sandstone injection zone formations occurred at the same rate as cultures that were not exposed to mineral preparations (i.e. albite, quartz, calcite, biotite, bytownite feldspar, olivine and diopside - identified and characterized by XRD and BET). Further characterization of interactions between MIT0214 and each mineral by scanning electron microscopy and energy-dispersive x-ray spectroscopy (SEM-EDAX) sheds light on the nature of microbe-mineral contacts under scCO2 and the extent to which heterotrophic microbial activity can transform minerals under the high pCO2 conditions associated with geologic CO2 sequestration. The ability to study the dynamics of biocatalyzed mineral dissolution, alteration and nucleation (e.g. silicate weathering

  1. Investigation of Potassium Feldspar Reactivity in Wet Supercritical CO2 by In Situ Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Thompson, C.; Widener, C.; Schaef, T.; Loring, J.; McGrail, B. P.

    2014-12-01

    Capture and subsequent storage of CO2 in deep geologic reservoirs is progressively being considered as a viable approach to reduce anthropogenic greenhouse gas emissions. In the long term, injected CO2 may become permanently entrapped as silicate minerals react with CO2 enriched fluids to form stable carbonate minerals. Potassium feldspars are highly abundant in the earth's crust and are present in the caprocks and storage formations of many target reservoirs. While the dissolution kinetics and carbonation reactions of feldspars have been well studied in the aqueous phase, comparatively little work has focused on K-feldspar reactivity in the CO2-rich fluid. In this study, we used in situ infrared spectroscopy to investigate the carbonation reactions of natural microcline samples. Experiments were carried out at 50 °C and 91 bar by circulating dry or wet supercritical CO2 (scCO2) past a thin film of powdered sample. Water concentrations ranged from 0% to 125% relative to saturation, and transmission-mode absorbance spectra were recorded as a function of time for 48 hours. No discernible reaction was detected when the samples were exposed to anhydrous scCO2. However, in fully water-saturated scCO2, a thin film of liquid-like water was observed on the samples' surfaces, and up to 0.6% of the microcline was converted to a carbonate phase. Potassium carbonate is the most likely reaction product, but minor amounts of sodium carbonate and siderite may also have formed from minor sample impurities. The extent of reaction appears to be related to the thickness of the water film and is likely a consequence of the film's ability to solvate and transport ions in the vicinity of the mineral surface. Other features observed in the spectra correspond to microcline dissolution and precipitation of amorphous silica. Implications about the role of water in these reactions and the relative effectiveness of alkali feldspars for mineral trapping of CO2 will be discussed.

  2. Investigation of Plagioclase Reactivity in Wet Supercritical CO2 by In Situ Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Thompson, C.; Gauglitz, K.; Loring, J.; Schaef, T.; Miller, Q.; Johnson, K. T.; Wang, Z.; Rosso, K. M.; McGrail, P.

    2013-12-01

    Increasingly, CO2 capture and subsequent storage in deep geologic reservoirs is being implemented as a viable approach for reducing anthropogenic emissions of CO2 into the atmosphere. Several mechanisms may act to secure the injected CO2, including hydrodynamic confinement, dissolution into reservoir fluids, retention of CO2 as a separate phase in pore spaces, and carbonation of reservoir minerals. This latter mechanism is the most permanent, but it requires the presence of reactive minerals and potentially significant amounts of time for the reactions to proceed. Plagioclase feldspars are highly abundant in the earth's crust and are present in the caprocks and storage formations of many target reservoirs. Although the dissolution kinetics and carbonation reactions of feldspars have been well studied in the aqueous phase, comparatively little work has focused on plagioclase reactivity in the CO2-rich fluid at conditions relevant to geologic carbon sequestration. In this study, we used in situ infrared spectroscopy to investigate the carbonation potential of a powdered plagioclase sample similar to labradorite [(Ca,Na)(Al,Si)4O8] that had been isolated from a Hawaiian basalt. Experiments were carried out at 50 °C and 91 bar by circulating a stream of dry or wet supercritical CO2 (scCO2) past a sample overlayer deposited on the window of a high-pressure infrared flow cell. Water concentrations ranged from 0% to 125% relative to saturation, and transmission-mode absorbance spectra were recorded as a function of time for 24 hours. In experiments with excess water, a controlled temperature gradient was used to intentionally condense a film of liquid water on the overlayers' surfaces. No discernible reaction was detected when the samples were exposed to anhydrous scCO2. When water was added, a thin film of liquid-like water was observed on the samples' surfaces, and up to 0.3% of the plagioclase was converted to a carbonate phase. Calcite is the most likely reaction

  3. Supercritical CO2 Cleaning System for Planetary Protection and Contamination Control Applications

    NASA Technical Reports Server (NTRS)

    Lin, Ying; Zhong, Fang; Aveline, David C.; Anderson, Mark S.

    2012-01-01

    Current spacecraft-compatible cleaning protocols involve a vapor degreaser, liquid sonication, and alcohol wiping. These methods are not very effective in removing live and dead microbes from spacecraft piece parts of slightly complicated geometry, such as tubing and loosely fitted nuts and bolts. Contamination control practices are traditionally focused on cleaning and monitoring of particulate and oily residual. Vapor degreaser and outgassing bakeout have not been proven to be effective in removing some less volatile, hydrophilic biomolecules of significant relevance to life detection. A precision cleaning technology was developed using supercritical CO2 (SCC). SCC is used as both solvent and carrier for removing organic and particulate contaminants. Supercritical fluid, like SCC, is characterized by physical and thermal properties that are between those of the pure liquid and gas phases. The fluid density is a function of the temperature and pressure. Its solvating power can be adjusted by changing the pressure or temperature, or adding a secondary solvent such as alcohol or water. Unlike a regular organic solvent, SCC has higher diffusivities, lower viscosity, and lower surface tension. It readily penetrates porous and fibrous solids and can reach hard-to-reach surfaces of the parts with complex geometry. Importantly, the CO2 solvent does not leave any residue. The results using this new cleaning device demonstrated that both supercritical CO2 with 5% water as a co-solvent can achieve cleanliness levels of 0.01 mg/cm2 or less for contaminants of a wide range of hydrophobicities. Experiments under the same conditions using compressed Martian air mix, which consists of 95% CO2, produced similar cleaning effectiveness on the hydrophobic compounds. The main components of the SCC cleaning system are a high-pressure cleaning vessel, a boil-off vessel located downstream from the cleaning vessel, a syringe-type high-pressure pump, a heat exchanger, and a back pressure

  4. Investigation of Mineral Transformations in Wet Supercritical CO2 by Electron Microscopy

    SciTech Connect

    Arey, Bruce W.; Kovarik, Libor; Wang, Zheming; Felmy, Andrew R.

    2011-10-10

    The capture and storage of carbon dioxide and other greenhouse gases in deep geologic formations represents one of the most promising options for mitigating the impacts of greenhouse gases on global warming. In this regard, mineral-fluid interactions are of prime importance since such reactions can result in the long term sequestration of CO2 by trapping in mineral phases. Recently it has been recognized that interactions with neat to water-saturated non-aqueous fluids are of prime importance in understanding mineralization reactions since the introduced CO2 is likely to contain water initially or soon after injection and the supercritical CO2 (scCO2) is less dense than the aqueous phase which can result in a buoyant scCO2 plume contacting the isolating caprock. As a result, unraveling the molecular/microscopic mechanisms of mineral transformation in neat to water saturated scCO2 has taken on an added important. In this study, we are examining the interfacial reactions of the olivine mineral forsterite (Mg2SiO4) over a range of water contents up to and including complete water saturation in scCO2. The surface precipitates that form on the reacted forsterite grains are extremely fragile and difficult to experimentally characterize. In order to address this issue we have developed experimental protocols for preparing and imaging electron-transparent samples from fragile structures. These electron-transparent samples are then examined using a combination of STEM/EDX, FIB-TEM, and helium ion microscope (HIM) imaging (Figures 1-3). This combination of capabilities has provided unique insight into the geochemical processes that occur on scCO2 reacted mineral surfaces. The experimental procedures and protocols that have been developed also have useful applications for examining fragile structures on a wide variety of materials. This research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and

  5. Chemical Processes with Supercritical CO2 in Engineered Geologic Systems: Significance, Previous Study, and Path Forward (Invited)

    NASA Astrophysics Data System (ADS)

    Xu, T.; Pruess, K.

    2009-12-01

    Chemical reactions with dissolved CO2 in the aqueous phase have long been considered in fundamental geosciences and practical applications. Recently, studies on geologic carbon sequestration and enhanced geothermal systems using CO2 as heat transmission fluid have brought new interests in chemical reaction processes directly with supercritical CO2 (scCO2, or gas phase). In the vicinity of a CO2 injection well, the aqueous fluid initially present in a geological formation would be quickly removed by dissolution (evaporation) into the flowing gas stream and by immiscible displacement by the scCO2, creating a gas phase dominant zone. In this zone, the water evaporation could cause formation dry-out and precipitation of salt near the injection well, reducing formation porosity, permeability, and injectivity. The scCO2 may directly attack well construction materials such as cement. Over time, the gas phase will tend to migrate upwards towards the caprock because the density of the scCO2 is lower than that of the aqueous phase. In the upper portions of the reservoir, the scCO2 will directly react with caprock minerals and alter the hydrological properties and mechanical strength. On the other hand, the scCO2 phase will maintain the dissolution into the aqueous phase, lowering pH, inducing mineral dissolution, complexing with dissolved cations, increasing CO2 solubility, increasing the density of the aqueous phase, and promoting “convective mixing”. Chemical processes are quite different in the scCO2 dominant geologic systems. The absence of an aqueous phase poses unique questions, as little is presently known about the chemistry of non-aqueous systems. Additional issues arise from the reactivity of water that is dissolved in the ScCO2 phase. In this presentation, the author will discuss the importance, state of the studies performed, and future research directions.

  6. Concentration dependent refractive index of CO2/CH4 mixture in gaseous and supercritical phase

    NASA Astrophysics Data System (ADS)

    Giraudet, C.; Marlin, L.; Bégué, D.; Croccolo, F.; Bataller, H.

    2016-04-01

    Carbon dioxide (CO2)/methane (CH4) binary mixtures are investigated at pressure values up to 20 MPa at 303 K in order to investigate the pressure dependence of the optical concentration contrast factor, (" separators=" ∂ n / ∂ c ) P , T , through gaseous and supercritical phase. Refractive index is measured by means of a Michelson interferometer. Refractivities of the mixtures are found in good agreement with Lorentz-Lorenz predictions after density calculations by means of the AGA8-DC92 equation of state. Experimental polarizabilities of pure fluids are compared to quantum calculations of monomers and dimers for each pressure; it results that the quantity of dimers is small in the investigated thermodynamic conditions. Finally, by extending our experimental database with numerical simulations, we evidence that (" separators=" ∂ n / ∂ c ) P , T presents a critical enhancement similar to heat capacity.

  7. 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. PMID:19269267

  8. 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

  9. 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.

  10. Design and Analysis of an Axial Bypass Compressor Blade in a Supercritical CO2 Gas Turbine

    NASA Astrophysics Data System (ADS)

    Ishizuka, Takao; Muto, Yasushi; Aritomi, Masanori; Tsuzuki, Nobuyoshi; Kikura, Hiroshige

    A supercritical carbon dioxide gas turbine can generate power at a high cycle thermal efficiency, even at modest temperatures of 500-550°C. Consequently, a more reliable and economically advantageous power generation system is achieved by coupling with a Na-cooled fast reactor. This paper mainly describes the bypass compressor (a key component) design and thermal hydraulic analysis using CFD (with FLUENT code). Fluid conditions of the bypass compressor are determined by the cycle calculation of this system. Aerodynamic design was conducted using the loss model described by Cohen et al., which enables the use of several stages while providing total adiabatic efficiency of 21 and 87%, respectivly. Blade shapes were prepared based on flow angles and chord length obtained for the aerodynamic design. In the CFD analysis, the calculated value of the mass flow rate for each stage was adjusted to that of the design. The value of the design outlet pressure was reached at stage No. 16, which is fewer stages than that for design, No. 21. The difference between these stage numbers is attributed to the three-dimensional effect in design. If these effects are eliminated, then the design calculation yields an almost identical number of stages. Therefore, it was concluded that the existing design method is applicable to the supercritical CO2 bypass compressor. Furthermore, CFD analysis appears to be an effective aerodynamic design tool, but these conclusions should be verified experimentally.

  11. Supercritical fluid synthesis of magnetic hexagonal nanoplatelets of magnetite.

    PubMed

    Li, Zhonglai; Godsell, Jeffrey F; O'Byrne, Justin P; Petkov, Nikolay; Morris, Michael A; Roy, Saibal; Holmes, Justin D

    2010-09-15

    A supercritical fluid technique was used to prepare hexagonal nanoplatelets of magnetite. Ferrocene was used as the Fe source, and sc-CO(2) acted as both a solvent and oxygen source in the process. Powder X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and magnetic measurements were used to characterize the products. It was found that the morphology and structure of the product strongly depended on the reaction conditions.

  12. 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).

  13. 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.

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

    PubMed

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

    2015-01-01

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

  15. Nanostructured Materials: Symthesis in Supercritical Fluids

    SciTech Connect

    Lin, Yuehe; Ye, Xiangrong; Wai, Chien M.

    2009-03-24

    This chapter summarizes the recent developent of synthesis and characterization of nanostructured materials synthesized in supercritical fluids. Nanocomposite catalysts such as Pt and Pd on carbon nanotube support have been synthesized and used for fuel cell applications.

  16. Scaling considerations for a multi-megawatt class supercritical CO2 brayton cycle and commercialization.

    SciTech Connect

    Fleming, Darryn D.; Holschuh, Thomas Vernon,; Conboy, Thomas M.; Pasch, James Jay; Wright, Steven A; Rochau, Gary E; Fuller, Robert Lynn

    2013-11-01

    Small-scale supercritical CO2 demonstration loops are successful at identifying the important technical issues that one must face in order to scale up to larger power levels. The Sandia National Laboratories supercritical CO2 Brayton cycle test loops are identifying technical needs to scale the technology to commercial power levels such as 10 MWe. The small size of the Sandia 1 MWth loop has demonstration of the split flow loop efficiency and effectiveness of the Printed Circuit Heat Exchangers (PCHXs) leading to the design of a fully recuperated, split flow, supercritical CO2 Brayton cycle demonstration system. However, there were many problems that were encountered, such as high rotational speeds in the units. Additionally, the turbomachinery in the test loops need to identify issues concerning the bearings, seals, thermal boundaries, and motor controller problems in order to be proved a reliable power source in the 300 kWe range. Although these issues were anticipated in smaller demonstration units, commercially scaled hardware would eliminate these problems caused by high rotational speeds at small scale. The economic viability and development of the future scalable 10 MWe solely depends on the interest of DOE and private industry. The Intellectual Property collected by Sandia proves that the ~10 MWe supercritical CO2 power conversion loop to be very beneficial when coupled to a 20 MWth heat source (either solar, geothermal, fossil, or nuclear). This paper will identify a commercialization plan, as well as, a roadmap from the simple 1 MWth supercritical CO2 development loop to a power producing 10 MWe supercritical CO2 Brayton loop.

  17. Pore-scale Evolution of Supercritical CO2 within Bentheimer Sandstone during Multiple Drainage-Imbibition Cycles

    NASA Astrophysics Data System (ADS)

    Herring, A. L.; Andersson, L.; Wildenschild, D.

    2014-12-01

    Geologic CO2 sequestration has been proposed as a climate change mitigation strategy to limit emissions of CO2 to the atmosphere from large fossil-fuel burning CO2 point sources; however, there are concerns associated with the long-term stability of a mobile subsurface CO2 plume. The large-scale movement of subsurface supercritical CO2 (scCO2) can be prevented via capillary trapping, wherein scCO2 is immobilized in the subsurface by capillary interactions between the solid surface, resident brine, and scCO2. Capillary trapping occurs in two steps: first, the porous medium undergoes drainage as scCO2 is injected into the system; then, wetting fluid re-enters the medium in an imbibition process, isolating small bubbles of scCO2 in the pore bodies of the medium. There are many empirical models which predict capillary trapping for a single drainage-imbibition cycle; however, in an engineered CO2 sequestration project, it is possible to implement cyclic scCO2-water injections in a water-alternating-gas (WAG) injection scheme in which the system may undergo multiple CO2 injections to potentially increase the trapping efficiency of scCO2. We present experimental results of multiple drainage-imbibition cycles of scCO2 and 1:6 by mass potassium iodide (KI) brine within Bentheimer sandstone. Capillary (differential) pressure and absolute pressures for each phase were continuously measured throughout each flow process, which is a unique feature of our experimental system. Experiments were conducted at a working pressure of 8.3 MPa (1200 PSI) and 40oC, and synchrotron x-ray computed microtomography (x-ray CMT) images were collected of the drainage and imbibition process endpoints at a resolution of 3.19 μm at the Advanced Photon Source at Argonne National Laboratory. The evolution of the connectivity, topology, morphology, and capillary trapping of scCO2 phase is analyzed as a function of capillary pressure, scCO2 saturation, and sample history. Preliminary results suggest

  18. A first principles approach to the electronic properties of liquid and supercritical CO2.

    PubMed

    Cabral, Benedito J Costa; Rivelino, Roberto; Coutinho, Kaline; Canuto, Sylvio

    2015-01-14

    The electronic absorption spectra of liquid and supercritical CO2 (scCO2) are investigated by coupling a many-body energy decomposition scheme to configurations generated by Born-Oppenheimer molecular dynamics. A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies were calculated with time dependent density functional theory. A red-shift of ∼ 0.2 eV relative to the gas-phase monomer is observed for the first electronic absorption maximum in liquid and scCO2. The origin of this shift, which is not very dependent on deviations from the linearity of the CO2 molecule, is mainly related to polarization effects. However, the geometry changes of the CO2 monomer induced by thermal effects and intermolecular interactions in condensed phase lead to the appearance of an average monomeric electric dipole moment〈μ〉= 0.26 ± 0.04 D that is practically the same at liquid and supercritical conditions. The predicted average quadrupole moment for both liquid and scCO2 is〈Θ〉= - 5.5 D Å, which is increased by ∼ -0.9 D Å relative to its gas-phase value. The importance of investigating the electronic properties for a better understanding of the role played by CO2 in supercritical solvation is stressed.

  19. A Procedure for the supercritical fluid extraction of coal samples, with subsequent analysis of extracted hydrocarbons

    USGS Publications Warehouse

    Kolak, Jonathan J.

    2006-01-01

    Introduction: This report provides a detailed, step-by-step procedure for conducting extractions with supercritical carbon dioxide (CO2) using the ISCO SFX220 supercritical fluid extraction system. Protocols for the subsequent separation and analysis of extracted hydrocarbons are also included in this report. These procedures were developed under the auspices of the project 'Assessment of Geologic Reservoirs for Carbon Dioxide Sequestration' (see http://pubs.usgs.gov/fs/fs026-03/fs026-03.pdf) to investigate possible environmental ramifications associated with CO2 storage (sequestration) in geologic reservoirs, such as deep (~1 km below land surface) coal beds. Supercritical CO2 has been used previously to extract contaminants from geologic matrices. Pressure-temperature conditions within deep coal beds may render CO2 supercritical. In this context, the ability of supercritical CO2 to extract contaminants from geologic materials may serve to mobilize noxious compounds from coal, possibly complicating storage efforts. There currently exists little information on the physicochemical interactions between supercritical CO2 and coal in this setting. The procedures described herein were developed to improve the understanding of these interactions and provide insight into the fate of CO2 and contaminants during simulated CO2 injections.

  20. In Situ Molecular Spectroscopic Evidence for CO2 Intercalation into Montmorillonite in Supercritical Carbon Dioxide

    SciTech Connect

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

    2012-04-25

    The interaction of anhydrous supercritical CO2 (scCO2) with both kaolinite and ~1W (i.e. close to but less than one layer of hydration) calcium-saturated montmorillonite was investigated under conditions relevant to geologic carbon sequestration (50 °C and 90 bar). The CO2 molecular environment was probed in situ using a combination of three novel high-pressure techniques: X-ray diffraction, magic angle spinning nuclear magnetic resonance spectroscopy and attenuated total reflection infrared spectroscopy. We report the first direct evidence that the expansion of montmorillonite under scCO2 conditions is due to CO2 migration into the interlayer. Intercalated CO2 molecules are rotationally constrained and do not appear to react with waters to form bicarbonate or carbonic acid. In contrast, CO2 does not intercalate into kaolinite. The findings show that predicting the seal integrity of caprock will have complex dependence on clay mineralogy and hydration state.

  1. 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.

  2. Supercritical fluid thermodynamics for coal processing

    SciTech Connect

    van Swol, F. . Dept. of Chemical Engineering); Eckert, C.A. . School of Chemical Engineering)

    1988-09-15

    The main objective of this research is to develop an equation of state that can be used to predict solubilities and tailor supercritical fluid solvents for the extraction and processing of coal. To meet this objective we have implemented a two-sided. approach. First, we expanded the database of model coal compound solubilities in higher temperature fluids, polar fluids, and fluid mixtures systems. Second, the unique solute/solute, solute/cosolvent and solute/solvent intermolecular interactions in supercritical fluid solutions were investigated using spectroscopic techniques. These results increased our understanding of the molecular phenomena that affect solubility in supercritical fluids and were significant in the development of an equation of state that accurately reflects the true molecular makeup of the solution. (VC)

  3. Non-fluorous polymers with very high solubility in supercritical CO2 down to low pressures

    PubMed

    Sarbu; Styranec; Beckman

    2000-05-11

    Liquid and supercritical carbon dioxide have attracted much interest as environmentally benign solvents, but their practical use has been limited by the need for high CO2 pressures to dissolve even small amounts of polar, amphiphilic, organometallic, or high-molecular-mass compounds. So-called 'CO2-philes' efficiently transport insoluble or poorly soluble materials into CO2 solvent, resulting in the development of a broad range of CO2-based processes, including homogeneous and heterogeneous polymerization, extraction of proteins and metals, and homogeneous catalysis. But as the most effective CO2-philes are expensive fluorocarbons, such as poly(perfluoroether), the commercialization of otherwise promising CO2-based processes has met with only limited success. Here we show that copolymers can act as efficient, non-fluorous CO2-philes if their constituent monomers are chosen to optimize the balance between the enthalpy and entropy of solute-copolymer and copolymer-copolymer interactions. Guided by heuristic rules regarding these interactions, we have used inexpensive propylene and CO2 to synthesize a series of poly(ether-carbonate) copolymers that readily dissolve in CO2 at low pressures. Even though non-fluorous polymers are generally assumed to be CO2-phobic, we expect that our design principles can be used to create a wide range of non-fluorous CO2-philes from low-cost raw materials, thus rendering a variety of CO2-based processes economically favourable, particularly in cases where recycling of CO2-philes is difficult.

  4. Analysis of drug residues in tissue by combined supercritical-fluid extraction-supercritical-fluid chromatography-mass spectrometry-mass spectrometry.

    PubMed

    Ramsey, E D; Perkins, J R; Games, D E; Startin, J R

    1989-03-01

    The combination of supercritical-fluid extraction-supercritical-fluid chromatography-tandem mass spectrometry has been evaluated for the detection of residues of a small group of veterinary drugs in freeze-dried pig's kidney. During extraction with supercritical CO2 the drugs were retained by the column while non-polar endogenous material was not retained and thus passed to waste. Subsequent changes to the mobile phase composition eluted the drugs which were detected with high specificity by tandem mass spectrometry. Although the sensitivity in this preliminary study was not adequate for surveillance or enforcement, there is potential for further development of the approach.

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

    PubMed

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

    2013-01-01

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

  6. Swelling-induced changes in coal microstructure due to supercritical CO2 injection

    NASA Astrophysics Data System (ADS)

    Zhang, Yihuai; Lebedev, Maxim; Sarmadivaleh, Mohammad; Barifcani, Ahmed; Iglauer, Stefan

    2016-09-01

    Enhanced coalbed methane recovery and CO2 geostorage in coal seams are severely limited by permeability decrease caused by CO2 injection and associated coal matrix swelling. Typically, it is assumed that matrix swelling leads to coal cleat closure, and as a consequence, permeability is reduced. However, this assumption has not yet been directly observed. Using a novel in situ reservoir condition X-ray microcomputed tomography flooding apparatus, for the first time we observed such microcleat closure induced by supercritical CO2 flooding in situ. Furthermore, fracturing of the mineral phase (embedded in the coal) was observed; this fracturing was induced by the internal swelling stress. We conclude that coal permeability is drastically reduced by cleat closure, which again is caused by coal matrix swelling, which again is caused by flooding with supercritical CO2.

  7. Recent patents on the sterilization of food and biomaterials by supercritical fluids.

    PubMed

    Sikin, Adi Md; Rizvi, Syed S H

    2011-09-01

    Supercritical fluid technology applies the unique characteristics of certain substances under particular conditions of pressure and temperature above their critical point. In particular, supercritical fluid sterilization provides a nonthermal solution to problems related to bacterial, viral, yeast and enzyme inactivation in the food and pharmaceutical industries as well as healthcare services. Supercritical fluid CO2 is versatile for sterilization due to its non-reactive nature, ability to penetrate into cells and tissues, reduced energy usage and improved quality retention of heat-sensitive substrates. Therefore, the purpose of this review is to illustrate the most recent and related patents for sterilizing food and biomaterials with supercritical fluids, published and/or granted from 2005 to present. Finally, the manuscript reports a discussion on the current challenges and development of supercritical fluid sterilization particularly for the food industry.

  8. Wettability effect on capillary trapping of supercritical CO2 at pore-scale: micromodel experiment and numerical modeling

    NASA Astrophysics Data System (ADS)

    Hu, R.; Wan, J.

    2015-12-01

    Wettability of reservoir minerals along pore surfaces plays a controlling role in capillary trapping of supercritical (sc) CO2 in geologic carbon sequestration. The mechanisms controlling scCO2 residual trapping are still not fully understood. We studied the effect of pore surface wettability on CO2 residual saturation at the pore-scale using engineered high pressure and high temperature micromodel (transparent pore networks) experiments and numerical modeling. Through chemical treatment of the micromodel pore surfaces, water-wet, intermediate-wet, and CO2-wet micromodels can be obtained. Both drainage and imbibition experiments were conducted at 8.5 MPa and 45 °C with controlled flow rate. Dynamic images of fluid-fluid displacement processes were recorded using a microscope with a CCD camera. Residual saturations were determined by analysis of late stage imbibition images of flow path structures. We performed direct numerical simulations of the full Navier-Stokes equations using a volume-of-fluid based finite-volume framework for the primary drainage and the followed imbibition for the micromodel experiments with different contact angles. The numerical simulations agreed well with our experimental observations. We found that more scCO2 can be trapped within the CO2-wet micromodel whereas lower residual scCO2 saturation occurred within the water-wet micromodels in both our experiments and the numerical simulations. These results provide direct and consistent evidence of the effect of wettability, and have important implications for scCO2 trapping in geologic carbon sequestration.

  9. Innovative pretreatment of sugarcane bagasse using supercritical CO2 followed by alkaline hydrogen peroxide.

    PubMed

    Phan, Duy The; Tan, Chung-Sung

    2014-09-01

    An innovative method for pretreatment of sugarcane bagasse using sequential combination of supercritical CO2 (scCO2) and alkaline hydrogen peroxide (H2O2) at mild conditions is proposed. This method was found to be superior to the individual pretreatment with scCO2, ultrasound, or H2O2 and the sequential combination of scCO2 and ultrasound regarding the yield of cellulose and hemicellulose, almost twice the yield was observed. Pretreatment with scCO2 could obtain higher amount of cellulose and hemicellulose but also acid-insoluble lignin. Pretreatment with ultrasound or H2O2 could partly depolymerize lignin, however, could not separate cellulose from lignin. The analysis of liquid products via enzymatic hydrolysis by HPLC and the characterization of the solid residues by SEM revealed strong synergetic effects in the sequential combination of scCO2 and H2O2.

  10. Influence of supercritical CO(2) pressurization on the phase behavior of mixed cholesteryl esters.

    PubMed

    Huang, Zhen; Feng, Mei; Su, Junfeng; Guo, Yuhua; Liu, Tie-Yan; Chiew, Yee C

    2010-09-15

    Evidences indicating the presence of phase transformations in the mixed cholesteryl benzoate (CBE) and cholesteryl butyrate (CBU) under the supercritical CO(2) pressurization, by means of differential scanning calorimetry (DSC) and X-ray diffraction (XRD), are presented in this work. These include (1) the DSC heating curve of pure CBU; (2) the DSC heating curves of CBU/CBE mixtures; (3) the XRD spectra of pure CBU; (4) the XRD spectra of CBU/CBE mixtures; (5) CBU and CBE are miscible in either solid phase or liquid phase over the whole composition range. As a result of the presence of these phase transformations induced by pressurization, it could be deduced that a solid solution of the CBU/CBE mixture might have formed at the interfaces under supercritical conditions, subsequently influencing their dissolving behaviors in supercritical CO(2). PMID:20654706

  11. Materials, Turbomachinery and Heat Exchangers for Supercritical CO2 Systems

    SciTech Connect

    Anderson, Mark; Nellis, Greg; Corradini, Michael

    2012-10-19

    The objective of this project is to produce the necessary data to evaluate the performance of the supercritical carbon dioxide cycle. The activities include a study of materials compatibility of various alloys at high temperatures, the heat transfer and pressure drop in compact heat exchanger units, and turbomachinery issues, primarily leakage rates through dynamic seals. This experimental work will serve as a test bed for model development and design calculations, and will help define further tests necessary to develop high-efficiency power conversion cycles for use on a variety of reactor designs, including the sodium fast reactor (SFR) and very high-temperature gas reactor (VHTR). The research will be broken into three separate tasks. The first task deals with the analysis of materials related to the high-temperature S-CO{sub 2} Brayton cycle. The most taxing materials issues with regard to the cycle are associated with the high temperatures in the reactor side heat exchanger and in the high-temperature turbine. The system could experience pressures as high as 20MPa and temperatures as high as 650°C. The second task deals with optimization of the heat exchangers required by the S-CO{sub 2} cycle; the S-CO{sub 2} flow passages in these heat exchangers are required whether the cycle is coupled with a VHTR or an SFR. At least three heat exchangers will be required: the pre-cooler before compression, the recuperator, and the heat exchanger that interfaces with the reactor coolant. Each of these heat exchangers is unique and must be optimized separately. The most challenging heat exchanger is likely the pre-cooler, as there is only about a 40°C temperature change but it operates close to the CO{sub 2} critical point, therefore inducing substantial changes in properties. The proposed research will focus on this most challenging component. The third task examines seal leakage through various dynamic seal designs under the conditions expected in the S-CO{sub 2} cycle

  12. 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.

  13. CO2-based mixtures as working fluids for geothermal turbines.

    SciTech Connect

    Wright, Steven Alan; Conboy, Thomas M.; Ames, David E.

    2012-01-01

    Sandia National Laboratories is investigating advanced Brayton cycles using supercritical working fluids for application to a variety of heat sources, including geothermal, solar, fossil, and nuclear power. This work is centered on the supercritical CO{sub 2} (S-CO{sub 2}) power conversion cycle, which has the potential for high efficiency in the temperature range of interest for these heat sources and is very compact-a feature likely to reduce capital costs. One promising approach is the use of CO{sub 2}-based supercritical fluid mixtures. The introduction of additives to CO{sub 2} alters the equation of state and the critical point of the resultant mixture. A series of tests was carried out using Sandia's supercritical fluid compression loop that confirmed the ability of different additives to increase or lower the critical point of CO{sub 2}. Testing also demonstrated that, above the modified critical point, these mixtures can be compressed in a turbocompressor as a single-phase homogenous mixture. Comparisons of experimental data to the National Institute of Standards and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties (REFPROP) Standard Reference Database predictions varied depending on the fluid. Although the pressure, density, and temperature (p, {rho}, T) data for all tested fluids matched fairly well to REFPROP in most regions, the critical temperature was often inaccurate. In these cases, outside literature was found to provide further insight and to qualitatively confirm the validity of experimental findings for the present investigation.

  14. Supercritical fluid (SCF) technologies: Assessment of applicability to installation restoration processes

    NASA Astrophysics Data System (ADS)

    1994-03-01

    USAEC has conducted an evaluation of supercritical fluid (SCF) technologies for their applicability to treatment of explosives, chlorinated hydrocarbons, and metals in soils, water, and/or waste sludge media. Off-specification explosives and propellants that have traditionally been open burned or openly detonated were also examined. Supercritical fluids are substances which have been heated and compressed to above their critical temperatures and pressures and which possess unique transport and mass transfer properties. Supercritical fluid extraction (SFE) uses the solvating properties of supercritical fluids to extract one or more organic components from a mixture into a supercritical solvent (commonly CO2). The concentrated extract stream may then be recycled, reclaimed, or destroyed by other methods.

  15. Supercritical CO2 Cleaning for Planetary Protection and Contamination Control

    NASA Technical Reports Server (NTRS)

    Lin, Ying; Zhong, Fang; Aveline, David; Anderson, Mark; Chung, Shirley; Mennella, Jerami; Schubert, Wayne

    2010-01-01

    We have designed and built a prototype Supercritical CO? Cleaning (SCC) system at JPL. The key features of the system are: 1) the parts inside a high-pressure vessel can be rotated at high speeds; 2) the same thermodynamic condition is maintained during First-In First-Out flushing to keep solvent power constant; and 3) the boil-off during decompression is induced in a separate vessel downstream. Our goal is to demonstrate SCC's ability to remove trace amounts of microbial and organic contaminants down to parts per billion levels from spacecraft material surfaces for future astrobiology missions. The initial cleaning test results showed that SCC can achieve cleanliness levels of 0.01 microgram/cm(sup 2) or less for hydrophobic contaminants such as dioctyl phthalate and silicone and it is less effective in the removal and inactivation of the hydrophilic bacterial spores as expected. However, with the use of a polar co-solvent, the efficacy may improve dramatically. The same results were obtained using liquid CO?. This opens up the possibility of using subcritical cleaning conditions, which may prove to be more compatible with certain spacecraft hardware.

  16. Development of a Novel Catalytic Membrane Reactor for Heterogeneous Catalysis in Supercritical CO2

    PubMed Central

    Islam, Nazrul M.; Chatterjee, Maya; Ikushima, Yutaka; Yokoyama, Toshiro; Kawanami, Hajime

    2010-01-01

    A novel type of high-pressure membrane reactor has been developed for hydrogenation in supercritical carbon dioxide (scCO2). The main objectives of the design of the reactor are the separate feeding of hydrogen and substrate in scCO2 for safe reactions in a continuous flow process, and to reduce the reaction time. By using this new reactor, hydrogenation of cinnamaldehyde into hydrocinnamaldehyde has been successfully carried out with 100% selectivity at 50 °C in 10 MPa (H2: 1 MPa, CO2: 9 MPa) with a flow rate of substrate ranging from 0.05 to 1.0 mL/min. PMID:20162008

  17. Design of preparative-supercritical fluid chromatography.

    PubMed

    Rajendran, Arvind

    2012-08-10

    Preparative supercritical fluid chromatography (prep-SFC) is an important separation process in the chromatographers toolbox. Owing to the unique properties of the mobile phase, which is predominantly CO(2), the behavior of SFC is markedly different from high performance liquid chromatography (HPLC). This review article focuses on the scale-up of preparative chromatography. The basics of SFC, with particular focus on highlighting the key differences between SFC and HPLC, are introduced. Then, a framework for rational design of prep-SFC is proposed. This framework is based on obtaining basic system parameters from analytical scale equipment, i.e., with very small amount of material, and performing design and optimization in silico to evaluate process performance and to identify operating conditions for scale-up. The tools required to obtain the input parameters such as adsorption isotherms are discussed and the development of the design and optimization framework is elaborated. Examples from the literature which use this approach for successful scale-up are provided. Finally the design of multi-column SFC systems is discussed.

  18. 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. PMID:22560346

  19. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  1. Solubility of caffeine from green tea in supercritical CO2: a theoretical and empirical approach.

    PubMed

    Gadkari, Pravin Vasantrao; Balaraman, Manohar

    2015-12-01

    Decaffeination of fresh green tea was carried out with supercritical CO2 in the presence of ethanol as co-solvent. The solubility of caffeine in supercritical CO2 varied from 44.19 × 10(-6) to 149.55 × 10(-6) (mole fraction) over a pressure and temperature range of 15 to 35 MPa and 313 to 333 K, respectively. The maximum solubility of caffeine was obtained at 25 MPa and 323 K. Experimental solubility data were correlated with the theoretical equation of state models Peng-Robinson (PR), Soave Redlich-Kwong (SRK), and Redlich-Kwong (RK). The RK model had regressed experimental data with 15.52 % average absolute relative deviation (AARD). In contrast, Gordillo empirical model regressed the best to experimental data with only 0.96 % AARD. Under supercritical conditions, solubility of caffeine in tea matrix was lower than the solubility of pure caffeine. Further, solubility of caffeine in supercritical CO2 was compared with solubility of pure caffeine in conventional solvents and a maximum solubility 90 × 10(-3) mol fraction was obtained with chloroform.

  2. Solubility of caffeine from green tea in supercritical CO2: a theoretical and empirical approach.

    PubMed

    Gadkari, Pravin Vasantrao; Balaraman, Manohar

    2015-12-01

    Decaffeination of fresh green tea was carried out with supercritical CO2 in the presence of ethanol as co-solvent. The solubility of caffeine in supercritical CO2 varied from 44.19 × 10(-6) to 149.55 × 10(-6) (mole fraction) over a pressure and temperature range of 15 to 35 MPa and 313 to 333 K, respectively. The maximum solubility of caffeine was obtained at 25 MPa and 323 K. Experimental solubility data were correlated with the theoretical equation of state models Peng-Robinson (PR), Soave Redlich-Kwong (SRK), and Redlich-Kwong (RK). The RK model had regressed experimental data with 15.52 % average absolute relative deviation (AARD). In contrast, Gordillo empirical model regressed the best to experimental data with only 0.96 % AARD. Under supercritical conditions, solubility of caffeine in tea matrix was lower than the solubility of pure caffeine. Further, solubility of caffeine in supercritical CO2 was compared with solubility of pure caffeine in conventional solvents and a maximum solubility 90 × 10(-3) mol fraction was obtained with chloroform. PMID:26604372

  3. Laboratory-scale interaction between CO2-rich brine and limestone and sandstone under supercritical CO2 conditions

    NASA Astrophysics Data System (ADS)

    Garcia-Rios, Maria; Cama, Jordi; Luquot, Linda; Soler, Josep

    2014-05-01

    A test site for a prospective CO2 geological storage is situated in Hontomín (Burgos, northern Spain) with a reservoir rock that is composed of limestone (calcite) and sandstone (66 wt.% calcite, 28 wt.% quartz and 6 wt.% microcline). During and after CO2 injection, the resulting CO2-rich acid brine will likely promote the dissolution of carbonate minerals (calcite) and aluminosilicates (microcline). Since the reservoir Hontomín brine contains sulfate, gypsum (or anhydrite at depth) may precipitate. These coupled dissolution and precipitation reactions may induce changes in porosity and pore structure of the repository rocks. Percolations experiments with mechanically fractured cores (8.6 mm in diameter and 18 mm length) were performed under CO2 supercritical conditions (Pfluid = 150 bar; pCO2 ≡ 90 bar and T = 60 ºC) in order to evaluate and quantify variations in fracture permeability, preferential path formation and fracture volume. The brine sulfate content and the flow rate were varied. Regarding limestone, as the synthetic brines circulated through the fracture, the fracture permeability initially increased slowly, to thereafter increase rapidly. This change was due to a localized dissolution process (wormhole formation) along the core that occurred regardless gypsum precipitation. Nonetheless, the originated fracture volume in the sulfate-rich brine experiments was a factor of two smaller than that in sulfate-free brine experiments. Also, an increase in flow rate from 0.2 to 60 mL/h increased the volume of both dissolved calcite and precipitated gypsum. Regarding sandstone, permeability increased gradually with time. Nonetheless, this increase was not always continuous due to eventual fracture clogging. Formation of wormholes was observed. Acknowledgements This study was financed by CIUDEN (Ciudad de la Energía), the Compostilla OXYCFB300 project and the PANACEA project (European Community's Seventh Framework Programme FP7/2007-2013 under grant

  4. 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.

  5. Control system options and strategies for supercritical CO2 cycles.

    SciTech Connect

    Moisseytsev, A.; Kulesza, K. P.; Sienicki, J. J.; Nuclear Engineering Division; Oregon State Univ.

    2009-06-18

    The Supercritical Carbon Dioxide (S-CO{sub 2}) Brayton Cycle is a promising alternative to Rankine steam cycle and recuperated gas Brayton cycle energy converters for use with Sodium-Cooled Fast Reactors (SFRs), Lead-Cooled Fast Reactors (LFRs), as well as other advanced reactor concepts. The S-CO{sub 2} Brayton Cycle offers higher plant efficiencies than Rankine or recuperated gas Brayton cycles operating at the same liquid metal reactor core outlet temperatures as well as reduced costs or size of key components especially the turbomachinery. A new Plant Dynamics Computer Code has been developed at Argonne National Laboratory for simulation of a S-CO{sub 2} Brayton Cycle energy converter coupled to an autonomous load following liquid metal-cooled fast reactor. The Plant Dynamics code has been applied to investigate the effectiveness of a control strategy for the S-CO{sub 2} Brayton Cycle for the STAR-LM 181 MWe (400 MWt) Lead-Cooled Fast Reactor. The strategy, which involves a combination of control mechanisms, is found to be effective for controlling the S-CO{sub 2} Brayton Cycle over the complete operating range from 0 to 100 % load for a representative set of transient load changes. While the system dynamic analysis of control strategy performance for STARLM is carried out for a S-CO{sub 2} Brayton Cycle energy converter incorporating an axial flow turbine and compressors, investigations of the S-CO{sub 2} Brayton Cycle have identified benefits from the use of centrifugal compressors which offer a wider operating range, greater stability near the critical point, and potentially further cost reductions due to fewer stages than axial flow compressors. Models have been developed at Argonne for the conceptual design and performance analysis of centrifugal compressors for use in the SCO{sub 2} Brayton Cycle. Steady state calculations demonstrate the wider operating range of centrifugal compressors versus axial compressors installed in a S-CO{sub 2} Brayton Cycle as

  6. 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.

  7. 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. PMID:20544439

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

    SciTech Connect

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

    2009-02-01

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

  9. Pore-scale supercritical CO2 dissolution and mass transfer under imbibition conditions

    NASA Astrophysics Data System (ADS)

    Chang, Chun; Zhou, Quanlin; Kneafsey, Timothy J.; Oostrom, Mart; Wietsma, Thomas W.; Yu, Qingchun

    2016-06-01

    In modeling of geological carbon storage, dissolution of supercritical CO2 (scCO2) is often assumed to be instantaneous with equilibrium phase partitioning. In contrast, recent core-scale imbibition experiments have shown a prolonged depletion of residual scCO2 by dissolution, implying a non-equilibrium mechanism. In this study, eight pore-scale scCO2 dissolution experiments in a 2D heterogeneous, sandstone-analog micromodel were conducted at supercritical conditions (9 MPa and 40 °C). The micromodel was first saturated with deionized (DI) water and drained by injecting scCO2 to establish a stable scCO2 saturation. DI water was then injected at constant flow rates after scCO2 drainage was completed. High resolution time-lapse images of scCO2 and water distributions were obtained during imbibition and dissolution, aided by a scCO2-soluble fluorescent dye introduced with scCO2 during drainage. These images were used to estimate scCO2 saturations and scCO2 depletion rates. Experimental results show that (1) a time-independent, varying number of water-flow channels are created during imbibition and later dominant dissolution by the random nature of water flow at the micromodel inlet, and (2) a time-dependent number of water-flow channels are created by coupled imbibition and dissolution following completion of dominant imbibition. The number of water-flow paths, constant or transient in nature, greatly affects the overall depletion rate of scCO2 by dissolution. The average mass fraction of dissolved CO2 (dsCO2) in water effluent varies from 0.38% to 2.72% of CO2 solubility, indicating non-equilibrium scCO2 dissolution in the millimeter-scale pore network. In general, the transient depletion rate decreases as trapped, discontinuous scCO2 bubbles and clusters within water-flow paths dissolve, then remains low with dissolution of large bypassed scCO2 clusters at their interfaces with longitudinal water flow, and finally increases with coupled transverse water flow and

  10. Chemicals loading in acetylated bamboo assisted by supercritical CO2 based on phase equilibrium data

    NASA Astrophysics Data System (ADS)

    Silviana, Petermann, M.

    2015-12-01

    Indonesia has a large tropical forest. However, the deforestation still appears annually and vastly. This reason drives a use of bamboo as wood alternative. Recently, there are many modifications of bamboo in order to prolong the shelf life. Unfortunately, the processes need more chemicals and time. Based on wood modification, esterifying of bamboo was undertaken in present of a dense gas, i.e. supercritical CO2. Calculation of chemicals loading referred to ASTM D1413-99 by using the phase equilibrium data at optimum condition by a statistical design. The results showed that the acetylation of bamboo assisted by supercritical CO2 required 14.73 kg acetic anhydride/m3 of bamboo for a treatment of one hour.

  11. H2O-CO2-S fluid triggering the 1991 Mount Pinatubo climactic eruption (Philippines)

    NASA Astrophysics Data System (ADS)

    Borisova, Anastassia Y.; Toutain, Jean-Paul; Dubessy, Jean; Pallister, John; Zwick, Antoine; Salvi, Stefano

    2014-02-01

    The factors that trigger explosive eruptions often remain elusive because of the lack of direct data from representative samples. Here, we report the first micro-Raman spectroscopy measurements of fluid and multiphase inclusions trapped in quartz xenocrysts and microlites from andesitic lavas and basaltic enclaves of the 1991 Mount Pinatubo eruption. Our analyses reveal two-phase H2O-CO2-S inclusions containing a CO2-dominated phase and an aqueous sulfate-bearing liquid phase and, less commonly, anhydrite (CaSO4(solid)). The two fluid phases are low-temperature products of a supercritical H2O-CO2-S fluid which was associated with a hydrous silicate melt prior to eruption. The average density of the CO2 phase is 0.4 ± 0.2 g/cm3 at room temperature, corresponding to a supercritical fluid density of 0.6 ± 0.1 g/cm3 at the conditions of entrapment at 760-1000 °C and up to ˜260 MPa. For the first time, a dense CO2-bearing fluid is reported in Mount Pinatubo volcanic samples. We suggest that this hybrid H2O-CO2-S fluid originated from mixing between sulfur-rich basaltic and hydrous dacitic magmas, as the former was intruded into and interacted with the pre-eruptive Mount Pinatubo dacite magma reservoir, at depths of at least 10 km. Thermodynamic modeling demonstrates that part of the SO2 liberated from the intruded basaltic magma was consumed via interaction with the aqueous fluid-saturated dacitic magma according to the reaction 4SO2 basalt + 4H2Odacite = 3HSO4 - + H2S + 3H+, yielding early Cu-rich sulfides, late abundant anhydrite, and SO4-rich apatites, which are commonly found in the Mount Pinatubo dacites. We suggest that this hybrid H2O-CO2-S fluid played an important role in triggering the 1991 climactic eruption.

  12. Measurement and visualization of supercritical CO2 in dynamic phase transition

    NASA Astrophysics Data System (ADS)

    Ushifusa, Hiroyuki; Inaba, Kazuaki; Sugasawa, Konosuke; Takahashi, Kosuke; Kishimoto, Kikuo

    2015-05-01

    A new experimental device was developed to observe and measure dynamical generations of supercritical CO2 in a chamber. Temperature and pressure were measured locally by thin thermocouple and pressure transducer. The Rayleigh scattering in the chamber was visualized by a high-speed video camera. Heating of the liquid CO2 was conducted by a ceramic heater from the upper or the lower side of the chamber. In the case of heating from the upper side, temperature profile was stable and generates scCO2 slowly within a few seconds. On the other hand, in the case of heating from the lower side, scCO2 was created faster within a second but natural convection and turbulence were observed. Numerical simulations of the scCO2 creation in a chamber were also performed using the COMSOL Multiphysics with a program package for themophysical properties of CO2 called the PROPATH. It showed that scCO2 creation in the heating from the upper side was stable due to the gas-like properties of the scCO2 near the heater. In the case of heating from the lower side, density distribution depended on temperature distribution firstly but after natural convection grows, flow in the chamber became disturbed and the density distribution depended not only on temperature distribution but also on the density fluctuation caused by the convection vortexes. Same tendency was observed in experimental results.

  13. Amphiphile self-assemblies in supercritical CO2 and ionic liquids.

    PubMed

    Zhang, Jianling; Peng, Li; Han, Buxing

    2014-08-28

    Supercritical (sc) CO2 and ionic liquids (ILs) are very attractive green solvents with tunable properties. Using scCO2 and ILs as alternatives of conventional solvents (water and oil) for forming amphiphile self-assemblies has many advantages. For example, the properties and structures of the amphiphile self-assemblies in these solvents can be easily modulated by tuning the properties of solvents; scCO2 has excellent solvation power and mass-transfer characteristics; ILs can dissolve both organic and inorganic substances and their properties are designable to satisfy the requirements of various applications. Therefore, the amphiphile self-assemblies in scCO2 and ILs have attracted considerable attention in recent years. This review describes the advances of using scCO2 or/and ILs as amphiphile self-assembly media in the last decade. The amphiphile self-assemblies in scCO2 and ILs are first reviewed, followed by the discussion on combination of scCO2 and ILs in creating microemulsions or emulsions. Some future directions on the amphiphile self-assemblies in scCO2 and ILs are highlighted. PMID:25000970

  14. Residual Supercritical CO2 Saturation in an Oil-wet Sandstone: a Pore-scale Analysis

    NASA Astrophysics Data System (ADS)

    Rahman, T.; Lebedev, M.; Barifcani, A.; Iglauer, S.

    2015-12-01

    Residual supercritical CO2 (scCO2) in an oil-wet Bentheimer sandstone was imaged at high 3D resolution (3.4μm)3 with an x-ray micro-computed tomograph (μCT). The residual saturation measured (SCO2,r = 12%) was significantly lower than in an analogue strongly water-wet plug (SCO2,r = 35%). The residual CO2 was split into many small disconnected clusters, and the cluster size distributions followed a power law correlation, similar to those reported for water-wet rock. However, the CO2 was more frequently located in smaller pores than in the analogue water-wet case. On the μCT images we were able to measure scCO2-water interfacial areas and capillary pressures of each CO2 bubble in-situ. These capillary pressures (Pc) showed a distribution function which ranged from -1 MPa to +1 MPa, and peaked at Pc = 0. This variation in Pc will influence the mass transfer process (of CO2 into water) as it changes the chemical potential; but it is clear that the interfacial areas are large and thus provide a good basis for dissolution trapping. Overall we conclude that oil-wet storage rock has a significantly lower capillary trapping capacity, although we still observed residual CO2 at the pore-scale.

  15. Microbial Inactivation by Ultrasound Assisted Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Benedito, Jose; Ortuño, Carmen; Castillo-Zamudio, Rosa Isela; Mulet, Antonio

    A method combining supercritical carbon dioxide (SC-CO2) and high power ultrasound (HPU) has been developed and tested for microbial/enzyme inactivation purposes, at different process conditions for both liquid and solid matrices. In culture media, using only SC-CO2, the inactivation rate of E. coli and S. cerevisiae increased with pressure and temperature; and the total inactivation (7-8 log-cycles) was attained after 25 and 140 min of SC-CO2 (350 bar, 36 °C) treatment, respectively. Using SC-CO2+HPU, the time for the total inactivation of both microorganisms was reduced to only 1-2 min, at any condition selected. The SC-CO2+HPU inactivation of both microorganisms was slower in juices (avg. 4.9 min) than in culture media (avg. 1.5 min). In solid samples (chicken, turkey ham and dry-cured pork cured ham) treated with SC-CO2 and SC-CO2+HPU, the inactivation rate of E. coli increased with temperature. The application of HPU to the SC-CO2 treatments accelerated the inactivation rate of E. coli and that effect was more pronounced in treatments with isotonic solution surrounding the solid food samples. The application of HPU enhanced the SC-CO2 inactivation mechanisms of microorganisms, generating a vigorous agitation that facilitated the CO2 solubilization and the mass transfer process. The cavitation generated by HPU could damage the cell walls accelerating the extraction of vital constituents and the microbial death. Thus, using the combined technique, reasonable industrial processing times and mild process conditions could be used which could result into a cost reduction and lead to the minimization in the food nutritional and organoleptic changes.

  16. Ideality contours and thermodynamic regularities in supercritical molecular fluids

    NASA Astrophysics Data System (ADS)

    Desgranges, Caroline; Margo, Abigail; Delhommelle, Jerome

    2016-08-01

    Using Expanded Wang-Landau simulations, we calculate the ideality contours for 3 molecular fluids (SF6, CO2 and H2O). We analyze how the increase in polarity, and thus, in the strength of the intermolecular interactions, impacts the contours and thermodynamic regularities. This effect results in the increase in the Boyle and H parameters, that underlie the Zeno line and the curve of ideal enthalpy. Furthermore, a detailed analysis reveals that dipole-dipole interactions lead to much larger enthalpic contributions to the Gibbs free energy. This accounts for the much higher temperatures and pressures that are necessary for supercritical H2O to achieve ideal-like thermodynamic properties.

  17. Catalytic nanoreactors in continuous flow: hydrogenation inside single-walled carbon nanotubes using supercritical CO2.

    PubMed

    Chamberlain, Thomas W; Earley, James H; Anderson, Daniel P; Khlobystov, Andrei N; Bourne, Richard A

    2014-05-25

    One nanometre wide carbon nanoreactors are utilised as the reaction vessel for catalytic chemical reactions on a preparative scale. Sub-nanometre ruthenium catalytic particles which are encapsulated solely within single-walled carbon nanotubes offering a unique reaction environment are shown to be active when embedded in a supercritical CO2 continuous flow reactor. A range of hydrogenation reactions were tested and the catalyst displayed excellent stability over extended reaction times.

  18. Solute Nucleation and Growth in Supercritical Fluid Mixtures

    NASA Technical Reports Server (NTRS)

    Smedley, Gregory T.; Wilemski, Gerald; Rawlins, W. Terry; Joshi, Prakash; Oakes, David B.; Durgin, William W.

    1996-01-01

    This research effort is directed toward two primary scientific objectives: (1) to determine the gravitational effect on the measurement of nucleation and growth rates near a critical point and (2) to investigate the nucleation process in supercritical fluids to aid in the evaluation and development of existing theoretical models and practical applications. A nucleation pulse method will be employed for this investigation using a rapid expansion to a supersaturated state that is maintained for approximately 1 ms followed by a rapid recompression to a less supersaturated state that effectively terminates nucleation while permitting growth to continue. Nucleation, which occurs during the initial supersaturated state, is decoupled from growth by producing rapid pressure changes. Thermodynamic analysis, condensation modeling, apparatus design, and optical diagnostic design necessary for the initiation of a theoretical and experimental investigation of naphthalene nucleation from supercritical CO2 have been completed.

  19. Supercritical fluid chromatography/mass spectrometry in metabolite analysis.

    PubMed

    Taguchi, Kaori; Fukusaki, Eiichiro; Bamba, Takeshi

    2014-01-01

    Supercritical fluid chromatography (SFC) owes many of its advantages to the properties of supercritical CO2, which possesses benefits as mobile phase. SFC has recently gained attention as a separation technique because it can be utilized for not only non-polar but also polar compound analysis. In addition, MS is widely adopted for SFC, and the options for MS are equivalent to liquid chromatography. Sensitive and selective detection is crucial in metabolite analysis. The SFC/MS system can be an alternative approach to liquid chromatography, as can metabolite analysis using packed-column SFC in biosamples. In this review we cover the fundamentals of SFC in combination with MS, and discuss the results of metabolite analysis using SFC/MS.

  20. Caryocar brasiliense supercritical CO2 extract possesses antimicrobial and antioxidant properties useful for personal care products

    PubMed Central

    2014-01-01

    Background The cosmetic and pharmaceutical industries have an increasing interest in replacing synthetic antimicrobials in dermatological products due to increased microbial resistance to conventional antimicrobial agents. Pequi (Caryocar brasiliense) is a native fruit tree of the Brazilian Cerrado, specifically used in cosmetics, in the food industry, and for medicinal purposes. Leishmanicidal and antifungal activities have been reported previously. This study was designed to evaluate the antimicrobial and antioxidant activities of a C. brasiliense extract obtained by supercritical CO2 extraction. Methods The minimum inhibitory concentrations (MICs) against Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus were determined by the classical microdilution method. Antiseptic activity against these organisms was evaluated by the plate diffusion method. The antioxidant potential of the extract was evaluated using a method based on the oxidation of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS). The extract’s chemical profile was analyzed for the presence of alkaloids, saponins, anthraquinones, steroids, tannins, flavonoids, and phenolic compounds according to standard colorimetric methods. Results The C. brasiliense supercritical CO2 extract exhibits antimicrobial activity against all bacteria tested. It also possesses antioxidant activity, when compared to a vitamin E standard. Conclusions The C. brasiliense supercritical CO2 extract may be useful for the development of personal care products, primarily for antiseptic skin products that inactivate, reduce, prevent, or arrest the growth of microorganisms with the inherent intent to mitigate or prevent disease as well as products that minimize damage caused by free radicals. PMID:24565304

  1. Supercritical CO2-assisted embossing for studying cell behaviour on microtextured surfaces.

    PubMed

    Fujita, Satoshi; Ono, Daizaburo; Ohshima, Masahiro; Iwata, Hiroo

    2008-12-01

    Recently, cell responses to micro- and nanoscale structures have attracted much attention. Although interesting phenomena have been observed, we have encountered some difficulties in elucidating purely topographical effects on cell behaviour. These problems are partially attributable to the introduction of functional groups and the persistence of chemicals during surface processing. In this study, we introduced supercritical CO(2)-assisted embossing, which plasticizes a polycarbonate plate by dissolving supercritical CO(2) and thus can emboss wide-scale patterns onto the plate at a lower temperature than the polycarbonate glass transition temperature. Uniform micro- and nanopatterned surfaces were observed across the whole area of the polycarbonate plate surfaces. Nickel, fluorine, and nitrogen were not detected on the fabricated surfaces, and the surface carbon-to-oxygen ratios were equivalent to the theoretical ratio (C:O=84.2:15.8) calculated from the polycarbonate molecular structure. Human mesenchymal stem cells were cultured on the fabricated microlens and nanogroove substrata. Cell-adhered areas became smaller on the microlens than on non-treated polycarbonate. Meanwhile, cells aligned along the ridges of nanogrooves with valleys deeper than 90 nm. This supercritical CO(2)-assisted embossing can produce fine substrates for studying the effects of surface topography of synthetic materials on cell behaviours.

  2. Supercritical CO2-assisted embossing for studying cell behaviour on microtextured surfaces.

    PubMed

    Fujita, Satoshi; Ono, Daizaburo; Ohshima, Masahiro; Iwata, Hiroo

    2008-12-01

    Recently, cell responses to micro- and nanoscale structures have attracted much attention. Although interesting phenomena have been observed, we have encountered some difficulties in elucidating purely topographical effects on cell behaviour. These problems are partially attributable to the introduction of functional groups and the persistence of chemicals during surface processing. In this study, we introduced supercritical CO(2)-assisted embossing, which plasticizes a polycarbonate plate by dissolving supercritical CO(2) and thus can emboss wide-scale patterns onto the plate at a lower temperature than the polycarbonate glass transition temperature. Uniform micro- and nanopatterned surfaces were observed across the whole area of the polycarbonate plate surfaces. Nickel, fluorine, and nitrogen were not detected on the fabricated surfaces, and the surface carbon-to-oxygen ratios were equivalent to the theoretical ratio (C:O=84.2:15.8) calculated from the polycarbonate molecular structure. Human mesenchymal stem cells were cultured on the fabricated microlens and nanogroove substrata. Cell-adhered areas became smaller on the microlens than on non-treated polycarbonate. Meanwhile, cells aligned along the ridges of nanogrooves with valleys deeper than 90 nm. This supercritical CO(2)-assisted embossing can produce fine substrates for studying the effects of surface topography of synthetic materials on cell behaviours. PMID:18793798

  3. Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O

    SciTech Connect

    Capobianco, Ryan; Gruszkiewicz, Miroslaw {Mirek} S; Wesolowski, David J; Cole, David R; Bodnar, Robert

    2013-01-01

    The need for accurate modeling of fluid-mineral processes over wide ranges of temperature, pressure and composition highlighted considerable uncertainties of available property data and equations of state, even for the CO2 + H2O binary system. In particular, the solubility, activity, and ionic dissociation equilibrium data for the CO2-rich phase, which are essential for understanding dissolution/precipitation, fluid-matrix reactions, and solute transport, are uncertain or missing. In this paper we report the results of a new experimental study of volumetric and phase equilibrium properties of CO2 + H2O, to be followed by measurements for bulk and confined multicomponent fluid mixtures. Mixture densities were measured by vibrating tube densimetry (VTD) over the entire composition range at T = 200 and 250 C and P = 20, 40, 60, and 80 MPa. Initial analysis of the mutual solubilities, determined from volumetric data, shows good agreement with earlier results for the aqueous phase, but finds that the data of Takenouchi and Kennedy (1964) significantly overestimated the solubility of water in supercritical CO2 (by a factor of more than two at 200 C). Resolving this well-known discrepancy will have a direct impact on the accuracy of predictive modeling of CO2 injection in geothermal reservoirs and geological carbon sequestration through improved equations of state, needed for calibration of predictive molecular-scale models and large-scale reactive transport simulations.

  4. [Optimization of supercritical fluid extraction of bioactive components in Ligusticum chuanxiong by orthogonal array design].

    PubMed

    Hu, Li-Cui; Wu, Xun; Yang, Xue-Dong

    2013-10-01

    With the yields of ferulic acid, coniferylferulate, Z-ligustilide, senkyunolide A, butylidenephthalide, butylphthalide, senkyunolide I, senkyunolide H, riligustilide, levistolide A, and total pharmacologically active ingredient as evaluation indexes, the extraction of Ligusticum chuanxiong by supercritical fluid technology was investigated through an orthogonal experiment L9 (3(4)). Four factors, namely temperature, pressure, flow rate of carbon dioxide, co-solvent concentration of the supercritical fluid, were investigated and optimized. Under the optimized conditions, namely 65 degrees C of temperature, 35 MPa of pressure, 1 L x min(-1) of CO2 flow rate, 8% of co-solvent concetration, supercritical fluid extraction could achieve a better yield than the conventional reflux extraction using methanol. And the supercritical fluid extraction process was validated to be stable and reliable. PMID:24490558

  5. 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.

  6. Supercritical CO2 foamed polycaprolactone scaffolds for controlled delivery of 5-fluorouracil, nicotinamide and triflusal.

    PubMed

    Salerno, Aurelio; Saurina, Javier; Domingo, Concepción

    2015-12-30

    The manufacture of porous polycaprolactone (PCL) scaffolds containing three different drugs, namely 5-fluorouracil, nicotinamide and triflusal, was investigated in this work with the aim of obtaining bioactive systems with controlled drug delivery capabilities. The scaffolds were prepared by means of a supercritical CO2 (scCO2) foaming technique by optimizing the drug loading process. This was achieved by dissolving the drugs in organic solvents miscible with scCO2 and by mixing these drug/solvent solutions with PCL powder. The as prepared mixtures were further compressed to eliminate air bubbles and finally processed by the scCO2 foaming technique. ScCO2 saturation and foaming conditions were optimized to create the porosity within the samples and to allow for the concomitant removal of the organic solvents. Physical and chemical properties of porous scaffolds, as well as drug content and delivery profiles, were studied by HPLC. The results of this study demonstrated that the composition of the starting PCL/drug/solvent mixtures affected polymer crystallization, scaffold morphology and pore structure features. Furthermore, it was found that drug loading efficiency depended on both initial solution composition and drug solubility in scCO2. Nevertheless, in the case of highly scCO2-soluble drugs, such as triflusal, loading efficiency was improved by adding a proper amount of free drug inside of the pressure vessel. The drug delivery study indicated that release profiles depended mainly upon scaffolds composition and pore structure features. PMID:26570986

  7. Multiphase Compositional Modelling of CO2 Injection Under Sub- and Supercritical Conditions

    NASA Astrophysics Data System (ADS)

    Afanasyev, Andrey

    2013-04-01

    Modelling of CO2-H2O mixture flows in a porous media under subcritical conditions remains a challenging issue for carbon sequestration and possible leakage scenarios. Currently, there is no widely used and generally accepted numerical model that can simulate three-phase flows with both gaseous and liquid CO2-rich phases. We propose a new compositional modelling approach for sub- and supercritical three-phase flows of water, liquid CO2 and gaseous CO2. The new approach is based on the calculation of the thermodynamic potential of the mixture as a function of pressure, total enthalpy and mixture composition and storing it values as a spline table, which is then used for the hydrodynamic simulation. A three-parametric generalisation of the Peng-Robinson equation of state is used to fit the experimental data on CO2-H2O mixture properties. Using the developed approach, we assess several sample problems of CO2 injection in shallow reservoirs for the purpose of testing the model. We provide the simulation results for a simple 1D problem with a homogeneous reservoir and for a more complicated 2D problem with a highly heterogeneous reservoir using data from the 10th SPE comparative project reservoir. We analyse the temperature variations in the reservoir due to the dissolution of CO2 in water and the evaporation of liquid CO2 under subcritical conditions. The interplay of these processes results in a complicated non-monotonic temperature distribution. At different distances from the CO2 injection point, the temperature can either decrease or increase with respect to the reservoir temperature before injection. The main phenomenon responsible for the considerable temperature decline around the CO2 injection point is the liquid CO2 evaporation process. We also consider parallel simulations of supercritical CO2 plume evolution at Johansen formation. Firstly, we consider a test scenario using a simplified geological model. Both the free CO2 phase saturation and the integral

  8. 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.

  9. How Do Deep Saline Aquifer Microbial Communities Respond to Supercritical CO2 Injection?

    NASA Astrophysics Data System (ADS)

    Mu, A.; Billman-Jacobe, H.; Boreham, C.; Schacht, U.; Moreau, J. W.

    2011-12-01

    Carbon Capture and Storage (CCS) is currently seen as a viable strategy for mitigating anthropogenic carbon dioxide pollution. The Cooperative Research Centre for Greenhouse Gas Technologies (CO2CRC) is currently conducting a field experiment in the Otway Basin (Australia) studying residual gas saturation in the water-saturated reservoir of the Paaratte Formation. As part of this study, a suite of pre-CO2 injection water samples were collected from approximately 1400 meters depth (60°C, 13.8 MPa) via an in situ sampling system. The in situ sampling system isolates aquifer water from sources of contamination while maintaining the formation pressure. Whole community DNA was extracted from these samples to investigate the prokaryotic biodiversity of the saline Paaratte aquifer (EC = 1509.6 uS/cm). Bioinformatic analysis of preliminary 16S ribosomal gene data revealed Thermincola, Acinetobacter, Sphingobium, and Dechloromonas amongst the closest related genera to environmental clone sequences obtained from a subset of pre-CO2 injection groundwater samples. Epifluorescent microscopy with 4',6-diamidino-2-phenylindole (DAPI) highlighted an abundance of filamentous cells ranging from 5 to 45 μM. Efforts are currently directed towards utilising a high throughput sequencing approach to capture an exhaustive profile of the microbial diversity of the Paaratte aquifer CO2 injection site, and to understand better the response of in situ microbial populations to the injection of large volumes (e.g. many kilotonnes) of supercritical CO2 (sc-CO2). Sequencing results will be used to direct cultivation efforts towards enrichment of a CO2-tolerant microorganism. Understanding the microbial response to sc-CO2 is an integral aspect of carbon dioxide storage, for which very little information exists in the literature. This study aims to elucidate molecular mechanisms, through genomic and cultivation-based methods, for CO2 tolerance with the prospect of engineering biofilms to enhance

  10. [Study on supercritical CO2 extraction of xiaoyaosan and its GC-MS fingerprint].

    PubMed

    Zuo, Ya-Mei; Tian, Jun-Sheng; Guo, Xiao-Qing; Zhou, Yu-Zhi; Gao, Xiao-Xia; Qin, Xue-Mei

    2014-02-01

    To determine the optimum conditions of supercritical CO2 extraction of Xiaoyaosan, and establish its fingerprint by gas chromatography-mass spectrometry (GC-MS), the yield of extract were investigated, an orthogonal test was used to quantify the effects of extraction temperature, pressure, CO2 flow rate and time, and fingerprint analysis of different batches of extracts were by GC-MS. The optimal extraction conditions were determined as follows: extraction pressure 20 MPa, extraction temperature 50 degrees C, CO2 flow rate 25 kg x h(-1), extraction time 3 h, and average yield 2.2%. The GC-MS fingerprint was established and 27 common peaks were found, whose contents add up to 81.89% of the total peak area. Among them, 21 compounds were identified, accounting for 53.20% of the total extract. The extraction process is reasonable and favorable for industrial production. The GC-MS method is accurate, reliable, reproducible, and can be used for quality control of supercritical CO2 extract from Xiaoyaosan.

  11. Experimental investigation of supercritical CO2 trapping mechanisms at the Intermediate Laboratory Scale in well-defined heterogeneous porous media

    DOE PAGES

    Trevisan, Luca; Pini, Ronny; Cihan, Abdullah; Birkholzer, Jens T.; Zhou, Quanlin; Illangasekare, Tissa H.

    2014-12-31

    The heterogeneous nature of typical sedimentary formations can play a major role in the propagation of the CO2 plume, eventually dampening the accumulation of mobile phase underneath the caprock. From core flooding experiments, it is also known that contrasts in capillary threshold pressure due to different pore size can affect the flow paths of the invading and displaced fluids and consequently influence the build- up of non-wetting phase (NWP) at interfaces between geological facies. The full characterization of the geologic variability at all relevant scales and the ability to make observations on the spatial and temporal distribution of the migrationmore » and trapping of supercritical CO2 is not feasible from a practical perspective. To provide insight into the impact of well-defined heterogeneous systems on the flow dynamics and trapping efficiency of supercritical CO2 under drainage and imbibition conditions, we present an experimental investigation at the meter scale conducted in synthetic sand reservoirs packed in a quasi-two-dimensional flow-cell. Two immiscible displacement experiments have been performed to observe the preferential entrapment of NWP in simple heterogeneous porous media. The experiments consisted of an injection, a fluid redistribution, and a forced imbibition stages conducted in an uncorrelated permeability field and a homogeneous base case scenario. We adopted x-ray attenuation analysis as a non-destructive technique that allows a precise measurement of phase saturations throughout the entire flow domain. By comparing a homogeneous and a heterogeneous scenario we have identified some important effects that can be attributed to capillary barriers, such as dampened plume advancement, higher non-wetting phase saturations, larger contact area between the injected and displaced phases, and a larger range of non-wetting phase saturations.« less

  12. Photoluminescence of fluoroacrylate polymers impregnated with Eu(bta)3 using supercritical CO2

    NASA Astrophysics Data System (ADS)

    Gerasimova, V. I.; Antoshkov, A. A.; Zavorotny, Yu. S.; Lemenovskii, D. A.

    2012-05-01

    Optical properties (photoluminescence and absorption) of Eu(bta)3(B) n (B = H2O or 1,10-phenanthroline) polycrystalline powders and fluoroacrylate polymers (FAPs) impregnated with these compounds using supercritical CO2 (SC CO2) were investigated. It was established that impregnation of Eu(bta)3phen into the FAPs using an SC CO2 solution was difficult to achieve. The type of B (ancillary ligand) and the polymer matrix were shown to influence the temperature quenching of photoluminescence of Eu3+ ions in the range 25-100°C. A comparative analysis of quantum yields (λex = 300 and 380 nm) and photoluminescence decay times (λex = 337.1 nm) for Eu(bta)3B n and for Eu(bta)3B n -doped FAPs was performed.

  13. Drug loading of polymer implants by supercritical CO2 assisted impregnation: A review.

    PubMed

    Champeau, M; Thomassin, J-M; Tassaing, T; Jérôme, C

    2015-07-10

    Drug loaded implants also called drug-eluting implants have proven their benefits over simple implants. Among the developed manufacturing processes, the supercritical CO2 (scCO2) assisted impregnation has attracted growing attention to load Active Pharmaceutical Ingredients into polymer implants since it enables to recover a final implant free of any solvent residue and to operate under mild temperature which is suitable for processing with thermosensitive drugs. This paper is a review of the state-of-the-art and the application of the scCO2 assisted impregnation process to prepare drug-eluting implants. It introduces the process and presents its advantages for biomedical applications. The influences of the characteristics of the implied binary systems and of the experimental conditions on the drug loading are described. Then, the various current applications of this process for manufacturing drug-eluting implants are reviewed. Finally, the new emerging variations of this process are described.

  14. Extraction of purine alkaloids from maté (Ilex paraguariensis) using supercritical CO(2).

    PubMed

    Saldaña, M D; Mohamed, R S; Baer, M G; Mazzafera, P

    1999-09-01

    Experimental data for the supercritical CO(2) extraction of purine alkaloids (caffeine, theobromine, and theophylline) from ground herbal maté tea (Ilex paraguaryensis) using a high-pressure apparatus are presented. Caffeine, theophylline, and theobromine were identified in the extracted fractions using HPLC. Results indicated a much higher CO(2) selectivity for caffeine in comparison with those for theophylline and theobromine. Solubilities of pure compounds in carbon dioxide were also determined at 313.2, 323.2, 338.2, and 343.2 K, and pressures ranging from 14 to 24 MPa. Caffeine solubility exhibited a retrograde behavior with temperature while theophylline and theobromine manifested a normal behavior at conditions explored in this study. Solubilities in binary CO(2)/purine alkaloid model systems were much higher than those obtained during extraction of maté tea, demonstrating the difficulty of using binary data in predicting complex multicomponent behavior.

  15. Processing of Materials for Regenerative Medicine Using Supercritical Fluid Technology.

    PubMed

    García-González, Carlos A; Concheiro, Angel; Alvarez-Lorenzo, Carmen

    2015-07-15

    The increase in the world demand of bone and cartilage replacement therapies urges the development of advanced synthetic scaffolds for regenerative purposes, not only providing mechanical support for tissue formation, but also promoting and guiding the tissue growth. Conventional manufacturing techniques have severe restrictions for designing these upgraded scaffolds, namely, regarding the use of organic solvents, shearing forces, and high operating temperatures. In this context, the use of supercritical fluid technology has emerged as an attractive solution to design solvent-free scaffolds and ingredients for scaffolds under mild processing conditions. The state-of-the-art on the technological endeavors for scaffold production using supercritical fluids is presented in this work with a critical review on the key processing parameters as well as the main advantages and limitations of each technique. A special stress is focused on the strategies suitable for the incorporation of bioactive agents (drugs, bioactive glasses, and growth factors) and the in vitro and in vivo performance of supercritical CO2-processed scaffolds. PMID:25587916

  16. Remote-Raman spectroscopic study of minerals under supercritical CO2 relevant to Venus exploration.

    PubMed

    Sharma, Shiv K; Misra, Anupam K; Clegg, Samuel M; Barefield, James E; Wiens, Roger C; Acosta, Tayro E; Bates, David E

    2011-10-01

    The authors have utilized a recently developed compact Raman spectrometer equipped with an 85 mm focal length (f/1.8) Nikon camera lens and a custom mini-ICCD detector at the University of Hawaii for measuring remote Raman spectra of minerals under supercritical CO(2) (Venus chamber, ∼102 atm pressure and 423 K) excited with a pulsed 532 nm laser beam of 6 mJ/pulse and 10 Hz. These experiments demonstrate that by focusing a frequency-doubled 532 nm Nd:YAG pulsed laser beam with a 10× beam expander to a 1mm spot on minerals located at 2m inside a Venus chamber, it is possible to measure the remote Raman spectra of anhydrous sulfates, carbonates, and silicate minerals relevant to Venus exploration during daytime or nighttime with 10s integration time. The remote Raman spectra of gypsum, anhydrite, barite, dolomite and siderite contain fingerprint Raman lines along with the Fermi resonance doublet of CO(2). Raman spectra of gypsum revealed dehydration of the mineral with time under supercritical CO(2) at 423 K. Fingerprint Raman lines of olivine, diopside, wollastonite and α-quartz can easily be identified in the spectra of these respective minerals under supercritical CO(2). The results of the present study show that time-resolved remote Raman spectroscopy with a compact Raman spectrometer of moderate resolution equipped with a gated intensified CCD detector and low power laser source could be a potential tool for exploring Venus surface mineralogy both during daytime and nighttime from a lander.

  17. Dry powders of stable protein formulations from aqueous solutions prepared using supercritical CO(2)-assisted aerosolization.

    PubMed

    Sellers, S P; Clark, G S; Sievers, R E; Carpenter, J F

    2001-06-01

    We report on the use of a new supercritical carbon dioxide-assisted aerosolization coupled with bubble drying technology to prepare stabilized, dry, finely divided powders from aqueous protein formulations. In this study, the feasibility of this new technology was tested using two model proteins, lysozyme and lactate dehydrogenase (LDH). In the absence of excipients, lysozyme was observed to undergo perturbations of secondary structure observed by solid-state infrared spectroscopy. In the presence of sucrose, this unfolding was minimized. Lysozyme did not, however, undergo irreversible loss of activity, as all lysozyme powders generated by supercritical CO(2)-assisted aerosolization (with or without excipients) regained almost complete activity on reconstitution. The more labile LDH suffered irrecoverable loss of activity on reconstituting after supercritical CO(2)-assisted aerosolization and bubble drying in the absence of carbohydrate stabilizers. LDH could be stabilized throughout the nebulization, drying, and rehydration processes with the addition of sucrose, and almost complete preservation of activity was achieved with the further addition of a surface active agent, such as Tween 20, to the aqueous formulation prior to processing.

  18. Pt and Pt-Ru/Carbon Nanotube Nanocomposites Synthesized in Supercritical Fluid as Electrocatalysts for Low-Temperature Fuel Cells

    SciTech Connect

    Lin, Yuehe; Cui, Xiaoli; Wang, Jun; Yen, Clive; Wai, Chien M.

    2006-06-01

    In recent years, the use of supercritical fluids (SCFs) for the synthesis and processing of nanomaterials has proven to be a rapid, direct, and clean approach to develop nanomaterials and nanocomposites. The application of supercritical fluid technology can result in products (and processes) that are cleaner, less expensive, and of higher quality than those that are produced using conventional technologies and solvents. In this work, carbon nanotube (CNT)-supported Pt and Pt-Ru nanoparticles catalysts have been synthesized in supercritical carbon dioxide (scCO2). The experimental results demonstrate that Pt, Pt-Ru/CNT nanocomposites synthesized in supercritical carbon dioxide are effective electrocatalysts for low-temperature fuel cells.

  19. Silicate Carbonation in Supercritical CO2 Containing Dissolved H2O: An in situ High Pressure X-Ray Diffraction Study

    SciTech Connect

    Schaef, Herbert T.; Miller, Quin RS; Thompson, Christopher J.; Loring, John S.; Bowden, Mark E.; Arey, Bruce W.; McGrail, B. Peter; Rosso, Kevin M.

    2013-06-30

    Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring between supercritical CO2 containing water and the silicate minerals forsterite (Mg2SiO4), wollastonite (CaSiO3), and enstatite (MgSiO3). This study utilizes newly developed in situ high pressure x-ray diffraction (HXRD) and in situ infra red (IR) to examine mineral transformation reactions. Forsterite and enstatite were selected as they are important minerals present in igneous and mafic rocks and have been the subject of a large number of aqueous dissolution studies that can be compared with non-aqueous fluid tests in this study. Wollastonite, classified as a pyroxenoid (similar to a pyroxene), was chosen as a suitably fast reacting proxy for examining silicate carbonation processes associated with a wet scCO2 fluid as related to geologic carbon sequestration. The experiments were conducted under modest pressures (90 to 160 bar), temperatures between 35° to 70° C, and varying concentrations of dissolved water. Under these conditions scCO2 contains up to 3,500 ppm dissolved water.

  20. Geophysical Signatures to Monitor Fluids and Mineralization for CO2 Sequestration in Basalts

    NASA Astrophysics Data System (ADS)

    Otheim, L. T.; Adam, L.; Van Wijk, K.; Batzle, M. L.; Mcling, T. L.; Podgorney, R. K.

    2011-12-01

    Carbon dioxide sequestration in large reservoirs can reduce emissions of this green house gas into the atmosphere. Basalts are promising host rocks due to their volumetric extend, worldwide distribution, and recent observations that CO2-water mixtures react with basalt minerals to precipitate as carbonate minerals, trapping the CO2. The chemical reaction between carbonic acid and minerals rich in calcium, magnesium and iron precipitates carbonates in the pore space. This process would increase the elastic modulus and velocity of the rock. At the same time, the higher compressibility of CO2 over water changes the elastic properties of the rock, decreasing the saturated rock bulk modulus and the P-wave velocity. Reservoirs where the rock properties change as a result of fluid or pressure changes are commonly monitored with seismic methods. Here we present experiments to study the feasibility of monitoring CO2 migration in a reservoir and CO2-rock reactions for a sequestration scenario in basalts. Our goal is to measure the rock's elastic response to mineralization with non-contacting ultrasonic lasers, and the effect of fluid substitution at reservoir conditions at seismic and ultrasonic frequencies. For the fluid substitution experiment we observe changes in the P- and S-wave velocities when saturating the sample with super-critical (sc) CO2, CO2-water mixtures and water alone for different pore and confining pressures. The bulk modulus of the rock is significantly dependent on frequency in the 2~to 106~Hz range, for CO2-water mixtures and pure water saturations. Dry and pure CO2 (sc or gas) do not show a frequency dependence on the modulus. Moreover, the shear wave modulus is not dispersive for either fluid. The frequency dependence of the elastic parameters is related to the attenuation (1/Q) of the rock. We will show the correlation between frequency dependent moduli and attenuation data for the different elastic moduli of the rocks. Three other basalt samples

  1. 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

  2. Comparative Reactivity Study of Natural Silicate Minerals in Wet Supercritical CO2 By In Situ Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Thompson, C.; Schaef, T.; Miller, Q. R.; Loring, J. S.; Wang, Z.; Johnson, K. T.; McGrail, P.

    2012-12-01

    Long-term storage of CO2 in deep geologic reservoirs is one of the strategies being developed and implemented for reducing anthropogenic emissions of CO2 into the atmosphere. Reservoirs containing basalt or peridotite have the potential to permanently entrap the CO2 as silicate minerals react with the CO2 and formation waters to form stable carbonate minerals. Although the relevant reactions have been well studied in the aqueous phase, comparatively little work has focused on silicate mineral reactivity in the CO2-rich fluid containing dissolved water at conditions relevant to geologic carbon sequestration. In this study, we used in situ infrared spectroscopy to investigate the carbonation of naturally occurring samples of San Carlos olivine (Mg2SiO4), Bramble enstatite (MgSiO3), and a Hawaiian picritic basalt rich in olivine. To enhance reactivity, subsamples were micronized to obtain higher surface area materials, in the range of 14 to 23 m2g-1. Experiments were carried out at 50 °C and 91 bar by circulating a stream of dry or wet supercritical CO2 (scCO2) past a sample overlayer deposited on the window of a high-pressure infrared flow cell. Water concentrations ranged from 0% to 135% relative to saturation, and transmission-mode absorbance spectra were recorded as a function of time for 24 hours. In experiments with excess water, a controlled temperature gradient was used to intentionally condense a film of liquid water on the overlayers' surfaces. No discernible reaction was detected when the samples were exposed to dry scCO2. When water was added to the scCO2, a thin film of liquid-like water formed on the surfaces of each sample, followed by spectral evidence of carbonation. The extents of reaction were dependent on both the thickness of the water films and the materials being tested. The thinnest water film was associated with the Bramble enstatite, which also appeared minimally reactive. The Hawaiian picritic basalt was slightly more reactive but contained

  3. Investigation of attractive and repulsive interactions associated with ketones in supercritical CO2, based on Raman spectroscopy and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Kajiya, Daisuke; Saitow, Ken-ichi

    2013-08-01

    Carbonyl compounds are solutes that are highly soluble in supercritical CO2 (scCO2). Their solubility governs the efficiency of chemical reactions, and is significantly increased by changing a chromophore. To effectively use scCO2 as solvent, it is crucial to understand the high solubility of carbonyl compounds, the solvation structure, and the solute-solvent intermolecular interactions. We report Raman spectroscopic data, for three prototypical ketones dissolved in scCO2, and four theoretical analyses. The vibrational Raman spectra of the C=O stretching modes of ketones (acetone, acetophenone, and benzophenone) were measured in scCO2 along the reduced temperature Tr = T/Tc = 1.02 isotherm as a function of the reduced density ρr = ρ/ρc in the range 0.05-1.5. The peak frequencies of the C=O stretching modes shifted toward lower energies as the fluid density increased. The density dependence was analyzed by using perturbed hard-sphere theory, and the shift was decomposed into attractive and repulsive energy components. The attractive energy between the ketones and CO2 was up to nine times higher than the repulsive energy, and its magnitude increased in the following order: acetone < acetophenone < benzophenone. The Mulliken charges of the three solutes and CO2 molecules obtained by using quantum chemistry calculations described the order of the magnitude of the attractive energy and optimized the relative configuration between each solute and CO2. According to theoretical calculations for the dispersion energy, the dipole-induced-dipole interaction energy, and the frequency shift due to their interactions, the experimentally determined attractive energy differences in the three solutes were attributed to the dispersion energies that depended on a chromophore attached to the carbonyl groups. It was found that the major intermolecular interaction with the attractive shift varied from dipole-induced dipole to dispersion depending on the chromophore in the ketones in

  4. Partitioning of Organic Compounds into Supercritical CO2 in Depleted Oil Reservoirs - A Review

    NASA Astrophysics Data System (ADS)

    Burant, A.; Lowry, G. V.; Karamalidis, A.

    2012-12-01

    Depleted oil reservoirs, with enhanced oil recovery, will be one of the first adopters of carbon capture and storage (CCS), which is a promising mitigation strategy for global climate change. The large scale implementation of CCS mandates better understanding of the risks associated with CO2 injection, especially in regards to potential leakage of the stored CO2. Organics, in the residual oil and dissolved in the brine, can partition into supercritical CO2 (sc-CO2) and move with that phase if it leaks. This review presents an overview of the thermodynamic models and trends in experimental partitioning data needed to understand what compounds may be expected to move with the sc-CO2. There are two main types of thermodynamic models used for predicting the solubility of organic compounds in sc-CO2, equations of state and quantitative structure activity relationships. Both can predict the partitioning behavior of one compound in sc-CO2, however only equations of state can predict solubility in multicomponent systems. In addition, equations of state have been developed to determine the effect of electrolytes on the partitioning behavior of organics dissolved in brines. There are three main trends in the partitioning behavior of organics in sc-CO2: Pure phase solubility follows trends in vapor pressure; compounds with higher volatility have higher solubility in sc-CO2. Second, the partitioning from water to sc-CO2 follows trends in Henry's constants, which follow the relative solubility of a compound in both the sc-CO2 and aqueous phases. Thirdly, the solubility of a compound can be enhanced by the presence of another; highly volatile compounds enhance the solubility of compounds with lower volatility. Finally, the review presents the gaps in experimental research that can be used to improve the modeling of the partitioning behavior of organics in sc-CO2, specifically in regards to co-solvency effects and the effects of electrolytes on the partitioning of dissolved

  5. MOLECULAR DESIGN OF COLLOIDS IN SUPERCRITICAL FLUIDS

    SciTech Connect

    Keith P. Johnston

    2009-04-06

    The environmentally benign, non-toxic, non-flammable fluids water and carbon dioxide (CO2) are the two most abundant and inexpensive solvents on earth. Emulsions of these fluids are of interest in many industrial processes, as well as CO2 sequestration and enhanced oil recovery. Until recently, formation of these emulsions required stabilization with fluorinated surfactants, which are expensive and often not environmentally friendly. In this work we overcame this severe limitation by developing a fundamental understanding of the properties of surfactants the CO2-water interface and using this knowledge to design and characterize emulsions stabilized with either hydrocarbon-based surfactants or nanoparticle stabilizers. We also discovered a new concept of electrostatic stabilization for CO2-based emulsions and colloids. Finally, we were able to translate our earlier work on the synthesis of silicon and germanium nanocrystals and nanowires from high temperatures and pressures to lower temperatures and ambient pressure to make the chemistry much more accessible.

  6. Assessment of Supercritical Fluid Extraction Use in Whole Sediment Toxicity Identification Evaluations

    EPA Science Inventory

    In this investigation, supercritical fluid extraction (SFE) with pure CO2 was assessed as a confirmatory tool in Phase III of whole sediment toxicity identification evaluations (TIEs). The SFE procedure was assessed on two reference sediments and three contaminated sediments usi...

  7. Silver nanoparticles generated by pulsed laser ablation in supercritical CO2 medium

    NASA Astrophysics Data System (ADS)

    Machmudah, Siti; Sato, Takayuki; Wahyudiono; Sasaki, Mitsuru; Goto, Motonobu

    2012-03-01

    Pulsed laser ablation (PLA) has been widely employed in industrial and biological applications and in other fields. The environmental conditions in which PLA is conducted are important parameters that affect both the solid particle cloud and the deposition produced by the plume. In this work, the generation of nanoparticles (NPs) has been developed by performing PLA of silver (Ag) plates in a supercritical CO2 medium. Ag NPs were successfully generated by allowing the selective generation of clusters. Laser ablation was performed with an excitation wavelength of 532 nm under various pressures and temperatures of CO2 medium. On the basis of the experimental result, both surface of the irradiated Ag plate and structure of Ag NPs were significantly affected by the changes in supercritical CO2 pressure and temperature. With increasing irradiation pressure, plume deposited in the surrounding crater created by the ablation was clearly observed. In Field Emission Scanning Electron Microscopy (FE-SEM) the image of the generated Ag NPs on the silicon wafer and the morphology of Ag particles were basically a sphere-like structure. Ag particles contain NPs with large-varied diameter ranging from 5 nm to 1.2 μm. The bigger Ag NPs melted during the ablation process and then ejected smaller spherical Ag NPs, which formed nanoclusters attached on the molten Ag NPs. The smaller Ag NPs were also formed around the bigger Ag NPs. Based on the results, this new method can also be used to obtain advanced nano-structured materials.

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

    SciTech Connect

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

    2012-11-25

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

  9. Experimental study on effects of geologic heterogeneity in enhancing dissolution trapping of supercritical CO2

    NASA Astrophysics Data System (ADS)

    Agartan, Elif; Trevisan, Luca; Cihan, Abdullah; Birkholzer, Jens; Zhou, Quanlin; Illangasekare, Tissa H.

    2015-03-01

    Dissolution trapping is one of the primary mechanisms that enhance the storage security of supercritical carbon dioxide (scCO2) in saline geologic formations. When scCO2 dissolves in formation brine produces an aqueous solution that is denser than formation brine, which leads to convective mixing driven by gravitational instabilities. Convective mixing can enhance the dissolution of CO2 and thus it can contribute to stable trapping of dissolved CO2. However, in the presence of geologic heterogeneities, diffusive mixing may also contribute to dissolution trapping. The effects of heterogeneity on mixing and its contribution to stable trapping are not well understood. The goal of this experimental study is to investigate the effects of geologic heterogeneity on mixing and stable trapping of dissolved CO2. Homogeneous and heterogeneous media experiments were conducted in a two-dimensional test tank with various packing configurations using surrogates for scCO2 (water) and brine (propylene glycol) under ambient pressure and temperature conditions. The results show that the density-driven flow in heterogeneous formations may not always cause significant convective mixing especially in layered systems containing low-permeability zones. In homogeneous formations, density-driven fingering enhances both storage in the deeper parts of the formation and contact between the host rock and dissolved CO2 for the potential mineralization. On the other hand, for layered systems, dissolved CO2 becomes immobilized in low-permeability zones with low-diffusion rates, which reduces the risk of leakage through any fault or fracture. Both cases contribute to the permanence of the dissolved plume in the formation.

  10. Supercritical fluid extraction of mercury species.

    PubMed

    Foy, G P; Pacey, G E

    2003-12-23

    Supercritical fluid extraction was used to recover organic and inorganic mercury species. Variations in pressure, water, methanol, and chelator create methods that allowed separation of inorganic from organic mercury species. When extracted using a compromised set of extraction conditions, the order of extraction was methyl, phenyl and inorganic mercury. For the individually optimized conditions, quantitative recoveries were observed. Level as low as 20 ppb were extracted and then determined using ICP.

  11. The U-tube: A novel system for acquiring borehole fluid samples from a deep geologic CO2 sequestration experiment

    USGS Publications Warehouse

    Freifeld, B.M.; Trautz, R.C.; Kharaka, Y.K.; Phelps, T.J.; Myer, L.R.; Hovorka, S.D.; Collins, D.J.

    2005-01-01

    A novel system has been deployed to obtain geochemical samples of water and gas, at in situ pressure, during a geologic CO2 sequestration experiment conducted in the Frio brine aquifer in Liberty County, Texas. Project goals required high-frequency recovery of representative and uncontaminated aliquots of a rapidly changing two-phase fluid (supercritical CO2 and brine) fluid from 1.5 km depth. The data sets collected, using both the liquid and gas portions of the downhole samples, provide insights into the coupled hydrogeochemical issues affecting CO2 sequestration in brine-filled formations. While the basic premise underlying the U-tube sampler is not new, the system is unique because careful consideration was given to the processing of the recovered two-phase fluids. In particular, strain gauges mounted beneath the high-pressure surface sample cylinders measured the ratio of recovered brine to supercritical CO2. A quadrupole mass spectrometer provided real-time gas analysis for perfluorocarbon and noble gas tracers that were injected along with the CO2. The U-tube successfully acquired frequent samples, facilitating accurate delineation of the arrival of the CO2 plume, and on-site analysis revealed rapid changes in geochemical conditions. Copyright 2005 by the American Geophysical Union.

  12. Microstructural Response of Variably Hydrated Ca-Rich Montmorillonite to Supercritical CO2

    SciTech Connect

    Lee, Mal Soon; McGrail, B. Peter; Glezakou, Vassiliki Alexandra

    2014-08-05

    We report on ab initio molecular dynamics simulations of Ca-rich montmorillonite systems, in different hydration states in the presence of supercritical CO2. Analysis of the molecular trajectories provides estimates of the relative H2O:CO2 ratio per interspatial cation. The vibrational density of states in direct comparison with dipole moment derived IR spectra for these systems provide unique signatures that can used to follow molecular transformation. In a co-sequestration scenario, these signatures could be used to identify the chemical state and fate of Sulfur compounds. Interpretation of CO2 asymmetric stretch shift is given based on a detailed analysis of scCO2 structure and intermolecular interactions of the intercalated species. Based on our simulations, smectites with higher charge interlayer cations at sub-single to single hydration states should be more efficient in capturing CO2, while maintaining caprock integrity. This research would not have been possible without the support of the office of Fossil Energy, Department of Energy. The computational resources were made available through a user proposal of the EMSL User facility, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

  13. Draft Genome Sequences of Supercritical CO2-Tolerant Bacteria Bacillus subterraneus MITOT1 and Bacillus cereus MIT0214.

    PubMed

    Peet, Kyle C; Thompson, Janelle R

    2015-01-01

    We report draft genome sequences of Bacillus subterraneus MITOT1 and Bacillus cereus MIT0214 isolated through enrichment of samples from geologic sequestration sites in pressurized bioreactors containing a supercritical (sc) CO2 headspace. Their genome sequences expand the phylogenetic range of sequenced bacilli and allow characterization of molecular mechanisms of scCO2 tolerance.

  14. Application of a phosphazene derivative as a flame retardant for cotton fabric using conventional method and supercritical CO2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Conventional pad-dry-cure (non-scCO2) and supercritical carbon dioxide (scCO2) application methods were investigated to study the effectiveness of a phosphazene derivative as a flame retardant on cotton fabric. 1,1',4,5-tetrahydrotrispiro[1,3,2-diazaphosphole-2,2'-[1,3,5,2,4,6]triazatriphosphinine-4...

  15. 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.

  16. Frenkel line and solubility maximum in supercritical fluids

    NASA Astrophysics Data System (ADS)

    Yang, C.; Brazhkin, V. V.; Dove, M. T.; Trachenko, K.

    2015-01-01

    A new dynamic line, the Frenkel line, has recently been proposed to separate the supercritical state into rigid-liquid and nonrigid gaslike fluid. The location of the Frenkel line on the phase diagram is unknown for real fluids. Here we map the Frenkel line for three important systems: CO2,H2O , and CH4. This provides an important demarcation on the phase diagram of these systems, the demarcation that separates two distinct physical states with liquidlike and gaslike properties. We find that the Frenkel line can have a similar trend as the melting line above the critical pressure. Moreover, we discuss the relationship between unexplained solubility maxima and Frenkel line, and we propose that the Frenkel line corresponds to the optimal conditions for solubility.

  17. Frenkel line and solubility maximum in supercritical fluids.

    PubMed

    Yang, C; Brazhkin, V V; Dove, M T; Trachenko, K

    2015-01-01

    A new dynamic line, the Frenkel line, has recently been proposed to separate the supercritical state into rigid-liquid and nonrigid gaslike fluid. The location of the Frenkel line on the phase diagram is unknown for real fluids. Here we map the Frenkel line for three important systems: CO(2), H(2)O, and CH(4). This provides an important demarcation on the phase diagram of these systems, the demarcation that separates two distinct physical states with liquidlike and gaslike properties. We find that the Frenkel line can have a similar trend as the melting line above the critical pressure. Moreover, we discuss the relationship between unexplained solubility maxima and Frenkel line, and we propose that the Frenkel line corresponds to the optimal conditions for solubility.

  18. Frenkel line and solubility maximum in supercritical fluids.

    PubMed

    Yang, C; Brazhkin, V V; Dove, M T; Trachenko, K

    2015-01-01

    A new dynamic line, the Frenkel line, has recently been proposed to separate the supercritical state into rigid-liquid and nonrigid gaslike fluid. The location of the Frenkel line on the phase diagram is unknown for real fluids. Here we map the Frenkel line for three important systems: CO(2), H(2)O, and CH(4). This provides an important demarcation on the phase diagram of these systems, the demarcation that separates two distinct physical states with liquidlike and gaslike properties. We find that the Frenkel line can have a similar trend as the melting line above the critical pressure. Moreover, we discuss the relationship between unexplained solubility maxima and Frenkel line, and we propose that the Frenkel line corresponds to the optimal conditions for solubility. PMID:25679575

  19. Biological Properties of Fucoxanthin in Oil Recovered from Two Brown Seaweeds Using Supercritical CO2 Extraction

    PubMed Central

    Periaswamy Sivagnanam, Saravana; Yin, Shipeng; Choi, Jae Hyung; Park, Yong Beom; Woo, Hee Chul; Chun, Byung Soo

    2015-01-01

    The bioactive materials in brown seaweeds hold great interest for developing new drugs and healthy foods. The oil content in brown seaweeds (Saccharina japonica and Sargassum horneri) was extracted by using environmentally friendly supercritical CO2 (SC-CO2) with ethanol as a co-solvent in a semi-batch flow extraction process and compared the results with a conventional extraction process using hexane, ethanol, and acetone mixed with methanol (1:1, v/v). The SC-CO2 method was used at a temperature of 45 °C and pressure of 250 bar. The flow rate of CO2 (27 g/min) was constant for the entire extraction period of 2 h. The obtained oil from the brown seaweeds was analyzed to determine their valuable compounds such as fatty acids, phenolic compounds, fucoxanthin and biological properties including antioxidant, antimicrobial, and antihypertension effects. The amounts of fucoxanthin extracted from the SC-CO2 oils of S. japonica and S. horneri were 0.41 ± 0.05 and 0.77 ± 0.07 mg/g, respectively. High antihypertensive activity was detected when using mixed acetone and methanol, whereas the phenolic content and antioxidant property were higher in the oil extracted by SC-CO2. The acetone–methanol mix extracts exhibited better antimicrobial activities than those obtained by other means. Thus, the SC-CO2 extraction process appears to be a good method for obtaining valuable compounds from both brown seaweeds, and showed stronger biological activity than that obtained by the conventional extraction process. PMID:26035021

  20. Biological Properties of Fucoxanthin in Oil Recovered from Two Brown Seaweeds Using Supercritical CO2 Extraction.

    PubMed

    Sivagnanam, Saravana Periaswamy; Yin, Shipeng; Choi, Jae Hyung; Park, Yong Beom; Woo, Hee Chul; Chun, Byung Soo

    2015-06-01

    The bioactive materials in brown seaweeds hold great interest for developing new drugs and healthy foods. The oil content in brown seaweeds (Saccharina japonica and Sargassum horneri) was extracted by using environmentally friendly supercritical CO2 (SC-CO2) with ethanol as a co-solvent in a semi-batch flow extraction process and compared the results with a conventional extraction process using hexane, ethanol, and acetone mixed with methanol (1:1, v/v). The SC-CO2 method was used at a temperature of 45 °C and pressure of 250 bar. The flow rate of CO2 (27 g/min) was constant for the entire extraction period of 2 h. The obtained oil from the brown seaweeds was analyzed to determine their valuable compounds such as fatty acids, phenolic compounds, fucoxanthin and biological properties including antioxidant, antimicrobial, and antihypertension effects. The amounts of fucoxanthin extracted from the SC-CO2 oils of S. japonica and S. horneri were 0.41 ± 0.05 and 0.77 ± 0.07 mg/g, respectively. High antihypertensive activity was detected when using mixed acetone and methanol, whereas the phenolic content and antioxidant property were higher in the oil extracted by SC-CO2. The acetone-methanol mix extracts exhibited better antimicrobial activities than those obtained by other means. Thus, the SC-CO2 extraction process appears to be a good method for obtaining valuable compounds from both brown seaweeds, and showed stronger biological activity than that obtained by the conventional extraction process. PMID:26035021

  1. Exfoliation Propensity of Oxide Scale in Heat Exchangers Used for Supercritical CO2 Power Cycles

    SciTech Connect

    Sabau, Adrian S; Shingledecker, John P.; Kung, Steve; Wright, Ian G.; Nash, Jim

    2016-01-01

    Supercritical CO2 (sCO2) Brayton cycle systems offer the possibility of improved efficiency in future fossil energy power generation plants operating at temperatures of 650 C and above. As there are few data on the oxidation/corrosion behavior of structural alloys in sCO2 at these temperatures, modeling to predict the propensity for oxide exfoliation is not well developed, thus hindering materials selection for these novel cycles. The ultimate goal of this effort is to provide needed data on scale exfoliation behavior in sCO2 for confident alloy selection. To date, a model developed by ORNL and EPRI for the exfoliation of oxide scales formed on boiler tubes in high-temperature, high-pressure steam has proven useful for managing exfoliation in conventional steam plants. A major input provided by the model is the ability to predict the likelihood of scale failure and loss based on understanding of the evolution of the oxide morphologies and the conditions that result in susceptibility to exfoliation. This paper describes initial steps taken to extend the existing model for exfoliation of steam-side oxide scales to sCO2 conditions. The main differences between high-temperature, high-pressure steam and sCO2 that impact the model involve (i) significant geometrical differences in the heat exchangers, ranging from standard pressurized tubes seen typically in steam-producing boilers to designs for sCO2 that employ variously-curved thin walls to create shaped flow paths for extended heat transfer area and small channel cross-sections to promote thermal convection and support pressure loads; (ii) changed operating characteristics with sCO2 due to the differences in physical and thermal properties compared to steam; and (iii) possible modification of the scale morphologies, hence properties that influence exfoliation behavior, due to reaction with carbon species from sCO2. The numerical simulations conducted were based on an assumed sCO2 operating schedule and several

  2. Extraction of Lutein Diesters from Tagetes Erecta using Supercritical CO2 and Liquid Propane.

    PubMed

    Skerget, Mojca; Bezjak, Miran; Makovšek, Katja; Knez, Zeljko

    2010-03-01

    The efficiency of high pressure extraction of lutein diesters from marigold (Tagetes erecta) flower petals has been investigated. The solvents used for extraction were supercritical carbon dioxide and liquid propane. Operating parameters were 300 bar and 40, 60 and 80 °C for CO2 and 100, 150, 200 bar and 40 and 60 °C for propane, respectively. The influence of process parameters on the total yield of extraction and content of lutein diesters in the extracts was investigated. The results show, that solvent power of propane for lutein diesters is approximately 3.5 times higher than of CO2. The calculation procedure based on the Fick's second law was applied to determine the diffusivities of lutein diesters during extraction from marigold flower petals for both extraction stages: a constant rate stage followed by a stage of decreasing rate. The mathematical model based on the Fick's second law well described the experimental extraction results.

  3. Lipase-catalyzed transesterification of soybean oil and phytosterol in supercritical CO2.

    PubMed

    Hu, Lizhi; Llibin, Sun; Li, Jun; Qi, Liangjun; Zhang, Xu; Yu, Dianyu; Walid, Elfalleh; Jiang, Lianzhou

    2015-12-01

    The transesterification of phytosterol and soybean oil was performed using Novozym 435 in supercritical carbon dioxide (SC-CO2). The transesterification reaction was conducted in soybean oil containing 5-25% phytosterol at 55-95 °C and free-water solvent. The effects of temperature, reaction time, phytosterol concentration, lipase dosage and reaction pressure on the conversion rate of transesterification were investigated. The optimal reaction conditions were the reaction temperature (85 °C), reaction time (1 h), phytosterol concentration (5%), reaction pressure (8 Mpa) and lipase dosage (1%). The highest conversion rate of 92% could be achieved under the optimum conditions. Compared with the method of lipase-catalyzed transesterification of phytosterol and soybean oil at normal pressure, the transesterification in SC-CO2 reduced significantly the reaction temperature and reaction time.

  4. Supercritical fluid extraction and separation of uranium from other actinides.

    PubMed

    Quach, Donna L; Mincher, Bruce J; Wai, Chien M

    2014-06-15

    The feasibility of separating U from nitric acid solutions of mixed actinides using tri-n-butylphosphate (TBP)-modified supercritical fluid carbon dioxide (sc-CO2) was investigated. The actinides U, Np, Pu, and Am were extracted into sc-CO2 modified with TBP from a range of nitric acid concentrations, in the absence of, or in the presence of, a number of traditional reducing and/or complexing agents to demonstrate the separation of these metals from U under sc-CO2 conditions. The separation of U from Pu using sc-CO2 was successful at nitric acid concentrations of less than 3M in the presence of acetohydroxamic acid (AHA) or oxalic acid (OA) to mitigate Pu extraction, and the separation of U from Np was successful at nitric acid concentrations of less than 1M in the presence of AHA, OA, or sodium nitrite to mitigate Np extraction. Americium was not well extracted under any condition studied.

  5. Effects of fluid dynamics on cleaning efficacy of supercritical fluids

    SciTech Connect

    Phelps, M.R.; Willcox, W.A.; Silva, L.J.; Butner, R.S.

    1993-03-01

    Pacific Northwest Laboratory (PNL) and Boeing Aerospace Company are developing a process to clean metal parts using a supercritical solvent. This work is part of an effort to address issues inhibiting the rapid commercialization of Supercritical Fluid Parts Cleaning (SFPC). PNL assembled a SFPC test stand to observe the relationship between the fluid dynamics of the system and the mass transfer of a contaminant from the surface of a contaminated metal coupon into the bulk fluid. The bench-scale test stand consists of a ``Berty`` autoclave modified for these tests and supporting hardware to achieve supercritical fluids parts cleaning. Three separate sets of tests were conducted using supercritical carbon dioxide. For the first two tests, a single stainless steel coupon was cleaned with organic solvents to remove surface residue, doped with a single contaminant, and then cleaned in the SFPC test stand. Contaminants studied were Dow Corning 200 fluid (dimethylpolysiloxane) and Castle/Sybron X-448 High-temperature Oil (a polybutane/mineral oil mixture). A set of 5-minute cleaning runs was conducted for each dopant at various autoclave impeller speeds. Test results from the first two sets of experiments indicate that precision cleaning for difficult-to-remove contaminants can be dramatically improved by introducing and increasing turbulence within the system. Metal coupons that had been previously doped with aircraft oil were used in a third set of tests. The coupons were placed in the SFPC test stand and subjected to different temperatures, pressures, and run times at a constant impeller speed. The cleanliness of each part was measured by Optically Stimulated Electron Emission. The third set of tests show that levels of cleanliness attained with supercritical carbon dioxide compare favorably with solvent and aqueous cleaning levels.

  6. Effects of fluid dynamics on cleaning efficacy of supercritical fluids

    SciTech Connect

    Phelps, M.R.; Willcox, W.A.; Silva, L.J.; Butner, R.S.

    1993-03-01

    Pacific Northwest Laboratory (PNL) and Boeing Aerospace Company are developing a process to clean metal parts using a supercritical solvent. This work is part of an effort to address issues inhibiting the rapid commercialization of Supercritical Fluid Parts Cleaning (SFPC). PNL assembled a SFPC test stand to observe the relationship between the fluid dynamics of the system and the mass transfer of a contaminant from the surface of a contaminated metal coupon into the bulk fluid. The bench-scale test stand consists of a Berty'' autoclave modified for these tests and supporting hardware to achieve supercritical fluids parts cleaning. Three separate sets of tests were conducted using supercritical carbon dioxide. For the first two tests, a single stainless steel coupon was cleaned with organic solvents to remove surface residue, doped with a single contaminant, and then cleaned in the SFPC test stand. Contaminants studied were Dow Corning 200 fluid (dimethylpolysiloxane) and Castle/Sybron X-448 High-temperature Oil (a polybutane/mineral oil mixture). A set of 5-minute cleaning runs was conducted for each dopant at various autoclave impeller speeds. Test results from the first two sets of experiments indicate that precision cleaning for difficult-to-remove contaminants can be dramatically improved by introducing and increasing turbulence within the system. Metal coupons that had been previously doped with aircraft oil were used in a third set of tests. The coupons were placed in the SFPC test stand and subjected to different temperatures, pressures, and run times at a constant impeller speed. The cleanliness of each part was measured by Optically Stimulated Electron Emission. The third set of tests show that levels of cleanliness attained with supercritical carbon dioxide compare favorably with solvent and aqueous cleaning levels.

  7. 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.

  8. TheU-Tube: A Novel System for Acquiring Borehole Fluid Samplesfrom a Deep Geologic CO2 Sequestration Experiment

    SciTech Connect

    Freifeld, Barry M.; Trautz, Robert C.; Kharaka, Yousif K.; Phelps, Tommy J.; Myer, Larry R.; Hovorka, Susan D.; Collins, Daniel J.

    2005-03-17

    A novel system has been deployed to obtain geochemical samples of water and gas, at in situ pressure, during a geologic CO2 sequestration experiment conducted in the Frio brine aquifer in Liberty County, Texas. Project goals required high-frequency recovery of representative and uncontaminated aliquots of a rapidly changing two-phase (supercritical CO2-brine) fluid from 1.5 km depth. The datasets collected, using both the liquid and gas portions of the downhole samples, provide insights into the coupled hydro-geochemical issues affecting CO2 sequestration in brine-filled formations. While the basic premise underlying the U-Tube sampler is not new, the system is unique because careful consideration was given to the processing of the recovered two-phase fluids. In particular, strain gauges mounted beneath the high-pressure surface sample cylinders measured the ratio of recovered brine to supercritical CO2. A quadrupole mass spectrometer provided real-time gas analysis for perfluorocarbon and noble gas tracers that were injected along with the CO2. The U-Tube successfully acquired frequent samples, facilitating accurate delineation of the arrival of the CO2 plume, and on-site analysis revealed rapid changes in geochemical conditions.

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

    SciTech Connect

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

    2013-01-01

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

  10. Photothermal deflection in a supercritical fluid

    NASA Astrophysics Data System (ADS)

    Briggs, Matthew E.; Gammon, Robert W.

    1994-11-01

    The total losses due to absorption and scatter from the best optical coatings can be made as low as supercritical fluid, instead of an ordinary (non-critical) fluid, as the sensing fluid in a collinear photothermal-deflection apparatus. The noise floor in our surface-absorption measurements using supercritical xenon, Tc equals 16.7 degree(s)C, corresponds to an absorptance A equals Pabsorbed/Pincident equals 10-10 under illumination of 1 W. Bulk absorption measurements are similarly enhanced: the noise floor corresponds to an absorption coefficient of (alpha) equals 10-13 cm-1 for 1 W of illumination in a sample of length 1 cm. These levels are three orders of magnitude more sensitive than any previously reported. The enhancement is brought about by the divergence in the coefficient of thermal expansion of a fluid near the critical point. In attempting to use this sensitivity to measure the absorption in transmission of low-absorbing (

  11. Occurrence of turbulent flow conditions in supercritical fluid chromatography.

    PubMed

    De Pauw, Ruben; Choikhet, Konstantin; Desmet, Gert; Broeckhoven, Ken

    2014-09-26

    Having similar densities as liquids but with viscosities up to 20 times lower (higher diffusion coefficients), supercritical CO2 is the ideal (co-)solvent for fast and/or highly efficient separations without mass-transfer limitations or excessive column pressure drops. Whereas in liquid chromatography the flow remains laminar in both the packed bed and tubing, except in extreme cases (e.g. in a 75 μm tubing, pure acetonitrile at 5 ml/min), a supercritical fluid can experience a transition from laminar to turbulent flow in more typical operation modes. Due to the significant lower viscosity, this transition for example already occurs at 1.3 ml/min for neat CO2 when using connection tubing with an ID of 127 μm. By calculating the Darcy friction factor, which can be plotted versus the Reynolds number in a so-called Moody chart, typically used in fluid dynamics, higher values are found for stainless steel than PEEK tubing, in agreement with their expected higher surface roughness. As a result turbulent effects are more pronounced when using stainless steel tubing. The higher than expected extra-column pressure drop limits the kinetic performance of supercritical fluid chromatography and complicates the optimization of tubing ID, which is based on a trade-off between extra-column band broadening and pressure drop. One of the most important practical consequences is the non-linear increase in extra-column pressure drop over the tubing downstream of the column which leads to an unexpected increase in average column pressure and mobile phase density, and thus decrease in retention. For close eluting components with a significantly different dependence of retention on density, the selectivity can significantly be affected by this increase in average pressure. In addition, the occurrence of turbulent flow is also observed in the detector cell and connection tubing. This results in a noise-increase by a factor of four when going from laminar to turbulent flow (e.g. going

  12. Injection of Super-Critical CO2 in Brine Saturated Sandstone:

    NASA Astrophysics Data System (ADS)

    Ott, Holger; de Kloe, Kees; Taberner, Conxita; Marcelis, Fons; Makurat, Axel

    2010-05-01

    Presently, large-scale geological sequestration of CO2, originating from sources like fossil-fueled power plants and contaminated gas production, is seen as an option to reduce anthropogenic emission of greenhouse gases to the atmosphere. Deep saline aquifers and depleted oil and gas fields are potential subsurface deposits for CO2. Injected CO2, however, interacts physically and chemically with the formation leading to uncertainties for CCS projects. One of these uncertainties is related to a dry-out zone that is likely to form around the well bore owing to the injection of dry CO2. Precipitation of salt (mainly halite) that is associated with that drying out of a saline formation has the potential to impair injectivity, and could even lead to the loss of a well. If dry (or under-saturated), super-critical (SC) CO2 is injected into water-bearing geological formations like saline aquifers, water is removed by either advection of the aqueous phase or by evaporation of water and subsequent advection in the injected CO2-rich phase. Both mechanisms act in parallel, however while advection of the aqueous phase decreases with increasing CO2 saturation (diminished mobility), evaporation becomes increasingly important as the aqueous phase becomes immobile. Below residual water saturation, only evaporation takes place and the formation dries out if no additional source of water is available. If water evaporates, the salts originally present in the water are left behind. In case of highly saline formations, the amount of salt that potentially precipitates per unit volume can be quite substantial. It depends on salinity, the solubility limit of water in the CO2 rich phase, and on the ratio of advection and evaporation rates. Since saturations and flow rates cover a large range as functions of space and time close to the well bore, there is no easy answer to the questions whether, where and how salt precipitation impacts injectivity. The present paper presents results of core

  13. Mineralogical changes of a well cement in various H2S-CO2(-brine) fluids at high pressure and temperature.

    PubMed

    Jacquemet, Nicolas; Pironon, Jacques; Saint-Marc, Jérémie

    2008-01-01

    The reactivity of a crushed well cement in contact with (1) a brine with dissolved H2S-CO2; (2) a dry H2S-CO2 supercritical phase; (3) a two-phase fluid associating a brine with dissolved H2S-CO2 and a H2S-CO2 supercritical phase was investigated in batch experiments at 500 bar and 120, 200 degrees C. All of the experiments showed that following 15-60 days cement carbonation occurred. The H2S reactivity with cement is limited since it only transformed the ferrites (minor phases) by sulfidation. It appeared that the primary parameter controlling the degree of carbonation (i.e., the rate of calcium carbonates precipitation and CSH (Calcium Silicate Hydrates) decalcification) is the physical state of the fluid phase contacting the minerals. The carbonation degree is complete when the minerals contact at least the dry H2S-CO2 supercritical phase and partial when they contactthe brine with dissolved H2S-CO2. Aragonite (calcium carbonate polymorph) precipitated specifically within the dry H2S-CO2 supercritical phase. CSH cristallinity is improved by partial carbonation while CSH are amorphized by complete carbonation. However, the features evidenced in this study cannot be directly related to effective features of cement as a monolith. Further studies involving cement as a monolith are necessary to ascertain textural, petrophysical, and mechanical evolution of cement.

  14. Study on the effect of temperature and pressure on nickel-electroplating characteristics in supercritical CO2.

    PubMed

    Kim, Moon-Sun; Kim, Jae-Youn; Kim, Chul Kyung; Kim, Nam-Ki

    2005-01-01

    In this work, it was investigated the effect of solubility in supercritical CO2 on the nickel-electroplating characteristics. The plating characteristics could be controlled by electric resistance and dispersion in emulsion as well. CO2 concentration had better be controlled at lower concentration than 50 CO2 wt% to decrease electric resistance since supercritical CO2 is non-polar material. Non-ionic surfactant with EO/PO block copolymer was more efficient than any other surfactant and the dispersion at 0.2 surfactant wt% was better than at any surfactant concentration and over-added surfactant concentration over 0.2 wt% brought to the decrease of dispersion properties. Electric resistance was constant at 20Omega in ranging from pH 2.2 to pH 3.5 and increased slowly to 50Omega at pH 4 and rapidly to 400Omega at pH 5. Characteristics of nickel film has a close relation with solubility in supercritical CO2 and solubility is dependent on pressure and temperature. Solubility at 16 MPa was higher than that any other at pressure and at constant pressure of 16 MPa, solubility in supercritical CO2 increased with an increasing temperature from 31 to 45 degrees C and decreased over 45 degrees C.

  15. Modeling and optimization of a concentrated solar supercritical CO2 power plant

    NASA Astrophysics Data System (ADS)

    Osorio, Julian D.

    Renewable energy sources are fundamental alternatives to supply the rising energy demand in the world and to reduce or replace fossil fuel technologies. In order to make renewable-based technologies suitable for commercial and industrial applications, two main challenges need to be solved: the design and manufacture of highly efficient devices and reliable systems to operate under intermittent energy supply conditions. In particular, power generation technologies based on solar energy are one of the most promising alternatives to supply the world energy demand and reduce the dependence on fossil fuel technologies. In this dissertation, the dynamic behavior of a Concentrated Solar Power (CSP) supercritical CO2 cycle is studied under different seasonal conditions. The system analyzed is composed of a central receiver, hot and cold thermal energy storage units, a heat exchanger, a recuperator, and multi-stage compression-expansion subsystems with intercoolers and reheaters between compressors and turbines respectively. The effects of operating and design parameters on the system performance are analyzed. Some of these parameters are the mass flow rate, intermediate pressures, number of compression-expansion stages, heat exchangers' effectiveness, multi-tank thermal energy storage, overall heat transfer coefficient between the solar receiver and the environment and the effective area of the recuperator. Energy and exergy models for each component of the system are developed to optimize operating parameters in order to lead to maximum efficiency. From the exergy analysis, the components with high contribution to exergy destruction were identified. These components, which represent an important potential of improvement, are the recuperator, the hot thermal energy storage tank and the solar receiver. Two complementary alternatives to improve the efficiency of concentrated solar thermal systems are proposed in this dissertation: the optimization of the system's operating

  16. Mass transfer in supercritical fluids instancing selected fluids in supercritical carbon dioxide

    NASA Astrophysics Data System (ADS)

    Hu, Miao; Benning, Rainer; Delgado, Antonio; Ertunc, Oezguer

    solvent -sub-critical CO2. The ex-periment pressure is reached by reducing the volume of the container above the critical pressure of the solvent. For nucleation the container is firstly filled with saturated mixture of solvent -supercritical CO2 and the sample, the experiment pressure is achieved by enlarging the volume of the container below the critical pressure of the solvent. During the experiments the pressure and temperature data are monitored and recorded. As a direct observation means a high speed camera is used, the visual changes inside are recorded through the windows integrated on the container. The experiments are carried out under three different initial conditions, namely with three start temperatures (313K, 333K and 353K), to cover the area from vicinity of the critical point. This research serves as a pilot project topic in cooperation with DLR, which has the ultimate aim of performing the experiments of mass transfer processes in a longtime microgravity facility (e.g. ISS) in order to further explore the influences and utilities of earth gravity on these basic transport processes.

  17. Modern supercritical fluid technology for food applications.

    PubMed

    King, Jerry W

    2014-01-01

    This review provides an update on the use of supercritical fluid (SCF) technology as applied to food-based materials. It advocates the use of the solubility parameter theory (SPT) for rationalizing the results obtained when employing sub- and supercritical media to food and nutrient-bearing materials and for optimizing processing conditions. Total extraction and fractionation of foodstuffs employing SCFs are compared and are illustrated by using multiple fluids and unit processes to obtain the desired food product. Some of the additional prophylactic benefits of using carbon dioxide as the processing fluid are explained and illustrated with multiple examples of commercial products produced using SCF media. I emphasize the role of SCF technology in the context of environmentally benign and sustainable processing, as well as its integration into an overall biorefinery concept. Conclusions are drawn in terms of current trends in the field and future research that is needed to secure new applications of the SCF platform as applied in food science and technology.

  18. 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.

  19. Modeling and optimization of a concentrated solar supercritical CO2 power plant

    NASA Astrophysics Data System (ADS)

    Osorio, Julian D.

    Renewable energy sources are fundamental alternatives to supply the rising energy demand in the world and to reduce or replace fossil fuel technologies. In order to make renewable-based technologies suitable for commercial and industrial applications, two main challenges need to be solved: the design and manufacture of highly efficient devices and reliable systems to operate under intermittent energy supply conditions. In particular, power generation technologies based on solar energy are one of the most promising alternatives to supply the world energy demand and reduce the dependence on fossil fuel technologies. In this dissertation, the dynamic behavior of a Concentrated Solar Power (CSP) supercritical CO2 cycle is studied under different seasonal conditions. The system analyzed is composed of a central receiver, hot and cold thermal energy storage units, a heat exchanger, a recuperator, and multi-stage compression-expansion subsystems with intercoolers and reheaters between compressors and turbines respectively. The effects of operating and design parameters on the system performance are analyzed. Some of these parameters are the mass flow rate, intermediate pressures, number of compression-expansion stages, heat exchangers' effectiveness, multi-tank thermal energy storage, overall heat transfer coefficient between the solar receiver and the environment and the effective area of the recuperator. Energy and exergy models for each component of the system are developed to optimize operating parameters in order to lead to maximum efficiency. From the exergy analysis, the components with high contribution to exergy destruction were identified. These components, which represent an important potential of improvement, are the recuperator, the hot thermal energy storage tank and the solar receiver. Two complementary alternatives to improve the efficiency of concentrated solar thermal systems are proposed in this dissertation: the optimization of the system's operating

  20. Modeling Study on Injection of Supercritical CO2 Into a Deep Saline Carbonate Formation

    NASA Astrophysics Data System (ADS)

    Zhang, G.; Taberner, C.; Xu, T.; Cartwright, L.

    2008-12-01

    A modeling study on injection of supercritical CO2 into a deep saline carbonate formation was performed using TOUGHREACT Pitzer ion-interaction model. The carbonate formation consists of calcite (72.5%), dolomite (21.5%) and anhydrite (<6%). The brine of the formation is known as NaCl-dominant with salinity at about 250,000 ppm (NaCl equivalent), temperature at 102° C and pressure at 225 bars. The detailed chemical composition of the brine was unknown. It was reconstructed according to the salinity and the known detailed composition of a brine from a similar formation with slightly lower salinity (about 190,000 ppm). The reconstructed formation brine has an ionic strength ~5 molal and pH 5.4 with considerable concentrations of Ca+2, Mg+2, HCO3- and SO4-2. CO2 injection was considered at a constant rate and for a period of 1 year, through a vertical well in a 2D radial model domain, and a horizontal well in a 3D model domain, respectively. The preliminary simulations found that: (1) at the end of the injection, a dryout zone is developed within a few meters from the injection well due to displacement by the injected supercritical CO2 and the evaporation of water from brine into CO2; (2) at the front of the dryout zone, brine is further concentrated (ionic strength up 20 molal) due to water evaporation, pH is lowered to 3.1, halite (NaCl) and anhydrite (CaSO4) precipitate, and the brine is converted into CaCl2-dominant; (3) precipitation of halite in the dryout zone reduces the formation porosity by about 5%-10%; (4) HCl gas is generated from the dryout front; (5) calcite dissolves close to the injection well and precipitates at areas far from the well, however, the overall mineral trapping is not significant in hundreds of years for this carbonate formation. These findings are valuable for the assessment of the potentials of this carbonate formation for CO2 sequestration, injectivity changes, and well degradation by potential corrosion.

  1. Research on Flow Characteristics of Supercritical CO2 Axial Compressor Blades by CFD Analysis

    NASA Astrophysics Data System (ADS)

    Takagi, Kazuhisa; Muto, Yasushi; Ishizuka, Takao; Kikura, Hiroshige; Aritomi, Masanori

    A supercritical CO2 gas turbine of 20MPa is suitable to couple with the Na-cooled fast reactor since Na - CO2 reaction is mild at the outlet temperature of 800K, the cycle thermal efficiency is relatively high and the size of CO2 gas turbine is very compact. In this gas turbine cycle, a compressor operates near the critical point. The property of CO2 and then the behavior of compressible flow near the critical point changes very sharply. So far, such a behavior is not examined sufficiently. Then, it is important to clarify compressible flow near the critical point. In this paper, an aerodynamic design of the axial supercritical CO2 compressor for this system has been carried out based on the existing aerodynamic design method of Cohen1). The cycle design point was selected to achieve the maximum cycle thermal efficiency of 43.8%. For this point, the compressor design conditions were determined. They are a mass flow rate of 2035kg/s, an inlet temperature of 308K, an inlet static pressure of 8.26MPa, an outlet static pressure of 20.6MPa and a rotational speed of 3600rpm. The mean radius was constant through axial direction. The design point was determined so as to keep the diffusion factor and blade stress within the allowable limits. Number of stages and an expected adiabatic efficiency was 14 and 87%, respectively. CFD analyses by FLUENT have been done for this compressor blade. The blade model consists of one set of a guide vane, a rotor blade and a stator blade. The analyses were conducted under the assumption both of the real gas properties and also of the modified ideal gas properties. Using the real gas properties, analysis was conducted for the 14th blade, whose condition is remote from the critical point and the possibility of divergence is very small. Then, the analyses were conducted for the blade whose conditions are nearer to the critical point. Gradually, divergence of calculation was encountered. Convergence was relatively easy for the modified ideal

  2. Dissolution of uranium dioxide in supercritical fluid carbon dioxide.

    PubMed

    Samsonov, M D; Wai, C M; Lee, S C; Kulyako, Y; Smart, N G

    2001-09-21

    Uranium dioxide can be dissolved in supercritical CO2 with a CO2-philic TBP-HNO3 complexant to form a highly soluble UO2(NO3)(2).2TBP complex; this new method of dissolving UO2 that requires no water or organic solvent may have important applications for reprocessing of spent nuclear fuels and for treatment of nuclear wastes.

  3. Supercritical CO2 extraction of oilseeds: review of kinetic and equilibrium models.

    PubMed

    del Valle, José M; de la Fuente, Juan C

    2006-01-01

    Mass transfer models on supercritical carbon dioxide (SC-CO2) extraction of vegetable oils are reviewed, that may facilitate the scale-up of laboratory data for industrial design purposes. Reviewed mechanisms of oil transport within the solid matrix include the desorption from the solid, the formation of a shrinking core of condensed oil in a non-adsorbing porous matrix, and diffusion in a homogenous medium. Analyzed simplificat ions of a general mass transfer model include external control of mass transfer rates, internal control of mass transfer rates, consideration of a linear driving force, and steady state approximations, among others. More complex two-stage models, and critical comparisons of some of the proposed models are also included. Trends for the external mass transfer coefficient and effective diffusivity in the solid matrix from studies on SC-CO2 extraction of oil from vegetable substrates are thoroughly discussed and contrasted with those obtained using simpler model systems. The possible effect of the axial dispersion on the rate of extraction is also discussed. Finally, the high-pressure vegetable oil-CO2 phase equilibrium is discussed in connection with its influence on the mass transfer process. Special emphasis is given to the role of the solid matrix on high-pressure phase equilibrium.

  4. Leaching of organic acids from macromolecular organic matter by non-supercritical CO2

    NASA Astrophysics Data System (ADS)

    Sauer, P.; Glombitza, C.; Kallmeyer, J.

    2012-04-01

    The storage of CO2 in underground reservoirs is discussed controversly in the scientific literature. The worldwide search for suitable storage formations also considers coal-bearing strata. CO2 is already injected into seams for enhanced recovery of coal bed methane. However, the effects of increased CO2 concentration, especially on organic matter rich formations, are rarely investigated. The injected CO2 will dissolve in the pore water, causing a decrease in pH and resulting in acidic formation waters. Huge amounts of low molecular weight organic acids (LMWOAs) are chemically bound to the macromolecular matrix of sedimentary organic matter and may be liberated by hydrolysis, which is enhanced by the acidic porewater. Recent investigations outlined the importance of LMWOAs as a feedstock for microbial life in the subsurface [1]. Therefore, injection of CO2 into coal formations may result in enhanced nutrient supply for subsurface microbes. To investigate the effect of high concentrations of dissolved CO2 on the release of LMWOAs from coal we developed an inexpensive high-pressure high temperature system that allows manipulating the partial pressure of dissolved gases at pressures and temperatures up to 60 MPa and 120° C, respectively. In a reservoir vessel, gases are added to saturate the extraction medium to the desired level. Inside the extraction vessel hangs a flexible and inert PVDF sleeve (polyvinylidene fluoride, almost impermeable for gases), holding the sample and separating it from the pressure fluid. The flexibility of the sleeve allows for subsampling without loss of pressure. Coal samples from the DEBITS-1 well, Waikato Basin, NZ (R0 = 0.29, TOC = 30%). were extracted at 90° C and 5 MPa, either with pure or CO2-saturated water. Subsamples were taken at different time points during the extraction. The extracted LMWOAs such as formate, acetate and oxalate were analysed by ion chromatography. Yields of LMWOAs were higher with pure water than with CO2

  5. Supercritical Fluid Immersion Deposition: A New Process for Selective Deposition of Metal Films on Silicon Substrates

    SciTech Connect

    Ye, Xiangrong; Wai, Chien M.; Lin, Yuehe; Young, James S.; Engelhard, Mark H.

    2005-01-01

    Supercritical CO2 is used as a new solvent for immersion deposition, a galvanic displacement process traditionally carried out in aqueous HF solutions containing metal ions, to selectively develop metal films on featured or non-featured silicon substrates. Components of supercritical fluid immersion deposition (SFID) solutions for fabricating Cu and Pd films on silicon substrates are described along with the corresponding experimental setup and procedure. Only silicon substrates exposed and reactive to SFID solutions can be coated. The highly pressurized and gas-like supercritical CO2, combined with the galvanic displacement property of immersion deposition, enables the SFID technique to selectively deposit metal films in small features. SFID may also provide a new method to fabricate palladium silicide in small features or to metallize porous silicon.

  6. Supercritical Fluid Extraction and Separation of Uranium from Other Actinides

    SciTech Connect

    Donna L. Quach; Bruce J. Mincher; Chien M. Wai

    2014-06-01

    This paper investigates the feasibility of separating uranium from other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of an extraction and counter current stripping technique, which would be a more efficient and environmentally benign technology for used nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U(VI), Np(VI), Pu(IV), and Am(III)) were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, the separation of uranium from plutonium in sc-CO2 modified with TBP was successful at nitric acid concentrations of less than 3 M in the presence of acetohydroxamic acid or oxalic acid, and the separation of uranium from neptunium was successful at nitric acid concentrations of less than 1 M in the presence of acetohydroxamic acid, oxalic acid, or sodium nitrite.

  7. Bio-oil production from biomass via supercritical fluid extraction

    NASA Astrophysics Data System (ADS)

    Durak, Halil

    2016-04-01

    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 were identified by GC-MS obtained in acetone and ethanol respectively.

  8. Ion mobility spectrometry after supercritical fluid chromatography

    SciTech Connect

    Morrissey, M.A.

    1988-01-01

    In this work, a Fourier transform ion mobility spectrometer (FT-IMS) was constructed and evaluated as a detector for supercritical fluid chromatography (SFC). The FT-IMS provides both quantitative and qualitative data of a wide range of compounds, selective and nonselective modes of chromatographic detection, and it is compatible with a wide range of SFC mobile phases. Drift spectra are presented for a number of samples, including polymers, lipids, herbicides, antibiotics, and pharmaceuticals. The unique properties of supercritical fluids made it possible to introduce these compounds into the spectrometer. While the drift spectra presented are generally simple, showing only a quasi-molecular ion, a few are surprising complex. Examples of selective and non-selective detection demonstrate the usefulness of the detector. Examples are presented for fish oil concentrate, bacon grease extract, soil extract, and polymer mixtures. In the case of Triton X-100, a non-ionic surfactant, the FT-IMS was able to selectively detect individual oligomers in the polymer mixture. In the case of a polydimethylsilicone mixture the detector isolated a contaminant in the mixture.

  9. [Optimization of extraction process for tannins from Geranium orientali-tibeticum by supercritical CO2 method].

    PubMed

    Xie, Song; Tong, Zhi-Ping; Tan, Rui; Liu, Xiao-Zhen

    2014-08-01

    In order to optimize extraction process conditions of tannins from Geranium orientali-tibeticum by supercritical CO2, the content of tannins was determined by phosphomolybdium tungsten acid-casein reaction, with extraction pressure, extraction temper- ature and extraction time as factors, the content of tannins from extract of G. orientali-tibeticum as index, technology conditions were optimized by orthogonal test. Optimum technology conditions were as follows: extraction pressure was 25 MPa, extraction temperature was 50 °C, extracted 1.5 h. The content of tannins in extract was 12.91 mg x g(-1), extract rate was 3.67%. The method established could be used for assay the contents of tannin in G. orientali-tibeticum. The circulated extraction was an effective extraction process that was stable and feasible, and that provides a way of the extraction process conditions of tannin from G. orientali-tibeticum.

  10. Geochemical modeling of fluid-fluid and fluid-mineral interactions during geological CO2 storage

    NASA Astrophysics Data System (ADS)

    Zhu, C.; Ji, X.; Lu, P.

    2013-12-01

    The long time required for effective CO2 storage makes geochemical modeling an indispensable tool for CCUS. One area of geochemical modeling research that is in urgent need is impurities in CO2 streams. Permitting impurities, such as H2S, in CO2 streams can lead to potential capital and energy savings. However, predicting the consequences of co-injection of CO2 and impurities into geological formations requires the understanding of the phase equilibrium and fluid-fluid interactions. To meet this need, we developed a statistical associating fluid theory (SAFT)-based equation of state (EOS) for the H2S-CO2-H2O-NaCl system at 373.15 CO2 streams may lead to two-phase flow in pipelines. For H2S-CO2 mixtures at a given temperature the bubble and dew pressures decrease with increasing H2S content, while the mass density increases at low pressures and decreases at high pressures. Furthermore, the EoS can be incorporated into reservoir simulators so that the dynamic development of mixed fluid plumes in the reservoir can be simulated. Accurate modeling of fluid-mineral interactions must confront unresolved uncertainties of silicate dissolution - precipitation reaction kinetics. Most prominent among these uncertainties is the well-known lab-field apparent discrepancy in dissolution rates. Although reactive transport models that simulate the interactions between reservoir rocks and brine, and their attendant effects on porosity and permeability changes, have proliferated, whether these results have acceptable uncertainties are unknown. We have conducted a series of batch experiments at elevated temperatures and numerical simulations of coupled dissolution and precipitation reactions. The results show that taking into account

  11. Toward modeling of supercritical CO2 flow using the one-dimensional turbulence model

    NASA Astrophysics Data System (ADS)

    Schulz, F. T.; Glawe, C.; Schmidt, H.; Kerstein, A. R.

    2012-04-01

    Within the CCS (Carbon Capture and Storage) technology the transport of captured CO2 is increasingly regarded as the missing link in research. For industrial applications it is essential to transport CO2 from power plants to geological sites through pipelines and well bores. The effectiveness of such a transport could be increased by keeping CO2 in a supercritical state. This however requires a temperature of at least 31Celsius and a pressure above 73.8 bar. If these conditions are not maintained throughout the whole pipeline, which is challenging and expensive under non-laboratory conditions, density and phase changes and pressure fluctuations may result in harmful vibrations of the pipelines. Typically, simulations of pipeline flow are based on large-eddy simulations (LES) or the Reynolds averaged Navier-Stokes (RANS) equations which both do not resolve the smallest turbulent scales or even phase boundaries. Due to the effect that on pipe diameter scales the flow statistically changes predominantly in the wall normal direction one might consider 1D modeling approaches. The work presented here is part of the GeoEn II activities funded by the Federal Ministry of Education and Research (BMBF) to better understand risks and benefits of CCS technology. Our project goal is to better understand the small scale physics in turbulent CO2 flows and to improve subgrid-scale models used in LES codes. To achieve this we use ODT (One-Dimensional Turbulence), a statistical turbulence modeling strategy, where turbulent flow evolution along a notional 1D line of sight is emulated by applying instantaneous maps to represent the effect of individual turbulent eddies on property profiles along the line. The occurrence of an eddy itself is affected by the property profiles, resulting in a self-contained flow evolution that obeys the applicable conservation laws. Using a 1D ansatz permits a higher resolution of boundary and single phase density gradients which is key to understand the

  12. Low-temperature, selective catalytic deoxygenation of vegetable oil in supercritical fluid media.

    PubMed

    Kim, Seok Ki; Lee, Hong-Shik; Hong, Moon Hyun; Lim, Jong Sung; Kim, Jaehoon

    2014-02-01

    The effects of supercritical fluids on the production of renewable diesel-range hydrocarbons from natural triglycerides were investigated. Various supercritical fluids, which included CO2 (scCO2 ), propane (scC3 H8 ) and n-hexane (scC6 H14 ), were introduced with H2 and soybean oil into a fixed-bed reactor that contained pre-activated CoMo/γ-Al2 O3 . Among these supercritical fluids, scC3 H8 and scC6 H14 efficiently allowed the reduction of the reaction temperature by as much as 50 °C as a result of facilitated heat and mass transfer and afforded similar yields to reactions in the absence of supercritical fluids. The compositional analyses of the gas and liquid products indicated that the addition of scC3 H8 during the hydrotreatment of soybean oil promoted specific deoxygenation pathways, decarbonylation and decarboxylation, which consumed less H2 than the hydrodeoxygenation pathway. As a result, the quantity of H2 required to obtain a high yield of diesel-range hydrocarbons could be reduced to 57 % if scC3 H8 was used. As decarboxylation and decarbonylation are mildly endothermic reactions, the reduced heat transfer resistance in scC3 H8 may drive the deoxygenation reaction to thermodynamically favourable pathways.

  13. Thermally and Acoustically Driven Transport in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Hasan, Nusair Mohammed Ibn

    Supercritical fluids are fluids at temperature and pressure above their respective critical values. Such fluids are increasingly being used in power generation, refrigeration and chemical process industry. The objectives of the current research were to develop a fundamental understanding of the transport phenomena in near-critical supercritical fluids via high-resolution numerical simulations and careful experiments for improved design of industrial processes and applications that employ supercritical fluids. A set of synergistic experimental and numerical studies were proposed in this research. Four main focus areas under the broad spectrum of supercritical fluid transport were chosen -- (a) characterization of thermoacoustic transport, (b) interaction of thermoacoustic transport with natural convection, (c) characterization of acoustically augmented transport and (d) enhancement of mass transport using acoustic waves. A numerical model to simulate thermoacoustic convection in near-critical fluids was developed. In the computational model, the conservation equations were solved along with a real-fluid equation of state for supercritical fluid and variable thermo-physical properties. Thermoacoustic waves in near-critical carbon dioxide were also investigated experimentally on acoustic time scales using a fast response measurement system. The predicted results from the calculation and the measurements provide interesting details regarding the thermal transport mechanisms at near-critical states. The numerical model was applied to investigate the interaction of buoyancy driven flows with thermoacoustic convection in near-critical supercritical fluids. This model can be extensively used for studying the steady-state thermal transport and stability behavior of near-critical fluids. Mechanically driven acoustic waves in supercritical fluid generated by a vibrating wall in a cylindrical resonator were studied both numerically and experimentally. The simulations revealed

  14. Preparation of monolithic matrices for oral drug delivery using a supercritical fluid assisted hot melt extrusion process.

    PubMed

    Lyons, John G; Hallinan, Mark; Kennedy, James E; Devine, Declan M; Geever, Luke M; Blackie, Paul; Higginbotham, Clement L

    2007-02-01

    The use of supercritical fluids as plasticisers in polymer processing has been well documented. The body of work described in this research paper outlines the use of a supercritical CO(2) assisted extrusion process in the preparation of a hot melt extruded monolithic polymer matrix for oral drug delivery. Several batches of matrix material were prepared with Carvedilol used as the active pharmaceutical ingredient (API). These batches were subsequently extruded both with and without supercritical CO(2) incorporation. The resultant matrices were characterised using steady-state parallel plate rheometry, differential scanning calorimetry (DSC), atomic force microscopy (AFM), micro-thermal analysis (microTA) and dissolution testing. Dissolution analysis showed that the use of supercritical CO(2) during the extrusion process resulted in a faster dissolution of API when compared with unassisted extrusion. The supercritical CO(2) incorporation also resulted in reduced viscosity during processing, therefore allowing for quicker throughput and productivity. The results detailed within this paper indicate that supercritical fluid assisted hot melt extrusion is a viable enhancement to conventional hot melt extrusion for the production of monolithic dosage forms.

  15. Quantifying the flow dynamics of supercritical CO2-water displacement in a 2D porous micromodel using fluorescent microscopy and microscopic PIV

    NASA Astrophysics Data System (ADS)

    Kazemifar, Farzan; Blois, Gianluca; Kyritsis, Dimitrios C.; Christensen, Kenneth T.

    2016-09-01

    The multi-phase flow of liquid/supercritical CO2 and water (non-wetting and wetting phases, respectively) in a two-dimensional silicon micromodel was investigated at reservoir conditions (80 bar, 24 °C and 40 °C). The fluorescent microscopy and microscopic particle image velocimetry (micro-PIV) techniques were combined to quantify the flow dynamics associated with displacement of water by CO2 (drainage) in the porous matrix. To this end, water was seeded with fluorescent tracer particles, CO2 was tagged with a fluorescent dye and each phase was imaged independently using spectral separation in conjunction with microscopic imaging. This approach allowed simultaneous measurement of the spatially-resolved instantaneous velocity field in the water and quantification of the spatial configuration of the two fluid phases. The results, acquired with sufficient time resolution to follow the dynamic progression of both phases, provide a comprehensive picture of the flow physics during the migration of the CO2 front, the temporal evolution of individual menisci, and the growth of fingers within the porous microstructure. During that growth process, velocity jumps 20-25 times larger in magnitude than the bulk velocity were measured in the water phase and these bursts of water flow occurred both in-line with and against the bulk flow direction. These unsteady velocity events support the notion of pressure bursts and Haines jumps during pore drainage events as previously reported in the literature [1-3]. After passage of the CO2 front, shear-induced flow was detected in the trapped water ganglia in the form of circulation zones near the CO2-water interfaces as well as in the thin water films wetting the surfaces of the silicon micromodel. To our knowledge, the results presented herein represent the first quantitative spatially and temporally resolved velocity-field measurements at high pressure for water displacement by liquid/supercritical CO2 injection in a porous micromodel.

  16. Experimental investigation of buoyancy effects on convection heat transfer of supercritical CO2 flow in a horizontal tube

    NASA Astrophysics Data System (ADS)

    Tanimizu, Katsuyoshi; Sadr, Reza

    2016-04-01

    The heat transfer characteristics of supercritical carbon dioxide (S-CO2) turbulent flow were investigated experimentally in a horizontal circular pipe with an inner diameter of 8.7 mm. Local convection coefficients and Nusselt numbers of the flow were obtained at different locations along the pipe with a constant heat flux ranging from 16 to 64 kW/m2. Experiments were performed for fluid mass flow rate ranging from 0.011 to 0.017 kg/s, an inlet fluid temperature ranging from 24 to 28 °C, and a flow pressure ranging from 7.5 to 9.0 MPa to investigate their effects on the convection heat transfer in the pipe. Both enhancement as well as deterioration in the heat transfer coefficient was observed for the flow conditions examined in this work. Experimental results were then compared with the widely used empirical correlation for pipe flow. Three commonly used buoyancy parameters were utilized to investigate their applicability in the present test conditions. Results indicate that all the parameters show a strong presence of buoyancy effects in the present test conditions. The trend and magnitude of these parameters, however, do not agree with the trend and magnitude of heat transfer enhancement and deterioration along the pipe.

  17. Supercritical CO2 Power Cycles: Design Considerations for Concentrating Solar Power

    SciTech Connect

    Neises, Ty; Turchi, Craig

    2014-09-01

    A comparison of three supercritical CO2 Brayton cycles: the simple cycle, recompression cycle and partial-cooling cycle indicates the partial-cooling cycle is favored for use in concentrating solar power (CSP) systems. Although it displays slightly lower cycle efficiency versus the recompression cycle, the partial-cooling cycle is estimated to have lower total recuperator size, as well as a lower maximum s-CO2 temperature in the high-temperature recuperator. Both of these effects reduce recuperator cost. Furthermore, the partial-cooling cycle provides a larger temperature differential across the turbine, which translates into a smaller, more cost-effective thermal energy storage system. The temperature drop across the turbine (and by extension, across a thermal storage system) for the partial-cooling cycle is estimated to be 23% to 35% larger compared to the recompression cycle of equal recuperator conductance between 5 and 15 MW/K. This reduces the size and cost of the thermal storage system. Simulations by NREL and Abengoa Solar indicate the partial-cooling cycle results in a lower LCOE compared with the recompression cycle, despite the former's slightly lower cycle efficiency. Advantages of the recompression cycle include higher thermal efficiency and potential for a smaller precooler. The overall impact favors the use of a partial-cooling cycle for CSP compared to the more commonly analyzed recompression cycle.

  18. Optimization of Supercritical CO2 Extraction of Fish Oil from Viscera of African Catfish (Clarias gariepinus)

    PubMed Central

    Sarker, Mohamed Zaidul Islam; Selamat, Jinap; Habib, Abu Sayem Md. Ahsan; Ferdosh, Sahena; Akanda, Mohamed Jahurul Haque; Jaffri, Juliana Mohamed

    2012-01-01

    Fish oil was extracted from the viscera of African Catfish using supercritical carbon dioxide (SC-CO2). A Central Composite Design of Response Surface methodology (RSM) was employed to optimize the SC-CO2 extraction parameters. The oil yield (Y) as response variable was executed against the four independent variables, namely pressure, temperature, flow rate and soaking time. The oil yield varied with the linear, quadratic and interaction of pressure, temperature, flow rate and soaking time. Optimum points were observed within the variables of temperature from 35 °C to 80 °C, pressure from 10 MPa to 40 MPa, flow rate from 1 mL/min to 3 mL/min and soaking time from 1 h to 4 h. However, the extraction parameters were found to be optimized at temperature 57.5 °C, pressure 40 MPa, flow rate 2.0 mL/min and soaking time 2.5 h. At this optimized condition, the highest oil yields were found to be 67.0% (g oil/100 g sample on dry basis) in the viscera of catfish which was reasonable to the yields of 78.0% extracted using the Soxhlet method. PMID:23109854

  19. HYDROGENATION OF 4-OXOISOPHORONE OVER PD/AL2/O2 CATALYST UNDER SUPERCRITICAL CO2 MEDIUM

    EPA Science Inventory

    Hydrogenation of 4-oxoisophorone has been studied over 1% Pd/Al2O3 impregnated catalyst in supercritical CO2 medium at different reaction conditions. The effect of temperature, pressure and reaction medium on the conversion and product selectivity is discussed. Phase behavior stu...

  20. Significant improvement of thermal stability for CeZrPrNd oxides simply by supercritical CO(2) drying.

    PubMed

    Fan, Yunzhao; Wang, Zizi; Xin, Ying; Li, Qian; Zhang, Zhaoliang; Wang, Yingxia

    2014-01-01

    Pr and Nd co-doped Ce-Zr oxide solid solutions (CZPN) were prepared using co-precipitation and microemulsion methods. It is found that only using supercritical CO(2) drying can result in a significant improvement of specific surface area and oxygen storage capacity at lower temperatures for CZPN after aging at 1000°C for 12 h in comparison with those using conventional air drying and even supercritical ethanol drying. Furthermore, the cubic structure was obtained in spite of the fact that the atomic ratio of Ce/(Ce+Zr+Pr+Nd) is as low as 29%. The high thermal stability can be attributed to the loosely aggregated morphology and the resultant Ce enrichment on the nanoparticle surface, which are caused by supercritical CO(2) drying due to the elimination of surface tension effects on the gas-liquid interface.

  1. Significant Improvement of Thermal Stability for CeZrPrNd Oxides Simply by Supercritical CO2 Drying

    PubMed Central

    Fan, Yunzhao; Wang, Zizi; Xin, Ying; Li, Qian; Zhang, Zhaoliang; Wang, Yingxia

    2014-01-01

    Pr and Nd co-doped Ce-Zr oxide solid solutions (CZPN) were prepared using co-precipitation and microemulsion methods. It is found that only using supercritical CO2 drying can result in a significant improvement of specific surface area and oxygen storage capacity at lower temperatures for CZPN after aging at 1000°C for 12 h in comparison with those using conventional air drying and even supercritical ethanol drying. Furthermore, the cubic structure was obtained in spite of the fact that the atomic ratio of Ce/(Ce+Zr+Pr+Nd) is as low as 29%. The high thermal stability can be attributed to the loosely aggregated morphology and the resultant Ce enrichment on the nanoparticle surface, which are caused by supercritical CO2 drying due to the elimination of surface tension effects on the gas-liquid interface. PMID:24516618

  2. Significant improvement of thermal stability for CeZrPrNd oxides simply by supercritical CO(2) drying.

    PubMed

    Fan, Yunzhao; Wang, Zizi; Xin, Ying; Li, Qian; Zhang, Zhaoliang; Wang, Yingxia

    2014-01-01

    Pr and Nd co-doped Ce-Zr oxide solid solutions (CZPN) were prepared using co-precipitation and microemulsion methods. It is found that only using supercritical CO(2) drying can result in a significant improvement of specific surface area and oxygen storage capacity at lower temperatures for CZPN after aging at 1000°C for 12 h in comparison with those using conventional air drying and even supercritical ethanol drying. Furthermore, the cubic structure was obtained in spite of the fact that the atomic ratio of Ce/(Ce+Zr+Pr+Nd) is as low as 29%. The high thermal stability can be attributed to the loosely aggregated morphology and the resultant Ce enrichment on the nanoparticle surface, which are caused by supercritical CO(2) drying due to the elimination of surface tension effects on the gas-liquid interface. PMID:24516618

  3. Supercritical fluid extraction of Beauvericin from maize.

    PubMed

    Ambrosino, P; Galvano, F; Fogliano, V; Logrieco, A; Fresa, R; Ritieni, A

    2004-02-27

    Beauvericin (BEA), a supercritical fluid extraction with supercritical carbon dioxide from maize was investigated. Extraction efficiencies under several different extraction conditions were examined. Pressure, temperature, extraction time, organic modifier and water matrix content (10%) were investigated. The best extraction conditions were at a temperature of 60 degrees C, 3200psi, for 30min static extraction time and methanol as modifier solvent. Extraction recovery of 36% without modifier by adding water to the matrix in the extraction vessel (reproducibility relative standard deviations (R.S.D.)=3-5%) were recorded. Extraction recovery of 76.9% with methanol as co-solvent (reproducibility R.S.D.=3-5%) was obtained. Data shows that SFE gives a lower BEA recovery compared to conventional extraction protocol with organic solvents while SFE with modifier and conventional extraction yields are comparable. BEA extract contents were determined by high pressure liquid chromatography (HPLC) with a diode array detector (DAD) at 205nm and BEA peak confirmed by LC-MS. Acetonitrile-water as mobile phase and column C-18 were both tested. Instrumental and analytical parameters were optimized in the range linear interval from 1 to 500mgkg(-1) and reached a detection limit of 2ng. PMID:18969327

  4. Liberation of microbial substrates from macromolecular organic matter by non-supercritical CO2

    NASA Astrophysics Data System (ADS)

    Sauer, P.; Glombitza, C.; Kallmeyer, J.

    2012-12-01

    The worldwide search for suitable underground storage formations for CO2 also considers coal-bearing strata. CO2 is already injected into coal seams for enhanced recovery of coal bed methane. However, the geochemical and microbiological effects of increased CO2 concentrations on organic matter rich formations are rarely investigated. The injected CO2 will dissolve in the pore water, causing a decrease in pH and resulting in acidic formation waters. Low molecular weight organic acids (LMWOAs) are chemically bound to the macromolecular matrix of sedimentary organic matter and may be liberated by hydrolysis, which is enhanced under acidic conditions. Recent investigations outlined the importance of LMWOAs as a feedstock for subsurface microbial life [1]. Therefore, injection of CO2 into coal formations may result in enhanced nutrient supply for subsurface microbes. To investigate the effects of highly CO2-saturated waters on the release of LMWOAs from coal, we developed an inexpensive high-pressure-high-temperature system that allows manipulating the concentration of dissolved gases up to 60 MPa and 120°C, respectively. The sample is placed in a flexible, gas-tight and inert PVDF sleeve, separating it from the pressure fluid and allowing for subsampling without loss of pressure. Lignite samples from the DEBITS-1 well, Waikato Basin, NZ and the Welzow-Süd open-cast mine, Niederlausitz, Germany, were extracted at 90° C and 5 MPa, with either pure water, CO2-saturated water, CO2/NO2 or CO2/SO2-saturated water. Subsamples were taken at different time points during the 72 hrs. long extraction. Extraction of LMWOAs from coal samples with our pressurised system resulted in yields that were up to four times higher than those reported for Soxhlet extraction [2]. These higher yields may be explained by the fact that during Soxhlet extraction the sample only gets into contact with freshly distilled water, whereas in our system the extraction fluid is circulated, resulting in

  5. Mass transport enhancement in modified supercritical fluid

    SciTech Connect

    Abaroudi, K.; Trabelsi, F.; Calloud-Gabriel, B.; Recasens, F.

    1999-09-01

    In this paper, the supercritical-fluid extraction (SCFE) of a packed bed of {beta}-naphthol-impregnated porous pellets was studied. An increasing number of industrial SCFE processes involve the extraction of a solute retained within a porous matrix, usually in the form of seeds or irregular grains. The interest in high-pressure extraction is due to certain advantages of dense gases and near-critical solvents over conventional liquid solvents. In this study, modified carbon dioxide was the fluid studied. The effects of temperature, pressure, fluid velocity, particle size, and gravity were experimentally studied using carbon dioxide, pure or mixed with varying amounts of toluene (6%, and 10%). For the solute, {beta}-naphthol, the solubilities in SC carbon dioxide mixtures (from 0 to 10% toluene) were available from separate experiments. The dispersed plug-flow model was used to describe the nonideal flow. Fitting the experimental data with the model solution allowed the measurements of the fluid-to-particle mass transfer coefficient, the intraparticle diffusivity, and the axial dispersion coefficient (the latter in terms of the axial Peclet number). The influence of cosolvent concentration on the three transport parameters, which were not available so far, is presented.

  6. Fluid chemistry of the onshore CO2 sequestration formation at Nagaoka, Japan: 5 years passed since CO2 injection

    NASA Astrophysics Data System (ADS)

    Mito, S.; Asahara, Y.; Xue, Z.

    2011-12-01

    The CO2 injection into structural reservoirs in deep permeable geologic formations is now expected one of the most realizable methods from the point of view of the cost and the CO2 preserving capability of the geological reservoirs. The first Japanese pilot-scale CO2 sequestration project has been done in an onshore saline aquifer at Nagaoka-site, Japan. 10,400 tones of CO2 were injected into a thin aquifer at the depth of 1110 m at a rate of 20-40 tones from July 2003 to January 2005. To investigate a chemical reaction between CO2 fluids and rock forming minerals at the sequestration formation, formation water was collected before and after 1year of the injection (Mito et al., 2008). The result of chemical analyses exhibited a high concentration of HCO3-, Ca, Mg, Fe, Mn and Si in the post-CO2 injection samples compared to the original formation water. The result indicated that a chemical reaction between CO2 and formation water and rock forming minerals had occurred in the sequestration formation at the early stage of CO2 storage. A continuous resistivity monitoring from 2003 to 2011 showed an existence of stagnant free CO2 at the depth of 1110m and gradual spreading of CO2 dissolved water at a top and a bottom of the free CO2 layer (Mito and Xue 2011). This observation suggests that the CO2 trapped by formation water have gradually diffused and chemical trapping of CO2 by surrounding minerals have progressed in the formation. For long-term CO2 storage, we should clarify the reaction between CO2 and minerals occurred at the edge of the spreading CO2 fluids. We are going to collect formation water in the sequestration site at November 2011. We will show the analytical result of the sampled water and discuss about the long-term chemical reaction between the diffused CO2 fluids and rock forming minerals at the Nagaoka sequestration site. References Mito et al., 2008. International Journal of Greenhouse Gas Control, 2, 309-318. Mito and Xue 2011. Energy procedia, 4

  7. Supercritical fluid chromatography in pharmaceutical analysis.

    PubMed

    Desfontaine, Vincent; Guillarme, Davy; Francotte, Eric; Nováková, Lucie

    2015-09-10

    In the last few years, there has been a resurgence of supercritical fluid chromatography (SFC), which has been stimulated by the introduction of a new generation of instruments and columns from the main providers of chromatographic instrumentation, that are strongly committed to advancing the technology. The known limitations of SFC, such as weak UV sensitivity, limited reliability and poor quantitative performance have been mostly tackled with these advanced instruments. In addition, due to the obvious benefits of SFC in terms of kinetic performance and its complementarity to LC, advanced packed-column SFC represents today an additional strategy in the toolbox of the analytical scientist, which may be particularly interesting in pharmaceutical analysis. In the present review, the instrumentation and experimental conditions (i.e. stationary phase chemistry and dimensions, mobile phase nature, pressure and temperature) to perform "advanced SFC" are discussed. The applicability of SFC in pharmaceutical analysis, including the determination of drugs in formulations and biofluids is critically discussed.

  8. Brucite [Mg(OH2)] Carbonation in Wet Supercritical CO2: An in situ High Pressure X-Ray Diffraction Study

    SciTech Connect

    Schaef, Herbert T.; Windisch, Charles F.; McGrail, B. Peter; Martin, Paul F.; Rosso, Kevin M.

    2011-11-01

    Understanding mechanisms and kinetics of mineral carbonation reactions relevant to sequestering carbon dioxide as a supercritical fluid (scCO2) in geologic formations is crucial to accurately predicting long-term storage risks. Most attention so far has been focused on reactions occurring between silicate minerals and rocks in the aqueous dominated CO2-bearing fluid. However, water-bearing scCO2 also comprises a reactive fluid, and in this situation mineral carbonation mechanisms are poorly understood. Using in situ high-pressure x-ray diffraction, the carbonation of brucite [Mg(OH)2] in wet scCO2 was examined at pressure (82 bar) as a function of water concentration and temperature (50 C and 75 C). Exposing brucite to anhydrous scCO2 at either temperature resulted in little or no detectable reaction over three days. However, addition of trace amounts of water resulted in partial carbonation of brucite into nesquehonite [MgCO3 3H2O] within a few hours at 50 C. By increasing water content to well above the saturation level of the scCO2, complete conversion of brucite into nesquehonite was observed. Tests conducted at 75 C resulted in the conversion of brucite into magnesite [MgCO3] instead, apparently through an intermediate nesquehonite step. Raman spectroscopy applied to brucite reacted with 18O-labeled water in scCO2 show it was incorporated into carbonate at relatively high concentration. This supports a carbonation mechanism with at least one step involving a direct reaction between the mineral and water molecules without mediation by a condensed aqueous layer.

  9. Fluid dynamic effects on precision cleaning with supercritical fluids

    SciTech Connect

    Phelps, M.R.; Hogan, M.O.; Silva, L.J.

    1994-06-01

    Pacific Northwest Laboratory staff have assembled a small supercritical fluids parts cleaning test stand to characterize how system dynamics affect the efficacy of precision cleaning with supercritical carbon dioxide. A soiled stainless steel coupon, loaded into a ``Berty`` autoclave, was used to investigate how changes in system turbulence and solvent temperature influenced the removal of test dopants. A pulsed laser beam through a fiber optic was used to investigate real-time contaminant removal. Test data show that cleaning efficiency is a function of system agitation, solvent density, and temperature. These data also show that high levels of cleaning efficiency can generally be achieved with high levels of system agitation at relatively low solvent densities and temperatures. Agitation levels, temperatures, and densities needed for optimal cleaning are largely contaminant dependent. Using proper system conditions, the levels of cleanliness achieved with supercritical carbon dioxide compare favorably with conventional precision cleaning methods. Additional research is currently being conducted to generalize the relationship between cleaning performance and parameters such as contaminant solubilities, mass transfer rates, and solvent agitation. These correlations can be used to optimize cleaning performance, system design, and time and energy consumption for particular parts cleaning applications.

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

    SciTech Connect

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

    2013-01-01

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

  11. Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

    NASA Astrophysics Data System (ADS)

    Loring, J.

    2015-12-01

    Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2-enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of Na-, Cs-, and NH4+-saturated montmorillonite (Na-, Cs-, and NH4-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane, carbon dioxide, and CO2/CH4 mixtures (3 and 25 mole% CO2) were investigated using in situ IR spectroscopic titrations, in situ XRD, in situ MAS-NMR, and ab initio electronic structure calculations. The overarching goal was to better understand the hydration/expansion behavior of Na-SWy-2 in CO2/CH4 fluid mixtures by comparison to Cs-, and NH4+-saturated clays. Specific aims were to (1) determine if CH4 intercalates the clays, (2) probe the effects of increasing dissolved CO2 and H2O concentrations, and (3) understand the role of cation solvation by H2O and/or CO2. In pure CH4, no evidence of CH4 intercalation was detected by IR for any of the clays. Similarly, no measurable changes to the basal spacing were observed by XRD in the presence of pure CH4. However, when dry Cs- and NH4-SWy-2 were exposed to dry fluids containing CO2, IR showed maximum CO2 penetrated the interlayer, XRD indicated the clays expanded, and NMR showed evidence for cation solvation by CO2, in line with theoretical predictions. IR titration of these clays with water showed sorbed H2O concentrations decreased with increasing dissolved CO2, suggesting competition for interlayer residency by CO2 and H2O. For Na-SWy-2, on the other

  12. Functionalization of polycaprolactone/hydroxyapatite scaffolds with Usnea lethariiformis extract by using supercritical CO2.

    PubMed

    Fanovich, M A; Ivanovic, J; Zizovic, I; Misic, D; Jaeger, P

    2016-01-01

    Investigation of an integrated supercritical fluid extraction and supercritical solvent impregnation process for fabrication of microporous polycaprolactone-hydroxyapatite (PCL-HA) scaffolds with antibacterial activity is presented. The HA content and particle size as well as the operating conditions of the integrated process is optimized regarding the amount of impregnated antibacterial agent (Usnea lethariiformis extract) in the PCL-HA matrix, scaffold morphology and antibacterial activity against methicillin resistant Staphylococcus aureus (MRSA) strains. High pressure differential scanning calorimetry (HP-DSC) assay reveals that an increasing amount of HA results in decreasing melting temperature as well as crystallinity at an operating pressure of 17 MPa. The PCL-HA composites with micrometric sizes of the HA particles are convenient for being processed by the integrated process due to the simple preparation, a good interaction between the PCL matrix and filler and the advantageous impact on sorption. The scaffold obtained from PCL-HA with 20% of the HA shows the highest impregnation yield at 17 MPa and 35 °C (5.9%) and subsequently also the best bactericidal effect on the tested MRSA strains at an initial bacterial inoculum of 2 × 10(-4)CFU/mL. PMID:26478304

  13. Interaction Between CO2-Rich Sulfate Solutions and Carbonate Reservoir Rocks from Atmospheric to Supercritical CO2 Conditions: Experiments and Modeling

    NASA Astrophysics Data System (ADS)

    Cama, J.; Garcia-Rios, M.; Luquot, L.; Soler Matamala, J. M.

    2014-12-01

    A test site for CO2 geological storage is situated in Hontomín (Spain) with a reservoir rock that is mainly composed of limestone. During and after CO2 injection, the resulting CO2-rich acid brine gives rise to the dissolution of carbonate minerals (calcite and dolomite) and gypsum (or anhydrite at depth) may precipitate since the reservoir brine contains sulfate. Experiments using columns filled with crushed limestone or dolostone were conducted under different P-pCO2 conditions (atmospheric: 1-10-3.5 bar; subcritical: 10-10 bar; and supercritical: 150-34 bar), T (25, 40 and 60 ºC) and input solution compositions (gypsum-undersaturated and gypsum-equilibrated solutions). We evaluated the effect of these parameters on the coupled reactions of calcite/dolomite dissolution and gypsum/anhydrite precipitation. The CrunchFlow and PhreeqC (v.3) numerical codes were used to perform reactive transport simulations of the experiments. Under the P-pCO2-T conditions, the volume of precipitated gypsum was smaller than the volume of dissolved carbonate minerals, yielding an increase in porosity (Δporosity up to ≈ 4%). A decrease in T favored limestone dissolution regardless of pCO2 owing to increasing undersaturation with decreasing temperature. However, gypsum precipitation was favored at high T and under atmospheric pCO2 conditions but not at high T and under 10 bar of pCO2 conditions. The increase in limestone dissolution with pCO2 was directly attributed to pH, which was more acidic at higher pCO2. Increasing pCO2, carbonate dissolution occurred along the column whereas it was localized in the very inlet under atmospheric conditions. This was due to the buffer capacity of the carbonic acid, which maintains pH at around 5 and keeps the solution undersaturated with respect to calcite and dolomite along the column. 1D reactive transport simulations reproduced the experimental data (carbonate dissolution and gypsum precipitation for different P-pCO2-T conditions). Drawing

  14. Supercritical CO2 direct cycle Gas Fast Reactor (SC-GFR) concept.

    SciTech Connect

    Wright, Steven Alan; Parma, Edward J., Jr.; Suo-Anttila, Ahti Jorma; Al Rashdan, Ahmad; Tsvetkov, Pavel Valeryevich; Vernon, Milton E.; Fleming, Darryn D.; Rochau, Gary Eugene

    2011-05-01

    This report describes the supercritical carbon dioxide (S-CO{sub 2}) direct cycle gas fast reactor (SC-GFR) concept. The SC-GFR reactor concept was developed to determine the feasibility of a right size reactor (RSR) type concept using S-CO{sub 2} as the working fluid in a direct cycle fast reactor. Scoping analyses were performed for a 200 to 400 MWth reactor and an S-CO{sub 2} Brayton cycle. Although a significant amount of work is still required, this type of reactor concept maintains some potentially significant advantages over ideal gas-cooled systems and liquid metal-cooled systems. The analyses presented in this report show that a relatively small long-life reactor core could be developed that maintains decay heat removal by natural circulation. The concept is based largely on the Advanced Gas Reactor (AGR) commercial power plants operated in the United Kingdom and other GFR concepts.

  15. Comparative analysis of the oil and supercritical CO2 extract of Elettaria cardamomum (L.) Maton.

    PubMed

    Marongiu, Bruno; Piras, Alessandra; Porcedda, Silvia

    2004-10-01

    The volatile oil of Elettaria cardamomum (L.) Maton seeds was obtained by supercritical CO(2) extraction (SC-CO(2)). The effect of the extraction conditions on the yield and composition of the resulting cardamom volatile oil was examined by testing two pressure values, 9.0 and 11.0 MPa; two temperatures, 40 and 50 degrees C; two flow rate values, 0.6 and 1.2 kg/h; and two particles size values, 250-425 and >850 microm. The extraction conditions that gave the highest yield, Y (grams of extract per gram of seeds), of 5.5%, were as follows: pressure, 9.0 MPa; temperature, 40 degrees C; carbon dioxide flow, phi = 1.2 kg/h; and particles sizes in the range of 250-425 microm. Waxes, recovered as traces, were entrapped in the first separator set at 9.0 MPa and -10 degrees C. The oil was recovered in the second separator working at 1.5 MPa and 10 degrees C. The main components were as follows: alpha-terpinyl acetate, 42.3%; 1,8-cineole, 21.4%; linalyl acetate, 8.2%; limonene, 5.6%; and linalool, 5.4%. A comparison with the hydrodistilled oil, obtained at a yield of 5.0%, did not reveal any consistent difference. In contrast, the extract obtained using hexane, Y = 7.6%, showed strong composition differences. Indeed, the volatile fraction of the extract was made up mainly of the following: limonene, 36.4%; 1,8-cineole, 23.5%; terpinolene, 8.6%; and myrcene, 6.6%.

  16. Supercritical fluid carbon dioxide cleaning of plutonium parts

    SciTech Connect

    Hale, S.J.

    1991-12-31

    Supercritical fluid carbon dioxide is under investigation in this work for use as a cleaning solvent for the final cleaning of plutonium parts. These parts must be free of organic residue to avoid corrosion in the stockpile. Initial studies on stainless steel and full-scale mock-up parts indicate that the oils of interest are easily and adequately cleaned from the metal surfaces with supercritical fluid carbon dioxide. Results from compatibility studies show that undesirable oxidation or other surface reactions are not occurring during exposure of plutonium to the supercritical fluid. Cleaning studies indicate that the oils of interest are removed from the plutonium surface under relatively mild conditions. These studies indicate that supercritical fluid carbon dioxide is a very promising cleaning medium for this application.

  17. Supercritical Fluid Extraction of Aflatoxin B 1 from Soil

    EPA Science Inventory

    This research describes the development of a Supercritical Fluid Extraction (SFE) method to recover aflatoxin B1 from fortified soil. The effects of temperature, pressure, modifier (identity and percentage), and extraction type were assessed. Using the optimized SFE conditions, ...

  18. Hydroxyapatite-TiO(2)-based nanocomposites synthesized in supercritical CO(2) for bone tissue engineering: physical and mechanical properties.

    PubMed

    Salarian, Mehrnaz; Xu, William Z; Wang, Zhiqiang; Sham, Tsun-Kong; Charpentier, Paul A

    2014-10-01

    Calcium phosphate-based nanocomposites offer a unique solution toward producing scaffolds for orthopedic and dental implants. However, despite attractive bioactivity and biocompatibility, hydroxyapatite (HAp) has been limited in heavy load-bearing applications due to its intrinsically low mechanical strength. In this work, to improve the mechanical properties of HAp, we grew HAp nanoplates from the surface of one-dimensional titania nanorod structures by combining a coprecipitation and sol-gel methodology using supercritical fluid processing with carbon dioxide (scCO2). The effects of metal alkoxide concentration (1.1-1.5 mol/L), reaction temperature (60-80 °C), and pressure (6000-8000 psi) on the morphology, crystallinity, and surface area of the resulting nanostructured composites were examined using scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and Brunauer-Emmet-Teller (BET) method. Chemical composition of the products was characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray absorption near-edge structure (XANES) analyses. HAp nanoplates and HAp-TiO2 nanocomposites were homogeneously mixed within poly(ε-caprolactone) (PCL) to develop scaffolds with enhanced physical and mechanical properties for bone regeneration. Mechanical behavior analysis demonstrated that the Young's and flexural moduli of the PCL/HAp-TiO2 composites were substantially higher than the PCL/HAp composites. Therefore, this new synthesis methodology in scCO2 holds promise for bone tissue engineering with improved mechanical properties.

  19. Tectonic impact on the dynamics of CO2-rich fluid migration in Utah

    NASA Astrophysics Data System (ADS)

    Nadine, E. Z.; Jean Luc, F.; Remy, D.; Battani, A.; Olivier, V.

    2009-12-01

    explain the existence of these distinct provinces? Is it due to the physical properties of the reservoirs, to the evolution of the fracture and fault patterns changing through time in connection with paleostress fields, to the occurrence of a thick salt pillow in the Moab area which has driven the tectonic style and played as local seal, to the shale sealing properties when PCO2 increased at depth to the physical phase of the CO2 during migration or storage (dissolved, super-critical or gas), or finally to the seismic cyclicity. A possible strong linkage between the seismicity and the volcanic activity, corresponding to large CO2-rich gas expel, have been investigated. In order to constrain the architecture of the deep buried reservoirs and traps we analyzed the deformation through analogue models, the models have been acquired with X-Ray tomography at IFP. These parameters have been analysed for the three investigated areas, allowing to propose an integrated model of the local circulation and/or storage of the CO2-enriched fluid for each area.

  20. Surface modification of chitin using ultrasound-assisted and supercritical CO2 technologies for cobalt adsorption.

    PubMed

    Dotto, Guilherme L; Cunha, Jeanine M; Calgaro, Camila O; Tanabe, Eduardo H; Bertuol, Daniel A

    2015-09-15

    Ultrasound-assisted (UA) and supercritical CO2 technologies (SCO2) were used to modify the chitin surface and, improve its adsorption characteristics regarding to cobalt. Chitin, before and after the treatments, was characterized by N2 adsorption isotherms (BET), infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Unmodified and surface modified chitins were used as adsorbents to remove cobalt from aqueous solutions. The adsorption study was performed by equilibrium isotherms and kinetic curves. The chitin particle characteristics, such as, surface area, pore volume and porosity were improved by the UA and SCO2 treatments. The crystallinity index decreased after the UA and SCO2 treatments, and also, intense surface modifications were observed. Langmuir and Freundlich models were adequate to represent the adsorption equilibrium. The maximum adsorption capacities were 50.03, 83.94 and 63.08 mg g(-1) for unmodified chitin, UA surface modified chitin and SCO2 surface modified chitin. The adsorption kinetic curves were well represented by the pseudo-second order model. UA and SCO2 technologies are alternatives to modify the chitin surface and improve its adsorption characteristics.

  1. Optimized, Competitive Supercritical-CO2 Cycle GFR for Gen IV Service

    SciTech Connect

    M.J. Driscoll; P. Hejzlar; G. Apostolakis

    2008-09-08

    An overall plant design was developed for a gas-cooled fast reactor employing a direct supercritical Brayton power conversion system. The most important findings were that (1) the concept could be capital-cost competitive, but startup fuel cycle costs are penalized by the low core power density, specified in large part to satisfy the goal of significatn post-accident passive natural convection cooling; (2) active decay heat removal is preferable as the first line of defense, with passive performance in a backup role; (3) an innovative tube-in-duct fuel assembly, vented to the primpary coolant, appears to be practicable; and (4) use of the S-Co2 GFR to support hydrogen production is a synergistic application, since sufficient energy can be recuperated from the product H2 and 02 to allow the electrolysis cell to run 250 C hotter than the reactor coolant, and the water boilers can be used for reactor decay heat removal. Increasing core poer density is identified as the top priority for future work on GFRs of this type.

  2. Phase behaviour and conductivity study on multi-component mixtures for electrodeposition in supercritical fluids.

    PubMed

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

    2010-01-14

    Electrochemistry in supercritical CO(2) (scCO(2)) is difficult because the very low dielectric constant of the fluid restricts the solubility of ionic species and the conductivity of dissolved electrolytes. To overcome this problem to allow us to carry out electrodeposition at macroelectrodes from scCO(2) we have investigated the use of co-solvents and modified electrolyte salts chosen to increase their solubility and dissociation in the supercritical fluid. Here we report results of phase behaviour studies for mixtures of CO(2) with [NBu(n)(4)][BF(4)] and either methanol (CH(3)OH) or acetonitrile (CH(3)CN) as the co-solvent. These show that the solubility of [NBu(n)(4)][BF(4)] is approximately 5 times larger when CH(3)CN is the co-solvent rather than CH(3)OH. Consequently the phase behaviour of the ternary of CO(2)-[NBu(n)(4)][BF(4)]-CH(3)CN was studied in greater detail over a range of compositions. To enhance the conductivity of scCO(2)-CH(3)CN a range of electrolyte salts was synthesised in which the [NBu(n)(4)](+) and/or [BF(4)](-) ion were replaced by different derivatives. Results for the phase behaviour and conductivity of these modified electrolyte salts in scCO(2)-CH(3)CN are reported for several different compositions. We find that increasing the degree of fluorination and size of the ions increases the solubility of the electrolyte salt in scCO(2)-CH(3)CN. Of the 11 electrolytes investigated [NBu(n)(4)][B{3,5-C(6)H(3)(CF(3))(2)}(4)] appears the most suitable for use in scCO(2)-CH(3)CN with a molar conductivity of 22-26 S cm(2) mol(-1) and a maximum measured conductivity of approximately 3 mS cm(-1) for 0.07 M [NBu(n)(4)][B{3,5-C(6)H(3)(CF(3))(2)}(4)] dissolved in scCO(2)-CH(3)CN (molar ratio CH(3)CN : CO(2) approximately 0.12) at 20 MPa and 328.15 K. This is an order of magnitude improvement over similar results for the [NBu(n)(4)][BF(4)] parent. Studies of the conductance as a function of the electrolyte concentration suggest that triple ions make an

  3. 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.

  4. Modeling of flow and heat transfer for fluids at supercritical conditions

    NASA Astrophysics Data System (ADS)

    Gallaway, Tara

    2011-12-01

    The Supercritical Water Reactor (SCWR) has been proposed as one of the six Generation IV reactor design concepts under consideration. The key feature of the SCWR is that water at supercritical pressures is used as the reactor coolant. At supercritical pressures, the working fluid does not undergo phase change as it is heated, but rather the fluid properties experience dramatic variations throughout what is known as the pseudo-critical region. Highly nonuniform temperature and uid property distributions are expected in the reactor core, which will have a significant impact on turbulence and heat transfer as well as stability limits for future SCWRs. The goal of this work is to understand and predict the effects of these fluid property variations on turbulence and heat transfer throughout the reactor core and to predict the potential onset of dynamic instabilities. CO2 at supercritical conditions is included in the current study due in some part to its use as a viable simulant fluid in place of water for experimental studies. The use of CO2 at supercritical conditions as a reactor coolant has also gained popularity in recent years. Spline-type property models have been developed for both water and CO2 at supercritical pressures in order to include the property variations into a numerical solver. Turbulence and heat transfer models for fluids at supercritical conditions have been developed and implemented into the NPHASE-CMFD computer code. The results of predictions using the proposed models have been compared to experimental data from the Korea Atomic Energy Research Institute (KAERI) for various heat transfer regimes. While no model is without some deficiency, the Chien Low-Reynolds k -- epsilon model performs best at predicting the experimental data. A stability model has been developed and is presented in this dissertation as well. This model utilizes three different solution methods and tests the effects of inlet temperature, mass flow rate, local loss

  5. Supercritical fluid extraction and bioactivity of cedarwood oil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Supercritical carbon dioxide (70°C, 4,000 psi) was used to extract cedarwood oil from Eastern redcedar, Juniperus virginiana L. The CO2-derived oil was tested for biological activity against several species of arthropods, including mosquitoes, ticks, houseflies, and ants. The cedarwood oil was found...

  6. Processing energetic materials with supercritical fluid precipitation techniques

    NASA Astrophysics Data System (ADS)

    Essel, Jonathan

    cm 50% drop height instead of the standard 17 cm by ERL impact test) or ESD sensitivity (4 no-gos for NAWC ESD test) but showed a significant reduction towards initiation by friction (521 lbs threshold initiation level force instead of the standard 468 lbs by ABL friction test). The RESS-N process was used to coat nano-sized ALEX ® aluminum particles with RDX. Coatings were observed on the ALEX ® particles by field emission scanning electron microscopy (FE-SEM) and by energy dispersive X-ray spectroscopy (EDS). A method of injecting ALEX ® particles into the RDX/CO2 supercritical solution was developed that was effective in coating small batches with RDX.

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

  8. Particle Formation by Supercritical Fluid Extraction and Expansion Process

    PubMed Central

    Zhou, Junbo; Li, Haiting; Quan, Can

    2013-01-01

    Supercritical fluid extraction and expansion (SFEE) patented technology combines the advantages of both supercritical fluid extraction (SFE) and rapid expansion of supercritical solution (RESS) with on-line coupling, which makes the nanoparticle formation feasible directly from matrix such as Chinese herbal medicine. Supercritical fluid extraction is a green separation technology, which has been developed for decades and widely applied in traditional Chinese medicines or natural active components. In this paper, a SFEE patented instrument was firstly built up and controlled by LABVIEW work stations. Stearic acid was used to verify the SFEE process at optimized condition; via adjusting the preexpansion pressure and temperature one can get different sizes of particles. Furthermore, stearic acid was purified during the SFEE process with HPLC-ELSD detecting device; purity of stearic acid increased by 19%, and the device can purify stearic acid. PMID:24223031

  9. Supercritical fluid extraction of vapor-deposited pyrene from carbonaceous coal stack ash.

    PubMed

    Mauldin, R F; Vienneau, J M; Wehry, E L; Mamantov, G

    1990-11-01

    The efficiencies of extraction of vapor-deposited pyrene from a high-carbon coal stack ash by Soxhlet extraction with methanol, ultrasonic extraction with toluene, acid pretreatment and subsequent ultrasonic extraction with toluene, batch extraction with toluene, and supercritical fluid extraction (SFE) are compared. SFE using CO(2) or isobutane yielded extraction recoveries virtually identical with those obtained using ultrasonic or Soxhlet extraction processes. Collection of the SFE extract was performed by expansion into a solvent or onto the head of a gas chromatography (GC) column. No loss of extracted pyrene was observed upon collection of methanol-modified CO(2) SFE by expansion into methanol. Also, no loss of pure CO(2) SFE extract was observed upon collection on the head of a GC column. However, use of a methanol or toluene modifier for CO(2) SFE directly coupled to GC effected complete loss of extracted pyrene.

  10. Supercritical CO2 Dissolution and Mass Transfer in a Heterogeneous Pore Network under Drainage and Imbibition Conditions

    NASA Astrophysics Data System (ADS)

    Kneafsey, T. J.; Chang, C.; Zhou, Q.; Oostrom, M.; Wietsma, T. W.; Yu, Q.

    2015-12-01

    Dissolution trapping of supercritical CO2 (scCO2) is usually modeled by assuming instantaneous scCO2 dissolution and equilibrium phase partitioning. Our recent core-scale imbibition experiments show a prolonged depletion of residual scCO2 by dissolution, implying a non-equilibrium mechanism. In our 2D sandstone-analogue micromodel experimental study, pore-scale scCO2 dissolution was inferred from imaging (1) drainage using a pH-sensitive water dye and (2) imbibition using a scCO2 dye. The drainage experiment was conducted by injecting scCO2 into the dissolved-CO2 (dsCO2)-free water-filled pore network. The time-lapse images of non-uniform dye intensities indicating varying pH show that dsCO2 concentration varies from zero to solubility in individual pores and pore clusters and the average concentration gradually increases with time. The different rates of dissolution in different pores/clusters can be attributed to (1) fast scCO2 dissolution at scCO2-water interfaces, (2) rate-limited mass transfer due to limited interface areas, and (3) a transition from rate-limited to diffusion-limited mass transfer, revealed by detailed analysis on selected pores and pore clusters. The imbibition experiments conducted by injecting deionized water at different rates show (1) water flow in channels bypassing scCO2 at high residual saturations, (2) subsequent, slow scCO2 depletion by dissolution and mass transfer as effluent dsCO2 concentration varies from 0.06% to 4.44% of solubility, and (3) creation of new water flow paths by dissolution, enhancing scCO2 depletion by coupled displacement and dissolution. Both the drainage and imbibitions experiments indicate non-equilibrium scCO2 dissolution in the centimeter-scale pore network over 4.5 hours and up to 14 hours, respectively. The pore-scale imaging can help better understand the effects of pore-throat characteristics on scCO2 dissolution and mass transfer during drainage and imbibition and the interplay between displacement and

  11. Initial assessment of Ni-base alloy performance in 0.1 MPa and supercritical CO2

    DOE PAGES

    Pint, B. A.; Keiser, J. R.

    2015-09-25

    There is considerable interest in increasing the working temperature of both open and closed supercritical CO2 (sCO2) cycles to ≥700 °C. At these temperatures, it is unlikely that any Fe-base alloys have suitable strength and therefore the focus is on Ni-base alloys for this application. To begin addressing the lack of compatibility data under these conditions, initial work exposed a wide range of candidate alloys in 500-h exposures at 20 MPa (200 bar) CO2 at 650 -750 °C in high purity CO2. In general, the reaction products were thin and protective in these exposures. A smaller group of alloy couponsmore » focusing on chromia- and alumina-forming alloys was exposed for 500h in 0.1 MPa (1bar) air, CO2, CO2+O2 and CO2+H2O for comparison. Thus, the thin surface oxides formed were very similar to those formed at high pressure and no clear detrimental effect of CO2 oxidation or O2 or H2O impurities could be observed in these exposures.« less

  12. Development and Validation of Multidimensional Models of Supercritical CO2 Energy Conversion Systems for Nuclear Power Reactors

    SciTech Connect

    Podowski, Michael Z.

    2015-01-22

    A general objective of this project was to develop, verify and validate mechanistic multidimensional models of local flow and heat transfer in supercritical carbon dioxide (S-CO2) devices and systems, and to demonstrate the application of the new models to selected components of S-CO2 nuclear energy transport systems. Both steady-state and time-dependent operating conditions have been investigated. The overall workscope consisted of the following three major parts: Development, testing and validation of a mechanistic model of forced-convection heat transfer in heated channels cooled using S-CO2 at slightly supercritical pressures; Development, testing and verification/validation of a new model of the dynamics of closed- loop S-CO2 heat transport systems; and, Formulation, testing and verification of a mechanistic model for the analysis of flow and pressure distribution in S-CO2 compressors. The results of the work performed for the project have been documented in several publications.

  13. A man-portable supercritical fluid extractor

    SciTech Connect

    Wright, B.W.; Zemanian, T.S.; Lee, R.N.; Wright, C.W.

    1995-02-01

    A new prototype supercritical fluid extraction (SFE) apparatus has been developed for the on-site preparation of solid matrix samples for subsequent organic analysis. The apparatus consists of two parts, each of which satisfy weight and size requirements for portability. They are a generator module that supplies high-pressure carbon dioxide (the source of which is dry ice) and a briefcase containing a pressure regulator, extraction cells, valves for flow control, flow restriction hardware, equipment for sample collection, temperature control devices, and ancillary supplies. The generator module provides carbon dioxide at pressures to 1 kbar ({approximately}14,500 psi), incorporates no moving parts, and allows rapid loading without tools due to novel fingertight closures. Samples are contained in sintered inserts that fit inside three extraction cells that also have rapid, fingertight closures. Analyte collection can be accomplished using liquid solvent or restrictorless rapid depressurization techniques. Control schemes allow operation at a wide variety of pressures and temperatures and the use of static, dynamic, or hybrid static/dynamic extraction strategies. The technical performance of the prototype apparatus was evaluated by comparison of results from the SFE of a soil sample spiked with six to nine organic compounds of environmental interest to Soxhlet extraction.

  14. A man-portable supercritical fluid extractor

    SciTech Connect

    Wright, B.W.; Zemanian, T.S.; Lee, R.N.; Wright, C.W.

    1995-12-31

    A new prototype supercritical fluid extraction (SFE) apparatus has been developed for the on-site preparation of solid matrix samples for subsequent organic analysis. The apparatus consists of two parts, each of which satisfy weight and size requirements for portability. They are a generator module that supplies high-pressure carbon dioxide (the source of which is dry ice) and a briefcase containing a pressure regulator, extraction cells, valves for flow control, flow restriction hardware, equipment for sample collection, temperature control devices, and ancillary supplies. The generator module provides carbon dioxide at pressures to 1 kbar ({approximately}14,500 psi), incorporates no moving parts, and allows rapid loading without tools due to novel fingertight closures. Samples are contained in sintered inserts that fit inside three extraction cells that also have rapid, fingertight closures. Analyte collection may be accomplished using liquid solvent or restrictorless rapid depressurization techniques. Control schemes allow operation at a wide variety of pressures and temperatures and the use of static, dynamic, or hybrid static/dynamic extraction strategies. The technical performance of the prototype apparatus was evaluated by comparison of results from the SFE of a soil sample spiked with six to nine organic compounds of environmental interest to Soxhlet extraction.

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

    NASA Astrophysics Data System (ADS)

    Hiratsuka, Y.; Yamamoto, H.

    2014-12-01

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

  16. Enabling the measurement of in-situ, atomic scale mineral transformation rates in supercritical CO2 through development of a high pressure AFM

    NASA Astrophysics Data System (ADS)

    Lea, S.; Higgins, S. R.; Knauss, K. G.; Rosso, K. M.

    2010-12-01

    Capture and storage of carbon dioxide in deep geologic formations represents one promising scenario for minimizing the impacts of greenhouse gases on global warming. The ability to demonstrate that CO2 will remain stored in the geological formation over the long-term is needed in support of widespread implementation decisions, and knowledge of mineral-fluid chemical transformation rates is an essential aspect. The majority of previous research on mineral-fluid interactions has focused primarily on the reactivity of minerals in aqueous solutions containing various amounts of dissolved CO2. Long-term caprock integrity, however, could also be dictated by mineral transformations occurring in low-water environments dominated by the supercritical CO2 (scCO2) fluid phase, which is expected to slowly displace or dessicate residual aqueous solution at the caprock-fluid interface. Many of the mechanisms of mineral interfacial reactions with hydrated or water-saturated scCO2 are unknown and there are unique challenges to obtain kinetic and thermodynamic data for mineral transformation reactions in these fluids. We are developing a high-pressure atomic force microscope (AFM) that will enable in-situ, atomic scale measurements of metal carbonate nucleation and growth rates on mineral surfaces in contact with hydrated scCO2 fluids. This apparatus is based on the hydrothermal AFM that was developed by Higgins et al.1, but includes some enhancements and is designed to handle pressures up to 100 bar. The noise in our optically-based cantilever deflection detection scheme is subject to perturbations in the density (due to index of refraction dependence) of the compressible supercritical fluid. Consequently, variations in temperature and pressure within the fluid cell are a primary technical challenge with possible significant impact in imaging resolution. We demonstrate with our test fluid cell that the equivalent rms noise in the deflection signal is similar to (and in some cases

  17. In Situ Study of CO2 and H2O Partitioning Between Na-Montmorillonite and Variably Wet Supercritical Carbon Dioxide

    SciTech Connect

    Loring, John S.; Ilton, Eugene S.; Chen, Jeffrey; Thompson, Christopher J.; Martin, Paul F.; Benezeth, Pascale; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

    2014-06-03

    Shale formations play fundamental roles in large-scale geologic carbon sequestration (GCS) aimed primarily to mitigate climate change, and in smaller-scale GCS targeted mainly for CO2-enhanced gas recovery operations. In both technologies, CO2 is injected underground as a supercritical fluid (scCO2), where interactions with shale minerals could influence successful GCS implementation. Reactive components of shales include expandable clays, such as montmorillonites and mixed-layer illite/smectite clays. In this work, we used in situ X-ray diffraction (XRD) and in situ infrared (IR) spectroscopy to investigate the swelling/shrinkage and water/CO2 sorption of a pure montmorillonite, Na-SWy-2, when the clay is exposed to variably hydrated scCO2 at 50 °C and 90 bar. Measured interlayer spacings and sorbed water concentrations at varying levels of scCO2 hydration are similar to previously reported values measured in air at ambient pressure over a range of relative humidities. IR spectra show evidence of both water and CO2 intercalation, and variations in peak shapes and positions suggest multiple sorbed types with distinct chemical environments. Based on the intensity of the asymmetric CO stretching band of the CO2 associated with the Na-SWy-2, we observed a significant increase in sorbed CO2 as the clay expands from a 0W to a 1W state, suggesting that water props open the interlayer so that CO2 can enter. However, as the clay transitions from a 1W to a 2W state, CO2 desorbs sharply. These observations were placed in the context of two conceptual models concerning hydration mechanisms for expandable clays and were also discussed in light of recent theoretical studies on CO2-H2O-clay interactions. The swelling/shrinkage of expandable clays could affect solid volume, porosity, and permeability of shales. Consequently, the results from this work could aid predictions of shale caprock integrity in large-scale GCS, as well as methane transmissivity in enhanced gas recovery

  18. 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.

  19. Optimization of Operation Parameters for Helical Flow Cleanout with Supercritical CO2 in Horizontal Wells Using Back-Propagation Artificial Neural Network

    PubMed Central

    Song, Xianzhi; Peng, Chi; Li, Gensheng

    2016-01-01

    Sand production and blockage are common during the drilling and production of horizontal oil and gas wells as a result of formation breakdown. The use of high-pressure rotating jets and annular helical flow is an effective way to enhance horizontal wellbore cleanout. In this paper, we propose the idea of using supercritical CO2 (SC-CO2) as washing fluid in water-sensitive formation. SC-CO2 is manifested to be effective in preventing formation damage and enhancing production rate as drilling fluid, which justifies tis potential in wellbore cleanout. In order to investigate the effectiveness of SC-CO2 helical flow cleanout, we perform the numerical study on the annular flow field, which significantly affects sand cleanout efficiency, of SC-CO2 jets in horizontal wellbore. Based on the field data, the geometry model and mathematical models were built. Then a numerical simulation of the annular helical flow field by SC-CO2 jets was accomplished. The influences of several key parameters were investigated, and SC-CO2 jets were compared to conventional water jets. The results show that flow rate, ambient temperature, jet temperature, and nozzle assemblies play the most important roles on wellbore flow field. Once the difference between ambient temperatures and jet temperatures is kept constant, the wellbore velocity distributions will not change. With increasing lateral nozzle size or decreasing rear/forward nozzle size, suspending ability of SC-CO2 flow improves obviously. A back-propagation artificial neural network (BP-ANN) was successfully employed to match the operation parameters and SC-CO2 flow velocities. A comprehensive model was achieved to optimize the operation parameters according to two strategies: cost-saving strategy and local optimal strategy. This paper can help to understand the distinct characteristics of SC-CO2 flow. And it is the first time that the BP-ANN is introduced to analyze the flow field during wellbore cleanout in horizontal wells. PMID

  20. Optimization of Operation Parameters for Helical Flow Cleanout with Supercritical CO2 in Horizontal Wells Using Back-Propagation Artificial Neural Network.

    PubMed

    Song, Xianzhi; Peng, Chi; Li, Gensheng; He, Zhenguo; Wang, Haizhu

    2016-01-01

    Sand production and blockage are common during the drilling and production of horizontal oil and gas wells as a result of formation breakdown. The use of high-pressure rotating jets and annular helical flow is an effective way to enhance horizontal wellbore cleanout. In this paper, we propose the idea of using supercritical CO2 (SC-CO2) as washing fluid in water-sensitive formation. SC-CO2 is manifested to be effective in preventing formation damage and enhancing production rate as drilling fluid, which justifies tis potential in wellbore cleanout. In order to investigate the effectiveness of SC-CO2 helical flow cleanout, we perform the numerical study on the annular flow field, which significantly affects sand cleanout efficiency, of SC-CO2 jets in horizontal wellbore. Based on the field data, the geometry model and mathematical models were built. Then a numerical simulation of the annular helical flow field by SC-CO2 jets was accomplished. The influences of several key parameters were investigated, and SC-CO2 jets were compared to conventional water jets. The results show that flow rate, ambient temperature, jet temperature, and nozzle assemblies play the most important roles on wellbore flow field. Once the difference between ambient temperatures and jet temperatures is kept constant, the wellbore velocity distributions will not change. With increasing lateral nozzle size or decreasing rear/forward nozzle size, suspending ability of SC-CO2 flow improves obviously. A back-propagation artificial neural network (BP-ANN) was successfully employed to match the operation parameters and SC-CO2 flow velocities. A comprehensive model was achieved to optimize the operation parameters according to two strategies: cost-saving strategy and local optimal strategy. This paper can help to understand the distinct characteristics of SC-CO2 flow. And it is the first time that the BP-ANN is introduced to analyze the flow field during wellbore cleanout in horizontal wells. PMID

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

    PubMed

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

    2016-09-13

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

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

    PubMed

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

    2016-09-13

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

  3. Identification of Fragile Microscopic Structures during Mineral Transformations in Wet Supercritical CO2

    SciTech Connect

    Arey, Bruce W.; Kovarik, Libor; Qafoku, Odeta; Wang, Zheming; Hess, Nancy J.; Felmy, Andrew R.

    2013-04-01

    In this study we examine the nature of highly fragile reaction products that form in low water content super critical carbon dioxide (scCO2) using a combination of scanning electron microscopy/focus ion beam (SEM/FIB), confocal Raman spectroscopy, helium ion microscopy (HeIM), and transmission electron microscopy (TEM). HeIM images show these precipitates to be fragile rosettes that can readily decompose even under slight heating from an electron beam. Using the TEM revealed details on the interfacial structure between the newly formed surface precipitates and the underlying initial solid phases. The detailed microscopic analysis revealed that the growth of the precipitates either followed a tip growth mechanism with precipitates forming directly on the forsterite surface if the initial solid was non-porous (natural forsterite) or growth from the surface of the precipitates where fluid was conducted through the porous (nanoforsterite) agglomerates to the growth center. The mechanism of formation of the hydrated/hydroxylated magnesium carbonate compound (HHMC) phases offers insight into the possible mechanisms of carbonate mineral formation from scCO2 solutions which has recently received a great deal of attention as the result of the potential for CO2 to act as an atmospheric greenhouse gas and impact overall global warming. The techniques used here to examine these fragile structures an also be used to examine a wide range of fragile material surfaces. SEM and FIB technologies have now been brought together in a single instrument, which represents a powerful combination for the studies in biological, geological and materials science.

  4. 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.

  5. Isolation of essential oil from different plants and herbs by supercritical fluid extraction.

    PubMed

    Fornari, Tiziana; Vicente, Gonzalo; Vázquez, Erika; García-Risco, Mónica R; Reglero, Guillermo

    2012-08-10

    Supercritical fluid extraction (SFE) is an innovative, clean and environmental friendly technology with particular interest for the extraction of essential oil from plants and herbs. Supercritical CO(2) is selective, there is no associated waste treatment of a toxic solvent, and extraction times are moderate. Further, supercritical extracts were often recognized of superior quality when compared with those produced by hydro-distillation or liquid-solid extraction. This review provides a comprehensive and updated discussion of the developments and applications of SFE in the isolation of essential oils from plant matrices. SFE is normally performed with pure CO(2) or using a cosolvent; fractionation of the extract is commonly accomplished in order to isolate the volatile oil compounds from other co-extracted substances. In this review the effect of pressure, temperature and cosolvent on the extraction and fractionation procedure is discussed. Additionally, a comparison of the extraction yield and composition of the essential oil of several plants and herbs from Lamiaceae family, namely oregano, sage, thyme, rosemary, basil, marjoram and marigold, which were produced in our supercritical pilot-plant device, is presented and discussed. PMID:22595519

  6. Design of experiments for enantiomeric separation in supercritical fluid chromatography.

    PubMed

    Landagaray, Elodie; Vaccher, Claude; Yous, Saïd; Lipka, Emmanuelle

    2016-02-20

    A new chiral melatoninergic ligand, potentially successor of Valdoxan(®), presenting an improved pharmacological profile with regard to agomelatine, was chosen as a probe for a supercritical fluid chromatographic separation carried-out on an amylose tris[(S)-1-α-methylbenzylcarbamate] based stationary phase. The goal of this work was to optimize simultaneously three factors identified to have a significant influence to obtain the best resolution in the shortest analysis time (i.e., retention time of the second eluting enantiomer) for this chiral compound. For this purpose a central circumscribed composite (CCC) design was developed with three factors: the flow-rate, the pressure outlet and the percentage of ethanol to optimize of two responses: shortest analysis time and best resolution. The optimal conditions obtained via the optimizer mode of the software (using the Nelder-Mead method) i.e., CO2/EtOH 86:14 (v:v), 104bar, 3.2mLmin(-1) at 35°C lead to a resolution of 3.27 in less than 6min. These conditions were transposed to a preparative scale where a concentrated methanolic solution of 40mM was injected with a sample loop of 100μL. This step allowed to separate an amount of around 65mg of racemic melatonin ligand in only 3h with impressive yields (97%) and enantiomeric excess (99.5%). PMID:26765267

  7. Supercritical fluid assisted production of chitosan oligomers micrometric powders.

    PubMed

    Du, Zhe; Shen, Yu-Bin; Tang, Chuan; Guan, Yi-Xin; Yao, Shan-Jing; Zhu, Zi-Qiang

    2014-02-15

    Chitosan oligomers (O-chitosan) micrometric particles were produced from aqueous solution using a novel process, i.e. supercritical fluid assisted atomization introduced by hydrodynamic cavitation mixer (SAA-HCM). Hydrodynamic cavitation was introduced to enhance mass transfer and facilitate the mixing between SC-CO2 and liquid solution for fine particles formation. Well defined, separated and spherical microparticles were obtained, and the particles size could be well controlled with narrow distribution ranging from 0.5 μm to 3 μm. XRD patterns showed amorphous structure of O-chitosan microparticles. FTIR, TGA and DSC analyses confirmed that no change in molecular structure and thermal stability after SAA-HCM processing, while the water content was between 5.8% and 8.4%. Finally, tap densities were determined to be below 0.45 g/cm(3) indicating hollow or porous structures of microparticles. By tuning process parameters, theoretical mass median aerodynamic sizes lied inside respirable range of 1-2 μm, which presented the potential of the O-chitosan microparticles in application as inhaled dry powders. SAA-HCM was demonstrated to be very useful in particle size engineering. PMID:24507297

  8. CO2-rich fluid inclusions in greenschists, migmatites, granulites, and hydrated granulites

    NASA Technical Reports Server (NTRS)

    Hollister, L. S.

    1988-01-01

    Data was discussed from several different terrains in which CO2-rich fluid inclusions occur despite parageneses that predict the presence of H2O-rich fluids. CO2-rich fluid inclusions, some having densities appropriate for peak-metamorphic conditions, were found in greenschists, amphibolites, migmatites, and hydrated granulites. The author suggested that there may be a common process that leads to CO2-rich secondary inclusions in metamorphic rocks.

  9. Using Combined X-ray Computed Tomography and Acoustic Resonance to Understand Supercritical CO2 Behavior in Fractured Sandstone

    NASA Astrophysics Data System (ADS)

    Kneafsey, T. J.; Nakagawa, S.

    2015-12-01

    Distribution of supercritical (sc) CO2 has a large impact on its flow behavior as well as on the properties of seismic waves used for monitoring. Simultaneous imaging of scCO2 distribution in a rock core using X-ray computed tomography (CT) and measurements of seismic waves in the laboratory can help understand how the distribution evolves as scCO2 invades through rock, and the resulting seismic signatures. To this end, we performed a series of laboratory scCO2 core-flood experiments in intact and fractured anisotropic Carbon Tan sandstone samples. In these experiments, we monitored changes in the CO2 saturation distribution and sonic-frequency acoustic resonances (yielding both seismic velocity and attenuation) over the course of the floods. A short-core resonant bar test system (Split-Hopkinson Resonant Bar Apparatus) custom fit into a long X-ray transparent pressure vessel was used for the seismic measurements, and a modified General Electric medical CT scanner was used to acquire X-ray CT data from which scCO2 saturation distributions were determined. The focus of the experiments was on the impact of single fractures on the scCO2 distribution and the seismic properties. For this reason, we examined several cases including 1. intact, 2. a closely mated fracture along the core axis, 3. a sheared fracture along the core axis (both vertical and horizontal for examining the buoyancy effect), and 4. a sheared fracture perpendicular to the core axis. For the intact and closely mated fractured cores, Young's modulus declined with increasing CO2 saturation, and attenuation increased up to about 15% CO2 saturation after which attenuation declined. For cores having wide axial fractures, the Young's modulus was lower than for the intact and closely mated cases, however did not change much with CO2 pore saturation. Much lower CO2 pore saturations were achieved in these cases. Attenuation increased more rapidly however than for the intact sample. For the core

  10. Flow behaviour of supercritical CO2 and brine in Berea sandstone during drainage and imbibition revealed by medical X-ray CT images

    NASA Astrophysics Data System (ADS)

    Zhang, Yi; Nishizawa, Osamu; Kiyama, Tamotsu; Chiyonobu, Shun; Xue, Ziqiu

    2014-06-01

    We injected Berea sandstone with supercritical CO2 and imaged the results with a medical X-ray computed tomography (CT) scanner. The images were acquired by injecting CO2 into a core of brine-saturated sandstone (drainage), and additional images were acquired during reinjection of brine (imbibition) after drainage. We then analysed the temporal variations of CO2 saturation maps obtained from the CT images. The experiments were performed under a confining pressure of 12 MPa, a pore pressure of 10 MPa and a temperature of 40 °C. Porosity and CO2 saturation were calculated for each image voxel of the rock on the basis of the Hounsfield unit values (CT numbers) measured at three states of saturation: dry, full brine saturation and full CO2 saturation. The saturation maps indicated that the distributions of CO2 and brine were controlled by the sub-core-scale heterogeneities which consisted of a laminated structure (bedding) with high- and low-porosity layers. During drainage, CO2 preferentially flowed through the high-porosity layers where most of the CO2 was entrapped during low flow-rate imbibition. The entrapped CO2 was flushed out when high flow-rate imbibition commenced. Plots of the voxel's CT number against porosity revealed the relationship between fluid replacement and porosity. By reference to the CT numbers at the full brine-saturated stage, differential CT numbers were classified into three bins corresponding to voxel porosity: high, medium and low porosity. Distributions of the differential CT number for the three porosity bins were bimodal and in order with respect to the porosity bins during both drainage and imbibitions; however, the order differed between the two stages. This difference suggested that different replacement mechanisms operated for the two processes. Spatial autocorrelation of CO2 saturation maps on sections perpendicular to the flow direction revealed remarkable changes during passage of the replacement fronts during both drainage and

  11. 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.

  12. Molecular modeling studies of interfacial reactions in wet supercritical CO2.

    NASA Astrophysics Data System (ADS)

    Glezakou, V.; McGrail, B. P.; Windisch, C. F.; Schaef, H. T.; Martin, P.

    2011-12-01

    In the recent years, Carbon Capture and Sequestration (CCS) technologies have gained considerable momentum in a globally organized effort to mitigate greenhouse emissions and adverse climate change. Co-sequestration refers to the capture and geologic sequestration of carbon dioxide and minor contaminants (sulfur compounds, NOx, Hg, etc.) in subsurface formations. Cosequestration offers the potential to make carbon management more economically acceptable to industry relative to sequestration of pure CO2. This may be achieved through significant savings in plant (and retrofit) capital cost, operating cost, and energy savings as well by eliminating the need for one or more individual pollutant capture systems (such as SO2 scrubbers). The latter point is important because co-sequestration may result in a net positive impact to the environment through avoided loss of power generation capacity from parasitic loads and reduced fuel needs. This paper will discuss our research on modeling, imaging and characterization of cosequestration processes and reactivity at a fundamental level. Our work examines the interactions of CO2-rich fluids with metal and mineral surfaces, and how these are affected by the presence of other gas components (e.g. SO2, H2O or NOx) commonly present in the CO2 streams. We have found that reactivity is also affected by the composition of the surface or, less obviously, by the surface exposed, for example, (104) vs (100 )of carbonate minerals. We combine experimental techniques such as XRD and Raman spectroscopy, which can detect and follow reactive processes, with ab initio modeling methods based on density functional theory, to establish a reliable correspondence between theory and experiment with predictive capability. Analysis of our molecular dynamics simulations, reveals structural information and vibrational density of states that can directly compare with XRD measurements and vibrational spectroscopy. While reactivity in CO2-containing

  13. On-line coupling of supercritical CO2 extraction with reversed-phase liquid chromatography for the quantitative analysis of analytes in aqueous matrices.

    PubMed

    Wang, Zhenyu; Ashraf-Khorassani, Mehdi; Taylor, Larry T

    2004-04-16

    The first report of on-line coupled supercritical fluid extraction (SFE) with reversed-phase liquid chromatography for the quantitative analysis of analytes in aqueous matrices is described. Two commercial systems (e.g. SFE and HPLC) were connected via a single six-port injection valve. By using water to eliminate residual decompressed CO2 gas in the solid-phase extraction trap, quantitative extraction and transfer were achieved for the target analytes (progesterone, phenanthrene, and pyrene) spiked in water, as well as in real samples (urine and environmental water). During each extraction, no restrictor plugging was realized. Extraction temperature and pressure were optimized. Different amounts of salt were added to the aqueous matrix to enhance ionic strength and thus extraction efficiency. Methanol and 2-propanol were used as CO2 modifiers. Compared with dynamically mixing modifier with the CO2 extraction fluid, pre-spiking the same amount of modifier in the extraction vessel enhanced the recovery approximately 30% for progesterone, phenanthrene, and pyrene due to a "co-extraction effect". PMID:15088742

  14. Fischer-Tropsch synthesis in supercritical fluids. Final report

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1998-12-31

    The objective of this study was to investigate Fischer-Tropsch Synthesis (FTS) in the supercritical phase employing a commercial precipitated iron catalysts. As the supercritical fluid the authors used propane and n-hexane. The catalyst had a nominal composition of 100 Fe/5 Cu/4.2 K/25 SiO{sub 2} on mass basis and was used in a fixed bed reactor under both normal (conventional) and supercritical conditions. Experimental data were obtained at different temperatures (235 C, 250 C, and 260 C) and synthesis gas feed compositions (H{sub 2}/CO molar feed ratio of 0.67, 1.0 and 2.0) in both modes of operation under steady state conditions. The authors compared the performance of the precipitated iron catalyst in the supercritical phase, with the data obtained in gas phase (fixed bed reactor) and slurry phase (STS reactor). Comparisons were made in terms of bulk catalyst activity and various aspects of product selectivity (e.g. lumped hydrocarbon distribution and olefin content as a function of carbon number). In order to gain better understanding of the role of intraparticle mass transfer during FTS under conventional or supercritical conditions, the authors have measured diffusivities of representative hydrocarbon products in supercritical fluids, as well as their effective diffusion rates into the pores of catalyst at the reaction conditions. They constructed a Taylor dispersion apparatus to measure diffusion coefficients of hydrocarbon products of FTS in sub and supercritical ethane, propane, and hexane. In addition, they developed a tracer response technique to measure the effective diffusivities in the catalyst pores at the same conditions. Based on these results they have developed an equation for prediction of diffusion in supercritical fluids, which is based on the rough hard sphere theory.

  15. Formation of Submicron Magnesite during Reaction of Natural Forsterite in H2O-Saturated Supercritical CO2

    SciTech Connect

    Qafoku, Odeta; Hu, Jian Z.; Hess, Nancy J.; Hu, Mary Y.; Ilton, Eugene S.; Feng, Ju; Arey, Bruce W.; Felmy, Andrew R.

    2014-06-01

    Natural forsterite was reacted in a) liquid water saturated with supercritical CO2 (scCO2) and in b) H2O-saturated scCO2 at 35-80 °C and 90 atm. The solid reaction products were analyzed with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and confocal Raman spectroscopy. Two carbonate phases, nesquehonite (MgCO3.3H2O) and magnesite (MgCO3), were identified with the proportions of the two phases depending on experimental conditions. In water saturated with scCO2, nesquehonite was the dominant carbonate phase at 35-80 °C with only a limited number of large, micron size magnesite particles forming at the highest temperature, 80 °C. In contrast, in H2O-saturated scCO2 magnesite formation was identified at all three temperatures: 35 °, 50 °, and 80 °C. Magnesite was the dominant carbonation reaction product at 50 ° and 80 °C; but nesquehonite was dominant at 35 °C. The magnesite particles formed under H2O-saturated scCO2 conditions exhibited an extremely uniform submicron grain-size and nearly identical rhombohedral morphologies at all temperatures. The distribution and form of the particles were not consistent with epitaxial nucleation and growth on the forsterite surface.

  16. Supercritical CO2 extraction of functional compounds from Spirulina and their biological activity.

    PubMed

    K G, Mallikarjun Gouda; K, Udaya Sankar; R, Sarada; G A, Ravishankar

    2015-06-01

    Supercritical carbon dioxide (SCCO2) extraction and fractionation of Spirulina platensis was carried out to obtain functional compounds with antioxidant, antimicrobial and enzyme inhibitory activities. Extraction of SCCO2 was carried out using 200 g of Spirulina powder at 40 ºC under 120 bar pressure with CO2 flow rate of 1.2 kg h(-1). SCCO2 fraction obtained was further treated with hexane and ethyl acetate to identify its components. Individual components were identified by comparing mass spectra of samples with standard data and retention indices (RI) of C5-C20 n-alkanes mixture using the kovat index formula. The phenolic and flavonoid content of the SCCO2 extract was found to be 0.34 ± 0.01 g/100 g and 0.12 ± 0.01 g/100 g respectively. The SCCO2 extract had antioxidant activity with IC50 value of 109.6 ± 3.0 μg mL(-1) for DPPH (2,2-Diphenyl-1-picryl hydrazyl radical), IC50 value of 81.66 ± 2.5 μg mL(-1) for reducing power and IC50 value of 112.70 ± 0.8 μg mL(-1) for hydroxyl radical scavenging activity. Further, antioxidant activity study on oxidative induced DNA damage was analysed to elucidate the positive role of SCCO2 extract. SCCO2 extracts showed high antimicrobial activity against Gram-positive bacteria (Staphylococcus aureus FRI 722 and Bacillus cereus F 4810) compared to that of Gram negative bacteria (Escherichia coli MTCC 108 and Yersinia enterocolitica MTCC 859). The SCCO2 extract exhibited inhibitory activity on both Angiotensin-1 converting enzyme and α-glucosidase with IC50 values of 274 ± 1.0 μg mL(-1) and 307 ± 2.0 μg mL(-1) respectively. PMID:26028745

  17. Supercritical CO2 interpolymer complex encapsulation improves heat stability of probiotic bifidobacteria.

    PubMed

    Thantsha, M S; Labuschagne, P W; Mamvura, C I

    2014-02-01

    The probiotic industry faces the challenge of retention of probiotic culture viability as numbers of these cells within their products inevitably decrease over time. In order to retain probiotic viability levels above the therapeutic minimum over the duration of the product's shelf life, various methods have been employed, among which encapsulation has received much interest. In line with exploitation of encapsulation for protection of probiotics against adverse conditions, we have previously encapsulated bifidobacteria in poly-(vinylpyrrolidone)-poly-(vinylacetate-co-crotonic acid) (PVP:PVAc-CA) interpolymer complex microparticles under supercritical conditions. The microparticles produced had suitable characteristics for food applications and also protected the bacteria in simulated gastrointestinal fluids. The current study reports on accelerated shelf life studies of PVP:PVAc-CA encapsulated Bifidobacterium lactis Bb12 and Bifidobacterium longum Bb46. Samples were stored as free powders in glass vials at 30 °C for 12 weeks and then analysed for viable counts and water activity levels weekly or fortnightly. Water activities of the samples were within the range of 0.25-0.43, with an average a(w) = 0.34, throughout the storage period. PVP:PVAc-CA interpolymer complex encapsulation retained viable levels above the recommended minimum for 10 and 12 weeks, for B. longum Bb46 and B. lactis Bb12, respectively, thereby extending their shelf lives under high storage temperature by between 4 and 7 weeks. These results reveal the possibility for manufacture of encapsulated probiotic powders with increased stability at ambient temperatures. This would potentially allow the supply of a stable probiotic formulation to impoverished communities without proper storage facilities recommended for most of the currently available commercial probiotic products. PMID:23990069

  18. Supercritical fluid extraction of explosives and metabolites from composted soil

    SciTech Connect

    Martinez, G.; Ho, C.H.; Griest, W.H.

    1995-06-01

    Supercritical fluid extraction (SFE) experiments with composted explosives lagoon soil suggest that recoveries of explosives and metabolites depend more on solvent diffusivity and viscosity than on the solubility of the analytes in the supercritical fluid. Preliminary evidence suggests that SFE recoveries for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX; a particularly difficult to extract explosive) can equal those for an 18 hr. ultrasonic extraction in acetonitrile. Much work is needed to confirm this observation, particularly to optimize the SFE conditions and improve the reproducibility of the extractions.

  19. High-pressure cell for neutron reflectometry of supercritical and subcritical fluids at solid interfaces

    NASA Astrophysics Data System (ADS)

    Carmichael, Justin R.; Rother, Gernot; Browning, James F.; Ankner, John F.; Banuelos, Jose L.; Anovitz, Lawrence M.; Wesolowski, David J.; Cole, David R.

    2012-04-01

    A new high-pressure cell design for use in neutron reflectometry (NR) for pressures up to 50 MPa and a temperature range of 300-473 K is described. The cell design guides the neutron beam through the working crystal without passing through additional windows or the bulk fluid, which provides for a high neutron transmission, low scattering background, and low beam distortion. The o-ring seal is suitable for a wide range of subcritical and supercritical fluids and ensures high chemical and pressure stability. Wafers with a diameter of 5.08 cm (2 in.) and 5 mm or 10 mm thickness can be used with the cells, depending on the required pressure and momentum transfer range. The fluid volume in the sample cell is very small at about 0.1 ml, which minimizes scattering background and stored energy. The cell design and pressure setup for measurements with supercritical fluids are described. NR data are shown for silicon/silicon oxide and quartz wafers measured against air and subsequently within the high-pressure cell to demonstrate the neutron characteristics of the high-pressure cell. Neutron reflectivity data for supercritical CO2 in contact with quartz and Si/SiO2 wafers are also shown.

  20. 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)

  1. 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.

  2. 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.

  3. Supercritical fluid extraction of natural antioxidants from rosemary:  comparison with liquid solvent sonication.

    PubMed

    Tena, M T; Valcárcel, M; Hidalgo, P J; Ubera, J L

    1997-02-01

    Supercritical fluid extraction (SFE) and liquid solvent sonication, in combination with two different sample treatments, were compared for the extraction of natural antioxidants from rosemary leaves. Dried, ground, and sieved rosemary leaves (20 mg) were subjected to SFE with CO(2) at 355 bar at 100 °C (CO(2) density 0.72 g/mL) for 20 min at a liquid flow rate of 4 mL/min. The analytes were concentrated on an ODS trap and subsequently eluted with acetone. Antioxidants in the SF and liquid solvent extract were analyzed by HPLC. Compounds of known antioxidant activity such as carnosol, carnosic acid, and methyl carnosate were identified by mass spectrometry of the HPLC fractions collected. Freezing and grinding the samples in liquid nitrogen resulted in decreased carnosic acid recoveries. Supercritical CO(2) extraction provided the highest recovery of carnosic acid from rosemary leaves (35.7 mg/g), the lowest relative standard deviation (4.4%), and the cleanest extract [Formula: see text] no cleanup prior to HPLC was required. Among the liquid solvents studies, only acetone provided comparable results (73% recovery relative to SC-CO(2) extraction); however, it required decoloration with active carbon prior to HPLC analysis. PMID:21639201

  4. Supercritical CO2 mediated incorporation of Pd onto templated carbons: a route to optimizing the Pd particle size and hydrogen uptake density.

    PubMed

    Masika, Eric; Bourne, Richard A; Chamberlain, Thomas W; Mokaya, Robert

    2013-06-26

    Palladium nanoparticles are deposited onto zeolite template carbon (ZTC) via supercritical CO2 (scCO2) mediated hydrogenation of a CO2-phillic transition metal precursor. The supercritical fluid (SCF) mediated metal incorporation approach enabled the decoration of ZTC with 0.2-2.0 wt % of well-dispersed Pd nanoparticles of size 2-5 nm. The resulting Pd-doped ZTCs exhibit enhanced hydrogen uptake and storage density. The ZTC (with surface area of 2046 m(2)/g) had a hydrogen storage capacity (at 77 K and 20 bar) of 4.9 wt %, while the Pd-ZTCs had uptake of 4.7-5.3 wt % despite a surface area in the range 1390-1858 m(2)/g. The Pd-ZTCs thus exhibit enhanced hydrogen storage density (14.3-18.3 μmol H2/m(2)), which is much higher than that of Pd-free ZTC (12.0 μmol H2/m(2)). The hydrogen isosteric heat of adsorption (Qst) was found to be higher for the Pd-doped carbons (6.7 kJ/mol) compared to the parent ZTC (5.3 kJ/mol). The deposition of small amounts of Pd (up to 2 wt %) along with well-dispersed Pd nanoparticles of size of 2-5 nm is essential for the enhancement of hydrogen uptake and illustrates the importance of optimizing the balance between metal loading/particle size and surface area to achieve the best metal/porous carbon composite for enhanced hydrogen uptake.

  5. 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.

  6. Comparative Reactivity Study of Forsterite and Antigorite in Wet Supercritical CO2 by In Situ Infrared Spectroscopy

    SciTech Connect

    Thompson, Christopher J.; Loring, John S.; Rosso, Kevin M.; Wang, Zheming

    2013-10-01

    The carbonation reactions of forsterite (Mg2SiO4) and antigorite [Mg3Si2O5(OH)4], representatives of olivine and serpentine minerals, in dry and wet supercritical carbon dioxide (scCO2) at conditions relevant to geologic carbon sequestration (35 °C and 100 bar) were studied by in-situ Fourier transform infrared (FT-IR) spectroscopy. Our results confirm that water plays a critical role in the reactions between metal silicate minerals and scCO2. For neat scCO2, no reaction was observed in 24 hr for either mineral. When water was added to the scCO2, a thin water film formed on the minerals’ surfaces, and the reaction rates and extents increased as the water saturation level was raised from 54% to 116% (excess water). For the first time, the presence of bicarbonate, a key reaction intermediate for metal silicate reactions with scCO2, was observed in a heterogeneous system where mineral solids, an adsorbed water film, and bulk scCO2 co-exist. In excess-water experiments, approximately 4% of forsterite and less than 2% of antigorite transformed into hydrated Mg-carbonates. A precipitate similar to nesquehonite (MgCO3•3H2O) was observed for forsterite within 6 hr of reaction time, but no such precipitate was formed from antigorite until after water was removed from the scCO2 following a 24-hr reaction period. The reduced reactivity and carbonate-precipitation behavior of antigorite was attributed to slower, incongruent dissolution of the mineral and lower concentrations of Mg2+ and HCO3- in the water film. The in situ measurements employed in this work make it possible to quantify metal carbonate precipitates and key reaction intermediates such as bicarbonate for the investigation of carbonation reaction mechanisms relevant to geologic carbon sequestration.

  7. Nanoparticles in the pharmaceutical industry and the use of supercritical fluid technologies for nanoparticle production.

    PubMed

    Sheth, Pratik; Sandhu, Harpreet; Singhal, Dharmendra; Malick, Waseem; Shah, Navnit; Kislalioglu, M Serpil

    2012-05-01

    Poor aqueous solubility of drug candidates is a major challenge for the pharmaceutical scientists involved in drug development. Particle size reduction appears as an effective and versatile option for solubility improvement. Nanonization is an attractive solution to improve the bioavailability of the poorly soluble drugs, improved therapies, in vivo imaging, in vitro diagnostics and for the production of biomaterials and active implants. In drug delivery, application of nanotechnology is commonly referred to as Nano Drug Delivery Systems (NDDS). In this article, commercially available nanosized drugs, their dosage forms and proprietors, as well as the methods used for preparation like milling, high pressure homogenization, vacuum deposition, and high temperature evaporation were listed. Unlike the traditional methods used for the particle size reduction, supercritical fluid-processing techniques offer advantages ranging from superior particle size control to clean processing. The primary focus of this review article is the use of supercritical CO2 based technologies for small particle generation. Particles that have the smooth surfaces, small particle size and distribution and free flowing can be obtained with particular SCF techniques. In almost all techniques, the dominating process variables may be thermodynamic and aerodynamic in nature, and the design of the particle collection environment. Rapid Expansion of Supercritical Solutions (RESS), Supercritical Anti Solvent (SAS) and Particles from Gas Saturated Solutions (PGSS) are three groups of processes which lead to the production of fine and monodisperse powders. Few of them may also control crystal polymorphism. Among the aforementioned processes, RESS involves dissolving a drug in a supercritical fluid (SCF) and passing it through an appropriate nozzle. Rapid depressurization of this solution causes an extremely rapid nucleation of the product. This process has been known for a long time but its application

  8. Optimization of conditions for supercritical fluid extraction of flavonoids from hops (Humulus lupulus L.)*

    PubMed Central

    He, Guo-qing; Xiong, Hao-ping; Chen, Qi-he; Ruan, Hui; Wang, Zhao-yue; Traoré, Lonseny

    2005-01-01

    Waste hops are good sources of flavonoids. Extraction of flavonoids from waste hops (SC-CO2 extracted hops) using supercritical fluids technology was investigated. Various temperatures, pressures and concentrations of ethanol (modifier) and the ratio (w/w) of solvent to material were tested in this study. The results of single factor and orthogonal experiments showed that at 50 °C, 25 MPa, the ratio of solvent to material (50%), ethanol concentration (80%) resulted in maximum extraction yield flavonoids (7.8 mg/g). HPLC-MS analysis of the extracts indicated that flavonoids obtained were xanthohumol, the principal prenylflavonoid in hops. PMID:16187413

  9. Basalt Reactivity Variability with Reservoir Depth in Supercritical CO2 and Aqueous Phases

    SciTech Connect

    Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

    2011-04-01

    Long term storage of CO{sub 2} in geologic formations is currently considered the most attractive option to reduce greenhouse gas emissions while continuing to utilize fossil fuels for energy production. Injected CO{sub 2} is expected to reside as a buoyant water-saturated supercritical fluid in contact with reservoir rock, the caprock system, and related formation waters. As was reported for the first time at the GHGT-9 conference, experiments with basalts demonstrated surprisingly rapid carbonate mineral formation occurring with samples suspended in the scCO{sub 2} phase. Those experiments were limited to a few temperatures and CO{sub 2} pressures representing relatively shallow (1 km) reservoir depths. Because continental flood basalts can extend to depths of 5 km or more, in this paper we extend the earlier results across a pressure-temperature range representative of these greater depths. Different basalt samples, including well cuttings from the borehole used in a pilot-scale basalt sequestration project (Eastern Washington, U.S.) and core samples from the Central Atlantic Magmatic Province (CAMP), were exposed to aqueous solutions in equilibrium with scCO{sub 2} and water-rich scCO{sub 2} at six different pressures and temperatures for select periods of time (30 to 180 days). Conditions corresponding to a shallow injection of CO{sub 2} (7.4 MPa, 34 C) indicate limited reactivity with basalt; surface carbonate precipitates were not easily identified on post-reacted basalt grains. Basalts exposed under identical times appeared increasingly more reacted with simulated depths. Tests, conducted at higher pressures (12.0 MPa) and temperatures (55 C), reveal a wide variety of surface precipitates forming in both fluid phases. Under shallow conditions tiny clusters of aragonite needles began forming in the wet scCO{sub 2} fluid, whereas in the CO{sub 2} saturated water, cation substituted calcite developed thin radiating coatings. Although these types of coatings

  10. Disintegration of fluids under supercritical conditions from mixing layer studies

    NASA Technical Reports Server (NTRS)

    Okong'o, N.; Bellan, J.

    2003-01-01

    Databases of transitional states obtained from Direct Numerical simulations (DNS) of temporal, supercritical mixing layers for two species systems, O2/H2 and C7H16/N2, are analyzed to elucidate species-specific turbulence aspects and features of fluid disintegration.

  11. Method for nucleic acid isolation using supercritical fluids

    DOEpatents

    Nivens, David E.; Applegate, Bruce M.

    1999-01-01

    A method for detecting the presence of a microorganism in an environmental sample involves contacting the sample with a supercritical fluid to isolate nucleic acid from the microorganism, then detecting the presence of a particular sequence within the isolated nucleic acid. The nucleic acid may optionally be subjected to further purification.

  12. Method for nucleic acid isolation using supercritical fluids

    DOEpatents

    Nivens, D.E.; Applegate, B.M.

    1999-07-13

    A method is disclosed for detecting the presence of a microorganism in an environmental sample involves contacting the sample with a supercritical fluid to isolate nucleic acid from the microorganism, then detecting the presence of a particular sequence within the isolated nucleic acid. The nucleic acid may optionally be subjected to further purification. 4 figs.

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  16. Supercritical fluid-mediated methods to encapsulate drugs: recent advances and new opportunities.

    PubMed

    Naylor, Andrew; Lewis, Andrew L; Ilium, Lisbeth

    2011-12-01

    With the advent of the development of novel pharmaceutical products and therapies, there is a need for effective delivery of these products to patients. Dependent on whether they are small-molecular weight drugs or biologics, many new compounds may suffer from poor solubility, poor stability or require frequent administration and therefore require optimized delivery. For example, the utilization of polymorphism and the enhanced solubility in the amorphous state is being exploited to improve the dissolution of small-molecular weight poorly soluble drugs. This can be achieved by the formation of solid dispersions in water-soluble matrices. In addition, encapsulation in biodegradable polymeric materials is one potential route to reduce the frequency of administration through the formation of sustained-release formulations. This is desirable for biologics, for example, which generally require administration once or twice daily. Supercritical fluid processing can achieve both of these outcomes, and this review focuses on the use of supercritical CO2 to encapsulate active pharmaceutical ingredients to enhance solubility or achieve sustained release. Using supercritical CO2-mediated processes provides a clean and potentially solvent-free route to prepare novel drug products and is therefore an attractive alternative to conventional manufacturing technologies.

  17. Supercritical fluid-mediated methods to encapsulate drugs: recent advances and new opportunities.

    PubMed

    Naylor, Andrew; Lewis, Andrew L; Ilium, Lisbeth

    2011-12-01

    With the advent of the development of novel pharmaceutical products and therapies, there is a need for effective delivery of these products to patients. Dependent on whether they are small-molecular weight drugs or biologics, many new compounds may suffer from poor solubility, poor stability or require frequent administration and therefore require optimized delivery. For example, the utilization of polymorphism and the enhanced solubility in the amorphous state is being exploited to improve the dissolution of small-molecular weight poorly soluble drugs. This can be achieved by the formation of solid dispersions in water-soluble matrices. In addition, encapsulation in biodegradable polymeric materials is one potential route to reduce the frequency of administration through the formation of sustained-release formulations. This is desirable for biologics, for example, which generally require administration once or twice daily. Supercritical fluid processing can achieve both of these outcomes, and this review focuses on the use of supercritical CO2 to encapsulate active pharmaceutical ingredients to enhance solubility or achieve sustained release. Using supercritical CO2-mediated processes provides a clean and potentially solvent-free route to prepare novel drug products and is therefore an attractive alternative to conventional manufacturing technologies. PMID:22833981

  18. Role of rock/fluid characteristics in carbon (CO2) storage and modeling

    USGS Publications Warehouse

    Verma, Mahendra K.

    2005-01-01

    The presentation ? Role of Rock/Fluid Characteristics in Carbon (CO2) Storage and Modeling ? was prepared for the meeting of the Environmental Protection Agency (EPA) in Houston, Tex., on April 6?7, 2005. It provides an overview of greenhouse gases, particularly CO2, and a summary of their effects on the Earth?s atmosphere. It presents methods of mitigating the effects of greenhouse gases, and the role of rock and fluid properties on CO2 storage mechanisms. It also lists factors that must be considered to adequately model CO2 storage.

  19. Enhanced Geothermal Systems (EGS) comparing water with CO2 as heattransmission fluids

    SciTech Connect

    Pruess, Karsten

    2007-11-01

    This paper summarizes our research to date into operatingEGS with CO2. Our modeling studies indicate that CO2 would achieve morefavorable heat extraction than aqueous fluids. The peculiarthermophysicalproperties of CO2 give rise to unusual features in the dependence ofenergy recovery on thermodynamic conditions and time. Preliminarygeochemical studies suggest that CO2 may avoid unfavorable rock-fluidinteractions that have been encountered in water-basedsystems. To morefully evaluate the potential of EGS with CO2 will require an integratedresearch programme of model development, and laboratory and fieldstudies.

  20. Effect of supercritical fluid extraction on the reduction of toxic elements in fish oil compared with other extraction methods.

    PubMed

    Hajeb, Parvaneh; Selamat, Jinap; Afsah-Hejri, Leili; Mahyudin, Nor Ainy; Shakibazadeh, Shahram; Sarker, Mohd Zaidul Islam

    2015-01-01

    High-quality fish oil for human consumption requires low levels of toxic elements. The aim of this study was to compare different oil extraction methods to identify the most efficient method for extracting fish oil of high quality with the least contamination. The methods used in this study were Soxhlet extraction, enzymatic extraction, wet reduction, and supercritical fluid extraction. The results showed that toxic elements in fish oil could be reduced using supercritical CO2 at a modest temperature (60°C) and pressure (35 MPa) with little reduction in the oil yield. There were significant reductions in mercury (85 to 100%), cadmium (97 to 100%), and lead (100%) content of the fish oil extracted using the supercritical fluid extraction method. The fish oil extracted using conventional methods contained toxic elements at levels much higher than the accepted limits of 0.1 μg/g.

  1. Dexamethasone-loaded poly(ε-caprolactone)/silica nanoparticles composites prepared by supercritical CO2 foaming/mixing and deposition.

    PubMed

    de Matos, M B C; Piedade, A P; Alvarez-Lorenzo, C; Concheiro, A; Braga, M E M; de Sousa, H C

    2013-11-18

    A supercritical carbon dioxide (scCO2)-assisted foaming/mixing method (SFM) was implemented for preparing dexamethasone (DXMT)-loaded poly(ε-caprolactone)/silica nanoparticles (PCL/SNPs) composite materials suitable for bone regeneration. The composites were prepared from PCL and mesoporous SNPs (MCM-41/SBA-15) by means of scCO2-assisted SFM at several operational pressures, processing times and depressurization conditions. DXMT was loaded into SNPs (applying a scCO2 solvent impregnation/deposition method - SSID) and into PCL/SNPs composites (using the SFM method). The effects of the employed operational and compositional variables on the physicochemical and morphological features as well as in the in vitro release profiles of DXMT were analyzed in detail. This work demonstrates that the above-referred scCO2-based methods can be very useful for the preparation of DXMT-loaded PCL/SNPs composites with tunable physicochemical, thermomechanical, morphological and drug release properties and suitable for hard-tissue regeneration applications.

  2. Uranium extraction from TRISO-coated fuel particles using supercritical CO2 containing tri-n-butyl phosphate.

    PubMed

    Zhu, Liyang; Duan, Wuhua; Xu, Jingming; Zhu, Yongjun

    2012-11-30

    High-temperature gas-cooled reactors (HTGRs) are advanced nuclear systems that will receive heavy use in the future. It is important to develop spent nuclear fuel reprocessing technologies for HTGR. A new method for recovering uranium from tristructural-isotropic (TRISO-) coated fuel particles with supercritical CO(2) containing tri-n-butyl phosphate (TBP) as a complexing agent was investigated. TRISO-coated fuel particles from HTGR fuel elements were first crushed to expose UO(2) pellet fuel kernels. The crushed TRISO-coated fuel particles were then treated under O(2) stream at 750°C, resulting in a mixture of U(3)O(8) powder and SiC shells. The conversion of U(3)O(8) into solid uranyl nitrate by its reaction with liquid N(2)O(4) in the presence of a small amount of water was carried out. Complete conversion was achieved after 60 min of reaction at 80°C, whereas the SiC shells were not converted by N(2)O(4). Uranyl nitrate in the converted mixture was extracted with supercritical CO(2) containing TBP. The cumulative extraction efficiency was above 98% after 20 min of online extraction at 50°C and 25 MPa, whereas the SiC shells were not extracted by TBP. The results suggest an attractive strategy for reprocessing spent nuclear fuel from HTGR to minimize the generation of secondary radioactive waste.

  3. Phase behaviour of propane- and scCO(2)-microemulsions and their prominent role for the recently proposed foaming procedure POSME (Principle of Supercritical Microemulsion Expansion).

    PubMed

    Schwan, Michael; Kramer, Lorenz G A; Sottmann, Thomas; Strey, Reinhard

    2010-06-21

    In this study we present a systematic investigation of the phase behaviour of microemulsions containing near- or supercritical solvents. The starting point of this study are microemulsions of the type water/NaCl-propane-polyethyleneglycol mono-n-alkyl ether at a pressure of p = 220 bar. Replacing propane stepwise by supercritical carbon dioxide the typical phase behavior of microemulsions systems can still be observed using scCO(2) as the only nonpolar solvent. Thus, increasing the temperature a phase inversion from a CO(2)-in-water to a water-in-CO(2) microemulsion via a balanced CO(2) microemulsion is found for the first time. Such mixtures of water and scCO(2) are expected to be versatile solvents in green chemistry. In addition, the formulation of supercritical microemulsions is the initial step in the Principle Of Supercritical Microemulsion Expansion (POSME) (DE Pat., 102 60 815 B4, 2008), which is a promising new approach for the production of low-cost nanocellular foams. In contrast to conventional foaming procedures, this approach suggests the formation of nanofoams by expanding micelles swollen with a supercritical blowing agent, thereby ensuring the unhindered formation and growth of bubbles without mass transport.

  4. Supercritical CO2/brine transport in a fractured rock under geologic sequestration conditions

    NASA Astrophysics Data System (ADS)

    Kim, Kue-Young; Oh, Junho; Han, Weon Shik

    2013-04-01

    Carbon capture and storage (CCS) is a promising technology for mitigating CO2 emissions into the atmosphere. In general, densely fractured natural reservoirs are rarely considered as suitable candidates due to issues related to safe and secure long-term storage. Nevertheless, assessment of CO2 storage processes in a storage medium with fractures is critical, as fractures occur in nearly all geological settings and play a major role in hydrocarbon migration as well as entrapment. We evaluated the impact of fractures on CO2/brine transport under geologic sequestration conditions by conducting both experimental and numerical studies. Laboratory experimental results showed a piston-like brine displacement with gravity over-run effects in the homogeneous core regardless of CO2 injection rates. In the fractured core, however, two distinctive types of brine displacements were observed; one showing brine displacement only in the fracture whereas the other shows brine displacement both in the fracture and matrix with different rates, depending on the magnitude of the pressure build-up in the matrix. In the experiments, the injectivity in the fractured core was twice greater than that in the homogeneous core at our experimental condition, while the estimated storage capacity was greater in the homogeneous core than in the fractured core by over 1.5 times. Capillary pressure curves were illustrated for both cores including entry pressures and irreducible brine saturation. The free-phase CO2 transfer in a fracture-matrix system was addressed by numerical simulation, and provided transient flux exchange processes during the brine displacement by CO2. The pressure gradient between the fracture and matrix induced CO2 transfer from fracture into matrix at the front of CO2 plume in fracture. In contrast, at the rear zone of CO2 plume, the reversal of pressure gradient resulted in a reverse CO2 flux. Additionally, the influence of fracture aperture on CO2 transfer between fracture

  5. Solubility of ferrocene and a nickel complex in supercritical fluids

    SciTech Connect

    Cowey, C.M.; Bartle, K.D.; Burford, M.D.; Clifford, A.A.; Zhu, S.; Smart, N.G.; Tinker, N.D.

    1995-11-01

    Supercritical fluid extraction of metals in the presence of complexing agents for environmental monitoring, cleanup, and metals processing is now being extensively researched, and there is a need for solubility data of metal complexes. In this paper, the method used is the combination of a study of chromatographic retention over a wide range of pressures at 40, 50, 60, and 70 `C, followed by selected direct solubility measurements, to provide a comprehensive set of solubility results obtained with minimum effort. The method relies on the assumption that an inverse relationship exists between chromatographic retention and solubility in the mobile phase. This assumption is checked in this study. Results are presented for the solubility of ferrocene in supercritical carbon dioxide and a nickel complex, (5,7,12,14-tetramethyl-2,3:9,10-dibenzo[b,i][1,4,8,11]tetraazacyclotetradecine)nickel(II), in supercritical carbon dioxide modified with 10 vol % methanol.

  6. Solvation effects on reactions of triplet benzophenone in supercritical fluids

    SciTech Connect

    Roberts, C.B.; Brennecke, J.F.; Chateauneuf, J.E.

    1995-05-01

    Laser flash photolysis of the hydrogen abstraction reaction of triplet benzophenone ({sup 3}BP) from 2-propanol and 1,4-cyclohexadiene in supercritical ethane and fluoroform was investigated. Bimolecular rate constants based on bulk concentrations decrease with an increase in pressure along both isotherms studied. These results corroborate previous studies in CO{sub 2} that show increased reaction rates due to enhanced local compositions of cosolvent around the {sup 3}BP solute. Analysis of the results includes prediction of the thermodynamic pressure effect on the rate constant, which suggests an increase in the rate constant with pressure, as well as the effects of increased local cosolvent concentrations about {sup 3}BP. Spectroscopic measurements of the local composition of 2-propanol about a solute in supercritical CO{sub 2} are used to explain the apparent discrepancy between experiment and prediction, providing reasonable evidence that the local environment can influence kinetically controlled reactions in supercritical fluids.

  7. Supercritical Fluid Extraction and Analysis of Tropospheric Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Hansen, Kristen J.

    An integrated sampling and supercritical fluid extraction (SFE) cell has been designed for whole-sample analysis of organic compounds on tropospheric aerosol particles. The low-volume extraction cell has been interfaced with a sampling manifold for aerosol particle collection in the field. After sample collection, the entire SFE cell was coupled to a gas chromatograph; after on-line extraction, the cryogenically -focused sample was separated and the volatile compounds detected with either a mass spectrometer or a flame ionization detector. A 20-minute extraction at 450 atm and 90 ^circC with pure supercritical CO _2 is sufficient for quantitative extraction of most volatile compounds in aerosol particle samples. A comparison between SFE and thermal desorption, the traditional whole-sample technique for analyses of this type, was performed using ambient aerosol particle samples, as well as samples containing known amounts of standard analytes. The results of these studies indicate that SFE of atmospheric aerosol particles provides quantitative measurement of several classes of organic compounds. SFE provides information that is complementary to that gained by the thermal desorption analysis. The results also indicate that SFE with CO _2 can be validated as an alternative to thermal desorption for quantitative recovery of several organic compounds. In 1989, the organic constituents of atmospheric aerosol particles collected at Niwot Ridge, Colorado, along with various physical and meteorological data, were measured during a collaborative field study. Temporal changes in the composition of samples collected during summertime at the rural site were studied. Thermal desorption-GC/FID was used to quantify selected compounds in samples collected during the field study. The statistical analysis of the 1989 Niwot Ridge data set is presented in this work. Principal component analysis was performed on thirty-one variables selected from the data set in order to ascertain

  8. The use of solvent extractions and solubility theory to discern hydrocarbon associations in coal, with application to the coal-supercritical CO2 system

    USGS Publications Warehouse

    Kolak, Jonathan J.; Burruss, Robert A.

    2014-01-01

    Samples of three high volatile bituminous coals were subjected to parallel sets of extractions involving solvents dichloromethane (DCM), carbon disulfide (CS2), and supercritical carbon dioxide (CO2) (40 °C, 100 bar) to study processes affecting coal–solvent interactions. Recoveries of perdeuterated surrogate compounds, n-hexadecane-d34 and four polycyclic aromatic hydrocarbons (PAHs), added as a spike prior to extraction, provided further insight into these processes. Soxhlet-DCM and Soxhlet-CS2 extractions yielded similar amounts of extractable organic matter (EOM) and distributions of individual hydrocarbons. Supercritical CO2 extractions (40 °C, 100 bar) yielded approximately an order of magnitude less EOM. Hydrocarbon distributions in supercritical CO2 extracts generally mimicked distributions from the other solvent extracts, albeit at lower concentrations. This disparity increased with increasing molecular weight of target hydrocarbons. Five- and six-ring ring PAHs generally were not detected and no asphaltenes were recovered in supercritical CO2 extractions conducted at 40 °C and 100 bar. Supercritical CO2 extraction at elevated temperature (115 °C) enhanced recovery of four-ring and five-ring PAHs, dibenzothiophene (DBT), and perdeuterated PAH surrogate compounds. These results are only partially explained through comparison with previous measurements of hydrocarbon solubility in supercritical CO2. Similarly, an evaluation of extraction results in conjunction with solubility theory (Hildebrand and Hansen solubility parameters) does not fully account for the hydrocarbon distributions observed among the solvent extracts. Coal composition (maceral content) did not appear to affect surrogate recovery during CS2 and DCM extractions but might affect supercritical CO2 extractions, which revealed substantive uptake (partitioning) of PAH surrogates into the coal samples. This uptake was greatest in the sample (IN-1) with the highest vitrinite content. These

  9. Pore-scale Evaluation of Immiscible Fluid Characteristics and Displacements: Comparison Between Ambient- and Supercritical-Condition Experimental Studies

    NASA Astrophysics Data System (ADS)

    Herring, A. L.; Wildenschild, D.; Andersson, L.; Harper, E.; Sheppard, A.

    2015-12-01

    The transport of immiscible fluids within porous media is a topic of great importance for a wide range of subsurface processes; e.g. oil recovery, geologic sequestration of CO2, gas-water mass transfer in the vadose zone, and remediation of non-aqueous phase liquids (NAPLs) from groundwater. In particular, the trapping and mobilization of nonwetting phase fluids (e.g. oil, CO2, gas, or NAPL in water-wet media) is of significant concern; and has been well documented to be a function of both wetting and nonwetting fluid properties, morphological characteristics of the porous medium, and system history. However, generalization of empirical trends and results for application between different fluid-fluid-medium systems requires careful consideration and characterization of the relevant system properties. We present a comprehensive and cohesive description of nonwetting phase behaviour as observed via a suite of three dimensional x-ray microtomography imaging experiments investigating immiscible fluid flow, trapping, and interfacial interactions of wetting (brine) and nonwetting (air, oil, and supercritical CO2) phase in sandstones and synthetic media. Microtomographic images, acquired for drainage and imbibition flow processes, allow for precise and extensive characterization of nonwetting phase fluid saturation, topology, and connectivity; imaging results are paired with externally measured capillary pressure data to provide a comprehensive description of fluid states. Fluid flow and nonwetting phase trapping behaviour is investigated as a function of system history, morphological metrics of the geologic media, and nonwetting phase fluid characteristics; and particular emphasis is devoted to the differences between ambient condition (air-brine) and reservoir condition (supercritical CO2-brine) studies. Preliminary results provide insight into the applicability of using ambient condition experiments to explore reservoir condition processes, and also elucidate the

  10. Time-resolved remote Raman study of minerals under supercritical CO2 and high temperatures relevant to Venus exploration.

    PubMed

    Sharma, Shiv K; Misra, Anupam K; Clegg, Samuel M; Barefield, James E; Wiens, Roger C; Acosta, Tayro

    2010-07-13

    We report time-resolved (TR) remote Raman spectra of minerals under supercritical CO(2) (approx. 95 atm pressure and 423 K) and under atmospheric pressure and high temperature up to 1003 K at distances of 1.5 and 9 m, respectively. The TR Raman spectra of hydrous and anhydrous sulphates, carbonate and silicate minerals (e.g. talc, olivine, pyroxenes and feldspars) under supercritical CO(2) (approx. 95 atm pressure and 423 K) clearly show the well-defined Raman fingerprints of each mineral along with the Fermi resonance doublet of CO(2). Besides the CO(2) doublet and the effect of the viewing window, the main differences in the Raman spectra under Venus conditions are the phase transitions, the dehydration and decarbonation of various minerals, along with a slight shift in the peak positions and an increase in line-widths. The dehydration of melanterite (FeSO(4).7H(2)O) at 423 K under approximately 95 atm CO(2) is detected by the presence of the Raman fingerprints of rozenite (FeSO(4).4H(2)O) in the spectrum. Similarly, the high-temperature Raman spectra under ambient pressure of gypsum (CaSO(4).2H(2)O) and talc (Mg(3)Si(4)O(10)(OH)(2)) indicate that gypsum dehydrates at 518 K, but talc remains stable up to 1003 K. Partial dissociation of dolomite (CaMg(CO(3))(2)) is observed at 973 K. The TR remote Raman spectra of olivine, alpha-spodumene (LiAlSi(2)O(6)) and clino-enstatite (MgSiO(3)) pyroxenes and of albite (NaAlSi(3)O(8)) and microcline (KAlSi(3)O(8)) feldspars at high temperatures also show that the Raman lines remain sharp and well defined in the high-temperature spectra. The results of this study show that TR remote Raman spectroscopy could be a potential tool for exploring the surface mineralogy of Venus during both daytime and nighttime at short and long distances.

  11. Supercritical fluid reactions for coal processing. Quarterly progress report, April 1, 1996--June 30, 1996

    SciTech Connect

    Eckert, C.A.

    1996-11-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as the model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane.

  12. Supercritical fluid reactions for coal processing. Quarterly report, January 1, 1996--March 31, 1996

    SciTech Connect

    Eckert, C.A.

    1996-10-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as the model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  14. Modeling of supercritical fluid extraction of phenanthrene from clayey soil.

    PubMed

    Elektorowicz, Maria; El-Sadi, Haifa; Ayadat, Tahar

    2008-05-01

    The supercritical fluid (SFC) extraction efficiency of phenanthrene from clayey soils was modeled. The model accounts for effective diffusion of the phenanthrene in the solid pores, axial dispersion in the fluid phase, and external mass transfer to the fluid phase from the particle surface. This model, involving partial differential equations, was solved using the finite difference. The model showed the relationship between diffusivity, mass transfer coefficient, and properties of porous media (clay texture). The porous media analysis was performed with a microscope and by an image analysis. The proposed model compared well with the experimental data available in the literature. PMID:18366027

  15. Modeling of supercritical fluid extraction of phenanthrene from clayey soil.

    PubMed

    Elektorowicz, Maria; El-Sadi, Haifa; Ayadat, Tahar

    2008-05-01

    The supercritical fluid (SFC) extraction efficiency of phenanthrene from clayey soils was modeled. The model accounts for effective diffusion of the phenanthrene in the solid pores, axial dispersion in the fluid phase, and external mass transfer to the fluid phase from the particle surface. This model, involving partial differential equations, was solved using the finite difference. The model showed the relationship between diffusivity, mass transfer coefficient, and properties of porous media (clay texture). The porous media analysis was performed with a microscope and by an image analysis. The proposed model compared well with the experimental data available in the literature.

  16. Supercritical fluid carbon dioxide cleaning of plutonium parts

    SciTech Connect

    Hale, S.J.; Haschke, J.M.; Cox, L.E.

    1993-09-01

    Supercritical fluid (SCF) carbon dioxide (CO{sub 2}) is being evaluated for use as a cleaning solvent to replace 1,1,1-trichloroethane for the final cleaning of plutonium (Pu) parts. These parts must be free of organic residue to avoid corrosion in the stockpile. Thermodynamic and kinetic data for selected reactions of Pu metal are evaluated as a basis for assessing the risk of a violent exothermic reaction during the use of SCF CO{sub 2} on Pu. The need for considering kinetic behavior of a reaction in assessing its thermal risk is demonstrated. Weight difference data and results of xray photoelectron spectroscopy to evaluate the surface after exposure to the supercritical fluid show that SCF CO{sub 2} is an effective and compatible cleaning solvent.

  17. Supercritical fluid fractionation of petroleum- and coal-derived mixtures

    SciTech Connect

    Campbell, R.M.

    1987-01-01

    A supercritical fluid chromatography system was constructed to provide separations and fraction collection on a semi-preparative scale. A variety of complex mixtures were fractionated according to the number of aromatic rings using columns packed with NH/sub 2/-modified silica particles. Effluents were monitored with an ultraviolet spectrophotometer and a flame ionization detector while fractions were collected in pressurized vessels for subsequent analysis by capillary gas chromatography. A supercritical fluid chromatographic method to determine the percentage of saturates, olefins and aromatics in gasolines and middle distillate fuels was developed. A microbore silica column was used to isolate the aromatics, while a silver-loaded strong cation exchange microbore column was used to isolate the saturates Olefins were determined by difference. A flame ionization detector provided uniform, linear response for quantitation without calibration. The method was found to be accurate, rapid and reproducible.

  18. Residual trapping of supercritical CO2 in oil-wet sandstone.

    PubMed

    Rahman, Taufiq; Lebedev, Maxim; Barifcani, Ahmed; Iglauer, Stefan

    2016-05-01

    Residual trapping, a key CO2 geo-storage mechanism during the first decades of a sequestration project, immobilizes micrometre sized CO2 bubbles in the pore network of the rock. This mechanism has been proven to work in clean sandstones and carbonates; however, this mechanism has not been proven for the economically most important storage sites into which CO2 will be initially injected at industrial scale, namely oil reservoirs. The key difference is that oil reservoirs are typically oil-wet or intermediate-wet, and it is clear that associated pore-scale capillary forces are different. And this difference in capillary forces clearly reduces the capillary trapping capacity (residual trapping) as we demonstrate here. For an oil-wet rock (water contact angle θ=130°) residual CO2 saturation SCO2,r (≈8%) was approximately halved when compared to a strongly water-wet rock (θ=0°; SCO2,r≈15%). Consequently, residual trapping is less efficient in oil-wet reservoirs.

  19. Surface and Electrochemical Behavior of HSLA in Supercritical CO2-H2O Environment

    SciTech Connect

    M. Ziomek-Moroz; G. R. Holcomb; J. Tylczak; J. Beck; M. Fedkin; S. Lvov

    2012-01-11

    General corrosion was observed on high strength low alloy carbon steel after electrochemical impedance spectroscopy experiments (EIS) performed in H{sub 2}O saturated with CO{sub 2} at 50 C and 15.2 MPa. However, general and localized were observed on the same material surfaces after the EIS experiments performed in supercritical CO{sub 2} containing approximately 6100 ppmv H{sub 2}O at 50 C and 15.2 MPa. The general corrosion areas were uniformly covered by the FeCO{sub 3}-like phase identified by X-ray diffraction (XRD). In the area of localized corrosion, XRD also revealed FeCO{sub 3}-rich islands embedded in {alpha}-iron. The energy dispersive X-ray (EDX) analysis revealed high concentrations of iron, carbon, and oxygen in the area affected by general corrosion and in the islands formed in the area of localized corrosion. The real and imaginary impedances were lower in H{sub 2}O saturated with CO{sub 2} than those in the supercritical CO{sub 2} containing the aqueous phase indicating faster corrosion kinetics in the former.

  20. Supercritical CO2 generation of nanometric structure from Ocimum basilicum mucilage prepared for pharmaceutical applications.

    PubMed

    Akbari, Iman; Ghoreishi, Seyyed M; Habibi, Neda

    2015-04-01

    Plant-derived polymers are widely used in the pharmaceutical industry due to their emollient, lack of toxicity, and irritating nature and low cost. In this work, basil seed mucilage was dried using supercritical carbon dioxide phase inversion technique to form a nanometric structure. The obtained polymeric structures were characterized by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) method, and Fourier transform infrared spectroscopy (FTIR) and compared with the oven-derived sample group. It was demonstrated that the product morphology could be controlled by altering the composition of methanol which functioned as the co-solvent in the nonsolvent stream. The most homogeneous product (60-nm mean pore size diameter, 78 m(2)/g BET surface area with no agglomeration) was obtained with 2.5% methanol. The FTIR data showed that the presence of hydroxyl and carboxyl groups suggested the bioadhesive property of basil seed mucilage was good and many active pharmaceutical compounds might be loaded to the resultant nanometric structure to enhance drug release. Furthermore, the FTIR analyses indicated that the nature of the final product did not change during the supercritical drying procedure.

  1. Supercritical Fluid Assisted Synthesis and Processing of Carbon Nanotubes

    SciTech Connect

    Ye, Sufang; Wu, Fengming; Ye, Xiangrong; Lin, Yuehe

    2009-03-26

    Carbon nanotubes (CNTs) constitute one of the most fascinating nanomaterials with specific properties and enormous applications. Taking advantages of the unique properties of supercritical fluids (SCFs), various techniques have been developed to produce and process CNTs and related nanostructured materials when conventional techniques become unviable. Herein we propose a critical review of these SCF based techniques. The most relevant characteristics of each technique and the enabled novel structures and functions which are difficult to accomplish by traditional techniques are highlighted.

  2. In Situ 13C and 23Na Magic Angle Spinning NMR Investigation of Supercritical CO2 Incorporation in Smectite-Natural Organic Matter Composites

    SciTech Connect

    Bowers, Geoffrey M.; Hoyt, David W.; Burton, Sarah D.; Ferguson, Brennan O.; Varga, Tamas; Kirkpatrick, Robert J.

    2014-01-29

    This paper presents an in situ NMR study of clay-natural organic polymer systems (a hectoritehumic acid [HA] composite) under CO2 storage reservoir conditions (90 bars CO2 pressure, 50°C). The 13C and 23Na NMR data show that supercritical CO2 interacts more strongly with the composite than with the base clay and does not react to form other C-containing species over several days at elevated CO2. With and without organic matter, the data suggest that CO2 enters the interlayer space of Na-hectorite equilibrated at 43% relative humidity. The presence of supercritical CO2 also leads to increased 23Na signal intensity, reduced line width at half height, increased basal width, more rapid 23Na T1 relaxation rates, and a shift to more positive resonance frequencies. Larger changes are observed for the hectorite-HA composite than for the base clay. In light of recently reported MD simulations of other polymer-Na-smectite composites, we interpret the observed changes as an increase in the rate of Na+ site hopping in the presence of supercritical CO2, the presence of potential new Na+ sorption sites when the humic acid is present, and perhaps an accompanying increase in the number of Na+ ions actively involved in site hopping. The results suggest that the presence of organic material either in clay interlayers or on external particle surfaces can significantly affect the behavior of supercritical CO2 and the mobility of metal ions in reservoir rocks.

  3. 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

  4. Magnetic resonance imaging study on near miscible supercritical CO2 flooding in porous media

    NASA Astrophysics Data System (ADS)

    Song, Yongchen; Zhu, Ningjun; Zhao, Yuechao; Liu, Yu; Jiang, Lanlan; Wang, Tonglei

    2013-05-01

    CO2 flooding is one of the most popular secondary or tertiary recoveries for oil production. It is also significant for studying the mechanisms of the two-phase and multiphase flow in porous media. In this study, an experimental study was carried out by using magnetic resonance imaging technique to examine the detailed effects of pressure and rates on CO2/decane flow in a bead-pack porous media. The displacing processes were conducted under various pressures in a region near the minimum miscibility pressure (the system tuned from immiscible to miscible as pressure is increasing in this region) and the temperature of 37.8 °C at several CO2 injection volumetric rates of 0.05, 0.10, and 0.15 ml/min (or linear rates of 3.77, 7.54, and 11.3 ft/day). The evolution of the distribution of decane and the characteristics of the two phase flow were investigated and analyzed by considering the pressure and rate. The area and velocity of the transition zone between the two phases were calculated and analyzed to quantify mixing. The area of transition zone decreased with pressure at near miscible region and a certain injection rate and the velocity of the transition zone was always less than the "volumetric velocity" due to mutual solution and diffusion of the two phases. Therefore, these experimental results give the fundamental understanding of tertiary recovery processes at near miscible condition.

  5. Sulfur Isotope Analysis of Minerals and Fluids in a Natural CO2 Reservoir, Green River, Utah

    NASA Astrophysics Data System (ADS)

    Chen, F.; Kampman, N.; Bickle, M. J.; Busch, A.; Turchyn, A. V.

    2013-12-01

    Predicting the security of geological CO2 storage sites requires an understanding of the geochemical behavior of the stored CO2, especially of fluid-rock reactions in reservoirs, caprocks and fault zones. Factors that may influence geochemical behavior include co-injection of sulfur gases along with the CO2, either in acid-gas disposal or as contaminants in CO2 storage sites, and microbial activity, such as bacterial sulfate reduction. The latter may play an important role in buffering the redox chemistry of subsurface fluids, which could affect toxic trace metal mobilization and transport in acidic CO2-rich fluids. These processes involving sulfur are poorly understood. Natural CO2-reservoirs provide natural laboratories, where the flow and reactions of the CO2-charged fluids and the activity of microbial communities are integrated over sufficient time-scales to aid prediction of long-term CO2 storage. This study reports on sulfur isotope analyses of sulfate and sulfide minerals in rock core and in CO2-charged fluids collected from a stacked sequence of natural CO2 reservoirs at Green River, Utah. Scientific drilling adjacent to a CO2-degassing normal fault to a depth of 325m retrieved core and fluid samples from two CO2 reservoirs in the Entrada and Navajo Sandstones and from the intervening Carmel Formation caprock. Fluid samples were collected from CO2-charged springs that discharge through the faults. Sulfur exists as sulfate in the fluids, as sedimentary gypsum beds in the Carmel Formation, as remobilized gypsum veins within a fault damage zone in the Carmel Fm. and in the Entrada Sandstone, and as disseminated pyrite and pyrite-mineralized open fractures throughout the cored interval. We use the stable sulfur (δ34S) and oxygen (δ18OSO4) isotopes of the sulfate, gypsum, and pyrite to understand the source of sulfur in the reservoir as well as the timing of gypsum vein and pyrite formation. The hydration water of the gypsum is also reported to explore the

  6. Effects of supercritical fluid extraction pressure on chemical composition, microbial population, polar lipid profile, and microstructure of goat cheese.

    PubMed

    Sánchez-Macías, D; Laubscher, A; Castro, N; Argüello, A; Jiménez-Flores, R

    2013-03-01

    The consumer trend for healthier food choices and preferences for low-fat products has increased the interest in low-fat cheese and nutraceutical dairy products. However, consumer preference is still for delicious food. Low- and reduced-fat cheeses are not completely accepted because of their unappealing properties compared with full-fat cheeses. The method reported here provides another option to the conventional cheese-making process to obtain lower fat cheese. Using CO(2) as a supercritical fluid offers an alternative to reduce fat in cheese after ripening, while maintaining the initial characteristics and flavor. The aim of this experiment was to evaluate the effect of pressure (10, 20, 30, and 40 × 10(6) Pa) of supercritical CO(2) on the amount of fat extracted, microbial population, polar lipid profile, and microstructure of 2 varieties of goat cheese: Majorero, a protected denomination of origin cheese from Spain, and goat Gouda-type cheese. The amount of fat was reduced 50 to 57% and 48 to 55% for Majorero and goat Gouda-type cheeses, respectively. Higher contents (on a fat basis) of sphingomyelin and phosphatidylcholine were found in Majorero cheese compared with control and goat Gouda-type cheeses. The microbial population was reduced after supercritical fluid extraction in both cheeses, and the lethality was higher as pressure increased in Majorero cheese, most noticeably on lactococcus and lactobacillus bacteria. The Gouda-type cheese did not contain any lactobacilli. Micrographs obtained from confocal laser scanning microscopy showed a more open matrix and whey pockets in the Majorero control cheese. This could explain the ease of extracting fat and reducing the microbial counts in this cheese after treatment with supercritical CO(2). Supercritical fluid extraction with CO(2) has great potential in the dairy industry and in commercial applications. The Majorero cheese obtained after the supercritical fluid extraction treatment was an excellent

  7. The effect of processing variables on morphological and mechanical properties of supercritical CO2 foamed scaffolds for tissue engineering.

    PubMed

    White, Lisa J; Hutter, Victoria; Tai, Hongyun; Howdle, Steven M; Shakesheff, Kevin M

    2012-01-01

    The porous structure of a scaffold determines the ability of bone to regenerate within this environment. In situations where the scaffold is required to provide mechanical function, balance must be achieved between optimizing porosity and maximizing mechanical strength. Supercritical CO(2) foaming can produce open-cell, interconnected structures in a low-temperature, solvent-free process. In this work, we report on foams of varying structural and mechanical properties fabricated from different molecular weights of poly(DL-lactic acid) P(DL)LA (57, 25 and 15 kDa) and by varying the depressurization rate. Rapid depressurization rates produced scaffolds with homogeneous pore distributions and some closed pores. Decreasing the depressurization rate produced scaffolds with wider pore size distributions and larger, more interconnected pores. In compressive testing, scaffolds produced from 57 kDa P(DL)LA exhibited typical stress-strain curves for elastomeric open-cell foams whereas scaffolds fabricated from 25 and 15 kDa P(DL)LA behaved as brittle foams. The structural and mechanical properties of scaffolds produced from 57 kDa P(DL)LA by scCO(2) ensure that these scaffolds are suitable for potential applications in bone tissue engineering.

  8. Simultaneous quantification of vitamin E, γ-oryzanols and xanthophylls from rice bran essences extracted by supercritical CO2.

    PubMed

    Sookwong, Phumon; Suttiarporn, Panawan; Boontakham, Pittayaporn; Seekhow, Pattawat; Wangtueai, Sutee; Mahatheeranont, Sugunya

    2016-11-15

    Since the nutrition value of rice is diminished during rice processing, technology that can preserve and sustain functional compounds is necessary. In this study, supercritical carbon dioxide (SC-CO2) extraction was optimized for operational conditions (time, temperature, pressure and modifier) to extract vitamin E, γ-oryzanols and xanthophylls from rice bran. The simultaneous quantification of the compounds was developed using high-performance liquid chromatography with diode array and fluorescence detectors. Central composite design and respond surface methodology were applied to achieve optimum extraction conditions. The optimized conditions were 60min, 43°C, 5420psi with 10% ethanol as a modifier. Pigmented rice bran extracts contained greater amounts of functional phytochemicals than non-pigmented rice bran extracts (0.68, 1410, and non-detectable μg/g compared with 16.65, 2480, and 0.10μg/g of vitamin E, γ-oryzanols and xanthophylls in pigmented and non-pigmented ones, respectively). SC-CO2 extraction with modifier would be promising for preparation of phytochemical essences for therapeutic purpose. PMID:27283617

  9. Development of supercritical fluid extraction and supercritical fluid chromatography purification methods using rapid solubility screening with multiple solubility chambers.

    PubMed

    Gahm, Kyung H; Huang, Ke; Barnhart, Wesley W; Goetzinger, Wolfgang

    2011-01-01

    Rapid solubility screening in diverse supercritical fluids (SCFs) was carried out via multiple solubility chambers with a trapping device and online ultraviolet (UV) detection. With this device, it was possible to rapidly study the solubility variations of multiple components in a mixture. Results from solubility studies have been used to develop efficient supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC) methods. After the investigation of solubilities of theophylline and caffeine in several neat organic solvents and SCFs, advantages of SFE over conventional organic solvent extraction were demonstrated with a model mixture of theophylline and caffeine. The highest solubility ratio of 1:40 (theophylline:caffeine) was observed in the SCF with 20% acetonitrile (MeCN), where a ratio of 1:11 was the highest in the neat organic solvents. A model mixture of theophylline:caffeine (85:15 w/w, caffeine as an impurity) was successfully purified by SFE by leveraging the highest solubility difference. The SCF with 20% MeCN selectively removed caffeine and left theophylline largely intact. Rapid SCF solubility screening was applied to development of SFE and SFC methods in a drug discovery environment. Two successful applications were demonstrated with proprietary Amgen compounds to either remove an achiral impurity before chiral purification or enhance chiral chromatographic throughput.

  10. Lattice-Boltzmann modeling of experimental fluid displacement patterns, interfacial area and capillary trapped CO2

    NASA Astrophysics Data System (ADS)

    Porter, M. L.; Kang, Q.; Tarimala, S.; Abdel-Fattah, A.; Backhaus, S.; Carey, J. W.

    2010-12-01

    Successful sequestration of CO2 into deep saline aquifers presents an enormous challenge that requires fundamental understanding of reactive-multiphase flow and transport across many temporal and spatial scales. Of critical importance is accurately predicting the efficiency of CO2 trapping mechanisms. At the pore scale (e.g., microns to millimeters) the interfacial area between CO2 and brine, as well as CO2 and the solid phase, directly influences the amount of CO2 trapped due to capillary forces, dissolution and mineral precipitation. In this work, we model immiscible displacement micromodel experiments using the lattice-Boltzmann (LB) method. We focus on quantifying interfacial area as a function of capillary numbers and viscosity ratios typically encountered in CO2 sequestration operations. We show that the LB model adequately predicts the steady-state experimental flow patterns and interfacial area measurements. Based on the steady-state agreement, we use the LB model to investigate interfacial dynamics (e.g., fluid-fluid interfacial velocity and the rate of production of fluid-fluid interfacial area). In addition, we quantify the amount of interfacial area and the interfacial dynamics associated with the capillary trapped nonwetting phase. This is expected to be important for predicting the amount of nonwetting phase subsequently trapped due to dissolution and mineral precipitation.

  11. Supercritical fluid technology. (Latest citations from the Biobusiness database). Published Search

    SciTech Connect

    1995-12-01

    The bibliography contains citations concerning applications of supercritical fluid technology. Topics include supercritical fluid technology use in chromatographic analysis, removal of cholesterol and caffeine from food products, extraction of essential oils, extraction of pesticide and other toxic contaminants from soil and food, and food analysis. Supercritical fluid technology patents and uses in the pharmaceutical industry are also described.(Contains 50-250 citations and includes a subject term index and title list.) (Copyright NERAC, Inc. 1995)

  12. SELECTIVE HYDROGENATION OF MALEIC ANHYDRIDE TO Y-BUTYROLACTONE OVER PD/AL(2)O(3) CATALYST USING SUPERCRITICAL CO(2) AS SOLVENT

    EPA Science Inventory

    A selective hydrogenation of maleic anhydride to either y-butyrolactone or succinic anhydride over simple Pd/Al(2)O(3) catalyst under supercritical CO(2) medium is described for the first time which has considerable promise for obht lab-scale as well as industrial selective hydro...

  13. Novel one pot synthesis of silver nanoparticle-polymer composites by supercritical CO2 polymerisation in the presence of a RAFT agent.

    PubMed

    Hasell, Tom; Thurecht, Kristofer J; Jones, Rhys D W; Brown, Paul D; Howdle, Steven M

    2007-10-14

    We report the one pot synthesis of a silver-polymer nanocomposite in supercritical carbon dioxide (scCO(2)) whereby an organometallic silver complex is thermally decomposed in the presence of a reversible addition fragmentation chain transfer (RAFT) agent during a polymerisation reaction in which the RAFT agent simultaneously stabilises the growing polymer microparticles and the formation of surface located silver nanoparticles.

  14. CO2 sequestration in feldspar-rich sandstone: Coupled evolution of fluid chemistry, mineral reaction rates, and hydrogeochemical properties

    NASA Astrophysics Data System (ADS)

    Tutolo, Benjamin M.; Luhmann, Andrew J.; Kong, Xiang-Zhao; Saar, Martin O.; Seyfried, William E.

    2015-07-01

    To investigate CO2 Capture, Utilization, and Storage (CCUS) in sandstones, we performed three 150 °C flow-through experiments on K-feldspar-rich cores from the Eau Claire formation. By characterizing fluid and solid samples from these experiments using a suite of analytical techniques, we explored the coupled evolution of fluid chemistry, mineral reaction rates, and hydrogeochemical properties during CO2 sequestration in feldspar-rich sandstone. Overall, our results confirm predictions that the heightened acidity resulting from supercritical CO2 injection into feldspar-rich sandstone will dissolve primary feldspars and precipitate secondary aluminum minerals. A core through which CO2-rich deionized water was recycled for 52 days decreased in bulk permeability, exhibited generally low porosity associated with high surface area in post-experiment core sub-samples, and produced an Al hydroxide secondary mineral, such as boehmite. However, two samples subjected to ∼3 day single-pass experiments run with CO2-rich, 0.94 mol/kg NaCl brines decreased in bulk permeability, showed generally elevated porosity associated with elevated surface area in post-experiment core sub-samples, and produced a phase with kaolinite-like stoichiometry. CO2-induced metal mobilization during the experiments was relatively minor and likely related to Ca mineral dissolution. Based on the relatively rapid approach to equilibrium, the relatively slow near-equilibrium reaction rates, and the minor magnitudes of permeability changes in these experiments, we conclude that CCUS systems with projected lifetimes of several decades are geochemically feasible in the feldspar-rich sandstone end-member examined here. Additionally, the observation that K-feldspar dissolution rates calculated from our whole-rock experiments are in good agreement with literature parameterizations suggests that the latter can be utilized to model CCUS in K-feldspar-rich sandstone. Finally, by performing a number of reactive

  15. Summarizing the effectiveness of supercritical fluid extraction of polycyclic aromatic hydrocarbons from natural matrix environmental samples.

    PubMed

    Benner, B A

    1998-11-01

    A summary of the supercritical fluid extraction (SFE) of polycyclic aromatic hydrocarbons (PAHs) from four natural matrix Standard Reference Materials (SRMs) is presented. The work involved the investigation of the effects of extraction fluid [carbon dioxide (CO(2)), chlorodifluoromethane (R22), and 1,1,1,2-tetrafluoroethane (HFC134a)], fluid modifier (dichloromethane and aniline), temperature (60, 150, and 200 °C) and added water on the SFE recoveries of PAHs compared to certified results from Soxhlet extractions. For SRM 1649a (Urban Dust/Organics), R22 yielded excellent recoveries (>90% of certified concentrations) of all PAHs measured, while results for the same SRM using HFC134a as the fluid were typically <80% of the certified concentrations for most of the PAHs measured. For SRM 1941a and 1944, both aquatic sediments with similar physical and chemical compositions, extractions of the wet materials with dichloromethane-modified CO(2) (10%, v/v) yielded quantitative recoveries of all PAHs for SRM 1944 but an obvious trend of lower recoveries for higher molecular weight PAHs (≥228 amu) for SRM 1941a. Results of SFEs of SRM 1650 (Diesel Particulate Matter) showed that this material is the most refractory of the SRMs investigated in this study, with recoveries of indeno[1,2,3-cd]pyrene and benzo[ghi]perylene at <20% of the Soxhlet results.

  16. Development of a slow non-viral DNA release system from PDLLA scaffolds fabricated using a supercritical CO2 technique.

    PubMed

    Heyde, Mieke; Partridge, Kris A; Howdle, Steven M; Oreffo, Richard O C; Garnett, Martin C; Shakesheff, Kevin M

    2007-10-15

    Polyamidoamine polymers (PAA) comprising methylene-bisacrylamide/dimethylethylene-diamine monomers were synthesized, complexed with DNA and incorporated into porous P(DL)LA scaffolds by using a supercritical CO(2) (scCO(2)) technique. Scaffolds were made in a dry state consequently there was a need to lyophilize the complexes. A statistically significant reduction of the transfection efficiency was observed in the absence of trehalose when compared to the original complex after freeze-drying. Increasing concentrations (0-10% w/v) of trehalose were added to the complex prior to freeze-drying. Structure dependent differences in DNA binding were evaluated by gel electrophoresis and thermal transition analysis. TEM and PCS showed aggregate formation after freeze-drying without trehalose. Scaffolds were characterized by pore sizes of 173 +/- 73 microm and a porosity of 71%. The transfection potential of the released DNA was investigated by seeding scaffolds with A549 cells and following firefly luciferase as a marker gene after 48 h exposure. Low but continuous levels of transfection were observed for PAA complexes during a 60-day study. Complexes made with Lipofectaminetrade mark gave initially higher levels of DNA release but no further expression was seen after 40 days. Uncomplexed DNA showed background levels of transfection. Culturing cells on 3D scaffolds showed a benefit in retention of transfection activity with time compared to 2D controls. Transfection levels could be increased when cells were grown in OptiMEM. This study demonstrated that PAA/DNA complexes incorporated into a P(DL)LA scaffold made by using scCO(2) processing exhibited a slow release and extended gene expression profile. PMID:17405179

  17. Proapoptotic and Antimetastatic Properties of Supercritical CO2 Extract of Nigella sativa Linn. Against Breast Cancer Cells

    PubMed Central

    Baharetha, Hussein M.; Nassar, Zeyad D.; Aisha, Abdalrahim F.; Ahamed, Mohamed B. Khadeer; Al-Suede, Foaud Saleih R.; Kadir, Mohd Omar Abd; Ismail, Zhari

    2013-01-01

    Abstract Nigella sativa, commonly referred as black cumin, is a popular spice that has been used since the ancient Egyptians. It has traditionally been used for treatment of various human ailments ranging from fever to intestinal disturbances to cancer. This study investigated the apoptotic, antimetastatic, and anticancer activities of supercritical carbon dioxide (SC-CO2) extracts of the seeds of N. sativa Linn. against estrogen-dependent human breast cancer cells (MCF-7). Twelve extracts were prepared from N. sativa seeds using the SC-CO2 extraction method by varying pressure and temperature. Extracts were analyzed using FTIR and UV-Vis spectrometry. Cytotoxicity of the extracts was evaluated on various human cancer and normal cell lines. Of the 12 extracts, 1 extract (A3) that was prepared at 60°C and 2500 psi (∼17.24 MPa) showed selective antiproliferative activity against MCF-7 cells with an IC50 of 53.34±2.15 μg/mL. Induction of apoptosis was confirmed by evaluating caspases activities and observing the cells under a scanning electron microscope. In vitro antimetastatic properties of A3 were investigated by colony formation, cell migration, and cell invasion assays. The elevated levels of caspases in A3 treated MCF-7 cells suggest that A3 is proapoptotic. Further nuclear condensation and fragmentation studies confirmed that A3 induces cytotoxicity through the apoptosis pathway. A3 also demonstrated remarkable inhibition in migration and invasion assays of MCF-7 cells at subcytotoxic concentrations. Thus, this study highlights the therapeutic potentials of SC-CO2 extract of N. sativa in targeting breast cancer. PMID:24328702

  18. Reaction of Water-Saturated Supercritical CO2 with Forsterite: Evidence for Magnesite Formation at Low Temperatures

    SciTech Connect

    Felmy, Andrew R.; Qafoku, Odeta; Arey, Bruce W.; Hu, Jian Z.; Hu, Mary Y.; Schaef, Herbert T.; Ilton, Eugene S.; Hess, Nancy J.; Pearce, Carolyn I.; Feng, Ju; Rosso, Kevin M.

    2012-08-01

    The nature of the reaction products that form on the surfaces of nanometer-sized forsterite particles during reaction with H2O saturated supercritical CO2 (scCO2) at 35 C and 50 C were examined under in situ conditions and ex situ following reaction. The in situ analysis was conducted by X-ray diffraction (XRD). Ex situ analysis consisted of scanning electron microscopy (SEM) examination of the surface phases and chemical characterization of precipitates using a combination of confocal Raman spectroscopy, 13C and 29Si NMR spectroscopy, and energy-dispersive X-ray Spectroscopy (EDS). The results show that the forsterite surface is highly reactive with the primary reaction products being a mixture of nesquehonite (MgCO3.3H2O) and magnesite (MgCO3) at short reaction times ({approx}3-4 days) and then magnesite (MgCO3) and a highly porous amorphous silica phase at longer reaction times (14 days). After 14 days of reaction most of the original forsterite transformed to reaction products. Importantly, the formation of magnesite was observed at temperatures much lower (35 C) than previously thought needed to overcome its well known sluggish precipitation kinetics. The conversion of nesquehonite to magnesite liberates H2O which can potentially facilitate further metal carbonation, as postulated by previous investigators, based upon studies at higher temperature (80 C). The observation that magnesite can form at lower temperatures implies that water recycling may also be important in determining the rate and extent of mineral carbonation in a wide range of potential CO2 storage reservoirs.

  19. Chemical modification of nanometric TiO2 particles by anchoring functional silane molecules in supercritical CO2

    NASA Astrophysics Data System (ADS)

    López-Periago, Ana M.; Sandoval, Wendy; Domingo, Concepción

    2014-03-01

    Supercritical carbon dioxide (scCO2) was used as a green solvent for the grafting of complex functional organosilanes containing nitrogen moieties on titanium dioxide (TiO2) nanoparticles using two strategies. The first strategy involved the preparation of two functional silanes, 4-nitrophenyl-(3-(trimethoxysilyl)-propyl)methanimine (NPTMS) and 4-(((3-(trimethoxysilyl)propyl)imino)methyl)-benzaldehyde (FPTMS) and further deposited under anhydrous conditions and scCO2 onto the TiO2 surface. The second strategy involved the scCO2 anhydrous deposition of bifunctional commercial silanes on the TiO2 surface. Two structures were synthesized. The first consisted in grafted TiO2 nanoparticles prepared by addition of the ligand, ((1R,2R)-N-(pyridin-2-ylmethyl)-2-(((E)-pyridin-2-ylmethylene) amino)-cyclohexan-1-amine (LPy-red), and designated as Ti-Cl-LPy-red. The second structure was synthesized by the reaction of (1,2)-diaminocylohexane (Dac), through the reactive site of 3-(Trimethoxysilyl)propyl methacrylate (MPTMS) previously deposited on the TiO2 surface and designated as Ti-MP-Dac. The synthesized silanes were characterized by ATR-FT and NMR spectroscopies and mass spectrometry. ATR-FT spectroscopy confirmed the presence of the silanes on the surface of the hybrid nanoparticles. Thermogravimetic analysis was used to estimate the loading of the silane grafted through both hydrogen and covalent bonding on the TiO2 surface. Further characterization of the solid samples was done by N2 adsorption-desorption and UV-vis diffuse reflectance.

  20. Trapping non-wettable fluid in porous rock: Implication to CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Kim, Y.; Yun, T.

    2013-12-01

    The residual saturation of CO2 mainly determines the effective storage capacity in geological formation whereas its transport and fate are dominated by fluid properties and pore characteristics. This experimental study evaluates the relative permeability of brine and non-wettable fluids in Berea sandstone. The surrogate fluids representing CO2 are continuously injected into the brine-saturated sandstone and the effluent is simultaneously separated to measure the residual volume. The variables under consideration include the viscosity and surface tension of injected fluids, porosity, anisotropy of rock, and injection pressure and the residual saturation of non-wettable fluids is quantified based on the proposed variables. Results highlight that the storage capacity can be readily modulated and maximized by controlling the cyclic injection, initial saturation of non-wettable fluids, and injection pressure.

  1. Modeling of supercritical fluid extraction from herbaceous matrices

    SciTech Connect

    Reverchon, E.; Donsi, G.; Osseo, L.S. . Dipt. di Ingegneria Chimica e Alimentare)

    1993-11-01

    Experimental results of supercritical fluid extraction from various herbaceous matrices are presented. In optimal extraction conditions, the use of a fractional separation technique allows a nearly complete separation of the extract in cuticular waxes and essential oil. The modeling of these results is proposed starting from the description of the mass transfer from a single spherical particle. The simultaneous extraction of two pseudocompounds is assumed to simulate the two compound families obtained by fractionation. The model is then extended to simulate the whole extractor. The yields of essential oil and cuticular waxes obtained from rosemary, basil, and marjoram leaves are fairly simulated by the model. Intraparticle mass transfer resulted as the controlling stage in supercritical extraction of essential oils.

  2. Economic Assessment of Supercritical CO2 Extraction of Waxes as Part of a Maize Stover Biorefinery

    PubMed Central

    Attard, Thomas M.; McElroy, Con Robert; Hunt, Andrew J.

    2015-01-01

    To date limited work has focused on assessing the economic viability of scCO2 extraction to obtain waxes as part of a biorefinery. This work estimates the economic costs for wax extraction from maize stover. The cost of manufacture (COM) for maize stover wax extraction was found to be €88.89 per kg of wax, with the fixed capital investment (FCI) and utility costs (CUT) contributing significantly to the COM. However, this value is based solely on scCO2 extraction of waxes and does not take into account the downstream processing of the biomass following extraction. The cost of extracting wax from maize stover can be reduced by utilizing pelletized leaves and combusting the residual biomass to generate electricity. This would lead to an overall cost of €10.87 per kg of wax (based on 27% combustion efficiency for electricity generation) and €4.56 per kg of wax (based on 43% combustion efficiency for electricity generation). A sensitivity analysis study showed that utility costs (cost of electricity) had the greatest effect on the COM. PMID:26263976

  3. Economic Assessment of Supercritical CO2 Extraction of Waxes as Part of a Maize Stover Biorefinery.

    PubMed

    Attard, Thomas M; McElroy, Con Robert; Hunt, Andrew J

    2015-07-31

    To date limited work has focused on assessing the economic viability of scCO2 extraction to obtain waxes as part of a biorefinery. This work estimates the economic costs for wax extraction from maize stover. The cost of manufacture (COM) for maize stover wax extraction was found to be € 88.89 per kg of wax, with the fixed capital investment (FCI) and utility costs (CUT) contributing significantly to the COM. However, this value is based solely on scCO2 extraction of waxes and does not take into account the downstream processing of the biomass following extraction. The cost of extracting wax from maize stover can be reduced by utilizing pelletized leaves and combusting the residual biomass to generate electricity. This would lead to an overall cost of € 10.87 per kg of wax (based on 27% combustion efficiency for electricity generation) and €4.56 per kg of wax (based on 43% combustion efficiency for electricity generation). A sensitivity analysis study showed that utility costs (cost of electricity) had the greatest effect on the COM.

  4. Modeling and experimental results for condensing supercritical CO2 power cycles.

    SciTech Connect

    Wright, Steven Alan; Conboy, Thomas M.; Radel, Ross F.; Rochau, Gary Eugene

    2011-01-01

    This Sandia supported research project evaluated the potential improvement that 'condensing' supercritical carbon dioxide (S-CO{sub 2}) power cycles can have on the efficiency of Light Water Reactors (LWR). The analytical portion of research project identified that a S-CO{sub 2} 'condensing' re-compression power cycle with multiple stages of reheat can increase LWR power conversion efficiency from 33-34% to 37-39%. The experimental portion of the project used Sandia's S-CO{sub 2} research loop to show that the as designed radial compressor could 'pump' liquid CO{sub 2} and that the gas-cooler's could 'condense' CO{sub 2} even though both of these S-CO{sub 2} components were designed to operate on vapor phase S-CO{sub 2} near the critical point. There is potentially very high value to this research as it opens the possibility of increasing LWR power cycle efficiency, above the 33-34% range, while lowering the capital cost of the power plant because of the small size of the S-CO{sub 2} power system. In addition it provides a way to incrementally build advanced LWRs that are optimally designed to couple to S-CO{sub 2} power conversion systems to increase the power cycle efficiency to near 40%.

  5. Investigations of Localized Corrosion of Stainless Steel after Exposure to Supercritical CO2

    SciTech Connect

    M. Ziomek-Moroz; W. O’Connor; S. Bullard

    2012-03-11

    Severe localized corrosion of a 316 stainless steel autoclave occurred during investigating Type H Portland cement stability in 0.16 M CaCl{sub 2} + 0.02 M MgCl{sub 2} + 0.82 M NaCl brine in contact with supercritical CO{sub 2} containing 4% O{sub 2}. The system operated at 85 C and pressure of 29 MPa. However, no corrosion was observed in the same type of autoclave being exposed to the same environment, containing Type H Portland cement cylindrical samples, also operating at pressure of 29 MPa but at 50 C. The operation time for the 85 C autoclave was 53 days (1272 hours) while that for the 50 C autoclave was 66 days (1584 hours). Debris were collected from the base of both autoclaves and analyzed by X-ray diffraction (XRD). Corrosion products were only found in the debris from the 85 C autoclave. The cement samples were analyzed before and after the exposure by X-ray florescence (XRF) methods. Optical microscopy was used to estimate an extent of the 316 stainless steel corrosion degradation.

  6. Improved neuroprotective effects by combining Bacopa monnieri and Rosmarinus officinalis supercritical CO2 extracts.

    PubMed

    Ramachandran, Cheppail; Quirin, Karl-Werner; Escalon, Enrique; Melnick, Steven J

    2014-04-01

    Ethnobotanical evidence suggests that herbs such as brahmi (Bacopa monnieri) and rosemary (Rosmarinus officinalis) may possess antioxidant and neuroprotective properties. We compared the antioxidant and neuroprotective effects of supercritical extract of Bacopa monnieri and rosemary antioxidant extract obtained from Rosmarinus officinalis as well as their combination to examine the effects on human glial (U-87 MG) and embryonic mouse hypothalamus cells. Bacopa monnieri extract, rosemary antioxidant extract, and their combination (1:1) are not cytotoxic in both glial and embryonic mouse hypothalamus cell lines up to 200 μg/mL concentration. The combination of extracts of Bacopa monnieri + rosemary antioxidant has better antioxidant potential and antilipid peroxidation activity than either agent alone. Although the extract of Bacopa monnieri + rosemary antioxidant showed almost similar inhibition of phospho tau expression as Bacopa monnieri or rosemary antioxidant extract alone, the combination has better inhibitory effect on amyloid precursor protein synthesis and higher brain-derived neurotrophic factor production in hypothalamus cells than single agents. These results suggest that the extract of Bacopa monnieri + rosemary antioxidant is more neuroprotective than Bacopa monnieri or rosemary antioxidant extract.

  7. Carbon dioxide-based supercritical fluids as IC manufacturing solvents

    SciTech Connect

    Rubin, J.B.; Davenhall, L.B.; Taylor, C.M.V.; Sivils, L.D.; Pierce, T.; Tiefert, K.

    1999-05-11

    The production of integrated circuits (IC's) involves a number of discrete steps which utilize hazardous or regulated solvents and generate large waste streams. ES&H considerations associated with these chemicals have prompted a search for alternative, more environmentally benign solvent systems. An emerging technology for conventional solvent replacement is the use of supercritical fluids based on carbon dioxide (CO{sub 2}). Research work, conducted at Los Alamos in conjunction with the Hewlett-Packard Company, has lead to the development of a CO{sub 2}-based supercritical fluid treatment system for the stripping of hard-baked photoresists. This treatment system, known as Supercritical CO{sub 2} Resist Remover, or CORR, uses a two-component solvent composed of a nonhazardous, non-regulated compound, dissolved in supercritical CO{sub 2}. The solvent/treatment system has been successfully tested on metallized Si wafers coated with negative and positive photoresist, the latter both before and after ion-implantation. A description of the experimental data will be presented. Based on the initial laboratory results, the project has progressed to the design and construction of prototype, single-wafer photoresist-stripping equipment. The integrated system involves a closed-loop, recirculating cycle which continuously cleans and regenerates the CO{sub 2}, recycles the dissolved solvent, and separates and concentrates the spent resist. The status of the current design and implementation strategy of a treatment system to existing IC fabrication facilities will be discussed. Additional remarks will be made on the use of a SCORR-type system for the cleaning of wafers prior to processing.

  8. Evidence for CO2-rich fluids in rocks from the type charnockite area near Pallavaram, Tamil Nadu

    NASA Technical Reports Server (NTRS)

    Hansen, E.; Hunt, W.; Jacob, S. C.; Morden, K.; Reddi, R.; Tacy, P.

    1988-01-01

    Fluid inclusion and mineral chemistry data was presented for samples from the type charnockite area near Pallavaram (Tamil Nadu, India). The results indicate the presence of a dense CO2 fluid phase, but the data cannot distinguish between influx of this fluid from elsewhere or localized migration of CO2-rich fluids associated with dehydration melting.

  9. Experimental Insights into Multiphase (H2O-CO2) Fluid-Rock Interactions in Geothermal Systems

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    Integrated hydrothermal experiments and geochemical modeling elucidate fluid-rock interactions and reaction pathways in both natural and anthropogenic systems, including enhanced geothermal systems (EGS) in which CO2 is introduced as a working fluid. Experiments are conducted in rocker bombs and flexible Au-Ti reaction cells. Individual experiments require one to three months to complete; intensive in-situ fluid/gas sampling gauges reaction progress. Investigation of granitic reservoirs and associated vein minerals are broadly based on the Roosevelt Hot Springs thermal area, Utah, USA. The granite consists of subequal amounts of quartz, perthitic K-feldspar (~25% wt% albite and 75% wt% K-feldspar), and oligoclase (An23), and 4 wt% Fe-rich biotite. Vein minerals include epidote and chlorite (clinochlore). Experiments are conducted at 250°C and 25 to 45 MPa. Each experiment uses mineral powders (75 wt% of rock mass, ground to <45 um) to increase reactivity and also mineral pieces (0.1-0.7 cm in size) to promote petrologic evaluation of mineral reactions. The water (I ≈ 0.1 molal) initially contains millimolal quantities of SiO2, Al, Ca, Mg, K, SO4, and HCO3 and is designed to be saturated with all of the minerals present at the start of each experiment. Excess CO2 is injected to saturate the water and maintain an immiscible supercritical fluid phase. The entire evolutionary path of the natural system is not replicated at laboratory scales. Instead, experiments define a segment of the reaction path and, in combination with geochemical modeling, provide clear trajectories towards equilibrium. Reaction of granite+water yields illite+zeolite; smectite subsequently precipitates in response to CO2 injection. Reaction of granite+epidote+water yields illite+zeolite+smectite; zeolite does not precipitate after CO2 is injected. Water in all experiments become saturated with chalcedony. Carbonate minerals do not precipitate but are predicted as final equilbrium products

  10. The key to commercial-scale geological CO2 sequestration: Displaced fluid management

    USGS Publications Warehouse

    Surdam, R.C.; Jiao, Z.; Stauffer, P.; Miller, T.

    2011-01-01

    The Wyoming State Geological Survey has completed a thorough inventory and prioritization of all Wyoming stratigraphic units and geologic sites capable of sequestering commercial quantities of CO2 (5-15 Mt CO 2/year). This multi-year study identified the Paleozoic Tensleep/Weber Sandstone and Madison Limestone (and stratigraphic equivalent units) as the leading clastic and carbonate reservoir candidates for commercial-scale geological CO2 sequestration in Wyoming. This conclusion was based on unit thickness, overlying low permeability lithofacies, reservoir storage and continuity properties, regional distribution patterns, formation fluid chemistry characteristics, and preliminary fluid-flow modeling. This study also identified the Rock Springs Uplift in southwestern Wyoming as the most promising geological CO2 sequestration site in Wyoming and probably in any Rocky Mountain basin. The results of the WSGS CO2 geological sequestration inventory led the agency and colleagues at the UW School of Energy Resources Carbon Management Institute (CMI) to collect available geologic, petrophysical, geochemical, and geophysical data on the Rock Springs Uplift, and to build a regional 3-D geologic framework model of the Uplift. From the results of these tasks and using the FutureGen protocol, the WSGS showed that on the Rock Springs Uplift, the Weber Sandstone has sufficient pore space to sequester 18 billion tons (Gt) of CO2, and the Madison Limestone has sufficient pore space to sequester 8 Gt of CO2. ?? 2011 Published by Elsevier Ltd.

  11. Feasibility of on-line supercritical fluid extraction of steroids from aqueous-based matrices with analysis via gas chromatography-mass spectrometry.

    PubMed

    Ashraf-khorassani, M; Taylor, L T

    2000-11-01

    The solubility of testosterone, boldenone, androstenone, etiocholanolone, and epitestosterone are measured in pure supercritical CO2. Testosterone exhibited the highest solubility in supercritical CO2. The solubility of all steroids except epitestosterone increased by one order of magnitude with increasing pressure from 100 to 400 atm. Epitestosterone had the lowest solubility in supercritical CO2 and its solubility was not affected by pressure. The extraction efficiency of steroids from an aqueous saline environment exceeded 95%. Because of the partial solubility of water in supercritical CO2, the addition of a moisture trap after the aqueous vessel is necessary to prevent the plugging and deterioration of the gas chromatographic (GC) column. It is demonstrated that on-line supercritical fluid extraction-GC-mass spectrometry is feasible for the quantitative extraction and analysis of steroids from both saline and urine solutions. However, it is determined that the adsorbent vessel filled with Hydromatrix is not sufficient to trap all the moisture, and after 3 to 4 extractions, the GC column efficiency lowered. PMID:11105770

  12. Characterization of the CO2 fluid adsorption in coal as a function of pressure using neutron scattering techniques (SANS and USANS)

    USGS Publications Warehouse

    Melnichenko, Y.B.; Radlinski, A.P.; Mastalerz, Maria; Cheng, G.; Rupp, J.

    2009-01-01

    Small angle neutron scattering techniques have been applied to investigate the phase behavior of CO2 injected into coal and possible changes in the coal pore structure that may result from this injection. Three coals were selected for this study: the Seelyville coal from the Illinois Basin (Ro = 0.53%), Baralaba coal from the Bowen Basin (Ro = 0.67%), and Bulli 4 coal from the Sydney Basin (Ro = 1.42%). The coals were selected from different depths to represent the range of the underground CO2 conditions (from subcritical to supercritical) which may be realized in the deep subsurface environment. The experiments were conducted in a high pressure cell and CO2 was injected under a range of pressure conditions, including those corresponding to in-situ hydrostatic subsurface conditions for each coal. Our experiments indicate that the porous matrix of all coals remains essentially unchanged after exposure to CO2 at pressures up to 200??bar (1??bar = 105??Pa). Each coal responds differently to the CO2 exposure and this response appears to be different in pores of various sizes within the same coal. For the Seelyville coal at reservoir conditions (16????C, 50??bar), CO2 condenses from a gas into liquid, which leads to increased average fluid density in the pores (??pore) with sizes (r) 1 ?? 105 ??? r ??? 1 ?? 104???? (??pore ??? 0.489??g/cm3) as well as in small pores with size between 30 and 300???? (??pore ??? 0.671??g/cm3). These values are by a factor of three to four higher than the density of bulk CO2 (??CO2) under similar thermodynamic conditions (??CO2 ??? 0.15??g/cm3). At the same time, in the intermediate size pores with r ??? 1000???? the average fluid density is similar to the density of bulk fluid, which indicates that adsorption does not occur in these pores. At in situ conditions for the Baralaba coal (35 OC, 100??bar), the average fluid density of CO2 in all pores is lower than that of the bulk fluid (??pore / ??CO2 ??? 0.6). Neutron scattering from the

  13. Growth and Morphology of Supercritical Fluids, a Fluid Physics Experiment Conducted on Mir, Complete

    NASA Technical Reports Server (NTRS)

    Wilkinson, R. Allen

    2001-01-01

    The Growth and Morphology of Supercritical Fluids (GMSF) is an international experiment facilitated by the NASA Glenn Research Center and under the guidance of U.S. principal investor Professor Hegseth of the University of New Orleans and three French coinvestigators: Daniel Beysens, Yves Garrabos, and Carole Chabot. The GMSF experiments were concluded in early 1999 on the Russian space station Mir. The experiments spanned the three science themes of near-critical phase separation rates, interface dynamics in near-critical boiling, and measurement of the spectrum of density fluctuation length scales very close to the critical point. The fluids used were pure CO2 or SF6. Three of the five thermostats used could adjust the sample volume with the scheduled crew time. Such a volume adjustment enabled variable sample densities around the critical density as well as pressure steps (as distinct from the usual temperature steps) applied to the sample. The French-built ALICE II facility was used for these experiments. It allows tightly thermostated (left photograph) samples (right photograph) to be controlled and viewed/measured. Its diagnostics include interferometry, shadowgraph, high-speed pressure measurements, and microscopy. Data were logged on DAT tapes, and PCMCIA cards and were returned to Earth only after the mission was over. The ground-breaking near critical boiling experiment has yielded the most results with a paper published in Physical Review Letters (ref. 1). The boiling work also received press in Science Magazine (ref. 2). This work showed that, in very compressible near-critical two-phase pure fluids, a vapor bubble was induced to temporarily overheat during a rapid heating of the sample wall. The temperature rise in the vapor was 23-percent higher than the rise in the driving container wall. The effect is due to adiabatic compression of the vapor bubble by the rapid expansion of fluid near the boundary during heatup. Thermal diffusivity is low near the

  14. Coupled Model for CO2 Leaks from Geological Storage: Geomechanics, Fluid Flow and Phase Transitions

    NASA Astrophysics Data System (ADS)

    Gor, G.; Prevost, J.

    2013-12-01

    Deep saline aquifers are considered as a promising option for long-term storage of carbon dioxide. However, risk of CO2 leakage from the aquifers through faults, natural or induced fractures or abandoned wells cannot be disregarded. Therefore, modeling of various leakage scenarios is crucial when selecting a site for CO2 sequestration and choosing proper operational conditions. Carbon dioxide is injected into wells at supercritical conditions (t > 31.04 C, P > 73.82 bar), and these conditions are maintained in the deep aquifers (at 1-2 km depth) due to hydrostatic pressure and geothermal gradient. However, if CO2 and brine start to migrate from the aquifer upward, both pressure and temperature will decrease, and at the depth of 500-750 m, the conditions for CO2 will become subcritical. At subcritical conditions, CO2 starts boiling and the character of the flow changes dramatically due to appearance of the third (vapor) phase and latent heat effects. When modeling CO2 leaks, one needs to couple the multiphase flow in porous media with geomechanics. These capabilities are provided by Dynaflow, a finite element analysis program [1]; Dynaflow has already showed to be efficient for modeling caprock failure causing CO2 leaks [2, 3]. Currently we have extended the capabilities of Dynaflow with the phase transition module, based on two-phase and three-phase isenthalpic flash calculations [4]. We have also developed and implemented an efficient method for solving heat and mass transport with the phase transition using our flash module. Therefore, we have developed a robust tool for modeling CO2 leaks. In the talk we will give a brief overview of our method and illustrate it with the results of simulations for characteristic test cases. References: [1] J.H. Prevost, DYNAFLOW: A Nonlinear Transient Finite Element Analysis Program. Department of Civil and Environmental Engineering, Princeton University, Princeton, NJ. http://www.princeton.edu/~dynaflow/ (last update 2013

  15. Determination of Organic Partitioning Coefficients in Water-Supercritical CO2 Systems by Simultaneous in Situ UV and Near-Infrared Spectroscopies.

    PubMed

    Bryce, David A; Shao, Hongbo; Cantrell, Kirk J; Thompson, Christopher J

    2016-06-01

    CO2 injected into depleted oil or gas reservoirs for long-term storage has the potential to mobilize organic compounds and distribute them between sediments and reservoir brines. Understanding this process is important when considering health and environmental risks, but little quantitative data currently exists on the partitioning of organics between supercritical CO2 and water. In this work, a high-pressure, in situ measurement capability was developed to assess the distribution of organics between CO2 and water at conditions relevant to deep underground storage of CO2. The apparatus consists of a titanium reactor with quartz windows, near-infrared and UV spectroscopic detectors, and switching valves that facilitate quantitative injection of organic reagents into the pressurized reactor. To demonstrate the utility of the system, partitioning coefficients were determined for benzene in water/supercritical CO2 over the range 35-65 °C and approximately 25-150 bar. Density changes in the CO2 phase with increasing pressure were shown to have dramatic impacts on benzene's partitioning behavior. Our partitioning coefficients were approximately 5-15 times lower than values previously determined by ex situ techniques that are prone to sampling losses. The in situ methodology reported here could be applied to quantify the distribution behavior of a wide range of organic compounds that may be present in geologic CO2 storage scenarios.

  16. Effect of debonded interfaces on corrosion of mild steel composites in supercritical CO2-saturated brines

    SciTech Connect

    John, Han; Carey, James W; Zhang, Jinsuo

    2010-10-07

    The geologic sequestration of CO{sub 2} is a proposed method to limit greenhouse gas emissions and has been the subject of many studies in the last decade. Wellbore systems achieve isolation of the storage reservoir through a combination of steel (generally carbon steel) and Portland cement. CO{sub 2} leakage along the steel-cement interface has the potential to accelerate corrosion. We conduct experiments to assess the corrosion risk at cement-steel interface under in situ wellbore conditions. Wellbore interfaces were simulated by assemblies constructed of J55 mild steel and Portland class G (Epoxy was used in this study to separate) cement and corrosion was investigated in supercritical CO{sub 2} saturated brines, (NaCl = 1 wt%) at T = 50 C, pCO{sub 2} = 1200 psi with interface gap size = 100 {micro}m and {infinity} (open surface). The experiments were carried out in a high-pressure, 1.8 L autoclave. The corrosion kinetics were measured employing electrochemical techniques including linear polarization resistance and electrochemical impedance spectroscopy techniques. The corrosion scales were analyzed using secondary electron microscopy, back scattering electron microscopy, energy dispersive spectroscopy and x-ray diffraction. Corrosion rates decreased as time with or without interface gap. In this case corrosion rates are controlled by scale protectivity through the interface gap. Scaled steel corrosion rates were two orders of magnitude less compared with fresh steel. The corrosion scale is pseudo crystalline at the open interface. Well-crystallized scale was observed at interface gap sizes 100 {micro}m. All corrosion scales were composed of iron carbonates.

  17. EVALUATION OF RESERVOIR ROCK AND WELL BORE CEMENT ALTERATION WITH SUPERCRITICAL CO2

    SciTech Connect

    William k. O'Connor; Gilbert E Rush

    2009-01-01

    An evaluation of the alteration of reservoir rock and well bore cement at their interface, under supercritical CO{sub 2} (SCCO{sub 2}), was conducted at the laboratory-scale using simulated brine solutions at down-hole conditions. These studies were intended to identify potential leakage pathways for injected CO{sub 2} due to degradation of the well bore. Two distinct test series were conducted on core samples of the Mt. Simon sandstone from the Illinois Basin, IL, and the Grand Ronde basalt from the Pasco Basin, WA. LaFarge Class H well bore cement was used for both series. Reservoir rock/cement cores were immersed within a CO{sub 2}-saturated brine for up to 2000 hours at 35 degrees C and 100 atm CO{sub 2}. Results suggest that the impact of SCCO{sub 2} injection is reservoir-specific, being highly dependent on the reservoir brine and rock type. Brine pH can be significantly altered by CO{sub 2} injection, which in turn can dramatically impact the dissolution characteristics of the reservoir rock. Finally, well bore cement alteration was identified, particularly for fresh cast cement allowed to cure at SCCO{sub 2} conditions. However, this alteration was generally limited to an outer rind of carbonate and Ca-depleted cement which appeared to protect the majority of the cement core from further attack. These studies indicate that at the cement-rock interface, the annular space may be filled by carbonate which could act as an effective barrier against further CO{sub 2} migration along the well bore.

  18. Conductivity measurements on H2O-bearing CO2-rich fluids

    DOE PAGES

    Capobianco, Ryan M.; Miroslaw S. Gruszkiewicz; Bodnar, Robert J.; Rimstidt, J. Donald

    2014-09-10

    Recent studies report rapid corrosion of metals and carbonation of minerals in contact with carbon dioxide containing trace amounts of dissolved water. One explanation for this behavior is that addition of small amounts of H2O to CO2 leads to significant ionization within the fluid, thus promoting reactions at the fluid-solid interface analogous to corrosion associated with aqueous fluids. The extent of ionization in the bulk CO2 fluid was determined using a flow-through conductivity cell capable of detecting very low conductivities. Experiments were conducted from 298 to 473 K and 7.39 to 20 MPa with H2O concentrations up to ~1600 ppmwmore » (xH2O ≈ 3.9 x 10-3), corresponding to the H2O solubility limit in liquid CO2 at ambient temperature. All solutions showed conductivities <10 nS/cm, indicating that the solutions were essentially ion-free. Furthermore, this observation suggests that the observed corrosion and carbonation reactions are not the result of ionization in CO2-rich bulk phase, but does not preclude ionization in the fluid at the fluid-solid interface.« less

  19. Flexible low-voltage polymer thin-film transistors using supercritical CO2-deposited ZrO2 dielectrics.

    PubMed

    Wei, Qingshuo; You, Eunyoung; Hendricks, Nicholas R; Briseno, Alejandro L; Watkins, James J

    2012-05-01

    The fabrication of low-voltage flexible organic thin film transistors using zirconia (ZrO(2)) dielectric layers prepared via supercritical fluid deposition was studied. Continuous, single-phase films of approximately 30 nm thick ZrO(2) were grown on polyimide (PI)/aluminum (Al) substrates at 250 °C via hydrolysis of tetrakis(2,2,6,6-tetramethyl-3,5-heptane-dionato) zirconium in supercritical carbon dioxide. This dielectric layer showed a high areal capacitance of 317 nF cm(-2) at 1 kHz and a low leakage current of 1.8 × 10(-6) A cm(-2) at an applied voltage of -3 V. By using poly(3-hexylthiophene) (P3HT) as a semiconductor, we have fabricated flexible thin film transistors operating at V(DS) = -0.5 V and V(G) in a range from 0.5 V to -4 V, with on/off ratios on the order of 1 × 10(3) and mobility values higher than 0.1 cm(2)/(V s).

  20. Reservoir fluid and gas chemistry during CO2 injection at the Cranfield field, Mississippi, USA

    NASA Astrophysics Data System (ADS)

    Lu, J.; Kharaka, Y. K.; Cole, D. R.; Horita, J.; Hovorka, S.

    2009-12-01

    At Cranfield field, Mississippi, USA, a monitored CO2-EOR project provides a unique opportunity to understand geochemical interactions of injected CO2 within the reservoir. Cranfield field, discovered in 1943, is a simple anticlinal four-way closure and had a large gas cap surrounded by an oil ring (Mississippi Oil and Gas Board, 1966). The field was abandoned in 1966. The reservoir returned to original reservoir pressure (hydrostatic pressure) by a strong aquifer drive by 2008. The reservoir is in the lower Tuscaloosa Formation at depths of more than 3000 m. It is composed of stacked and incised channel fills and is highly heterogeneous vertically and horizontally. A variable thickness (5 to 15 m) of terrestrial mudstone directly overlies the basal sandstone providing the primary seal, isolating the injection interval from a series of fluvial sand bodies occurring in the overlying 30 m of section. Above these fluvial channels, the marine mudstone of the Middle Tuscaloosa forms a continuous secondary confining system of approximately 75 m. The sandstones of the injection interval are rich in iron, containing abundant diagenetic chamosite (ferroan chlorite), hematite and pyrite. Geochemical modeling suggests that the iron-bearing minerals will be dissolved in the face of high CO2 and provide iron for siderite precipitation. CO2 injection by Denbury Resources Inc. begun in mid-July 2008 on the north side of the field with rates at ~500,000 tones per year. Water and gas samples were taken from seven production wells after eight months of CO2 injection. Gas analyses from three wells show high CO2 concentrations (up to 90 %) and heavy carbon isotopic signatures similar to injected CO2, whereas the other wells show original gas composition and isotope. The mixing ratio between original and injected CO2 is calculated based on its concentration and carbon isotope. However, there is little variation in fluid samples between the wells which have seen various levels of CO2

  1. Functional properties of spice extracts obtained via supercritical fluid extraction.

    PubMed

    Leal, Patrícia F; Braga, Mara E M; Sato, Daisy N; Carvalho, João E; Marques, Marcia O M; Meireles, M Angela A

    2003-04-23

    In the present study the antioxidant, anticancer, and antimycobacterial activities of extracts from ginger (Zingiber officinale Roscoe), rosemary (Rosmarinus officinalis L.), and turmeric (Curcuma longa L.) were evaluated. The extracts were obtained using supercritical CO(2) with and without ethanol and/or isopropyl alcohol as cosolvent. The extracts' antioxidant power was assessed using the reaction between beta-carotene and linolenic acid, the antimycobacterial activity against M. tuberculosis was measured by the MABA test, and their anticancer action was tested against nine human cancer ancestries: lung, breast, breast resistant, melanoma, colon, prostate, leukemia, and kidney. The rosemary extracts exhibited the strongest antioxidant and the lowest antimycobacterial activities. Turmeric extracts showed the greatest antimycobacterial activity. Ginger and turmeric extracts showed selective anticancer activities. PMID:12696930

  2. Chiral separation of a diketopiperazine pheromone from marine diatoms using supercritical fluid chromatography.

    PubMed

    Frenkel, Johannes; Wess, Carsten; Vyverman, Wim; Pohnert, Georg

    2014-03-01

    The proline derived diketopiperazine has been identified in plants, insects and fungi with unknown function and was recently also reported as the first pheromone from a diatom. Nevertheless the stereochemistry and enantiomeric excess of this natural product remained inaccessible using direct analytical methods. Here we introduce a chiral separation of this metabolite using supercritical fluid chromatography/mass spectrometry. Several chromatographic methods for chiral analysis of the diketopiperazine from the diatom Seminavis robusta and synthetic enantiomers have been evaluated but neither gas chromatography nor high performance liquid chromatography on different chiral cyclodextrin phases were successful in separating the enantiomers. In contrast, supercritical fluid chromatography achieved baseline separation within four minutes of run time using amylose tris(3,5-dimethylphenylcarbamate) as stationary phase and 2-propanol/CO2 as mobile phase. This very rapid chromatographic method in combination with ESI mass spectrometry allowed the direct analysis of the cyclic dipeptide out of the complex sea water matrix after SPE enrichment. The method could be used to determine the enantiomeric excess of freshly released pheromone and to follow the rapid degradation observed in diatom cultures. Initially only trace amounts of c(d-Pro-d-Pro) were found besides the dominant c(l-Pro-l-Pro) in the medium. However the enantiomeric excess decreased upon pheromone degradation within few hours indicating that a preferential conversion and thus inactivation of the l-proline derived natural product takes place.

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

    NASA Astrophysics Data System (ADS)

    Movassat, Mohammad; Bailey, Joanne; Yetisir, Metin

    2015-11-01

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

  4. 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.

  5. Separations of petroleum products involving supercritical fluid chromatography.

    PubMed

    Thiébaut, Didier

    2012-08-24

    This paper gives a survey of the most attractive trends and applications of supercritical fluid chromatography in the petroleum industry: simulated distillation, group-type analysis and related applications including the implementation of multidetection in a so-called "hypernated" system, as well as the hyphenation to GC×GC for improved group-type separation, SFC×GC and first promising SFC×SFC results. Some specific technical information related to the use of capillary columns or conventional packed columns in combination with FID (or detectors that require decompression and in some instances splitting of the mobile phase prior detection) is also provided.

  6. Packed column supercritical fluid chromatography using deactivated stationary phases

    SciTech Connect

    Ashraf-Khorassani, M.; Taylor, L.T.; Henry, R.A.

    1988-08-01

    A new cross-linked cyanopropyl bonded phase silica (Delta-bond) has been studied as a stationary phase for packed column supercritical fluid chromatography of basic nitrogen-containing compounds. The bonded phase impedes access to uncapped silanol sites, thereby giving rise to better peak shapes and more rapid elution without the necessity of a polar modifier in the mobile phase. Experiments both at elevated temperature and in the presence of a methanol modifier revealed that there is no short- or long-term deleterious effect on the column as opposed to the conventional cyanopropyl phase.

  7. Structural and Collisional Relaxations in Liquids and Supercritical Fluids

    SciTech Connect

    Bencivenga, F.; Krisch, M.; Monaco, G.; Sette, F.; Cunsolo, A.; Ruocco, G.; Vispa, A.

    2007-02-23

    The dynamic structure factor S(Q,{omega}) of both associated (water and ammonia) and simple fluids (nitrogen and neon) has been determined by high-resolution inelastic x-ray scattering in the 2-14 nm{sup -1} momentum transfer range. A line-shape analysis with a generalized hydrodynamic model was used to study the involved relaxation process and to characterize its strength and time scale. We observe that in the liquid phase such a process is governed by rearrangements of intermolecular bonds, whereas in the supercritical region it assumes a collisional nature.

  8. Supercritical fluid reactions for coal processing. Quarterly report, July 1--September 30, 1996

    SciTech Connect

    Eckert, C.A.

    1996-12-31

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The Diels-Alder reaction of anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) was chosen as the model system and was investigated in supercritical carbon dioxide.

  9. Genomic insights into growth and survival of supercritical-CO2 tolerant bacterium MIT0214 under conditions associated with geologic carbon dioxide sequestration

    NASA Astrophysics Data System (ADS)

    Peet, K. C.; Freedman, A. J.; Hernandez, H.; Thompson, J. R.

    2011-12-01

    Carbon capture and storage (CCS) of CO2 has the potential to significantly reduce the emissions of greenhouse gasses associated with fossil fuel combustion. The largest potential for storing captured CO2 in the United Sates is in deep geologic saline formations. Currently, little is known about the effects of CO2 storage on biologically active microbial communities found in the deep earth biosphere. Therefore, to investigate how deep earth microbial communities will be affected by the storage of CO2 we have enriched for a microbial consortium from the saline formation waters of the Frio 2 project site (Texas Gulf Coast) that is capable of growth in nutrient media under a supercritical CO2 headspace (Hernandez, et al). The cultivation of actively growing cells in an environment containing scCO2 is unexpected based on previous experimental evidence of microbial sterilization attributed to the acidic, desiccating, and solvent-like properties of scCO2. We have isolated strain MIT0214 from this supercritical CO2 based enrichment and have sequenced its genome using the Illumina platform followed by de novo assembly of reads and targeted Sanger sequencing to reduce gaps in the draft assembly. The genome of strain MIT0214 is approximately 5,551,062 base pairs with 35% GC-content and is most similar to nonpathogenic Bacillus cereus strain ATCC 14597. Annotation of the draft assembly of the MIT0214 genome by the Rapid Annotation using Subsystem Technology (RAST) server revealed 5538 coding sequences where 4145 of the coding sequences were assigned putative functions. These functions were enriched in cell wall and capsule formation, phage/prophage and plasmids, gene regulation and signaling, and nitrogen and sulfur metabolism relative to the genome of the most closely-related surface-isolated B. cereus reference (ATCC 14597) and in total 773,416 bp of the MIT0214 genome content was distinct from the B. cereus reference. Notably, this set of distinct sequences were most

  10. Nitrous oxide versus carbon dioxide for supercritical fluid extraction and chromatography of amines

    SciTech Connect

    Ashraf-Khorassani, M.; Taylor, L.T. ); Zimmerman, P. )

    1990-06-01

    Supercritical N{sub 2}O has been evaluated and compared with supercritical CO{sub 2} as a solvent for supercritical fluid extraction of different amines. Supercritical N{sub 2}O showed a higher solubility for amines and easily extracted both aliphatic and aromatic amines. The effect of substrate on extraction has been also examined. Supercritical N{sub 2}O has been used as a mobile phase, with different diameter columns, for supercritical fluid chromatography. The total response of flame ionization detection to supercritical N{sub 2}O using packed capillary and open tubular capillary columns demonstrated the feasibility of flame ionization detection with N{sub 2}O in a density programmed mode.

  11. Effect of ultrasound on the supercritical CO2 extraction of bioactive compounds from dedo de moça pepper (Capsicum baccatum L. var. pendulum).

    PubMed

    Dias, Arthur Luiz Baião; Arroio Sergio, Camilla Scarelli; Santos, Philipe; Barbero, Gerardo Fernandéz; Rezende, Camila Alves; Martínez, Julian

    2016-07-01

    Extracts with bioactive compounds were obtained from the red pepper variety "dedo de moça" (Capsicum baccatum L. var. pendulum) through supercritical fluid extraction with carbon dioxide assisted by ultrasound (SFE-US). The process was tested at pressures of 15, 20 and 25 MPa; temperatures of 40, 50 and 60 °C, and ultrasonic powers of 200, 400 and 600 W applied during 40, 60 and 80 min of extraction. The CO2 mass flow rate was fixed at 1.7569 × 10(-4) kg/s. Global yield, phenolic content, antioxidant capacity and capsaicinoid concentration were evaluated in the extracts. The application of ultrasound raised the global extraction yield of SFE up to 45%. The phenolic content of the extract increased with the application of higher ultrasound power and radiation time. The capsaicinoid yield was also enhanced with ultrasound up to 12%. However, the antioxidant capacity did not increase with the ultrasound application. The BET-based model and the broken and intact cell model fitted well to the kinetic SFE curves. The BET-based model with three adjustable parameters resulted in the best fits to the experimental data. Field emission scanning electron microscopy (FESEM) images showed that SFE disturbed the vegetable matrix, releasing particles from the inner region of the plant cells to their surface. When the ultrasound was applied this effect was more pronounced. On the other hand, cracks, fissures or any sign of rupture were not identified on the sample surface.

  12. Effects of process parameters on supercritical CO2 extraction of total phenols from strawberry (Arbutus unedo L.) fruits: An optimization study.

    PubMed

    Akay, Seref; Alpak, Ilknur; Yesil-Celiktas, Ozlem

    2011-08-01

    The aim of this work was to optimize total phenolic yield of Arbutus unedo fruits using supercritical fluid extraction. A Box-Behnken statistical design was used to evaluate the effect of various values of pressure (50-300 bar), temperature (30-80°C) and concentration of ethanol as co-solvent (0-20%) by CO2 flow rate of 15 g/min for 60 min. The most effective variable was co-solvent ratio (p<0.005). Evaluative criteria for both dependent variables (total phenols and radical scavenging activity) in the model were assigned maximum. Optimum extraction conditions were elicited as 60 bar, 48°C and 19.7% yielding 25.72 mg gallic acid equivalent (GAE) total phenols/g extract and 99.9% radical scavenging capacity, which were higher than the values obtained by conventional water (24.89 mg/g; 83.8%) and ethanol (15.12 mg/g; 95.8%) extractions demonstrating challenges as a green separation process with improved product properties for industrial applications. PMID:21695688

  13. Effect of ultrasound on the supercritical CO2 extraction of bioactive compounds from dedo de moça pepper (Capsicum baccatum L. var. pendulum).

    PubMed

    Dias, Arthur Luiz Baião; Arroio Sergio, Camilla Scarelli; Santos, Philipe; Barbero, Gerardo Fernandéz; Rezende, Camila Alves; Martínez, Julian

    2016-07-01

    Extracts with bioactive compounds were obtained from the red pepper variety "dedo de moça" (Capsicum baccatum L. var. pendulum) through supercritical fluid extraction with carbon dioxide assisted by ultrasound (SFE-US). The process was tested at pressures of 15, 20 and 25 MPa; temperatures of 40, 50 and 60 °C, and ultrasonic powers of 200, 400 and 600 W applied during 40, 60 and 80 min of extraction. The CO2 mass flow rate was fixed at 1.7569 × 10(-4) kg/s. Global yield, phenolic content, antioxidant capacity and capsaicinoid concentration were evaluated in the extracts. The application of ultrasound raised the global extraction yield of SFE up to 45%. The phenolic content of the extract increased with the application of higher ultrasound power and radiation time. The capsaicinoid yield was also enhanced with ultrasound up to 12%. However, the antioxidant capacity did not increase with the ultrasound application. The BET-based model and the broken and intact cell model fitted well to the kinetic SFE curves. The BET-based model with three adjustable parameters resulted in the best fits to the experimental data. Field emission scanning electron microscopy (FESEM) images showed that SFE disturbed the vegetable matrix, releasing particles from the inner region of the plant cells to their surface. When the ultrasound was applied this effect was more pronounced. On the other hand, cracks, fissures or any sign of rupture were not identified on the sample surface. PMID:26964951

  14. Experimental study on supercritical CO2 adsorption on coals from Upper Silesian coal Basin

    NASA Astrophysics Data System (ADS)

    Weishauptová, Zuzana; Přibyl, Oldřich; Sýkorová, Ivana

    2014-05-01

    Although coal seams, besides saline aquifers and depleted oil and gas reservoirs, have the lowest capacity for deposition of carbon dioxide yet this relatively new technology is considered advantageous from an economical standpoint, especially in the case of location of a repository in the vicinity of a power plant producing carbon dioxide. Another appreciable positive aspect is injection of carbon dioxide into unmineable methane-bearing seams, which simultaneously increases production of coal methane as a valuable energetic resource. Suitability of coal seams as carbon dioxide repositories is given by exceptional properties of coal, which during the coalification process retained in its interior spatial arrangement a substantial part of the porous structure of the original plant material with predominance of cavities of an effective size < 2nm. The major mechanism of the storage is represented by sorption processes taking place in the coal porous system. The effectivity of the sorption process depends on properties of the coal matter, seam environment, and carbon dioxide under the conditions corresponding to the situation in situ. Among the basic parameters for selection of a suitable repository based on simulation of the deposition process there is determination of its sorption capacity. The capacity can be determined in a laboratory by measuring the amount of carbon dioxide captured in a coal sample at a pressure and temperature corresponding to supercritical conditions in situ using high pressure sorption techniques. Similarly, the amount of methane bound in coal is based on high pressure measurement of it sorbed amount The present study has been aimed at investigation of the effect of the coal properties on the carbon dioxide and methane sorption capacities. High pressure sorption experiments with carbon dioxide and methane were carried out at the temperature 45 oC and the pressure up to 15 MPa with three samples of methane-bearing, medium rank coals in a

  15. Effects of seawater pCO2 changes on the calcifying fluid of scleractinian corals

    NASA Astrophysics Data System (ADS)

    Hohn, S.; Merico, A.

    2012-03-01

    Rising atmospheric CO2 concentrations due to anthropogenic emissions induce changes in the ocean carbonate chemistry and a drop in ocean pH. This acidification process is expected to harm calcifying organisms like coccolithophores, molluscs, echinoderms, and corals. A severe decline in coral abundance is, for example, expected by the end of this century with associated disastrous effects on reef ecosystems. Despite the growing importance of the topic, little progress has been made with respect to modelling the impact of acidification on coral calcification. Here we present a model for a coral polyp that simulates the carbonate system in four different compartments: the seawater, the polyp tissue, the coelenteron, and the calicoblastic layer. Precipitation of calcium carbonate takes place in the metabolically controlled calicoblastic layer beneath the polyp tissue. The model is adjusted to a state of activity as observed by direct microsensor measurements in the calcifying fluid. Simulated CO2 perturbation experiments reveal decreasing calcification rates under elevated pCO2 despite strong metabolic control of the calcifying fluid. Diffusion of CO2 through the tissue into the calicoblastic layer increases with increasing seawater pCO2 leading to decreased aragonite saturation in the calcifying fluid of the coral polyp. Our modelling study provides important insights into the complexity of the calcification process at the organism level and helps to quantify the effect of ocean acidification on corals.

  16. MIXTURES OF CO2-SF6 AS WORKING FLUIDS FOR GEOTHERMAL PLANTS

    SciTech Connect

    Sabau, Adrian S; Yin, Hebi; Gruszkiewicz, Miroslaw {Mirek} S; McFarlane, Joanna; Qualls, A L; Conklin, Jim; Pawel, Steven J

    2011-01-01

    In this paper, mixtures of CO2 and SF6 were evaluated as working fluids for geothermal plants based on property measurements, molecular dynamics modeling, thermodynamic cycle analysis, and materials compatibility assessment. The CO2 - SF6 was evaluated for a reservoir temperature of 160 oC. Increasing the efficiency for these low reservoir sources will increase the options available for geothermal energy utilization in more sites across the country. The properties for the mixtures were obtained either from thermodynamic property measurements and molecular dynamics simulations. Optimum compositions of the CO2 - SF6 were identified for a well reservoir temperature and a given water-cooling condition. Concerning the global warming potential, it was estimated that the equivalent CO2 emissions per 1kWh for a Rankine cycle operating with 100% SF6 would be approximately of 7.6% than those for a coal-fired power plant.

  17. CO2- and Ca-rich Fluids Drive Dolomite Formation During Hydrothermal Alteration of Peridotite

    NASA Astrophysics Data System (ADS)

    Grozeva, N. G.; Klein, F.; Seewald, J.; Sylva, S.

    2014-12-01

    We present an experimental study investigating reaction pathways during the interaction of CO2-rich aqueous fluids with mantle peridotite, which have major implications for geochemical budgets and microbial life in oceanic lithosphere. Powdered harzburgite was reacted with a Ca-enriched fluid in a flexible-cell hydrothermal apparatus at 300°C and 35 MPa for 1.7 years. A CO2-rich fluid was subsequently injected and allowed to react for 8 months to examine the formation of carbonates under reducing conditions. Fluids were sampled throughout the experiment to monitor changes in fluid chemistry, and the secondary mineralogy was analyzed at the end of the experiment. Fluid speciation and mineral analyses suggest that initial serpentinization of harzburgite led to the precipitation of serpentine, brucite, magnetite, chlorite, calcite and Ni-sulfides. Fluids during this stage were characterized by low concentrations of dissolved Si, Mg and CO2, alkaline pH(25°C), and high concentrations of dissolved Ca, consistent with buffering by serpentine-brucite-diopside-calcite equilibria. H2(aq) concentrations increased during the first 10 months of reaction (due to magnetite formation), but subsequently plateaued, suggesting that serpentinization approached completion prior to CO2 injection. The introduction of CO2 resulted in acidic pH(25°C), substantial decreases in H2(aq) concentrations, and increases in dissolved SiO2 and Mg2+ concentrations. Dolomite and high-Mg calcite appear to have formed at the expense of olivine, calcite and likely brucite. However, petrographic observations suggest that Mg-calcite was only a transient phase and was ultimately destabilized in favor of dolomite. Replacement textures with carbonate in mesh centers are strikingly similar to those found in dolomite-altered abyssal serpentinites from the Atlantis Massif. While magnesite precipitation seems possible in ridge environments, high CO2(aq) and Ca2+ activities in serpentinization systems appear

  18. Impact of solvents and supercritical CO2 drying on the morphology and structure of polymer-based biofilms

    NASA Astrophysics Data System (ADS)

    Causa, Andrea; Salerno, Aurelio; Domingo, Concepción; Acierno, Domenico; Filippone, Giovanni

    2014-05-01

    In the present work, two-dimensional systems based on biodegradable polymers such as poly(ɛ-caprolactone) (PCL), poly(ethylene oxide) (PEO) and polylactic acid (PLA) are fabricated by means of a sustainable approach which consists in inducing phase separation in solutions of such polymers and "green" solvents, namely ethyl lactate (EL) and ethyl acetate (EA). The extraction of the solvent is promoted by a controlled drying process, which is performed in either air or supercritical CO2. The latter can indeed act as both an antisolvent, which favors the deposition of the polymer by forming a mixture with EL and EA, and a plasticizing agent, whose solvation and transport properties may considerably affect the microstructure and crystallinity of the polymer films. The morphological, topographical and crystalline properties of the films are tailored through a judicial selection of the materials and the processing conditions and assessed by means of thermal analyses, polarized optical microscopy, scanning electron microscopy and confocal interferometric microscopy. The results show that the morphological and crystalline properties of the films are strongly dependent on the choice of both the polymer/solvent system and the operating conditions during the drying step. In particular, the morphological, topographical and thermal properties of films prepared starting from highly crystalline polymers, namely PCL and PEO, are greatly affected by the crystallization of the material. Conversely, the less crystalline PLA forms almost completely amorphous films.

  19. Evaluation of Anticancer and Antioxidant Activity of a Commercially Available CO2 Supercritical Extract of Old Man's Beard (Usnea barbata).

    PubMed

    Zugic, Ana; Jeremic, Ivica; Isakovic, Aleksandra; Arsic, Ivana; Savic, Snezana; Tadic, Vanja

    2016-01-01

    There is a worldwide ongoing investigation for novel natural constituents with cytotoxic and antioxidant properties. The aim of this study was to investigate chemical profile and stated biological activities of the supercritical CO2 extract (SCE) of old man's beard compared to the extracts obtained using the conventional techniques (Soxhlet extracts and macerate). The most abundant compound identified was usnic acid, which content was inversely proportional to the polarity of the solvent used and was the highest in the SCE, which was the sample revealing the highest cytotoxic activity in tested tumor cell lines (B16 mouse melanoma and C6 rat glioma), with lower IC50 values compared to pure usnic acid. Further investigations suggested both SCE and usnic acid to induce apoptosis and/or autophagy in B16 and C6, indicating higher cytotoxicity of SCE to be related to the higher degree of ROS production. A good correlation of usnic acid content in the extracts and their antioxidant capacity was established, extricating SCE as the most active one. Presented results support further investigations of SCE of old man's beard as a prospective therapeutic agent with potential relevance in the treatment of cancer and/or in oxidative stress-mediated conditions. PMID:26745885

  20. Antioxidant effect of supercritical CO2 extracted Nigella sativa L. seed extract on deep fried oil quality parameters.

    PubMed

    Solati, Zeinab; Baharin, Badlishah Sham

    2015-06-01

    Effect of supercritical CO2 extracted Nigella sativa L. seed extract (NE) on frying performance of sunflower oil and refined, bleached and deodorized (RBD) palm olein was investigated at concentrations of 1.2 % and 1.0 % respectively. Two frying systems containing 0 % N. sativa L. extract (Control) and 0.02 % butylated hydroxytoluene (BHT) were used for comparison. Physicochemical properties such as fatty acid composition (FAC), Peroxide Value (PV), Anisidine Value (AV), Totox Value (TV), Total Polar Content (TPC), C18:2/C16:0 ratio and viscosity of frying oils were determined during five consecutive days of frying. Results have shown that N. sativa L. extract was able to improve the oxidative stability of both frying oils during the frying process compared to control. The stabilizing effect of antioxidants were in the order of BHT > NE. RBD palm olein was found to be more stable than sunflower oil based on the ratio of linoleic acid (C18:2) to palmitic acid (C16:0) and fatty acid composition.

  1. Capillary pressure-saturation relations for supercritical CO2 and brine in limestone/dolomite sands: implications for geologic carbon sequestration in carbonate reservoirs.

    PubMed

    Wang, Shibo; Tokunaga, Tetsu K

    2015-06-16

    In geologic carbon sequestration, capillary pressure (Pc)-saturation (Sw) relations are needed to predict reservoir processes. Capillarity and its hysteresis have been extensively studied in oil-water and gas-water systems, but few measurements have been reported for supercritical (sc) CO2-water. Here, Pc-Sw relations of scCO2 displacing brine (drainage), and brine rewetting (imbibition) were studied to understand CO2 transport and trapping behavior under reservoir conditions. Hysteretic drainage and imbibition Pc-Sw curves were measured in limestone sands at 45 °C under elevated pressures (8.5 and 12.0 MPa) for scCO2-brine, and in limestone and dolomite sands at 23 °C (0.1 MPa) for air-brine using a new computer programmed porous plate apparatus. scCO2-brine drainage and imbibition curves shifted to lower Pc relative to predictions based on interfacial tension, and therefore deviated from capillary scaling predictions for hydrophilic interactions. Fitting universal scaled drainage and imbibition curves show that wettability alteration resulted from scCO2 exposure over the course of months-long experiments. Residual trapping of the nonwetting phases was determined at Pc = 0 during imbibition. Amounts of trapped scCO2 were significantly larger than for those for air, and increased with pressure (depth), initial scCO2 saturation, and time. These results have important implications for scCO2 distribution, trapping, and leakage potential. PMID:25945400

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

    PubMed

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

    2011-10-01

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

  3. Separation of supercritical slab-fluids to form aqueous fluid and melt components in subduction zone magmatism.

    PubMed

    Kawamoto, Tatsuhiko; Kanzaki, Masami; Mibe, Kenji; Matsukage, Kyoko N; Ono, Shigeaki

    2012-11-13

    Subduction-zone magmatism is triggered by the addition of H(2)O-rich slab-derived components: aqueous fluid, hydrous partial melts, or supercritical fluids from the subducting slab. Geochemical analyses of island arc basalts suggest two slab-derived signatures of a melt and a fluid. These two liquids unite to a supercritical fluid under pressure and temperature conditions beyond a critical endpoint. We ascertain critical endpoints between aqueous fluids and sediment or high-Mg andesite (HMA) melts located, respectively, at 83-km and 92-km depths by using an in situ observation technique. These depths are within the mantle wedge underlying volcanic fronts, which are formed 90 to 200 km above subducting slabs. These data suggest that sediment-derived supercritical fluids, which are fed to the mantle wedge from the subducting slab, react with mantle peridotite to form HMA supercritical fluids. Such HMA supercritical fluids separate into aqueous fluids and HMA melts at 92 km depth during ascent. The aqueous fluids are fluxed into the asthenospheric mantle to form arc basalts, which are locally associated with HMAs in hot subduction zones. The separated HMA melts retain their composition in limited equilibrium with the surrounding mantle. Alternatively, they equilibrate with the surrounding mantle and change the major element chemistry to basaltic composition. However, trace element signatures of sediment-derived supercritical fluids remain more in the melt-derived magma than in the fluid-induced magma, which inherits only fluid-mobile elements from the sediment-derived supercritical fluids. Separation of slab-derived supercritical fluids into melts and aqueous fluids can elucidate the two slab-derived components observed in subduction zone magma chemistry. PMID:23112158

  4. Separation of supercritical slab-fluids to form aqueous fluid and melt components in subduction zone magmatism.

    PubMed

    Kawamoto, Tatsuhiko; Kanzaki, Masami; Mibe, Kenji; Matsukage, Kyoko N; Ono, Shigeaki

    2012-11-13

    Subduction-zone magmatism is triggered by the addition of H(2)O-rich slab-derived components: aqueous fluid, hydrous partial melts, or supercritical fluids from the subducting slab. Geochemical analyses of island arc basalts suggest two slab-derived signatures of a melt and a fluid. These two liquids unite to a supercritical fluid under pressure and temperature conditions beyond a critical endpoint. We ascertain critical endpoints between aqueous fluids and sediment or high-Mg andesite (HMA) melts located, respectively, at 83-km and 92-km depths by using an in situ observation technique. These depths are within the mantle wedge underlying volcanic fronts, which are formed 90 to 200 km above subducting slabs. These data suggest that sediment-derived supercritical fluids, which are fed to the mantle wedge from the subducting slab, react with mantle peridotite to form HMA supercritical fluids. Such HMA supercritical fluids separate into aqueous fluids and HMA melts at 92 km depth during ascent. The aqueous fluids are fluxed into the asthenospheric mantle to form arc basalts, which are locally associated with HMAs in hot subduction zones. The separated HMA melts retain their composition in limited equilibrium with the surrounding mantle. Alternatively, they equilibrate with the surrounding mantle and change the major element chemistry to basaltic composition. However, trace element signatures of sediment-derived supercritical fluids remain more in the melt-derived magma than in the fluid-induced magma, which inherits only fluid-mobile elements from the sediment-derived supercritical fluids. Separation of slab-derived supercritical fluids into melts and aqueous fluids can elucidate the two slab-derived components observed in subduction zone magma chemistry.

  5. Separation of supercritical slab-fluids to form aqueous fluid and melt components in subduction zone magmatism

    PubMed Central

    Kawamoto, Tatsuhiko; Kanzaki, Masami; Mibe, Kenji; Ono, Shigeaki

    2012-01-01

    Subduction-zone magmatism is triggered by the addition of H2O-rich slab-derived components: aqueous fluid, hydrous partial melts, or supercritical fluids from the subducting slab. Geochemical analyses of island arc basalts suggest two slab-derived signatures of a melt and a fluid. These two liquids unite to a supercritical fluid under pressure and temperature conditions beyond a critical endpoint. We ascertain critical endpoints between aqueous fluids and sediment or high-Mg andesite (HMA) melts located, respectively, at 83-km and 92-km depths by using an in situ observation technique. These depths are within the mantle wedge underlying volcanic fronts, which are formed 90 to 200 km above subducting slabs. These data suggest that sediment-derived supercritical fluids, which are fed to the mantle wedge from the subducting slab, react with mantle peridotite to form HMA supercritical fluids. Such HMA supercritical fluids separate into aqueous fluids and HMA melts at 92 km depth during ascent. The aqueous fluids are fluxed into the asthenospheric mantle to form arc basalts, which are locally associated with HMAs in hot subduction zones. The separated HMA melts retain their composition in limited equilibrium with the surrounding mantle. Alternatively, they equilibrate with the surrounding mantle and change the major element chemistry to basaltic composition. However, trace element signatures of sediment-derived supercritical fluids remain more in the melt-derived magma than in the fluid-induced magma, which inherits only fluid-mobile elements from the sediment-derived supercritical fluids. Separation of slab-derived supercritical fluids into melts and aqueous fluids can elucidate the two slab-derived components observed in subduction zone magma chemistry. PMID:23112158

  6. CO2-induced smart viscoelastic fluids based on mixtures of sodium erucate and triethylamine.

    PubMed

    Zhang, Yongmin; Feng, Yujun

    2015-06-01

    Simple "green" triggers such as CO2 for switching viscoelastic surfactant solutions between an "on" and "off" state without compromising their inherent properties have been a key focus of research in smart soft matter over the past decade. Here we report a CO2-induced anionic wormlike micellar fluid by introducing triethylamine (TEA) into natural anionic surfactant sodium erucate (NaOEr) at a molar ratio (CNaOEr:CTEA) of 3:10. When CO2 is bubbled, pH of the solution decreases from 12.3 to 10.0, and TEA is protonated into a quaternary ammonium salt, which facilitates the growth of micelles as a hydrotrope by screening electrostatic repulsion between the anionic headgroups in NaOEr molecules, resulting in the formation of wormlike micelles and viscoelasticity buildup; upon removal of CO2, the quaternized TEA is deprotonated back into a non-ionic tertiary amine, thus electrostatic repulsion strengthens and the viscoelastic fluid converting it back to the initial low viscosity spherical micellar solution. Such a reversible sphere-to-worm transition could be repeated several cycles without any loss of response to CO2 in the pH range of 12.3-10.0, but when further bubbling excess CO2 to pH<9.50, the solution transforms into a cloudy dispersion with low viscosity due to the de-neutralization of NaOEr, and this process is irreversible. This study offers a facile way to fabricate smart viscoelastic fluids by incorporating a low-molecular weight CO2-sensitive hydrotrope with conventional long-chain surfactants.

  7. CO2-induced smart viscoelastic fluids based on mixtures of sodium erucate and triethylamine.

    PubMed

    Zhang, Yongmin; Feng, Yujun

    2015-06-01

    Simple "green" triggers such as CO2 for switching viscoelastic surfactant solutions between an "on" and "off" state without compromising their inherent properties have been a key focus of research in smart soft matter over the past decade. Here we report a CO2-induced anionic wormlike micellar fluid by introducing triethylamine (TEA) into natural anionic surfactant sodium erucate (NaOEr) at a molar ratio (CNaOEr:CTEA) of 3:10. When CO2 is bubbled, pH of the solution decreases from 12.3 to 10.0, and TEA is protonated into a quaternary ammonium salt, which facilitates the growth of micelles as a hydrotrope by screening electrostatic repulsion between the anionic headgroups in NaOEr molecules, resulting in the formation of wormlike micelles and viscoelasticity buildup; upon removal of CO2, the quaternized TEA is deprotonated back into a non-ionic tertiary amine, thus electrostatic repulsion strengthens and the viscoelastic fluid converting it back to the initial low viscosity spherical micellar solution. Such a reversible sphere-to-worm transition could be repeated several cycles without any loss of response to CO2 in the pH range of 12.3-10.0, but when further bubbling excess CO2 to pH<9.50, the solution transforms into a cloudy dispersion with low viscosity due to the de-neutralization of NaOEr, and this process is irreversible. This study offers a facile way to fabricate smart viscoelastic fluids by incorporating a low-molecular weight CO2-sensitive hydrotrope with conventional long-chain surfactants. PMID:25476785

  8. Varying rock responses as an indicator of changes in CO2-H2O fluid composition

    NASA Technical Reports Server (NTRS)

    Friend, C. R. L.

    1986-01-01

    The formation of the late Archean charnockite zone of southern India was ascribed to dehydration recrystallization due to an influx of CO2. Pressure temperature conditions for the metamorphism were calculated at about 750 C and 7.5 Kbar. The composition of the volatile species presently contained in fluid inclusions in the rocks changes across the transition zone. The transition zone was studied at Kabbaldurga and the paths taken by the fluids were identified.

  9. 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.

  10. Intramolecular vibrational energy redistribution and intermolecular energy transfer of benzene in supercritical CO 2: measurements from the gas phase up to liquid densities

    NASA Astrophysics Data System (ADS)

    von Benten, R.; Charvat, A.; Link, O.; Abel, B.; Schwarzer, D.

    2004-03-01

    Femtosecond pump probe spectroscopy was employed to measure intramolecular vibrational energy redistribution (IVR) and intermolecular vibrational energy transfer (VET) of benzene in the gas phase and in supercritical (sc) CO 2. We observe two IVR time scales the faster of which proceeds within τ IVR(1)<0.5 ps. The slower IVR component has a time constant of τ IVR(2)=(48±5) ps in the gas phase and in scCO 2 is accelerated by interactions with the solvent. At the highest CO 2 density it is reduced to τ IVR(2)=(6±1) ps. The corresponding IVR rate constants show a similar density dependence as the VET rate constants. Model calculations suggest that both quantities correlate with the local CO 2 density in the immediate surrounding of the benzene molecule.

  11. Modeling of CO2 solubility in single and mixed electrolyte solutions using statistical associating fluid theory

    NASA Astrophysics Data System (ADS)

    Jiang, Hao; Panagiotopoulos, Athanassios Z.; Economou, Ioannis G.

    2016-03-01

    Statistical associating fluid theory (SAFT) is used to model CO2 solubilities in single and mixed electrolyte solutions. The proposed SAFT model implements an improved mean spherical approximation in the primitive model to represent the electrostatic interactions between ions, using a parameter K to correct the excess energies ("KMSA" for short). With the KMSA formalism, the proposed model is able to describe accurately mean ionic activity coefficients and liquid densities of electrolyte solutions including Na+, K+, Ca2+, Mg2+, Cl-, Br- and SO42- from 298.15 K to 473.15 K using mostly temperature independent parameters, with sole exception being the volume of anions. CO2 is modeled as a non-associating molecule, and temperature-dependent CO2-H2O and CO2-ion cross interactions are used to obtain CO2 solubilities in H2O and in single ion electrolyte solutions. Without any additional fitting parameters, CO2 solubilities in mixed electrolyte solutions and synthetic brines are predicted, in good agreement with experimental measurements.

  12. On the production behavior of enhanced geothermal systems with CO2as working fluid

    SciTech Connect

    Pruess, K.

    2007-05-31

    Numerical simulation is used to evaluate mass flow and heatextraction rates from enhanced geothermal injection-production systemsthat are operated using either CO2 or water as heat transmission fluid.For a model system patterned after the European hot dry rock experimentat Soultz, we find significantly greater heat extraction rates for CO2 ascompared to water. The strong dependence of CO2 mobility (=density/viscosity) upon temperature and pressure may lead to unusualproduction behavior, where heat extraction rates can actually increasefor a time, even as the reservoir is subject to thermal depletion. Wepresent the first-ever three-dimensional simulations of CO2injection-production systems. These show strong effects of gravity onmass flow and heat extraction, due to the large contrast of CO2 densitybetween cold injection and hot production conditions. The tendency forpreferential flow of cold, dense CO2 along the reservoir bottom can leadto premature thermal breakthrough. The problem can be avoided byproducing from only a limited depth interval at the top of thereservoir.

  13. Antiageing Mechanisms of a Standardized Supercritical CO 2 Preparation of Black Jack (Bidens pilosa L.) in Human Fibroblasts and Skin Fragments.

    PubMed

    Dieamant, Gustavo; Pereda, Maria Del Carmen V; Nogueira, Cecília; Eberlin, Samara; Facchini, Gustavo; Checon, Juliana Tibério; Cesar, Camila Kappke; Mussi, Lilian; Polezel, Márcio Antonio; Martins-Oliveira, Divino; Di Stasi, Luiz Claudio

    2015-01-01

    The use of topical retinoids to treat skin disorders and ageing can induce local reactions, while oral retinoids are potent teratogens and produce several unwanted effects. This way, efforts to explore complementary care resources should be supported. Based on this, we evaluate the antiageing effects of a supercritical CO2 extract from Bidens pilosa L. (BPE-CO2A) containing a standardized multicomponent mixture of phytol, linolenic, palmitic, linoleic, and oleic acids. BPE-CO2A was assessed for its effects on human dermal fibroblasts (TGF-β1 and FGF levels using ELISA; collagen, elastin, and glycosaminoglycan by colorimetric assays, and mRNA expression of RXR, RAR, and EGFr by qRT-PCR) and human skin fragments (RAR, RXR, collagen, elastin, and glycosaminoglycan by immunohistochemical analysis). Levels of extracellular matrix elements, TGF-β1 and FGF, and EGFr gene expression were significantly increased by BPE-CO2A. The modulation of RXR and RAR was positively demonstrated after the treatment with BPE-CO2A or phytol, a component of BPE-CO2A. The effects produced by BPE-CO2A were similar to or better than those produced by retinol and retinoic acid. The ability to stimulate extracellular matrix elements, increase growth factors, and modulate retinoid and rexinoid receptors provides a basis for the development of preparation containing BPE-CO2A as an antiageing/skin-repair agent.

  14. Antiageing Mechanisms of a Standardized Supercritical CO2 Preparation of Black Jack (Bidens pilosa L.) in Human Fibroblasts and Skin Fragments

    PubMed Central

    Dieamant, Gustavo; Pereda, Maria Del Carmen V.; Nogueira, Cecília; Eberlin, Samara; Facchini, Gustavo; Checon, Juliana Tibério; Cesar, Camila Kappke; Mussi, Lilian; Polezel, Márcio Antonio; Martins-Oliveira, Divino; Di Stasi, Luiz Claudio

    2015-01-01

    The use of topical retinoids to treat skin disorders and ageing can induce local reactions, while oral retinoids are potent teratogens and produce several unwanted effects. This way, efforts to explore complementary care resources should be supported. Based on this, we evaluate the antiageing effects of a supercritical CO2 extract from Bidens pilosa L. (BPE-CO2A) containing a standardized multicomponent mixture of phytol, linolenic, palmitic, linoleic, and oleic acids. BPE-CO2A was assessed for its effects on human dermal fibroblasts (TGF-β1 and FGF levels using ELISA; collagen, elastin, and glycosaminoglycan by colorimetric assays, and mRNA expression of RXR, RAR, and EGFr by qRT-PCR) and human skin fragments (RAR, RXR, collagen, elastin, and glycosaminoglycan by immunohistochemical analysis). Levels of extracellular matrix elements, TGF-β1 and FGF, and EGFr gene expression were significantly increased by BPE-CO2A. The modulation of RXR and RAR was positively demonstrated after the treatment with BPE-CO2A or phytol, a component of BPE-CO2A. The effects produced by BPE-CO2A were similar to or better than those produced by retinol and retinoic acid. The ability to stimulate extracellular matrix elements, increase growth factors, and modulate retinoid and rexinoid receptors provides a basis for the development of preparation containing BPE-CO2A as an antiageing/skin-repair agent. PMID:25883669

  15. Complex fluid flow revealed by monitoring CO2 injection in a fluvial formation

    NASA Astrophysics Data System (ADS)

    Lu, Jiemin; Cook, Paul J.; Hosseini, Seyyed A.; Yang, Changbing; Romanak, Katherine D.; Zhang, Tongwei; Freifeld, Barry M.; Smyth, Rebecca C.; Zeng, Hongliu; Hovorka, Susan D.

    2012-03-01

    At Cranfield, Mississippi, United States, a large-scale carbon dioxide (CO2) injection through an injection well (˜3,080 m deep) was continuously monitored using U-tube samplers in two observation wells located 68 and 112 m east of the injector. The Lower Tuscaloosa Formation injection zone, which consists of amalgamated fluvial point-bar and channel-fill deposits, presents an interesting environment for studying fluid flow in heterogeneous formations. Continual fluid sampling was carried out during the first month of CO2 injection. Two subsequent tracer tests using sulfur hexafluoride (SF6) and krypton were conducted at different injection rates to measure flow velocity change. The field observations showed significant heterogeneity of fluid flow and for the first time clearly demonstrated that fluid flow evolved with time and injection rate. It was found the wells were connected through numerous, separate flow pathways. CO2 flowed through an increasing fraction of the reservoir and sweep efficiency improved with time. The field study also first documented in situ component exchange between brine and gas phases during CO2 injection. It was found that CH4 degassed from brine and is enriched along the gas-water contact. Multiple injectate flow fronts with high CH4 concentration arrived at different times and led to gas composition fluctuations in the observation wells. The findings provide valuable insights into heterogeneous multiphase flow in rock formations and show that conventional geological models and static fluid flow simulations are unable to fully describe the heterogeneous and dynamic flow during fluid injection.

  16. An H2O-CO2 mixed fluid saturation model compatible with rhyolite-MELTS

    NASA Astrophysics Data System (ADS)

    Ghiorso, Mark S.; Gualda, Guilherme A. R.

    2015-06-01

    A thermodynamic model for estimating the saturation conditions of H2O-CO2 mixed fluids in multicomponent silicate liquids is described. The model extends the capabilities of rhyolite-MELTS (Gualda et al. in J Petrol 53:875-890, 2012a) and augments the water saturation model in MELTS (Ghiorso and Sack in Contrib Mineral Petrol 119:197-212, 1995). The model is internally consistent with the fluid-phase thermodynamic model of Duan and Zhang (Geochim Cosmochim Acta 70:2311-2324, 2006). It may be used independently of rhyolite-MELTS to estimate intensive variables and fluid saturation conditions from glass inclusions trapped in phenocrysts. The model is calibrated from published experimental data on water and carbon dioxide solubility, and mixed fluid saturation in silicate liquids. The model is constructed on the assumption that water dissolves to form a hydroxyl melt species, and that carbon dioxide both a molecular species and a carbonate ion, the latter complexed with calcium. Excess enthalpy interaction terms in part compensate for these simplistic assumptions regarding speciation. The model is restricted to natural composition liquids over the pressure range 0-3 GPa. One characteristic of the model is that fluid saturation isobars at pressures greater than ~100 MPa always display a maximum in melt CO2 at nonzero H2O melt concentrations, regardless of bulk composition. This feature is universal and can be attributed to the dominance of hydroxyl speciation at low water concentrations. The model is applied to four examples. The first involves estimation of pressures from H2O-CO2-bearing glass inclusions found in quartz phenocrysts of the Bishop Tuff. The second illustrates H2O and CO2 partitioning between melt and fluid during fluid-saturated equilibrium and fractional crystallization of MORB. The third example demonstrates that the position of the quartz-feldspar cotectic surface is insensitive to melt CO2 contents, which facilitates geobarometry using phase

  17. Effects of supercritical fluid chromatography conditions on enantioselectivity and performance of polyproline-derived chiral stationary phases.

    PubMed

    Novell, Arnau; Méndez, Alberto; Minguillón, Cristina

    2015-07-17

    The chromatographic behaviour and performance of four polyproline-derived chiral stationary phases (CSPs) were tested using supercritical fluid chromatography (SFC). A series of structurally related racemic compounds, whose enantioseparation was proved to be sensitive to the type of mobile phase used in NP-HPLC, were chosen to be tested in the SFC conditions. Good enantioselection ability was shown by the CSPs for the analytes tested in the new conditions. Resolution, efficiency and analysis time, were considerably improved with respect to NP-HPLC when CO2/alcohol mobile phases were used. Monolithic columns clearly show enhanced chromatographic parameters and improved performance respect to their bead-based counterparts.

  18. Direct growth of highly dispersed MnCl2 · 4H2O nanostructures with different morphologies on graphene in supercritical CO2

    NASA Astrophysics Data System (ADS)

    Xu, Qin-Qin; Zhao, Xiao-Chen; Yin, Jian-Zhong; Xu, Gang

    2016-06-01

    Willow leaf-like Mn3O4 nanoplates@graphene nanocomposites were synthesized using graphene instead of graphene oxide as initial materials with the assistance of supercritical CO2. The near-zero surface tension and the gas-like viscosity of supercritical CO2 favored the intercalation and dispersion of precursors among the graphene nanosheets. In addition, MnCl2 · 4H2O ultra-small nanoparticles with diameter of 1–3 nm were supported on graphene using MnCl2 · 4H2O as precursor, supercritical CO2 as solvent and methanol as co-solvent under very moderate conditions. It was also found that the specific capacitance of the MnCl2 · 4H2O ultra-small nanoparticles@graphene with a metal loading of only 12.4% was twice that of pure graphene. In addition, the capacitance retention ratio of the MnCl2 · 4H2O ultra-small nanoparticles@graphene composite decreased by only 5.4% when the cycle number increased from 200 to 1000.

  19. Direct growth of highly dispersed MnCl2 · 4H2O nanostructures with different morphologies on graphene in supercritical CO2

    NASA Astrophysics Data System (ADS)

    Xu, Qin-Qin; Zhao, Xiao-Chen; Yin, Jian-Zhong; Xu, Gang

    2016-06-01

    Willow leaf-like Mn3O4 nanoplates@graphene nanocomposites were synthesized using graphene instead of graphene oxide as initial materials with the assistance of supercritical CO2. The near-zero surface tension and the gas-like viscosity of supercritical CO2 favored the intercalation and dispersion of precursors among the graphene nanosheets. In addition, MnCl2 · 4H2O ultra-small nanoparticles with diameter of 1-3 nm were supported on graphene using MnCl2 · 4H2O as precursor, supercritical CO2 as solvent and methanol as co-solvent under very moderate conditions. It was also found that the specific capacitance of the MnCl2 · 4H2O ultra-small nanoparticles@graphene with a metal loading of only 12.4% was twice that of pure graphene. In addition, the capacitance retention ratio of the MnCl2 · 4H2O ultra-small nanoparticles@graphene composite decreased by only 5.4% when the cycle number increased from 200 to 1000.

  20. Growth factors delivery from hybrid PCL-starch scaffolds processed using supercritical fluid technology.

    PubMed

    Diaz-Gomez, Luis; Concheiro, Angel; Alvarez-Lorenzo, Carmen; García-González, Carlos A

    2016-05-20

    Synthetic polymeric scaffolds to be used as surrogates of autologous bone grafts should not only have suitable physicochemical and mechanical properties, but also contain bioactive agents such as growth factors (GFs) to facilitate the tissue growth. For this purpose, cost-effective and autologous GFs sources are preferred to avoid some post-surgery complications after implantation, like immunogenicity or disease transmission, and the scaffolds should be processed using methods able to preserve GFs activity. In this work, poly(ɛ-caprolactone) (PCL) scaffolds incorporating GFs were processed using a green foaming process based on supercritical fluid technology. Preparation rich in growth factors (PRGF), a natural and highly available cocktail of GFs obtained from platelet rich plasma (PRP), was used as GF source. PCL:starch:PRGF (85:10:5 weight ratio) porous solid scaffolds were obtained by a supercritical CO2-assisted foaming process at 100 bar and 37 °C with no need of post-processing steps. Bioactivity of GFs after processing and scaffold cytocompatibility were confirmed using mesenchymal stem cells. The performance of starch as GF control release component was shown to be dependent on starch pre-gelification conditions.

  1. Selective chelation and extraction of lanthanides and actinides with supercritical fluids

    SciTech Connect

    Brauer, R.D.; Carleson, T.E.; Harrington, J.D.; Jean, F.; Jiang, H.; Lin, Y.; Wai, C.M.

    1994-01-01

    This report is made up of three independent papers: (1) Supercritical Fluid Extraction of Thorium and Uranium with Fluorinated Beta-Diketones and Tributyl Phosphate, (2) Supercritical Fluid Extraction of Lanthanides with Beta-Diketones and Mixed Ligands, and (3) A Group Contribution Method for Predicting the Solubility of Solid Organic Compounds in Supercritical Carbon Dioxide. Experimental data are presented demonstrating the successful extraction of thorium and uranium using fluorinated beta-diketones to form stable complexes that are extracted with supercritical carbon dioxide. The conditions for extracting the lanthanide ions from liquid and solid materials using supercritical carbon dioxide are presented. In addition, the Peng-Robison equation of state and thermodynamic equilibrium are used to predict the solubilities of organic solids in supercritical carbon dioxide from the sublimation pressure, critical properties, and a centric factor of the solid of interest.

  2. Supercritical CO2 Foaming of Thermoplastic Materials Derived from Maize: Proof-of-Concept Use in Mammalian Cell Culture Applications

    PubMed Central

    Trujillo-de Santiago, Grissel; Portales-Cabrera, Cynthia Guadalupe; Portillo-Lara, Roberto; Araiz-Hernández, Diana; Del Barone, Maria Cristina; García-López, Erika; Rojas-de Gante, Cecilia; de los Angeles De Santiago-Miramontes, María; Segoviano-Ramírez, Juan Carlos; García-Lara, Silverio; Rodríguez-González, Ciro Ángel; Alvarez, Mario Moisés; Di Maio, Ernesto; Iannace, Salvatore

    2015-01-01

    Background Foams are high porosity and low density materials. In nature, they are a common architecture. Some of their relevant technological applications include heat and sound insulation, lightweight materials, and tissue engineering scaffolds. Foams derived from natural polymers are particularly attractive for tissue culture due to their biodegradability and bio-compatibility. Here, the foaming potential of an extensive list of materials was assayed, including slabs elaborated from whole flour, the starch component only, or the protein fraction only of maize seeds. Methodology/Principal Findings We used supercritical CO2 to produce foams from thermoplasticized maize derived materials. Polyethylene-glycol, sorbitol/glycerol, or urea/formamide were used as plasticizers. We report expansion ratios, porosities, average pore sizes, pore morphologies, and pore size distributions for these materials. High porosity foams were obtained from zein thermoplasticized with polyethylene glycol, and from starch thermoplasticized with urea/formamide. Zein foams had a higher porosity than starch foams (88% and 85%, respectively) and a narrower and more evenly distributed pore size. Starch foams exhibited a wider span of pore sizes and a larger average pore size than zein (208.84 vs. 55.43 μm2, respectively). Proof-of-concept cell culture experiments confirmed that mouse fibroblasts (NIH 3T3) and two different prostate cancer cell lines (22RV1, DU145) attached to and proliferated on zein foams. Conclusions/Significance We conducted screening and proof-of-concept experiments on the fabrication of foams from cereal-based bioplastics. We propose that a key indicator of foamability is the strain at break of the materials to be foamed (as calculated from stress vs. strain rate curves). Zein foams exhibit attractive properties (average pore size, pore size distribution, and porosity) for cell culture applications; we were able to establish and sustain mammalian cell cultures on zein

  3. Therapeutic Effect of Supercritical CO2 Extracts of Curcuma Species with Cancer Drugs in Rhabdomyosarcoma Cell Lines.

    PubMed

    Ramachandran, Cheppail; Quirin, Karl-W; Escalon, Enrique A; Lollett, Ivonne V; Melnick, Steven J

    2015-08-01

    Synergistic effect of supercritical CO2 extracts of Curcuma species with conventional chemotherapeutic drugs was investigated in human alveolar (SJRH30) and embryonal (RD) rhabdomyosarcoma cell lines. The Curcuma amada (mango ginger) (CA) extract showed the highest levels of cytotoxicity with inhibitory concentration IC50 values of 7.133 µg/ml and 7.501 µg/ml for SJRH30 and RD cell lines, respectively, as compared with Curcuma longa (turmeric) and Curcuma xanthorrhiza (Javanese turmeric) extracts. CA showed synergistic cytotoxic effects with vinblastine (VBL) and cyclophosphamide (CP) as indicated by the combination index values of <1 for VBL + CA, CP + CA, and VBL + CP + CA combinations in both embryonal and alveolar rhabdomyosarcomas. When lower doses of CA (0.1-0.2 µg/ml) were combined with cancer drugs like CP and VBL, caspase-3 activity increased significantly compared with individual agents and correlated with the percentage of apoptotic cells. CA in combination with VBL and CP induced a higher percentage of apoptosis than single agents in both cell lines. CA also modulated the expression of genes associated with intrinsic pathway of apoptosis (Bcl-2, Bax, Bak, and p53) and also inhibited the expression of genes associated with inflammation such as COX-2 and NF-κB. Xenograft studies with SJRH30 tumors in nude mice showed that CA treatment inhibited tumor growth rate with and without VBL and increased the survival rate significantly. These results suggest that CA can be evaluated further as an adjuvant with cancer drugs for the treatment of rhabdomyosarcoma patients. Copyright © 2015 John Wiley & Sons, Ltd.

  4. Numerical Simulation of CO2 Flooding of Coalbed Methane Considering the Fluid-Solid Coupling Effect.

    PubMed

    Liu, Jianjun; Li, Guang; Zhang, Yue

    2016-01-01

    CO2 flooding of coalbed methane (CO2-ECBM) not only stores CO2 underground and reduces greenhouse gas emissions but also enhances the gas production ratio. This coupled process involves multi-phase fluid flow and coal-rock deformation, as well as processes such as competitive gas adsorption and diffusion from the coal matrix into fractures. A dual-porosity medium that consists of a matrix and fractures was built to simulate the flooding process, and a mathematical model was used to consider the competitive adsorption, diffusion and seepage processes and the interaction between flow and deformation. Due to the effects of the initial pressure and the differences in pressure variation during the production process, permeability changes caused by matrix shrinkage were spatially variable in the reservoir. The maximum value of permeability appeared near the production well, and the degree of rebound decreased with increasing distance from the production well.

  5. Numerical Simulation of CO2 Flooding of Coalbed Methane Considering the Fluid-Solid Coupling Effect

    PubMed Central

    Liu, Jianjun; Li, Guang; Zhang, Yue

    2016-01-01

    CO2 flooding of coalbed methane (CO2-ECBM) not only stores CO2 underground and reduces greenhouse gas emissions but also enhances the gas production ratio. This coupled process involves multi-phase fluid flow and coal-rock deformation, as well as processes such as competitive gas adsorption and diffusion from the coal matrix into fractures. A dual-porosity medium that consists of a matrix and fractures was built to simulate the flooding process, and a mathematical model was used to consider the competitive adsorption, diffusion and seepage processes and the interaction between flow and deformation. Due to the effects of the initial pressure and the differences in pressure variation during the production process, permeability changes caused by matrix shrinkage were spatially variable in the reservoir. The maximum value of permeability appeared near the production well, and the degree of rebound decreased with increasing distance from the production well. PMID:27031096

  6. Numerical Simulation of CO2 Flooding of Coalbed Methane Considering the Fluid-Solid Coupling Effect.

    PubMed

    Liu, Jianjun; Li, Guang; Zhang, Yue

    2016-01-01

    CO2 flooding of coalbed methane (CO2-ECBM) not only stores CO2 underground and reduces greenhouse gas emissions but also enhances the gas production ratio. This coupled process involves multi-phase fluid flow and coal-rock deformation, as well as processes such as competitive gas adsorption and diffusion from the coal matrix into fractures. A dual-porosity medium that consists of a matrix and fractures was built to simulate the flooding process, and a mathematical model was used to consider the competitive adsorption, diffusion and seepage processes and the interaction between flow and deformation. Due to the effects of the initial pressure and the differences in pressure variation during the production process, permeability changes caused by matrix shrinkage were spatially variable in the reservoir. The maximum value of permeability appeared near the production well, and the degree of rebound decreased with increasing distance from the production well. PMID:27031096

  7. Operation and performance of the Supercritical Fluids Reactor (SFR)

    SciTech Connect

    Hanush, R.G.; Rice, S.F.; Hunter, T.B.; Aiken, J.D.

    1995-11-01

    The Supercritical Fluids Reactor (SFR) at Sandia National Laboratories, CA has been developed to examine and solve engineering, process, and fundamental chemistry issues regarding the development of supercritical water oxidation (SCWO). This report details the experimental apparatus, procedures, analytical methods used in these experiments, and performance characteristics of the reactor. The apparatus consists of pressurization, feed, preheat, reactor, cool down, and separation subsystems with ancillary control and data acquisition hardware and software. Its operating range is from 375 - 650{degrees} at 3250 - 6300 psi with resident times from 0.09 to 250 seconds. Procedures required for experimental operations are described. They include maintenance procedures conducted between experiments, optical alignment for acquisition of spectroscopic data, setup of the experiment, reactor start up, experimental operations, and shutdown of apparatus. Analytical methods used are Total Organic Carbon analysis, Gas Chromatography, ion probes, pH probes, turbidity measurements and in situ Raman spectroscopy. Experiments conducted that verify the accuracy of measurement and sampling methods are described.

  8. Analysis of antioxidants extracted from polypropylene by supercritical fluid extraction.

    PubMed

    Garde, J A; Catalá, R; Gavara, R

    1998-01-01

    Maximal potential migration of six antioxidants (AO) from five polypropylene (PP) formulations was determined by two supercritical fluid extraction (SFE) procedures, both of which contained static and dynamic steps. All analytical conditions affecting the extraction were studied and optimized using Irgafos 168 as standard. SFE was more efficient as temperature and fluid density increased. During the static step in which the samples were exposed to the fluid without flux, the introduction of hexane and methanol as fluid modifiers significantly improved the extraction. Hexane appears to facilitate polymer swelling while methanol solvates the antioxidants. In the dynamic step (in which the extraction actually occurs) time is the key parameter. Extraction for 90 min results in an efficiency of around 75%. The introduction of modifiers during this step (by an HPLC-SFE procedure) did not produce any significant improvement. When SFE was carried out on all samples, extraction efficiency was around 75% except for Irganox 1010 and Hostanox O3. The large molecular volume of these antioxidants may be responsible for the considerable reduction of extraction efficiency. Particle size and shape of polymer sample were also important. The greater the surface to volume ratio the greater the extraction efficiency.

  9. Supercritical fluid extraction of methyltestosterone, nortestosterone and testosterone at low ppb levels from fortified bovine urine.

    PubMed

    Stolker, A A; van Ginkel, L A; Stephany, R W; Maxwell, R J; Parks, O W; Lightfield, A R

    1999-04-16

    A multi-residue supercritical fluid extraction (SFE) method is proposed for the isolation of nortestosterone, testosterone and methyltestosterone from bovine urine. Prior to SFE, bovine urine was hydrolyzed and then fortified with the three steroids at 100 ng/ml and 50 ng/ml each for HPLC analysis and 25 ng/ml and 12.5 ng/ml each for GC-MS analysis. The samples then were mixed with an adsorbent material, placed in an SFE extraction vessel prepacked with a 3-ml SPE column containing neutral alumina and the testosterones were extracted from the urine matrix using unmodified supercritical CO2 at 27.2 MPa and 40 degrees C. The steroids were retained in-line on the neutral alumina sorbent in the SPE column while co-extracted artifactial material was trapped off-line after CO2 decompression. After SFE, the SPE column was removed from the extraction vessel, and the trapped steroids were eluted from the neutral alumina sorbent with 3 ml of a methanol-water mixture. Eluates were used directly without post-SFE clean-up either for HPLC analysis (detection limit 50 ng/ml) or for GC-MS analysis (detection limit 5 ng/ml after steroid derivatization). The multi-residue SFE recoveries (n=6) for nortestosterone, testosterone and methyltestosterone from hydrolyzed bovine urine by GC-MS analysis were 90.8+/-6%, 93.9+/-3% and 92.5+/-5%, respectively for each steroid at the 12.5 ng fortification level.

  10. Micronutrient and protein-fortified whole grain puffed rice made by supercritical fluid extrusion.

    PubMed

    Paraman, Ilankovan; Wagner, Michael E; Rizvi, Syed S H

    2012-11-01

    Supercritical fluid extrusion (SCFX) was used to produce shelf-stable puffed rice fortified with protein, dietary fiber, and micronutrients. Product ingredients and process parameters were evaluated for end-product nutritional and textural qualities. Supercritical carbon dioxide (SC-CO(2)) served as a viscosity-lowering plasticizer and blowing agent during the process, which has been shown to produce expanded products with good textural qualities at lower temperatures (~100 °C) than conventional steam-based extrusion (130-180 °C). The fortified puffed rice contained 8% dietary fiber, 21.5% protein, and iron, zinc, and vitamins A and C at their recommended daily values in 100 g of product. The SCFX process allowed for the complete retention of all added minerals, 55-58% retention of vitamin A, and 64-76% retention of vitamin C. All essential amino acids including lysine were retained at exceptionally high levels (98.6%), and no losses were observed due to Maillard reaction or oxidation. All of the essential amino acid contents were equal to the reference protein recommended by FAO/WHO. Soy protein fortification improved the total amount of protein in the final rice products and provided a complementary amino acid profile to that of rice; the lysine content improved from 35 to 60 mg/protein, making the end product an excellent source of complete protein. Thus, SC-CO(2)-assisted extrusion is an effective process-based approach to produce cereal grain-based, low-moisture (5-8%) expanded products fortified with protein and any cocktail of micronutrients, without compromising the end-product sensory or nutritional qualities. These products are ideally suited for consumption as breakfast cereals, snack foods, and as part of nutrition bars for school lunch programs. The balanced nutritional profile and use of staple crop byproducts such as broken rice makes these expanded crisps unique to the marketplace. PMID:23066826

  11. Separation of derivatized glucoside anomers using supercritical fluid chromatography.

    PubMed

    Montañés, Fernando; Rose, Paul; Tallon, Stephen; Shirazi, Rahau

    2015-10-30

    Preparative scale supercritical fluid chromatography was used to separate derivatized anomeric monosaccharides. Methyl 2,3,4,6-tetra-O-benzoyl-α-d-glucopyranoside and methyl 2,3,4,6-tetra-O-benzoyl-β-d-glucopyranoside were synthesized by benzoyl derivatization of the parent anomerically pure monosaccharides. The elution profiles of each anomer were studied, suggesting that separation was possible. Mixtures of the compounds were then prepared at different ratios and separation was achieved using carbon dioxide/ethanol mixtures as the mobile phase and GreenSep™ 5micron particle size silica as the stationary phase. Ethanol co-solvent in the mobile phase was required to give a successful separation of the anomers however over the range 6.5-10.4wt% ethanol concentration studied here there was little variation in the degree of separation. In fractionation trials, separation of mixtures into fractions with >98% purity was achieved, with recoveries greater than 96%. PMID:26411481

  12. Supercritical fluid extraction of plant flavors and fragrances.

    PubMed

    Capuzzo, Andrea; Maffei, Massimo E; Occhipinti, Andrea

    2013-06-19

    Supercritical fluid extraction (SFE) of plant material with solvents like CO₂, propane, butane, or ethylene is a topic of growing interest. SFE allows the processing of plant material at low temperatures, hence limiting thermal degradation, and avoids the use of toxic solvents. Although today SFE is mainly used for decaffeination of coffee and tea as well as production of hop extracts on a large scale, there is also a growing interest in this extraction method for other industrial applications operating at different scales. In this review we update the literature data on SFE technology, with particular reference to flavors and fragrance, by comparing traditional extraction techniques of some industrial medicinal and aromatic crops with SFE. Moreover, we describe the biological activity of SFE extracts by describing their insecticidal, acaricidal, antimycotic, antimicrobial, cytotoxic and antioxidant properties. Finally, we discuss the process modelling, mass-transfer mechanisms, kinetics parameters and thermodynamic by giving an overview of SFE potential in the flavors and fragrances arena.

  13. Separation of metal-containing compounds by supercritical fluid chromatography

    SciTech Connect

    Ashraf-Khorassani, M.; Hellgeth, J.W.; Taylor, L.T.

    1987-09-01

    Supercritical fluid chromatography using packed, analytical-scale chromatographic columns was applied to gain separations of several metal-containing systems. Mixtures of substituted ferrocenes and metal ..beta..-diketonates were separated by using methanol-modified CO/sub 2/ under moderate temperatures (50-100/sup 0/C) and pressures (2000-5000 psi) as the mobile phase. Two different types of chromatographic behaviors were observed which were found to be dependent on whether the separated metallic species was either substitutionally inert or substitutionally labile. For inert species, proper chromatographic behavior indicative of a reversible adsorption mechanism was found. For labile species, retention time variation with injected amount, appearance of broad component peaks, and observation of multiple species for a single injection gave indication of irreversible adsorptive mechanism.

  14. High-resolution analysis of polyprenols by supercritical fluid chromatography.

    PubMed

    Bamba, T; Fukasaki, W; Kajiyama, S; Ute, K; Kitayama, T; Kobayashi, A

    2001-03-01

    A high-resolution analysis of polyprenol mixtures was achieved by supercritical fluid chromatography (SFC). The separation of polyprenols was examined on an octadecylsilane-packed column with liquid carbon dioxide as the mobile phase and ethanol as modifier. Using this chromatography system, the resolution of separation (Rs) between octadecaprenol (prenol 18) and nonadecaprenol (prenol 19) was two times higher than that using conventional reversed-phase high-performance liquid chromatography. Our SFC technique allows the advantage of baseline separation of polyprenol samples containing hydrophobic components such as terpenes or fatty acids that are unfavorable for good separation. This method is very useful for the analysis of structurally close polyprenol analogues of rubber plant metabolites.

  15. Comprehensive Review of Applicable Supercritical Fluid Extraction Research

    SciTech Connect

    Harvey, Scott; Wright, Cherylyn W.; Wright, Bob W.

    2001-09-10

    This comprehensive supercritical fluid extraction (SFE) literature review is divided into three major sections. The first section describes the electronic literature search details including the abstract service used and the different topics searched. This section also contains an overview of the seven search topics that yielded relevant references along with a brief synopsis of the most significant literature citations. These seven groupings are (1) chemical warfare agents; (2) explosives; (3) hazardous chemicals; (4) poisons, toxins and mycotoxins; (5) toxic (lethal) chemical and toxicants; (6) pesticides in soil; and (7) pesticides from plant and animal tissues. The second section contains tables of each of these groupings. Each of the seven tables contains entries for individual literature citations listed along with the specific compounds or compound classes that are addressed. The third section refers to the abstracts used in the literature search.

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

    PubMed

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

    2013-08-13

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

  17. Application of supercritical CO2 for extraction of polyisoprenoid alcohols and their esters from plant tissues[S

    PubMed Central

    Jozwiak, Adam; Brzozowski, Robert; Bujnowski, Zygmunt; Chojnacki, Tadeusz; Swiezewska, Ewa

    2013-01-01

    In this study, a method of supercritical fluid extraction (SFE) with carbon dioxide of polyisoprenoids from plant photosynthetic tissues is described. SFE was an effective extraction method for short- and medium-chain compounds with even higher yield than that observed for the “classical extraction” method with organic solvents. Moreover, SFE-derived extracts contained lower amounts of impurities (e.g., chlorophylls) than those obtained by extraction of the same tissue with organic solvents. Elevated temperature and extended extraction time of SFE resulted in a higher rate of extraction of long-chain polyisoprenoids. Ethanol cofeeding did not increase the extraction efficiency of polyisoprenoids; instead, it increased the content of impurities in the lipid extract. Optimization of SFE time and temperature gives the opportunity of prefractionation of complex polyisoprenoid mixtures accumulated in plant tissues. Extracts obtained with application of SFE are very stable and free from organic solvents and can further be used directly in experimental diet supplementation or as starting material for preparation of semisynthetic polyisoprenoid derivatives, e.g., polyisoprenoid phosphates. PMID:23673976

  18. 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 ...

  19. Subsurface fluid data from Longyearbyen CO2 storage site: Basin history and compartmentalization

    NASA Astrophysics Data System (ADS)

    Huq, Farhana; Mueller, Kristin; Tore Mørkved, Pål; Johansen, Ingar; Johansen, Harald

    2015-04-01

    The Longyearbyen CO2 storage site, located on the main island of Svalbard at the northwestern margin of the Barents Sea Shelf, is a demonstration project for a "green showcase", which aims to make a full value chain of power generation, CO2 capture and storage by achieving a net zero carbon footprint. The key objective of this study was to assess the local geological conditions for CO2 storage by defining a seal sequence stratigraphy above and within the reservoir from gas and fluid geochemical data. Seven wells were drilled at two sites to collect core material and gas samples at various defined depths. Gas composition (C1-5, CO2) and stable isotope (δ13C) analyses were performed on gas samples obtained from both core material and well heads. In addition, Sr isotope data from residual salts extracted from core material were used to look at compartmentalization. The combined analysis of trends in isotope and gas composition data as a function of depth revealed three major breaks and permitted the identification of three major fluid compartments. These compartments are suggested to be associated with impervious caprock and reservoir barriers. The first break in the data trends occurs at approximately 250-300 m depth, which is interpreted as the depth limit of the meteoric water system. A second hydrologic barrier, most likely produced by reservoir uplift was identified. Finally, a very distinct change in trend around 800 m depth may be associated with an observed significant change in reservoir pressure. Three clear breaks in the geochemical data as a function of depth all point towards an efficient seal sequence and demonstrate the potential for CO2 storage at the Longyearbyen site.

  20. Supercritical CO2 desorption of activated carbon loaded with 2,2,3,3-tetrafluoro-1-propanol in a rotating packed bed.

    PubMed

    Tan, Chung-Sung; Lee, Pei-Lun

    2008-03-15

    Desorption of activated carbon loaded with 2,2,3,3-tetrafluoro-1-propanol (TFP) by supercritical carbon dioxide in a rotating packed bed was investigated in this study. The experimental data show that the time required to achieve complete desorption of TFP from activated carbon in a rotating packed bed was much lower than that in a static packed bed. The reduction of desorption time is attributed to the presence of centrifugal force. The supercritical CO2 desorption efficiency in a rotating packed bed was observed to increase with increasing rotation speed, pressure, and C02 flow rate. To enhance desorption efficiency, a smaller activated carbon particle size was suggested. At low operating pressures such as 8.96 and 11.72 MPa, a better desorption efficiency was found to occur at lower temperatures in a temperature range of 305-335 K. However, at high operating pressures such as 15.86 MPa, a temperature of 315 K was found to be more appropriate for desorption, as compared to other temperatures. Due to a reduction of packed bed volume and an increase in desorption efficiency, supercritical CO2 desorption in a rotating packed bed is suggested for recovering TFP from the exhaust gases. PMID:18409651

  1. Metal Carbonation of Forsterite in Wet Supercritical CO2: The Role of H2O Studied by Solid State C-13 and Si-29 NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Hu, J.; Kwak, J.; Turcu, R. V.; Rosso, K. M.; Ilton, E. S.; Wang, C.; Sears, J. A.; Felmy, A. R.; Hoyt, D. W.

    2010-12-01

    Selected as a model mineral carbonation system for geological carbon sequestration in mafic host rocks, chemical mechanisms of forsterite carbonation in supercritical CO2 containing water varied from dry to well above saturation, including at saturation, were investigated by a combination of solid state NMR (C-13 SP-, CP-MAS, Si-29 SP-, CP-MAS), XRD, TEM and XPS. Run conditions were 80 degrees (C) and 75 bars. Major findings are as follows. At high water contents where a bulk aqueous solution coexisted with water-saturated scCO2, forsterite was converted into magnesite and a separate Mg-free amorphous SiO2 reaction product characterized by highly polymerized oligomeric Q4, and to a lesser extent by Q3 silica species. As the amount of added water was reduced, hydrated intermediate reaction products that did not evolve to magnesite could be identified until at zero water no reaction intermediates or magnesite carbonation products were observed. The intermediate reaction products identified were a complex mixture of partially hydrated/hydroxylated magnesium carbonate species and a variety of surface silica species with low polymerization extent. The intermediates were mainly in an amorphous state, forming a thin layer on the surface. Formation of these intermediate species consumes water by hydrolysis of Mg-O-Si linkages at the forsterite surface as well as by incorporation of water in the lattice. If insufficient water is available, the reaction is found not to proceed far enough to form magnesite and amorphous SiO2. Water in excess of this limit appears necessary for the intermediates to evolve to anhydrous magnesite, a process that is expected to liberate water for continued reaction. Hence, for a given fluid/forsterite ratio there appears to be a water threshold (i.e., the formation of H2O film with sufficient thickness estimated to be between 3.2 and 18.4 nm) above which a significant portion of the water is recycled in an apparent quasi-catalytic role for the

  2. Geothermal Recovery System Using Natural Circulating CO2 as A Heat Transfer Fluid

    NASA Astrophysics Data System (ADS)

    Soma, Hiroshi; Iwasawa, Kenji; Fukumiya, Kenji

    In the conventional system, heat is recovered as sensible heat through liquid anti-freezer circulating in a piping laid underground, but if CO2 is used as a heat transfer fluid, heat is recovered as latent heat which increases the capacity and enables to promote downsize of the equipment and reduction of the electric consumption. It also enables the diameter or the length of heat recovery piping for the same heat exchange performance, thus the installation cost of the piping would be reduced. In our study, a geothermal recovery system using CO2 for air-conditioning was installed, and the heating capacity and the electric consumption were measured. Also, those of a conventional propylene-glycol system were measured. As a result, the CO2-system exerted the same heating ability with the propylene-glycol system with a half length of heat recovery piping and a half electric consumption of the propylene-glycol system. And the reduction in the diameter of the CO2 recovery piping was possible to 50 mm at most to gain more than adequate heating effect.

  3. Numerical studies of fluid-rock interactions in EnhancedGeothermal Systems (EGS) with CO2 as working fluid

    SciTech Connect

    Xu, Tianfu; Pruess, Karsten; Apps, John

    2008-01-17

    There is growing interest in the novel concept of operating Enhanced Geothermal Systems (EGS) with CO{sub 2} instead of water as heat transmission fluid. Initial studies have suggested that CO{sub 2} will achieve larger rates of heat extraction, and can offer geologic storage of carbon as an ancillary benefit. Fluid-rock interactions in EGS operated with CO{sub 2} are expected to be vastly different in zones with an aqueous phase present, as compared to the central reservoir zone with anhydrous supercritical CO{sub 2}. Our numerical simulations of chemically reactive transport show a combination of mineral dissolution and precipitation effects in the peripheral zone of the systems. These could impact reservoir growth and longevity, with important ramifications for sustaining energy recovery, for estimating CO{sub 2} loss rates, and for figuring tradeoffs between power generation and geologic storage of CO{sub 2}.

  4. Effect of pressure on an enzymatic reaction in a supercritical fluid

    SciTech Connect

    Erickson, J.C.; Schyns, P.; Cooney, C.L. . Dept. of Chemical Engineering)

    1990-02-01

    Three different authors have reported on the use of four different enzymes in supercritical fluids. Lipase carries out transesterification reactions in the presence of supercritical carbon dioxide. Polyphenyl oxidase is active in supercritical CO{sub 2} and fluoroform. It has been shown that alkaline phosphatase and cholesterol oxidase are active in supercritical CO{sub 2}. More recently, an examination of the effect of aggregation of cholesterol on cholesterol oxidase activity in CO{sub 2} using electron paramagnetic resonance (EPR) was done. They found that when cosolvents which promoted aggregation were added, the reaction rate increased in proportion to the amount of aggregation. To date, no data on the effect of pressure on reaction rate have been presented. The objective of this work is to determine whether pressure-induced changes in the physical properties of a supercritical fluid solvent affect the rate of an enzymatic reaction and if so, which properties are responsible for the change.

  5. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, April 1, 1995--June 30, 1995

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1996-05-01

    Our objective for this quarter was to study the effect of co-feeding a 1-olefin on the Ruhrchemie catalyst activity and selectivity, during-both conventional Fisher-Tropsch synthesis (FTS) and FTS under supercritical conditions. We used propane as the supercritical fluid and 1-dodecene (1-C{sub 12}H{sub 24}) in this test. Motivation for this study was the work of Fujimoto and co-workers who reported that suppression of methane and enhancement of high molecular weight hydrocarbons selectivities occurs with co-feeding of 1-olefins (1-heptene, 1-tetradecene, or 1-hexadecene) during FTS under supercritical conditions, but not during the conventional FTS (Co-La catalyst supported on silica in supercritical n-pentane).The diffusion coefficients of products in supercritical fluids is discussed.

  6. Designed polar cosolvent-modified supercritical CO2 removing caffeine from and retaining catechins in green tea powder using response surface methodology.

    PubMed

    Huang, Kuo-Jong; Wu, Jia-Jiuan; Chiu, Yung-Ho; Lai, Cheng-Yung; Chang, Chieh-Ming J

    2007-10-31

    This study examines cosolvent-modified supercritical carbon dioxide (SC-CO2) to remove caffeine from and to retain catechins in green tea powder. The response surface method was adopted to determine the optimal operation conditions in terms of the extraction efficiencies and concentration factors of caffeine and catechins during the extractions. When SC-CO2 was used at 333 K and 300 bar, 91.5% of the caffeine was removed and 80.8% of catechins were retained in the tea: 3600 g of carbon dioxide was used in the extraction of 4 g of tea soaked with 1 g of water. Under the same extraction conditions, 10 g of water was added to <800 g of carbon dioxide in an extraction that completely removed caffeine (that is, the caffeine extraction efficiency was 100%). The optimal result as predicted by three-factor response surface methodology and supported by experimental data was that in 1.5 h of extraction, 640 g of carbon dioxide at 323 K and 275 bar with the addition of 6 g of water extracted 71.9% of the caffeine while leaving 67.8% of the catechins in 8 g of tea. Experimental data indicated that supercritical carbon dioxide decaffeination increased the concentrations of caffeine in the SC-CO2 extracts at 353 K.

  7. Designed polar cosolvent-modified supercritical CO2 removing caffeine from and retaining catechins in green tea powder using response surface methodology.

    PubMed

    Huang, Kuo-Jong; Wu, Jia-Jiuan; Chiu, Yung-Ho; Lai, Cheng-Yung; Chang, Chieh-Ming J

    2007-10-31

    This study examines cosolvent-modified supercritical carbon dioxide (SC-CO2) to remove caffeine from and to retain catechins in green tea powder. The response surface method was adopted to determine the optimal operation conditions in terms of the extraction efficiencies and concentration factors of caffeine and catechins during the extractions. When SC-CO2 was used at 333 K and 300 bar, 91.5% of the caffeine was removed and 80.8% of catechins were retained in the tea: 3600 g of carbon dioxide was used in the extraction of 4 g of tea soaked with 1 g of water. Under the same extraction conditions, 10 g of water was added to <800 g of carbon dioxide in an extraction that completely removed caffeine (that is, the caffeine extraction efficiency was 100%). The optimal result as predicted by three-factor response surface methodology and supported by experimental data was that in 1.5 h of extraction, 640 g of carbon dioxide at 323 K and 275 bar with the addition of 6 g of water extracted 71.9% of the caffeine while leaving 67.8% of the catechins in 8 g of tea. Experimental data indicated that supercritical carbon dioxide decaffeination increased the concentrations of caffeine in the SC-CO2 extracts at 353 K. PMID:17914876

  8. Analysis of semi-volatile organic compounds using supercritical fluid methodologies

    SciTech Connect

    Wright, B.W.; Chess, E.K.; Yonker, C.R.; Smith, R.D.

    1985-06-01

    This study demonstrates the applicability of supercritical fluid chromatography (SFC) and analytical supercritical fluid extraction (SFE) for the analysis of semi-volatile compounds. Mixtures of nitro-polycyclic aromatic hydrocarbons that are not ammenable to gas chromatography were separated using SFC with tentative compound identifications made by SFC-MS. Comparisons of analytical SFE of XAD-2 resin and NBS Urban Dust (SRM 1649) to conventional Soxhlet extraction are also discussed.

  9. Supercritical fluid methods for the analysis of complex fuel and environmental samples

    SciTech Connect

    Smith, R.D.; Yonker, C.R.; Kalinoski, H.T.; Chess, E.K.; Udseth, H.R.; Frye, S.L.; Wright, B.W.

    1985-11-01

    The application of supercritical fluid methods can greatly improve the analysis of complex mixtures spanning wide chemical classes. In separations from complex matrices supercritical fluids can be used to improve both extraction efficiency and speed. The variable solvating powers and gas-like diffusion coefficients and viscosities can provide efficient new methods for sample enrichment, cleanup and fractionation. Supercritical fluid chromatography (SFC) is applicable to both thermally labile and less volatile materials. The use of small diameter (25- to 50-..mu..m) fused silica capillary columns provides chromatographic efficiencies for SFC that are nearly comparable to conventional capillary gas chromatography and much greater than practical by liquid chromatography (LC). The development of practical capillary SFC-MS instrumentation, allowing both electron impact and chemical ionization mass spectrometry (MS), is expected to provide a powerful alternative to LC-MS for complex mixture analysis. Recent results will be presented on the development of methods for the analysis of fuels, labile pollutants, hazardous solid waste materials, and related complex environmental mixtures. The application of various supercritical fluids for sample extraction, SFC and SFC-MS, and the recent development of a system for automated supercritical fluid extraction-chromatography will also be described. Finally, the potential role of supercritical fluid methods in routine chemical analysis will be discussed. 16 refs., 11 figs.

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

    NASA Astrophysics Data System (ADS)

    Huo, Hongfa

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

  11. Remediation of contaminated soils using supercritical fluid extraction: a review (1994-2004).

    PubMed

    Saldaña, M D A; Nagpal, V; Guigard, S E

    2005-09-01

    Considerable effort is being made to remediate soils contaminated with petroleum hydrocarbons, polyaromatic hydrocarbons, polychlorinated biphenyls, dioxins, heavy metals and other organic and inorganic compounds that have resulted from industrial activities, accidental spills and improper waste disposal practices. Current remediation technologies may be limited when treating certain types of contaminated soils and therefore new, efficient and cost effective technologies are being investigated. Supercritical fluid extraction is a potential remediation technology for contaminated soils. It is a simple, fast and selective solvent extraction process that uses a supercritical fluid as the solvent. A commonly used fluid is carbon dioxide at pressures and temperatures greater than 7.4 MPa and 31 degrees C, respectively. In supercritical fluid extraction, the extracted contaminants first dissolve into the supercritical solvent and then these contaminants are separated from the supercritical solvent via a simple change in pressure and temperature conditions or by using a separation process. This paper provides a review of supercritical fluid extraction and its application to the remediation of contaminated soils. This review focuses on the removal of organic contaminants (such as petroleum hydrocarbons, polyaromatic hydrocarbons, polychlorinated biphenyls and others) and inorganic contaminants (such as heavy metals and radioactive elements) from soils. Recent data (1994-2004) on the supercritical fluid extraction of spiked soils and field-contaminated soils were collected. The success of supercritical fluid extraction as a method for removing these contaminants from soils is highlighted and some of the future research needed to develop it as a commercial-scale economic remediation technology are discussed. PMID:16196410

  12. Supercritical fluid thermodynamics for coal processing. Final report, September 15, 1988--September 14, 1991

    SciTech Connect

    van Swol, F.; Eckert, C.A.

    1988-09-15

    The main objective of this research is to develop an equation of state that can be used to predict solubilities and tailor supercritical fluid solvents for the extraction and processing of coal. To meet this objective we have implemented a two-sided. approach. First, we expanded the database of model coal compound solubilities in higher temperature fluids, polar fluids, and fluid mixtures systems. Second, the unique solute/solute, solute/cosolvent and solute/solvent intermolecular interactions in supercritical fluid solutions were investigated using spectroscopic techniques. These results increased our understanding of the molecular phenomena that affect solubility in supercritical fluids and were significant in the development of an equation of state that accurately reflects the true molecular makeup of the solution. (VC)

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

    PubMed

    Taguchi, Kaori; Fukusaki, Eiichiro; Bamba, Takeshi

    2014-10-01

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

  14. Combined analysis by GC (RI), GC-MS and 13C NMR of the supercritical fluid extract of Abies alba twigs.

    PubMed

    Duquesnoy, Emilie; Marongiu, Bruno; Castola, Vincent; Piras, Alessandra; Porcedda, Silvia; Casanova, Joseph

    2010-12-01

    Two samples (leaves and twigs) of Abies alba Miller from Corsica were extracted using supercritical CO2 and their chemical compositions were compared with those of the essential oils obtained from the same batch of plant material. In total 45 components were identified using combined analysis by GC (RI), GC-MS and 13C NMR. It was observed that the contents of monoterpenes (mainly represented by limonene, alpha-pinene and camphene) were significantly lower in the supercritical fluid extract (SFE) than in the essential oil (EO). Conversely, the proportions of sesquiterpenes were much higher in CO2 extracts than in essential oils (around 30% vs 4%). Cis-abienol, a diterpene alcohol, was identified only in SFE, and the proportions of this constituent (7.5% and 17.3%) were determined using quantitative 13C NMR since it was under estimated using the standard conditions of GC. PMID:21299139

  15. Combined analysis by GC (RI), GC-MS and 13C NMR of the supercritical fluid extract of Abies alba twigs.

    PubMed

    Duquesnoy, Emilie; Marongiu, Bruno; Castola, Vincent; Piras, Alessandra; Porcedda, Silvia; Casanova, Joseph

    2010-12-01

    Two samples (leaves and twigs) of Abies alba Miller from Corsica were extracted using supercritical CO2 and their chemical compositions were compared with those of the essential oils obtained from the same batch of plant material. In total 45 components were identified using combined analysis by GC (RI), GC-MS and 13C NMR. It was observed that the contents of monoterpenes (mainly represented by limonene, alpha-pinene and camphene) were significantly lower in the supercritical fluid extract (SFE) than in the essential oil (EO). Conversely, the proportions of sesquiterpenes were much higher in CO2 extracts than in essential oils (around 30% vs 4%). Cis-abienol, a diterpene alcohol, was identified only in SFE, and the proportions of this constituent (7.5% and 17.3%) were determined using quantitative 13C NMR since it was under estimated using the standard conditions of GC.

  16. Fluid-rock interactions in CO2-saturated, granite-hosted geothermal systems: Implications for natural and engineered systems from geochemical experiments and models

    NASA Astrophysics Data System (ADS)

    Lo Ré, Caroline; Kaszuba, John P.; Moore, Joseph N.; McPherson, Brian J.

    2014-09-01

    Hydrothermal experiments were conducted and geochemical models constructed to evaluate the geochemical and mineralogical response of fractured granite and granite + epidote in contact with thermal water, with and without supercritical CO2, at 250 °C and 25-45 MPa. Illite ± smectite ± zeolite(?) precipitate as secondary minerals at the expense of K-feldspar, oligoclase, and epidote. Illite precipitates in experiments reacting granite and granite + epidote with water; metastable smectite forms in the experiments injected with supercritical CO2. Waters are supersaturated with respect to quartz and saturated with respect to chalcedony in CO2-charged experiments, but neither mineral formed. Carbonate formation is predicted for experiments injected with supercritical CO2, but carbonate only formed during cooling and degassing of the granite + epidote + CO2 experiment. Experimental results provide insight into the buffering capacity of granites as well as the drivers of clay formation. Metastable smectite in the experiments is attributed to high water-rock ratios, high silica activities, and high CO2 and magnesium-iron concentrations. Smectite precipitation in supercritical CO2-bearing geothermal systems may affect reservoir permeability. Silicate formation may create or thicken caps within or on the edges of geothermal reservoirs. Carbonate formation, as desired for carbon sequestration projects coinciding with geothermal systems, may require extended periods of time; cooling and degassing of CO2-saturated waters leads to carbonate precipitation, potentially plugging near-surface production pathways.

  17. Fluid modelling of CO2 dissociation in a dielectric barrier discharge

    NASA Astrophysics Data System (ADS)

    Ponduri, S.; Becker, M. M.; Welzel, S.; van de Sanden, M. C. M.; Loffhagen, D.; Engeln, R.

    2016-03-01

    The dissociation of CO2 in a geometrically symmetric dielectric barrier discharge has been analysed by means of numerical modelling. A time- and space-dependent fluid model has been used, taking into account the spatial variation of the plasma between the plane-parallel dielectrics covering the electrodes. The main features of the model, including an extensive reaction kinetics for the vibrational states of CO2, are given. The modelling studies have been performed for different applied voltages, discharge frequencies, pressures, gas temperatures, and relative permittivities of the dielectrics. The model calculations show that the discharges in the positive and negative half-cycles are different for the considered standard condition, leading to a spatially asymmetric distribution of the stable neutrals like CO molecules and O atoms. The generation of CO mainly takes place during the discharge pulses, and it is dominated by electron impact dissociation. The specific energy input obtained for the broad range of parameters considered and determined for residence times reported in the literature agrees well with the corresponding experimental values. In accordance with these experiments, the calculated degree of CO2 conversion has been found to increase almost linearly with the specific energy input. Remaining discrepancies between the measured and calculated energy efficiencies are discussed.

  18. 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.

  19. Supercritical fluid molecular spray film deposition and powder formation

    DOEpatents

    Smith, Richard D.

    1986-01-01

    Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. Upon expansion and supersonic interaction with background gases in the low pressure region, any clusters of solvent are broken up and the solvent is vaporized and pumped away. Solute concentration in the solution is varied primarily by varying solution pressure to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solvent clustering and solute nucleation are controlled by manipulating the rate of expansion of the solution and the pressure of the lower pressure region. Solution and low pressure region temperatures are also controlled.

  20. Supercritical fluid molecular spray thin films and fine powders

    DOEpatents

    Smith, Richard D.

    1988-01-01

    Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. The solvent is vaporized and pumped away. Solution pressure is varied to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solution temperature is varied in relation to formation of a two-phase system during expansion to control porosity of the film or powder. A wide variety of film textures and powder shapes are produced of both organic and inorganic compounds. Films are produced with regular textural feature dimensions of 1.0-2.0 .mu.m down to a range of 0.01 to 0.1 .mu.m. Powders are formed in very narrow size distributions, with average sizes in the range of 0.02 to 5 .mu.m.

  1. Update on Area Production in Mixing of Supercritical Fluids

    NASA Technical Reports Server (NTRS)

    Okongo, Nora; Bellan, Josette

    2003-01-01

    The focus of this research is on supercritical C7H16/N2 and O2/H2 mixing layers undergoing transitions to turbulence. The C7H16/N2 system serves as a simplified model of hydrocarbon/air systems in gas-turbine and diesel engines; the O2/H2 system is representative of liquid rocket engines. One goal of this research is to identify ways of controlling area production to increase disintegration of fluids and enhance combustion in such engines. As used in this research, "area production" signifies the fractional rate of change of surface area oriented perpendicular to the mass-fraction gradient of a mixing layer. In the study, a database of transitional states obtained from direct numerical simulations of the aforementioned mixing layers was analyzed to investigate global layer characteristics, phenomena in regions of high density-gradient magnitude (HDGM), irreversible entropy production and its relationship to the HDGM regions, and mechanisms leading to area production.

  2. Optimisation of powders for pulmonary delivery using supercritical fluid technology.

    PubMed

    Rehman, Mahboob; Shekunov, Boris Y; York, Peter; Lechuga-Ballesteros, David; Miller, Danforth P; Tan, Trixie; Colthorpe, Paul

    2004-05-01

    Supercritical fluid technology exploited in this work afforded single-step production of respirable particles of terbutaline sulphate (TBS). Different crystal forms of TBS were produced consistently, including two polymorphs, a stoichiometric monohydrate and amorphous material as well as particles with different degrees of crystallinity, size, and morphology. Different solid-state and surface characterisation techniques were applied in conjunction with measurements of powder flow properties using AeroFlow device and aerosol performance by Andersen Cascade Impactor tests. Improved fine particle fraction (FPF) was demonstrated for some powders produced by the SCF process when compared to the micronised material. Such enhanced flow properties and dispersion correlated well with the reduced surface energy parameters demonstrated by these powders. It is shown that semi-crystalline particles exhibited lower specific surface energy leading to a better performance in the powder flow and aerosol tests than crystalline materials. This difference of the surface and bulk crystal structure for selected powder batches is explained by the mechanism of precipitation in SCF which can lead to surface conditioning of particles produced. PMID:15113578

  3. Supercritical fluid extraction of plant flavors and fragrances.

    PubMed

    Capuzzo, Andrea; Maffei, Massimo E; Occhipinti, Andrea

    2013-01-01

    Supercritical fluid extraction (SFE) of plant material with solvents like CO₂, propane, butane, or ethylene is a topic of growing interest. SFE allows the processing of plant material at low temperatures, hence limiting thermal degradation, and avoids the use of toxic solvents. Although today SFE is mainly used for decaffeination of coffee and tea as well as production of hop extracts on a large scale, there is also a growing interest in this extraction method for other industrial applications operating at different scales. In this review we update the literature data on SFE technology, with particular reference to flavors and fragrance, by comparing traditional extraction techniques of some industrial medicinal and aromatic crops with SFE. Moreover, we describe the biological activity of SFE extracts by describing their insecticidal, acaricidal, antimycotic, antimicrobial, cytotoxic and antioxidant properties. Finally, we discuss the process modelling, mass-transfer mechanisms, kinetics parameters and thermodynamic by giving an overview of SFE potential in the flavors and fragrances arena. PMID:23783457

  4. Enhanced geothermal systems (EGS) with CO2 as heat transmission fluid--A scheme for combining recovery of renewable energy with geologic storage of CO2

    SciTech Connect

    Pruess, K.; Spycher, N.

    2009-05-01

    It has been suggested that enhanced geothermal systems (EGS) may be operated with supercritical CO{sub 2} instead of water as heat transmission fluid (D.W. Brown, 2000). Such a scheme could combine recovery of geothermal energy with simultaneous geologic storage of CO{sub 2}, a greenhouse gas. At geothermal temperature and pressure conditions of interest, the flow and heat transfer behavior of CO{sub 2} would be considerably different from water, and chemical interactions between CO{sub 2} and reservoir rocks would also be quite different from aqueous fluids. This paper summarizes our research to date into fluid flow and heat transfer aspects of operating EGS with CO{sub 2}. (Chemical aspects of EGS with CO{sub 2} are discussed in a companion paper; Xu and Pruess, 2010.) Our modeling studies indicate that CO{sub 2} would achieve heat extraction at larger rates than aqueous fluids. The development of an EGS-CO{sub 2} reservoir would require replacement of the pore water by CO{sub 2} through persistent injection. We find that in a fractured reservoir, CO{sub 2} breakthrough at production wells would occur rapidly, within a few weeks of starting CO{sub 2} injection. Subsequently a two-phase water-CO{sub 2} mixture would be produced for a few years,followed by production of a single phase of supercritical CO{sub 2}. Even after single-phase production conditions are reached,significant dissolved water concentrations will persist in the CO{sub 2} stream for many years. The presence of dissolved water in the production stream has negligible impact on mass flow and heat transfer rates.

  5. Instrumental Idiosyncrasies Affecting the Performance of Ultrafast Chiral and Achiral Sub/Supercritical Fluid Chromatography.

    PubMed

    Barhate, Chandan L; Wahab, M Farooq; Tognarelli, D J; Berger, Terry A; Armstrong, Daniel W

    2016-09-01

    It is widely accepted that column technology is ahead of existing chromatographic instruments. The chromatographic output may not reflect the true picture of the peak profile inside the column. The instrumental optimization parameters become far more important when peaks elute in a few seconds. In this work, the low viscosity advantage of the supercritical/subcritical CO2 is coupled with the high efficiency of narrow particle size distribution silica. Using short efficient columns and high flow rates (up to 19 mL/min), separations on the order of a few seconds are demonstrated. In the domain of ultrafast supercritical fluid chromatography (SFC), unexpected results are seen which are absent in ultrafast liquid chromatography. These effects arise due to the compressible nature of the mobile phase and detector idiosyncrasies to eliminate back-pressure regulator noise. We demonstrate unusual connection tubing effects with 50, 75, 127, 254, and 500 μm tubings and show the complex relation of dead time, retention time, efficiency, and optimum velocity with the tubing diameter (via column outlet pressure). Fourier analysis at different back-pressure regulator (BPR) settings shows that some instruments have very specific noise frequencies originating from the BPR, and those specific frequencies vanish under certain conditions. The performance of embedded digital filters, namely, moving average, numerically simulated low pass RC, and Gaussian kernels, is compared. This work also demonstrates, using a simple derivative test, that some instruments employ interpolation techniques while sampling at "true" low frequencies to avoid picking up high frequency noise. Researchers engaged in ultrafast chromatography need to be aware of the instrumental nuances and optimization procedures for achieving ultrafast chiral or achiral separations in SFC mode. PMID:27500473

  6. The Impact of Fluid Properties and Flow Conditions on the Measurement of Relative Permeability and Residual CO2 Trapping Saturation for CO2-Brine Systems

    NASA Astrophysics Data System (ADS)

    Niu, B.; Al-Menhali, A.; Krevor, S. C.

    2014-12-01

    Successful industrial scale carbon dioxide injection into deep saline aquifers will be dependent on the ability to model the flow of the fluid and to quantify the impact of various trapping mechanisms. The effectiveness of the models is in turn dependent on high quality laboratory measurements of basic multiphase flow properties such as relative permeability and residual trapping at reservoir conditions. Compared with typical oil-brine systems, however, a unique defining characteristic of the CO2-brine system is its combination of high viscosity ratio and low density ratio. This combination of properties results in unique complications for experiments with CO2 and brine and unique flow conditions must be used to achieve the combined goals of observations across a large saturation range and the avoidance of the effects of heterogeneity as well as capillary forces and gravity segregation. We have simulated the corefloods experiments at various conditions and calculated with different interpretation techniques: Steady state method, JBN-type method and history matching. As one of the essential mechanisms for CO2 storage underground, residual trapping refers to the trapping of CO2 through capillary forces within the pore space of a permeable aquifer. There are few studies that have observed the trapping characteristics for CO2-brine systems in permeable rocks, including the impact of reservoir conditions, and this remains a major uncertainty for geologic CO2 storage. This work presents results from a core-flooding laboratory that has been recently developed at Imperial College dedicated to observations of CO2-brine systems. The apparatus includes high precision pumps, accurate temperature control and a rotating X-ray CT scanner that allows experiments to be performed in both vertical and horizontal directions. The proper approach to measuring relative permeability for CO2-brine system is proposed and demonstrated. The changes in residual trapping correlated to pressure

  7. Mineralization of atmospheric CO2 via fluid reaction with mafic/ultramafic rocks

    NASA Astrophysics Data System (ADS)

    Westfield, I. T.; Kendall, T. A.; Ries, J. B.

    2011-12-01

    Atmospheric CO2 has increased nearly 50% since the Industrial Revolution, due primarily to increased fossil fuel combustion, cement production, and deforestation. Although subterranean reservoirs are presently considered the most viable sink for anthropogenically liberated CO2, concerns exist over the stability of these systems and their impacts on regional tectonics, aquifers, and subterranean microbial ecosystems. Direct mineralization of CO2 at the Earth's surface provides an alternative capable of generating useful carbon-negative mineral byproducts that may be used to supplement or replace conventional carbon-positive building materials, like cement. However, mineralization of anthropogenic CO2 requires large sources of alkalinity to convert CO2 to CO32-, and divalent cations (e.g., Mg2+, Ca2+, Fe2+, etc.) to bond with the aqueous CO32-. Ultramafic and mafic rocks, such as peridotites, serpentinites, and basalts, are globally abundant, naturally occurring sources of the divalent cations, and alkalinity required for CO2 mineralization. Here, we present the results of accelerated reactions between ultramafic/mafic rocks, water, and CO2/N2 gases, aimed at quantifying the carbonation potential of mafic/ultramafic rocks. Rock-fluid-gas batch reactions were carried out in vented 4 L borosilicate glass flasks filled with 3 L DI water and 200 g acetone-washed, 49-180μm-diameter grains of four ultramafic/mafic rock types: peridotite, dunite, websterite and basalt. Each of the four rock-water mixtures was reacted under pure CO2 and pure N2 and at 25 and 200 °C, for a total of 16 reactions. Mixtures were continuously heated and stirred for 14 days. Samples (330 mL) were obtained at 0, 1, 6, 24, 48, 96, 168, and 336 hrs and filtered at 0.4 μm. The pH of filtered samples was measured with a single-junction Ag/AgCl glass electrode, salinity was determined with a conductivity probe, total alkalinity (TA) was determined by closed-cell potentiometric Gran titration, and DIC

  8. Significance for secure CO2 storage of earthquakes induced by fluid injection

    NASA Astrophysics Data System (ADS)

    Verdon, James P.

    2014-05-01

    The link between subsurface fluid injection and induced seismicity has gained recent significance with an increase in earthquakes associated with the disposal of oilfield waste fluids. There are obvious similarities between wastewater reinjection and proposed CO2 storage (CCS) operations. However, as well as the seismic hazard, induced seismicity during CCS operations poses additional risks, because an induced event located above the target reservoir could compromise the hydraulic integrity of the caprock. In this paper we re-examine case examples where earthquakes have been induced by wastewater injection into deep aquifers in the light of proposed future CCS operations. In particular we consider possible controls on event magnitudes, and look at the spatial distributions of events. We find that the majority of events are located below the target reservoirs. This is an encouraging observation from the perspective of caprock integrity, although it presents a challenge in terms of pre-injection characterization of deep-lying faults several kilometres below the target zone. We observe that 99% of events are found within 20 km of injection wells, suggesting a minimum radius for geomechanical characterization and monitoring. We conclude by making recommendations for modelling and monitoring strategies to be followed prior to and during commercial-scale deployment of CO2 storage projects.

  9. Capillary pressure - saturation relations for supercritical CO2 and brine: Implications for capillary/residual trapping in carbonate reservoirs during geologic carbon sequestration

    NASA Astrophysics Data System (ADS)

    Wang, S.; Tokunaga, T. K.

    2014-12-01

    In geologic carbon sequestration (GCS), data on capillary pressure (Pc) - saturation (Sw) relations are routinely needed to appraise reservoir processes. Capillarity and its hysteresis have been often experimentally studied in oil-water, gas-water and three phase gas-oil-water systems, but fewer works have been reported on scCO2-water under in-situ reservoir conditions. Here, Pc-Sw relations of supercritical (sc) CO2 displacing brine, and brine rewetting the porous medium to trap scCO2 were studied to understand CO2 transport and trapping behavior in carbonate reservoirs under representative reservoir conditions. High-quality drainage and imbibition (and associated capillary pressure hysteresis) curves were measured under elevated temperature and pressure (45 ºC, 8.5 and 12 MPa) for scCO2-brine as well as at room temperature and pressure (23 ºC, 0.1 MPa) for air-brine in unconsolidated limestone and dolomite sand columns using newly developed semi-automated multistep outflow-inflow porous plate apparatus. Drainage and imbibition curves for scCO2-brine deviated from the universal scaling curves for hydrophilic interactions (with greater deviation under higher pressure) and shifted to lower Pc than predicted based on interfacial tension (IFT) changes. Augmented scaling incorporating differences in IFT and contact angle improved the scaling results but the scaled curves still did not converge onto the universal curves. Equilibrium residual trapping of the nonwetting phase was determined at Pc =0 during imbibition. The capillary-trapped amounts of scCO2 were significantly larger than for air. It is concluded that the deviations from the universal capillary scaling curves are caused by scCO2-induced wettability alteration, given the fact that pore geometry remained constant and IFT is well constrained. In-situ wettability alteration by reactive scCO2 is of critical importance and must be accounted for to achieve reliable predictions of CO2 behavior in GCS reservoirs.

  10. Why do co-solvents enhance the solubility of solutes in supercritical fluids? New evidence and opinion.

    PubMed

    Zhang, Xiaogang; Han, Buxing; Hou, Zhenshan; Zhang, Jianling; Liu, Zhimin; Jiang, Tao; He, Jun; Li, Hongping

    2002-11-15

    The effects of two polar co-solvents, chlorodifluoromethane and acetone, on the solubility and enthalpy of a solution of 1,4-naphthoquinone in supercritical (SC) CO2 were studied. We found that the dissolution process becomes less exothermic in the presence of the co-solvents relative to that in pure CO2, although the solubility is enhanced significantly by the co-solvents. This indicates that the increase in the solubility by adding co-solvents results from the increase of the entropy of solution. On the basis of the unexpected results we propose a new mechanism for the solubility enhancement of the solute by the co-solvents in supercritical fluids (SCF); this should be applicable to cases in which the local density of the SC solvent around the solute and the co-solvent is larger, and the co-solvent associates preferentially with the solute. The results are also very important for the understanding of other fundamental questions of SCF science, such as the effect of co-solvents on the thermodynamic and kinetic properties of the reactions in SCFs.

  11. Supercritical fluid extraction from spent coffee grounds and coffee husks: antioxidant activity and effect of operational variables on extract composition.

    PubMed

    Andrade, Kátia S; Gonçalvez, Ricardo T; Maraschin, Marcelo; Ribeiro-do-Valle, Rosa Maria; Martínez, Julian; Ferreira, Sandra R S

    2012-01-15

    The present study describes the chemical composition and the antioxidant activity of spent coffee grounds and coffee husks extracts, obtained by supercritical fluid extraction (SFE) with CO(2) and with CO(2) and co-solvent. In order to evaluate the high pressure method in terms of process yield, extract composition and antioxidant activity, low pressure methods, such as ultrasound (UE) and soxhlet (SOX) with different organic solvents, were also applied to obtain the extracts. The conditions for the SFE were: temperatures of 313.15K, 323.15K and 333.15K and pressures from 100 bar to 300 bar. The SFE kinetics and the mathematical modeling of the overall extraction curves (OEC) were also investigated. The extracts obtained by LPE (low pressure extraction) with ethanol showed the best results for the global extraction yield (X(0)) when compared to SFE results. The best extraction yield was 15±2% for spent coffee grounds with ethanol and 3.1±04% for coffee husks. The antioxidant potential was evaluated by DPPH method, ABTS method and Folin-Ciocalteau method. The best antioxidant activity was showed by coffee husk extracts obtained by LPE. The quantification and the identification of the extracts were accomplished using HPLC analysis. The main compounds identified were caffeine and chlorogenic acid for the supercritical extracts from coffee husks.

  12. Flow regime analysis for fluid