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Sample records for supercritical co2 fluid

  1. Supercritical CO2 fluid radiochromatography system used to purify [11C]toluene for PET.

    PubMed

    Muller, Ryan D; Ferrieri, Richard A; Gerasimov, Madina; Garza, Victor

    2002-04-01

    Abuse of inhalants in today's society has become such a widespread problem among today's adolescents that in many parts of the world their use exceeds that of many other illicit drugs or alcohol. Even so, little is known how such inhalants affect brain function to an extent that can lead to an abuse liability. While methodologies exist for radiolabeling certain inhalants of interest with short-lived positron emitting radioisotopes that would allow their investigation in human subjects using positron emission tomography (PET), the purification methodologies necessary to separate these volatile substances from the organic starting materials have not been developed. We've adapted supercritical fluid technology to this specific PET application by building a preparative-scale supercritical CO2 fluid radiochromatograph, and applied it to the purification of [11C]toluene. We've demonstrated that [11C]toluene can be separated from the starting materials using a conventional C18 HPLC column and pure supercritical CO2 fluid as the mobile phase operating at 2000 psi and 40 degrees C. We've also shown that the purified radiotracer can be quantitatively captured on Tenax GR, a solid support material, as it exits the supercritical fluid stream, thus allowing for later desorption into a 1.5% cyclodextrin solution that is suitable for human injection, or into a breathing tube for direct inhalation. PMID:11929706

  2. 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

  3. Two-Dimensional Nanoparticle Cluster Formation in Supercritical Fluid CO2.

    PubMed

    Wang, Joanna S; Wai, Chien M; Brown, Gail J; Apt, Scott D

    2016-05-10

    Supercritical fluid carbon dioxide (sc-CO2) is capable of depositing nanoparticles in small structures of silicon substrates because of its gas-like penetration, liquid-like solvation abilities, and near-zero surface tension. In nanometer-sized shallow wells on silicon surface, formation of two-dimensional (2D) monolayer metal nanoparticle (NP) clusters can be achieved using the sc-CO2 deposition method. Nanoparticles tend to fill nanostructured holes first, and then, if sufficient nanoparticles are available, they will continue to cover the flat areas nearby, unless defects or other surface imperfections are available. In addition, SEM images of two-dimensional gold (Au) nanoparticle clusters formed on a flat silicon surface with two to a dozen or more of the nanoparticles are provided to illustrate the patterns of nanoparticle cluster formation in sc-CO2. PMID:27088712

  4. 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.

  5. 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

  6. 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.

  7. 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

  8. Calcite solubility in supercritical CO 2H 2O fluids

    NASA Astrophysics Data System (ADS)

    Fein, Jeremy B.; Walther, John V.

    1987-06-01

    An extraction-quench apparatus was used to measure calcite solubilities in supercritical CO 2H 2O mixtures. Experiments were conducted at 1 kbar and 2 kbar, between 240°C and 620°C and from XCO 2 = .02 toXCO 2 = .15 in order to determine the solubility behavior as a function of pressure, temperature and CO 2 content. The results indicate that calcite solubilities under these conditions behave similarly to previously investigated calcite solubilities at lower pressures and temperatures (SHARP and Kennedy, 1965). At constant XCO 2, the solubility increases with increasing pressure, but it decreases with increasing temperature. When the temperature and pressure are constant, the calcite solubility rises with increasing XCO 2 to a maximum value at XCO 2 between 0.02 and 0.05. For higher CO 2 contents, up to XCO 2 = .15, the calcite solubility decreases, probably due to the decrease of H 2O activities to values significantly below unity. The solubility behavior can be successfully modeled by making the assumption that Ca ++ is the dominant calcium species and that the carbon-bearing species are CO 2(aq) and HCO -3. Since for these dilute H 2OCO 2 fluids, all activity coefficients can be assumed to not differ significantly from unity, ionization constants for the reaction H 2O + CO 2(aq) H + + HCO -3 can be calculated at 1 and 2 kbar between 250°C and 550°C. These calculated values are in good agreement with the low temperature determinations of the ionization constants for this reaction determined by Read (1975). Values of the molal Gibbs free energy of CO 2(aq) obtained in our study exhibit a much greater positive departure from ideality than those calculated with the modified Redlich-Kwong equations of either Flowers (1979) or Kerrick and Jacobs (1981) for dilute CO 2 aqueous solutions.

  9. Shale Micromodel Experiments: Fluid Flow and Mobilization using Supercritical CO2

    NASA Astrophysics Data System (ADS)

    Porter, M. L.; Carey, J. W.; Viswanathan, H.

    2014-12-01

    In recent years, use of engineered micromodels to investigate pore-scale fluid flow and transport phenomena to better understand and model field-scale observables has steadily increased. Micromodels are thin porous structures in which flow is restricted to two-dimensions and have become common since they are effective, relatively inexpensive tools for visualizing and quantifying complex flow phenomena. We describe a unique micromodel experimental system recently developed at Los Alamos National Laboratory (LANL). The system consists of a pressure chamber, which allows us to conduct experiments at geologic conditions. The maximum working pressure and temperature is 1500 psig and 80° C, respectively, allowing for supercritical carbon dioxide (scCO2) to be used as a working fluid. Additionally, we have developed micromodels fabricated in geomaterials (e.g., shale and Portland cement), whereas typical micromodels are fabricated in engineered materials such as glass or silicon. The use of geomaterial micromodels allows us to better represent the fluid-rock interactions including wetting angles and chemical reactivity at conditions representative of natural subsurface environments. In this work, we present experimental results in simple fracture systems (e.g., straight channels, pore doublets) with applications to hydrocarbon mobility in hydraulically fractured shale. We use both shale and glass micromodels, allowing for a detailed comparison between flow phenomena in different materials. In the straight channel micromodels, we investigate interfacial velocities and compare the results with theoretical models. In the pore doublet micromodels, we investigate mobilization of oil blobs and contrast the effectiveness of water and scCO2 in the extraction of hydrocarbon from fracture networks. Next, we present experimental results in complex fracture network patterns derived from 3D x-ray tomography images of actual fractures created in shale rock cores. We discuss

  10. 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...

  11. 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. PMID:24320192

  12. 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. PMID:18418588

  13. Reducing operation current of Ni-doped silicon oxide resistance random access memory by supercritical CO2 fluid treatment

    NASA Astrophysics Data System (ADS)

    Chang, Kuan-Chang; Tsai, Tsung-Ming; Chang, Ting-Chang; Syu, Yong-En; Wang, Chia-C.; Chuang, Siang-Lan; Li, Cheng-Hua; Gan, Der-Shin; Sze, Simon M.

    2011-12-01

    In the study, we reduced the operation current of resistance random access memory (RRAM) by supercritical CO2 (SCCO2) fluids treatment. The power consumption and joule heating degradation of RRAM device can be improved greatly by SCCO2 treatment. The defect of nickel-doped silicon oxide (Ni:SiOx) was passivated effectively by the supercritical fluid technology. The current conduction of high resistant state in post-treated Ni:SiOx film was transferred to Schottky emission from Frenkel-Pool due to the passivation effect. Additionally, we can demonstrate the passivation mechanism of SCCO2 for Ni:SiOx by material analyses of x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy.

  14. Diameter-sensitive biocompatibility of anodic TiO2 nanotubes treated with supercritical CO2 fluid

    PubMed Central

    2013-01-01

    This work reports on the diameter-sensitive biocompatibility of anodic TiO2 nanotubes with different nanotube diameters grown by a self-ordering process and subsequently treated with supercritical CO2 (ScCO2) fluid. We find that highly hydrophilic as-grown TiO2 nanotubes become hydrophobic after the ScCO2 treatment but can effectively recover their surface wettability under UV light irradiation as a result of photo-oxidation of C-H functional groups formed on the nanotube surface. It is demonstrated that human fibroblast cells show more obvious diameter-specific behavior on the ScCO2-treated TiO2 nanotubes than on the as-grown ones in the range of diameters of 15 to 100 nm. This result can be attributed to the removal of disordered Ti(OH)4 precipitates from the nanotube surface by the ScCO2 fluid, thus resulting in purer nanotube topography and stronger diameter dependence of cell activity. Furthermore, for the smallest diameter of 15 nm, ScCO2-treated TiO2 nanotubes reveal higher biocompatibility than the as-grown sample. PMID:23547743

  15. Electrodeposition from supercritical fluids.

    PubMed

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

    2014-05-28

    Recent studies have shown that it is possible to electrodeposit a range of materials, such as Cu, Ag and Ge, from various supercritical fluids, including hydrofluorocarbons and mixtures of CO2 with suitable co-solvents. In this perspective we discuss the relatively new field of electrodeposition from supercritical fluids. The perspective focuses on some of the underlying physical chemistry and covers both practical and scientific aspects of electrodeposition from supercritical fluids. We also discuss possible applications for supercritical fluid electrodeposition and suggest some key developments that are required to take the field to the next stage. PMID:24469309

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

    DOE PAGESBeta

    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

  17. 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

  18. 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

  19. HPLC Method for the Simultaneous Determination of Ten Annonaceous Acetogenins after Supercritical Fluid CO2 Extraction

    PubMed Central

    Yang, Haijun; Zhang, Ning; Zeng, Qingqi; Yu, Qiping; Ke, Shihuai; Li, Xiang

    2010-01-01

    Annonaceous acetogenins (ACGs) isolated from Annonaceae plants exhibited a broad range of biological bioactivities such as cytotoxic, antitumoral, antiparasitic, pesticidal and immunosuppresive activities. However, their structures were liable to change at more than 60°C and their extraction yields were low using traditional organic solvent extraction. In the present study, all samples from Annona genus plant seeds were extracted by supercritical carbon dioxide under optimized conditions and a high-performance liquid chromatography (HPLC) method was established for simultaneously determining ten ACGs. All of the ten compounds were simultaneously separated on reversed-phase C18 column (250 mm × 4.6 mm, 5 μm) with the column temperature at 30°C. The mobile phase was composed of (A) methanol and (B) distilled water, the flow rate was 1.0 ml/min and the detection wavelength was set at 220 nm. All calibration curves showed good linear regression (γ>0.9995) within the test range. The established method showed good precision and accuracy with overall intra-day and inter-day variations of 0.99-2.56% and 1.93-3.65%, respectively, and overall recoveries of 95.16-105.01% for the ten compounds analyzed. The established method can be applied to evaluate the intrinsic quality of Annonaceae plant seeds. The determination results recover the content-variation regularities of various ACGs in different species, which are helpful to choose the good-quality Annonaceae plant seeds for anticancer lead compound discovery. PMID:23675194

  20. ANALYSIS OF FLAVOR COMPOUNDS FROM MICROWAVE POPCORN USING SUPERCRITICAL FLUID CO2 FOLLOWED BY DYNAMIC/STATIC HEADSPACE TECHNIQUES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dynamic headspace purge (DHP) analysis was used to observe volatile compounds from freshly popped commercial flavored and non-flavored microwave popcorn. The obtained results were compared with supercritical fluid extraction (SFE) followed by DHP. The sensitivity of the latter method (SFE-DHP), in...

  1. Pulsed laser ablation plasmas generated in CO2 under high-pressure conditions up to supercritical fluid

    NASA Astrophysics Data System (ADS)

    Kato, Toru; Stauss, Sven; Kato, Satoshi; Urabe, Keiichiro; Baba, Motoyoshi; Suemoto, Tohru; Terashima, Kazuo

    2012-11-01

    Pulsed laser ablation of solids in supercritical media has a large potential for nanomaterials fabrication. We investigated plasmas generated by pulsed laser ablation of Ni targets in CO2 at pressures ranging from 0.1 to 16 MPa at 304.5 K. Plasma species were characterized by optical emission spectroscopy, and the evolution of cavitation bubbles and shockwaves were observed by time-resolved shadowgraph imaging. Ni and O atomic emissions decreased with increasing gas pressure; however, near the critical point the intensities reached local maxima, probably due to the enhancement of the plasma excitation and effective quenching resulting from the large density fluctuation.

  2. 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

  3. 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

  4. 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.

  5. Applications of supercritical fluids.

    PubMed

    Brunner, Gerd

    2010-01-01

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

  6. 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

  7. 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

  8. 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.

  9. Separation of biomolecules using supercritical fluid extraction.

    PubMed

    Lucien, F P; Liong, K K; Cotton, N J; Macnaughton, S J; Foster, N R

    1993-01-01

    Supercritical fluids are increasingly being used as a replacement for more conventional organic solvents in the extraction of biomolecules from a range of matrices. Supercritical fluid extraction of essential fatty acids from fish oils is discussed. Supercritical CO2 was used to fractionate two fatty acids, EPA and DHA from fish oil ethyl esters. EPA and DHA were obtained with a purity of 58% and 67% respectively from Sardine oil with an original composition of 17% and 12%. PMID:7763846

  10. Biofilm enhanced subsurface sequestration of supercritical CO2

    NASA Astrophysics Data System (ADS)

    Mitchell, A. C.; Phillips, A.; Hiebert, R.; Gerlach, R.; Kaszuba, J.; Cunningham, A.

    2007-12-01

    In order to develop subsurface CO2 storage as a viable engineered mechanism to reduce concentrations of atmospheric CO2, any potential ¡°leakage¡± of injected supercritical CO2 (scCO2) from the ground to the atmosphere must be reduced. Here, we investigate the utility of biofilms, which are microorganism assemblages firmly attached to a surface, as a means of reducing scCO2 leakage. Firstly, experiments were performed to test whether biofilms were more resilient than planctonic cells to scCO2. Bacillus mojavensis biofilms were grown on a sand support matrix in scCO2 extractor cartridges at 30°C. B. mojavensis was also grown under suspended planctonic conditions in the same media overnight and aliquots were decanted into scCO2 extractor cartridges. Biofilm and suspended B. mojavensis samples were processed on a Supercritical Fluid Extractor with pressurization to 2000 psi at 35°C, and a 20 minute flow of scCO2. Suspended growth samples revealed a 3 log reduction in cell viability while biofilm only showed a 1 log reduction, demonstrating that B. mojavensis biofilms are more resilient than planctonic cells to scCO2. Protective extra cellular polymeric substances which make up the biofilm matrix likely provide a protective barrier against scCO2. Secondly, the ability of biofilms to grow under high pressure and reduce the permeability of porous geological matrices was investigated using a unique high pressure (8.9MPa), moderate temperature (¡Ý 32°C) flow reactor containing 40 millidarcy Berea sandstone cores. The flow reactor was inoculated with the biofilm forming organism Shewanella fridgidimarina. Electron microscopy of the rock core revealed substantial biofilm accumulation in rock pores which resulted in <99% reduction in core permeability. Permeability did not increase in response to starvation and scCO2 challenges. Viable population assays of organisms in the effluent indicated survival of the microorganisms following scCO2 challenges of <71h and

  11. 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.

  12. 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. PMID:27082277

  13. 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.

  14. 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.

  15. 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.

  16. Electrochemistry in supercritical fluids.

    PubMed

    Branch, Jack A; Bartlett, Philip N

    2015-12-28

    A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide-acetonitrile and supercritical HFCs. PMID:26574527

  17. 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

  18. 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

  19. Homopolymers and Micelles in Supercritical CO2 : a SANS Study

    NASA Astrophysics Data System (ADS)

    Chillura-Martino, D.; McClain, J. B.; Canelas, D.; Betts, D.; Samulski, E. T.; Desimone, J. M.; Wignall, G. D.; Londono, J. D.; Triolo, R.

    1996-03-01

    Supercritical Carbon Dioxide (SC-CO_2) is becoming an attractive alternative to the liquid solvents traditionally used as polymerization media. We have applied small-angle neutron scattering (SANS) to characterize homopolymers and micellar systems in SC-CO_2. Although polymerizations are carried out at high pressures, the penetrating power of the neutron beam means that typical cell windows are virtually transparent. Homopolymers studied include polyfluoro-octyl acrylate (PFOA), hexafluoro-polypropylene oxide and Polydimethyl-siloxane. Also, copolymers of amphiphilic character in CO_2, were characterized via SANS. Systems studied were PFOA-polystyrene diblocks and PFOA-polyethyleneoxide (PFOA-PEO) graft copolymers, which swell as the CO2 medium is saturated with water. This work illustrates the utility of SANS to measure molecular dimensions, thermodynamic variables, molecular weights, micelle structures etc. in supercritical CO_2.

  20. 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.

  1. QENS from polymeric micelles in supercritical CO2

    NASA Astrophysics Data System (ADS)

    Triolo, R.; Arrighi, V.; Triolo, A.; Migliardo, P.; Magazù, S.; McClain, J. B.; Betts, D.; DeSimone, J. M.; Middendorf, H. D.

    2000-04-01

    We report QENS measurements from PS-b-PFOA aggregates in supercritical CO2. These consist of dense cores of CO2-insoluble polystyrene surrounded by a `corona' of PFOA surfactant molecules whose CO2-philic groups interface with supercritical CO2. Lineshapes are dominated by localized diffusive modes and segmental dynamics of the anchored, finite-length PFOA chains. For Q˜0.6 Å-1, we obtain effective diffusion coefficients of ≈0.8×10-6 cm2/sec. At higher Q, a single component is not sufficient as shown by excess intensity on the flanks. For Q>1.5 Å-1, the wings reflect contributions due to a distribution of faster, more localized chain modes.

  2. Investigations of supercritical CO2 Rankine cycles for geothermal power plants

    SciTech Connect

    Sabau, Adrian S; Yin, Hebi; Qualls, A L; McFarlane, Joanna

    2011-01-01

    Supercritical CO2 Rankine cycles are investigated for geothermal power plants. The system of equations that describe the thermodynamic cycle is solved using a Newton-Rhapson method. This approach allows a high computational efficiency of the model when thermophysical properties of the working fluid depend strongly on the temperature and pressure. Numerical simulation results are presented for different cycle configurations in order to assess the influences of heat source temperature, waste heat rejection temperatures and internal heat exchanger design on cycle efficiency. The results show that thermodynamic cycle efficiencies above 10% can be attained with the supercritical brayton cycle while lower efficiencies can be attained with the transcritical CO2 Rankine cycle.

  3. Metal extraction from the artificially contaminated soil using supercritical CO2 with mixed ligands.

    PubMed

    Park, Kwangheon; Lee, Jeongken; Sung, Jinhyun

    2013-04-01

    Supercritical fluids have good penetrating power with a high capacity to dissolve certain solutes in the fluid itself, making it applicable for soil cleaning. Supercritical CO2 along with mixed ligands has been used for cleaning artificially contaminated soil. The extraction of metal from the soil was successful, and the molar ratio of ligands to the extracted metal was as low as 3. Complicated structures with a large surface area of the real soil seemed to cause the lower efficiency. Reduced efficiency was also observed over time after the sample preparation, indicating the possibility of chemisorption of the metal ion onto the soil. The use of supercritical CO2 with dissolved mixed ligands was sufficient to extract metal from the soil. PMID:23347618

  4. 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.

  5. 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...

  6. 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.

  7. 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.

  8. 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.

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

    Energy Science and Technology Software Center (ESTSC)

    2012-09-12

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

  10. Supercritical fluid extraction in natural products analyses.

    PubMed

    Nahar, Lutfun; Sarker, Satyajit D

    2012-01-01

    Supercritical fluids (SCFs) are increasingly replacing the organic solvents, e.g., n-hexane, chloroform, dichloromethane, or methanol, that are conventionally used in industrial extraction, purification, and recrystallization operations because of regulatory and environmental pressures on hydrocarbon and ozone-depleting emissions. In natural products extraction and isolation, supercritical fluid extraction (SFE), especially employing supercritical CO(2), has become a popular choice. Sophisticated modern technologies allow precise regulation of changes in temperature and pressure, and thus manipulation of solvating property of the SCF, which helps the extraction of natural products of a wide range of polarities. This chapter deals mainly with the application of the SFE technology in the natural products extraction and isolation, and outlines various methodologies with specific examples. PMID:22367893

  11. 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.)

  12. 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.

  13. 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

  14. 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.

  15. Supercritical CO2 extraction and purification of compounds with antioxidant activity.

    PubMed

    Díaz-Reinoso, Beatriz; Moure, Andrés; Domínguez, Herminia; Parajó, Juan Carlos

    2006-04-01

    Supercritical fluid extraction (SCFE), based on the utilization of a fluid under supercritical conditions, is a technology suitable for extraction and purification of a variety of compounds, particularly those that have low volatility and/or are susceptible to thermal degradation. The interest in SCFE is promoted by legal limitations of conventional solvents for food and pharmaceutical uses. The physicochemical properties of supercritical CO2 (higher diffusivity, lower viscosity, and lower surface tension than conventional solvents) facilitate mass transfer and allow an environmentally friendly operation. This article presents a comprehensive compilation of data on the supercritical CO2 extraction of antioxidant compounds from vegetal materials, with particular attention to those of a phenolic nature. Aspects concerning the supercritical operation for extraction and fractionation of antioxidants compounds are considered, including equilibrium solubility of pure compounds and effects of the operational conditions on the antioxidant activity of isolated fractions. The data are compared to those reported for synthetic antioxidants and natural extracts obtained by conventional solvent extraction from vegetal matrices. PMID:16569029

  16. Modification of SiO2 nanowires with metallic nanocrystals from supercritical CO2.

    PubMed

    Ye, Xiang-Rong; Zhang, Hai-Feng; Lin, Yuehe; Wang, Lai-Sheng; Wai, Chien M

    2004-01-01

    Through hydrogen reduction of metal precursors in supercritical CO2, Cu, and Pd, nanocrystals were deposited onto SiO2 nanowires to form different types of nanostructured materials, including nanocrystal-nanowire, spherical aggregation-nanowire, shell-nanowire composites, and "mesoporous" metals supported by the framework of nanowires. This supercritical fluid deposition technique is an attractive approach for modifying nanowires because of its generality and simplicity; the modified nanowires could be useful as catalysts and for further fabrication of multifunctional composites. PMID:15112546

  17. 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

  18. Solvation of Esters and Ketones in Supercritical CO2.

    PubMed

    Kajiya, Daisuke; Imanishi, Masayoshi; Saitow, Ken-ichi

    2016-02-01

    Vibrational Raman spectra for the C═O stretching modes of three esters with different functional groups (methyl, a single phenyl, and two phenyl groups) were measured in supercritical carbon dioxide (scCO2). The results were compared with Raman spectra for three ketones involving the same functional groups, measured at the same thermodynamic states in scCO2. The peak frequencies of the Raman spectra of these six solute molecules were analyzed by decomposition into the attractive and repulsive energy components, based on the perturbed hard-sphere theory. For all solute molecules, the attractive energy is greater than the repulsive energy. In particular, a significant difference in the attractive energies of the ester-CO2 and ketone-CO2 systems was observed when the methyl group is attached to the ester or ketone. This difference was significantly reduced in the solute systems with a single phenyl group and was completely absent in those with two phenyl groups. The optimized structures among the solutes and CO2 molecules based on quantum chemical calculations indicate that greater attractive energy is obtained for a system where the oxygen atom of the ester is solvated by CO2 molecules. PMID:26741296

  19. 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

  20. Supercritical Fluid Reactions for Coal Processing

    SciTech Connect

    Eckert, Charles A

    1997-07-01

    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 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. Kinetic data have been previously collected for pure CO2 at 40C and pressures between the critical pressure of CO2 (73.8 bar) and 216 bar. These data support the theory of local density enhancements suggested in the literature. Data taken at 50C and pressures ranging from 70 bar to 195 bar are currently reported; they do not exhibit the molecular clustering evident closer to the critical temperature. The data taken at 40C are now being used to construct mathematical forms which can model these pressure-induced kinetic changes. One promising avenue of investigation involves treating the supercritical medium as a dense gas, which allows a kinetic model based on high reference pressure fugacity coefficients to be derived.

  1. QENS from polymer aggregates in supercritical CO 2

    NASA Astrophysics Data System (ADS)

    Triolo, R.; Arrighi, V.; Triolo, A.; Migliardo, P.; Magazù, S.; McClain, J. B.; Betts, D.; DeSimone, J. M.; Middendorf, H. D.

    2000-03-01

    We report QENS measurements from PS-b-PFOA aggregates in supercritical CO 2. Line shapes are dominated by localized diffusive modes and segmental dynamics of the anchored, finite-length PFOA chains. For Q⩽0.6 Å -1, we obtain effective diffusion coefficients of ≅0.8 10 -6 cm 2/s. At higher Q, a single component is not sufficient as shown by excess intensity on the flanks. For Q⩾1.5 Å -1, the wings reflect contributions due to a distribution of faster, more localized chain modes.

  2. 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.

  3. Surface Studies of HSLA Steel after Electrochemical Corrosion in Supercritical CO2-H2O Environment

    SciTech Connect

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

    2011-10-01

    In aqueous phase saturated with CO2, X-65 sample underwent general corrosion with formation of FeCO3. In supercritical CO2 containing water phase, two major regions are present on the sample surface after the EIS experiment. One region covered with corrosion products identified as FeCO3 and the other containing Fe, oxygen, and carbon-rich islands embedded in metal matrix identified as {alpha}-Fe. Precipitation of FeCO3 from Fe2+ and CO3 2- is responsible for formation of passive layer in oxygen-deficient, CO2 rich aqueous environment. Mechanisms of corrosion degradation occurring in supercritical CO2 as a function. Transport of supercritical CO{sub 2} is a critical element for carbon capture from fossil fuel power plants and underground sequestration. Although acceptable levels of water in supercritical CO{sub 2} (up to {approx} 5 x 10{sup -4}g/dm{sup 3}) have been established, their effects on the corrosion resistance of pipeline steels are not fully known. Moreover, the presence of SO{sub 2}, O{sub 2} impurities in addition to the water can make the fluid more corrosive and, therefore, more detrimental to service materials. Also, in this case, limited data are available on materials performance of carbon steels. to advance this knowledge, other service alloys are being investigated in the high pressure high temperature cell containing impure CO{sub 2} fluids using reliable non-destructive in-situ electrochemical methods. The electrochemical results are being augmented by a number of surface analyses of the corroded surfaces.

  4. 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.

  5. High Resolution X-ray CMT Imaging of Supercritical CO2 in Porous Media: Experimental Challenges, Solutions, and Results

    NASA Astrophysics Data System (ADS)

    Herring, A. L.; Andersson, L.; Newell, D. L.; Carey, J. W.; Wildenschild, D.

    2013-12-01

    Geologic carbon dioxide (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. Capillary trapping of supercritical CO2 (scCO2), wherein the CO2 is held within the pore structure of the geologic matrix by capillary forces, is a more secure form of subsurface storage than structural trapping, which relies on an impermeable caprock to contain the buoyant CO2 plume. To understand the multiphase physics of CO2 transport, and to subsequently produce quantitative estimates of potential CO2 capillary trapping, it is necessary to study field, core, and pore-scale processes. X-ray computed microtomography (x-ray CMT) allows for three-dimensional (3D) in-situ visualization of fluid phases within and the physical structure of a porous medium at the pore-scale. We have designed and built a mobile experimental set-up capable of running at pressures up to 2000 PSI and temperatures up to 50°C, made with materials that are compatible with corrosive fluids. Our experimental procedure includes pressurizing, mixing, and separating fluids; and subsequently running immiscible drainage and imbibition flow experiments with brine and supercritical CO2. With this set-up and procedure, we successfully conducted a brine-scCO2 drainage experiment in Bentheimer sandstone at 1200 PSI and 36°C, and confirmed and quantified CO2 flow in the sandstone core via synchrotron-based x-ray CMT with a resolution of 4.65 μm at the Advanced Photon Source at Argonne National Laboratory. We have proven that we can observe, on a pore-scale basis, the movement of supercritical CO2 within a porous media. The properties of supercritical CO2 (e.g. viscosity, density, interfacial tension and solubility in brine) vary significantly with changes in pressure and temperature; consequently, precise

  6. 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.

  7. Assessment of supercritical fluids for drug analysis.

    PubMed

    Messer, D C; Taylor, L T; Moore, W N; Weiser, W E

    1993-12-01

    Supercritical fluid (SF) CO2 is receiving a great deal of interest in the scientific and engineering community as a replacement for toxic organic solvents. Analytical chemists employ large quantities of organic solvents during preparation of the sample for analysis. The application of SF extraction with CO2 and modified CO2 to the isolation of active drug components and metabolites from various pharmaceutical and biological matrices is reviewed. Studies are described that deal with spiked drugs in animal feed, residual solvent in drug formulations, and active ingredients in over-the-counter products. The experimental challenges to implementing this technology for trace analysis are discussed. While much of the impetus for working with SFs is prompted by regulatory issues, it would appear that SFs afford the analyst a better-cheaper-faster-safer way of performing drug analysis. PMID:8122298

  8. 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

  9. 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).

  10. MALEIC ANHYDRIDE HYDROGENATION OF PD/AL2O3 CATALYST UNDER SUPERCRITICAL CO2 MEDIUM

    EPA Science Inventory

    Hydrogenation of maleic anhydride (MA) to either y-butyrolactone of succinic anhydride over simple Pd/Al2O3 impregnated catalyst in supercritical CO2 medium has been studied at different temperatures and pressures. A comparison of the supercritical CO2 medium reaction with the c...

  11. 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.

  12. In situ infrared spectroscopic study of forsterite carbonation in wet supercritical CO2.

    PubMed

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

    2011-07-15

    Carbonation reactions are central to the prospect of CO(2) trapping by mineralization in geologic reservoirs. In contrast to the relevant aqueous-mediated reactions, little is known about the propensity for carbonation in the key partner fluid: supercritical carbon dioxide containing dissolved water ("wet" scCO(2)). We employed in situ mid-infrared spectroscopy to follow the reaction of a model silicate mineral (forsterite, Mg(2)SiO(4)) for 24 h with wet scCO(2) at 50 °C and 180 atm. The results show a dramatic dependence of reactivity on water concentration and the presence of liquid water on the forsterite particles. Exposure to neat scCO(2) showed no detectable carbonation reaction. At 47% and 81% water saturation, an Ångstrom-thick liquid-like water film was detected on the forsterite particles and less than 1% of the forsterite transformed. Most of the reaction occurred within the first 3 h of exposure to the fluid. In experiments at 95% saturation and with an excess of water (36% above water saturation), a nanometer-thick water film was detected, and the carbonation reaction proceeded continuously with approximately 2% and 10% conversion, respectively. Our collective results suggest constitutive links between water concentration, water film formation, reaction rate and extent, and reaction products in wet scCO(2). PMID:21699182

  13. 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. PMID:17966976

  14. 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.

  15. 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.

  16. An environmentally friendly approach for contaminants removal using supercritical CO2 for remanufacturing industry

    NASA Astrophysics Data System (ADS)

    Liu, Wei-wei; Zhang, Bin; Li, Yan-zeng; He, Yan-ming; Zhang, Hong-chao

    2014-02-01

    The cleaning technology plays an important role in product quality during the remanufacturing processing. Remanufacturing cleaning is among the most demanding steps and is a particularly essential process in remanufacturing. In the meantime, remanufacturing cleaning is often the main source of pollution in the remanufacturing process. During the past decades, supercritical fluids due to their unique properties gained an increasingly attention in many cleaning industries. The supercritical carbon dioxide as a novel cleaning technology for remanufacturing cleaning process is discussed, which can realize cleaning and drying at the same time, promoting a greener solution for remanufacturing industry. In this paper, we reported the experimental results of the effect of some operating parameters. The CO2 at different operating pressures, temperatures and residence time was made to continuously flowing over this. The decontamination rate and amount were monitored and compared. The obtained results show that the optimum parameters were operating temperature and pressure of 60 °C and 20 MPa respectively, to have the highest decontamination rate value at the investigated experimental conditions. In additon, the success of supercritical CO2 cleaning effectively promotes the research for next-generation cleaning methods for remanufacturing industry.

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    In Carbon dioxide Capture and Storage (CCS), the monitoring of injected CO2 is critical for (1) predicting the risk of CO2 leakage from storage reservoirs, (2) reducing the cost and increasing the efficiency of CO2 injection, (3) reducing the risk of injection-induced seismicity, and (4) reducing the risk of creating new fractures, and hence opening new flow paths in an otherwise low-permeability capping formation. In seismic approaches, the change in seismic velocity derived from time-lapse seismic surveys can be used to evaluate the distribution of injected CO2, because the P-wave velocity decreases dramatically as the CO2 starts to invade the pore space of a rock initially saturated with brine. However, the rate of change decreases considerably when the saturation of CO2 reaches a value of 20% making the estimation of higher saturations a difficult task. Usefulness of resistivity to estimate CO2 saturation in wide porosity range was presented from laboratory experiments; the resistivity value increases with CO2 saturation even in higher saturation range. However, we cannot characterize the CO2 distribution within pore space only from laboratory experiments. The detailed investigation is needed to generate quantitative description of CO2 migration in porous media and to construct relationship between CO2 saturation and field-derived properties (i.e., seismic velocity and electric resistivity) for the quantitative monitoring of injected CO2. In this study, we apply two-phase lattice Boltzmann method (LBM) to the digital rock models, in order to investigate (a) seismic velocity and (b) electric resistivity under several pressure-temperature (PT) conditions. The simulation study has been compared with laboratory experiments. LBM is one of the computational fluid dynamics methods. In this algorithm, fluid as well as supercritical CO2 is represented as aggregation of imaginary fluid particles, then the movement of microscopic and discretized particles is calculated

  19. 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

  20. Lipidomics by Supercritical Fluid Chromatography.

    PubMed

    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

  1. Diffusion of gaseous and supercritical CO2 through polycarbonate

    NASA Astrophysics Data System (ADS)

    Goodman, Michael; Ozisik, Rahmi

    2013-03-01

    The design of polymeric materials for applications such as separation membranes and nanostructured foams requires prediction of gas transport properties under a wide range of pressures. In the current study, transport of CO2 both in gaseous and supercritical state through samples of polycarbonate at 51 °C and pressures from 15 to 2000 psi was measured using an asymptotic time lag apparatus. Through volumetric calibration, the traditional analysis was extended to yield permeability (P) and solubility (S), in addition to the usual asymptotic diffusivity (Da). Nonlinear least squares fitting to a truncated series solution then provided an alternative measurement of the (transient) diffusivity (Dt), as well as the surface concentration (Co) of adsorbed gas. At 1 atm, Da and Dt were within a factor of 2 from selected handbook values; and with increasing pressure, both exhibited an overall downward trend, consistent with other studies, but an unexpected dropoff occurred between 1350 and 1500 psi. As expected, Co showed an overall increase with pressure, but as with P and S, displayed a peculiar drop between 1350 and 1500 psi. Measurement of Co in polycarbonate has never been done before and constitutes a novel feature of this study. This work was partially supported by DUE-1003574.

  2. 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.

  3. 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

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. 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.

  11. Relative permeability hysteresis and capillary trapping characteristics of supercritical CO2/brine systems: An experimental study at reservoir conditions

    NASA Astrophysics Data System (ADS)

    Akbarabadi, Morteza; Piri, Mohammad

    2013-02-01

    We present the results of an experimental study on the effects of hysteresis on capillary trapping and relative permeability of CO2/brine systems at reservoir conditions. We performed thirty unsteady- and steady-state drainage and imbibition full-recirculation flow experiments in three different sandstone rock samples, low- and high-permeability Berea and Nugget sandstones. The experiments were carried out at various flow rates with both supercritical CO2 (scCO2)/brine and gaseous CO2 (gCO2)/brine fluid systems. The unsteady-state experiments were carried out with a wide range of flow rates to establish a broad range of initial brine saturations (Swi). This allowed investigation of the sensitivity of residual trapped CO2 saturation (S) to changes in Swi. The values were successfully compared with those available in the literature. For a given Swi, the trapped scCO2 saturation was less than that of gCO2 in the same sample. This was attributed to brine being less wetting in the presence of scCO2 than in the presence of gCO2. Post-imbibition dissolution of trapped CO2 and formation of dissolution front was also investigated. During the steady-state experiments, scCO2 and brine were co-injected with monotonically increasing or decreasing fractional flows to perform drainage and imbibition processes. We carried out seven sets of steady-state flow tests with various trajectories generating a comprehensive group of relative permeability hysteresis curves. The scanning curves revealed distinct features with potentially important implications for storage of scCO2 in geological formations. For both series of experiments, the ratio of S to initial CO2 saturation (1- Swi) was found to be much higher for low initial CO2 saturations. The results indicate that very promising fractions (about 49 to 83%) of the initial CO2 saturation can be stored through capillary trapping.

  12. 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

  13. 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

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

    PubMed

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

    2011-05-19

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

  15. 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

  16. SPECTROSCOPY, MODELING AND COMPUTATION OF METAL CHELATE SOLUBILITY IN SUPERCRITICAL CO2

    EPA Science Inventory

    The objectives of this project are to gain a fundamental understanding of the solubility and stability of metal chelates in supercritical CO2. Extraction with CO2 is a excellent way to remove organic compounds from soils, sludges and aqueous solutions and recent research has demo...

  17. Identification of fragile microscopic structures during mineral transformations in wet supercritical CO2.

    PubMed

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

    2013-04-01

    This study examines the nature of highly fragile reaction products that form in low water content supercritical carbon dioxide (scCO2) using a combination of focus ion beam/scanning electron microscopy, confocal Raman spectroscopy, helium ion microscopy (HeIM), and transmission electron microscopy (TEM). HeIM images show these precipitates are fragile rosettes. Using the TEM revealed details on the interfacial structure between the newly formed surface precipitates and the underlying initial solid phases. Detailed microscopy analysis revealed that growth of the precipitates either followed a tip growth mechanism, with precipitates forming directly on the forsterite surface if the initial solid was nonporous (natural forsterite) or growth from the surface of the precipitates, where fluid was conducted through the porous (nanoforsterite) agglomerates to the growth center. Identification of the mechanism of formation of hydrated/hydroxylated magnesium carbonate compound phases is a key factor in unraveling the impact of water recycling on mineral reactivity in low water content scCO2 solutions, which has received a great deal of attention as a result of the potential for CO2 to act as an atmospheric greenhouse gas. Techniques used here to examine these fragile structures are also used to examine a wide range of fragile material surfaces. PMID:23388324

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

    PubMed

    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, ∂n/∂cP,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 ∂n/∂cP,T presents a critical enhancement similar to heat capacity. PMID:27059567

  19. 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.

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

    PubMed

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

    2010-12-01

    The corrosion property of carbon steel was evaluated using an autoclave under CO(2)-saturated water phase and water-saturated CO(2) phase with impurities (O(2) and SO(2)) at 80 bar CO(2) and 50 °C to simulate the condition of CO(2) transmission pipeline in the carbon capture and storage (CCS) applications. The results showed that the corrosion rate of carbon steel in CO(2)-saturated water was very high and it increased with adding O(2) in the system due to the inhibition effect of O(2) on the formation of protective FeCO(3). It is noteworthy that corrosion took place in the water-saturated CO(2) phase under supercritical condition when no free water is present. The addition of O(2) increased the corrosion rates of carbon steel in water-saturated CO(2) phase. The addition of 0.8 bar SO(2) (1%) in the gas phase dramatically increased the corrosion rate of carbon steel from 0.38 to 5.6 mm/y. This then increased to more than 7 mm/y with addition of both O(2) and SO(2). SO(2) can promote the formation of iron sulfite hydrate (FeSO(3)·3H(2)O) on the steel surface which is less protective than iron carbonate (FeCO(3)), and it is further oxidized to become FeSO(4) and FeOOH when O(2) is present with SO(2) in the CO(2)-rich phase. The corrosion rates of 13Cr steel were very low compared with carbon steel in CO(2)-saturated water environments with O(2), whereas it was as high as carbon steel in a water-saturated CO(2) phase with O(2) and SO(2). PMID:21049923

  1. 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

  2. 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.

  3. 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.

  4. Mechanism of extreme ultraviolet photoresist development with a supercritical CO2 compatible salt.

    PubMed

    Zweber, Amy E; Wagner, Mark; DeYoung, James; Carbonell, Ruben G

    2009-06-01

    The mechanism of developing an extreme ultraviolet (EUV) commercial photoresist with supercritical carbon dioxide (scCO2) and a CO2 compatible salt (CCS) solution was studied. The cloud point of CCS in CO2 and the pressure at which the photoresist dissolves in CCS/scCO2 were determined for temperatures between 35 and 50 degrees C. For this temperature range, it was found that the CCS cloud point ranges between 11.2 and 16.1 MPa, while the photoresist dissolution point ranges from 15.5 to 21.3 MPa. The kinetics of the CCS/scCO2 development was modeled using a simplified rate equation, where the rate-limiting steps were photoresist dissolution and mass transfer. The effects of temperature, mass transfer, pressure, and CCS concentration on photoresist removal rate were further explored experimentally using a high-pressure quartz crystal microbalance (QCM). Increasing temperature (35-50 degrees C) at a constant fluid density of 0.896 g/mL was found to increase the removal rate following an Arrhenius behavior with a photoresist dissolution energy of activation, Ea, equal to 79.0 kJ/mol. The removal was zero order in CCS concentration, signifying photoresist phase transfer, photoresist mass transfer, or both were rate limiting. Mass transfer studies showed that circulation enhanced the photoresist removal rate, but that the mass transfer coefficient was independent of temperature from 35 degrees C to 50 degrees C. In pressure studies, increasing pressure (27.6-34.5 MPa) at a constant temperature of 40 degrees C increased the removal rate by enhancing the fluid density, but at 50 degrees C increasing pressure had little effect on the removal rate. When the total CCS concentration was in large global excess over the number of Bronsted acid groups in the polymer (2400:1 at 5 mM CCS concentration), the mass of photoresist removed varied linearly with time. At lower CCS concentrations but still in global excess of the number of Bronsted acid groups, the photoresist removal

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

    PubMed

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

    2015-01-01

    CO2 geosequestration in deep aquifers requires the displacement of water (wetting phase) from the porous media by supercritical CO2 (nonwetting phase). However, the interfacial instabilities, such as viscous and capillary fingerings, develop during the drainage displacement. Moreover, the burstlike Haines jump often occurs under conditions of low capillary number. To study these interfacial instabilities, we performed lattice Boltzmann simulations of CO2-water drainage displacement in a 3D synthetic granular rock model at a fixed viscosity ratio and at various capillary numbers. The capillary numbers are varied by changing injection pressure, which induces changes in flow velocity. It was observed that the viscous fingering was dominant at high injection pressures, whereas the crossover of viscous and capillary fingerings was observed, accompanied by Haines jumps, at low injection pressures. The Haines jumps flowing forward caused a significant drop of CO2 saturation, whereas Haines jumps flowing backward caused an increase of CO2 saturation (per injection depth). We demonstrated that the pore-scale Haines jumps remarkably influenced the flow path and therefore equilibrium CO2 saturation in crossover domain, which is in turn related to the storage efficiency in the field-scale geosequestration. The results can improve our understandings of the storage efficiency by the effects of pore-scale displacement phenomena. PMID:25427299

  6. 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

  7. 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 Alan; Rochau, Gary Eugene; 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.

  8. 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.

  9. In situ molecular spectroscopic evidence for CO2 intercalation into montmorillonite in supercritical carbon dioxide.

    PubMed

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

    2012-05-01

    The interaction of anhydrous supercritical CO(2) (scCO(2)) 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 CO(2) 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 scCO(2) conditions is due to CO(2) migration into the interlayer. Intercalated CO(2) molecules are rotationally constrained and do not appear to react with waters to form bicarbonate or carbonic acid. In contrast, CO(2) 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. PMID:22533894

  10. 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. PMID:25591369

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    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.

  12. 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.

  13. EMPIRICAL METHOD TO PREDICT SOLUBILITY IN SUPERCRITICAL FLUIDS

    EPA Science Inventory

    The ability to predict the solubility of analytes in supercritical fluids is important in understanding supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC). n SFE, an analyte must dissolve in the supercritical solvent before it can be extracted. n SF...

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

    PubMed

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

    2013-01-01

    Carbon sequestration in saline aquifers involves displacing brine from the pore space by supercritical CO(2) (scCO(2)). The displacement process is considered unstable due to the unfavorable viscosity ratio between the invading scCO(2) and the resident brine. The mechanisms that affect scCO(2)-water displacement under reservoir conditions (41 °C, 9 MPa) were investigated in a homogeneous micromodel. A large range of injection rates, expressed as the dimensionless capillary number (Ca), was studied in two sets of experiments: discontinuous-rate injection, where the micromodel was saturated with water before each injection rate was imposed, and continuous-rate injection, where the rate was increased after quasi-steady conditions were reached for a certain rate. For the discontinuous-rate experiments, capillary fingering and viscous fingering are the dominant mechanisms for low (logCa ≤ -6.61) and high injection rates (logCa ≥ -5.21), respectively. Crossover from capillary to viscous fingering was observed for logCa = -5.91 to -5.21, resulting in a large decrease in scCO(2) saturation. The discontinuous-rate experimental results confirmed the decrease in nonwetting fluid saturation during crossover from capillary to viscous fingering predicted by numerical simulations by Lenormand et al. (J. Fluid Mech.1988, 189, 165-187). Capillary fingering was the dominant mechanism for all injection rates in the continuous-rate experiment, resulting in monotonic increase in scCO(2) saturation. PMID:22676368

  15. 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.

  16. 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)

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  18. Mineral Carbonation in Wet Supercritical CO2: An in situ High-Pressure Magic Angle Spinning Nuclear Magnetic Resonance Study

    NASA Astrophysics Data System (ADS)

    Turcu, R. V.; Hoyt, D. H.; Sears, J. A.; Rosso, K. M.; Felmy, A. R.; Hu, J. Z.

    2011-12-01

    Understanding the mechanisms and kinetics of mineral carbonation reactions relevant to sequestering carbon dioxide as a supercritical fluid (scCO2) in geologic formations is crucial for accurately predicting long-term storage risks. In situ probes that provide molecular-level information at geologically relevant temperatures and pressures are highly desirable and challenging to develop. Magic angle spinning nuclear magnetic resonance (MAS NMR) is a powerful tool for obtaining detailed molecular structure and dynamics information of a system regardless whether the system is in a solid, a liquid, a gaseous, a supercritical state, or a mixture thereof. However, MAS NMR under scCO2 conditions has never been realized due to the tremendous technical difficulties of achieving and maintaining high pressure within a fast spinning MAS sample rotor. In this work, we report development of a unique high pressure MAS NMR capability capable of handling fluid pressure exceeding 170 bars and temperatures up to 80°C, and its application to mineral carbonation in scCO2 under geologically relevant temperatures and pressures. Mineral carbonation reactions of the magnesium silicate mineral forsterite and the magnesium hydroxide brucite reacted with scCO2 (up to 170 bar) and containing variable content of H2O (at, below, and above saturation in scCO2) were investigated at 50 to 70°C. In situ 13C MAS NMR spectra show peaks corresponding to the reactants, intermediates, and the magnesium carbonation products in a single spectrum. For example, Figure 1 shows the reaction dynamics, i.e., the formation and conversion of reaction intermediates, i.e., HCO3- and nesquehonite, to magnesite as a function of time at 70°C. This capability offers a significant advantage over traditional ex situ 13C MAS experiments on similar systems, where, for example, CO2 and HCO3- are not directly observable.

  19. 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

  20. 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.

  1. 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.

  2. High-resolution x-ray tomography imaging of supercritical CO2: Investigating capillary trapping under reservoir conditions and addressing wettability alteration

    NASA Astrophysics Data System (ADS)

    Andersson, L.; Herring, A. L.; Newell, D. L.; Carey, B.; Wildenschild, D.

    2013-12-01

    In geological carbon sequestration, CO2 is stored in a supercritical state in subsurface reservoirs. Deep saline aquifers are particularly attractive because of their abundance and potentially large storage volumes. Despite very broad research efforts there are still substantial uncertainties related to the effectiveness of the trapping processes controlling the permanent storage of CO2. After injection of CO2 the saline water (brine) will imbibe back and reoccupy the pore space as the buoyant CO2 moves upwards. Some of the CO2 will remain behind in a trapping mechanism known as capillary trapping that occurs as CO2 bubbles are isolated by the brine inside some of the pore space. The large-scale movement of the trapped CO2 within the brine is thereby prevented. Capillary trapping thus constitutes an important storage mechanism following CO2 injection until subsequent aqueous dissolution and precipitation of carbonate minerals depletes the reservoir of free-phase CO2. We present pressure-saturation curves derived from drainage and imbibition experiments with brine and supercritical CO2 at 1200 PSI and at 36°C for Bentheimer sandstone cores. We compare the supercritical CO2 experiments with ambient pressure and temperature experiments using water and air (supercritical CO2 proxy fluid) for Bentheimer sandstone. The pressure-saturation curves are accompanied with quantitative results on non-wetting phase saturation, topology and connectivity as determined from three-dimensional (3D) images. The 3D data with a resolution of 4.65 μm were derived from high-resolution synchrotron x-ray computed micro-tomography (CMT), collected at the GSECARS beam line 13-BM-D at the Advanced Photon Source, Argonne National Laboratory. Drainage and imbibition experiments, performed under ambient pressure and temperature conditions, indicate that the topology of the non-wetting phase after drainage correlates with the final trapping of the non-wetting phase, after imbibition. Pressure

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  4. 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.

  5. Bioanalytical applications using supercritical fluid techniques.

    PubMed

    Ríos, Angel; Zougagh, Mohammed; de Andrés, Fernando

    2010-01-01

    The bioanalytical applications of supercritical fluid techniques, such as supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC), are of increasing interest. The main role of these techniques is in the sample preparation and separation of biologically active compounds, particularly drugs and their metabolites, as well as endogenous compounds. An insight is given into the different types of extracting fluids and modifiers, detectors, stationary phases, mobile phases and collection strategies. A critical discussion is presented on the existing state of the art concerning the applications of SFC and SFE with a specific focus on its advantages and limitations in the bioanalytical field. New developments and the possibilities for routine work in the near future are also covered. PMID:21083113

  6. 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.

  7. Synthesis of higher diamondoids by pulsed laser ablation plasmas in supercritical CO2

    NASA Astrophysics Data System (ADS)

    Nakahara, Sho; Stauss, Sven; Kato, Toru; Sasaki, Takehiko; Terashima, Kazuo

    2011-06-01

    Pulsed laser ablation (wavelength 532 nm; fluence 18 J/cm2; pulse width 7 ns; repetition rate 10 Hz) of highly oriented pyrolytic graphite was conducted in adamantane-dissolved supercritical CO2 with and without cyclohexane as a cosolvent. Micro-Raman spectroscopy of the products revealed the presence of hydrocarbons possessing sp3-hybridized carbons similar to diamond structures. The synthesis of diamantane and other possible diamondoids consisting of up to 12 cages was confirmed by gas chromatography-mass spectrometry. Furthermore, gas chromatography-mass spectrometry measurements of samples before and after pyrolysis treatment indicate the synthesis of the most compact decamantane, namely, superadamantane. It is thought that oxidant species originating from CO2 during pulsed laser ablation might lead to the selective dissociation of C-H bonds, enabling the synthesis of low H/C ratio molecules. Therefore, laser ablation in supercritical CO2 is proposed as a practical method for synthesizing diamondoids.

  8. 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

  9. 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

  10. 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.

  11. Hydraulic fracture characterization resulting from low-viscosity fluid injection: Implications for CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Burbey, T. J.; Zhou, X.

    2013-12-01

    The initiation of hydraulic fractures during CO2 sequestration can be either engineered or induced unintentionally. Some fractures may be desirable such as horizontal fractures that can facilitate fluid injection and migration; whereas some fractures may be unfavorable if the fractures tend to extend vertically above a certain limit, thus creating a potential leaking condition. Historically, carbon dioxide as a liquefied gas has been used in oil and gas field stimulation since the early1960s because it eliminates formation damage and residual fluids. Carbon dioxide injection is considered to be one of the most effective technologies for improving oil recovery from hard-to-extract oil reserves because CO2 is effective in penetrating the formation due to its high diffusivity, while the rock associated with petroleum-containing formations is generally porous. However, low viscosity and high compressibility fluids such as CO2 exhibit different effects on the hydraulic fracture initiation/propagation behavior in comparison with high viscosity and low compressibility fluids. Laboratory tests show that viscous fluids tend to generate thick and planar cracks with few branches, while low viscosity fluids tend to generate narrow and wavelike cracks with many secondary branches. A numerical comparison between water and supercritical CO2-like fluid has been made to investigate the influence of fluids to fracture propagation behavior. Simulation results indicate that the pore pressure fields are very different for different pore fluids even when the initial field conditions and injection schemes (rate and time) are kept the same. Thin fluids with properties of supercritical CO2 will create relatively thin and much shorter fractures in comparison to fluids exhibiting properties of water under similar injection schemes. Two significant times are recognized during fracture propagation. One is the time at which a crack ceases opening, and he other is the time at which a crack

  12. Optical emission spectroscopy and shadowgraph imaging of pulsed laser plasmas generated in gaseous, liquid and supercritical CO2

    NASA Astrophysics Data System (ADS)

    Kato, Toru; Takizawa, Yoshihiko; Stauss, Sven; Baba, Motoyoshi; Suemoto, Tohru; Terashima, Kazuo

    2012-10-01

    Pulsed laser ablation (PLA) in liquids has attracted a lot of attention due to its potential for the synthesis of a wide range of nanomaterials. Contrary to PLA in vacuum, in liquids the plasma plume is confined due to the high density of the medium. This restricts the diffusion of active species and leads to rapid quenching, which limits particle growth. Compared to liquids, supercritical fluids (SCFs) possess superior transport properties and PLA in SCFs has been used for realizing chemical synthesis of nanomaterials such as diamondoids. We have investigated the dynamics of PLA (laser: Nd-YAG, wavelength 532 nm; pulse width 7 ns; frequency 10 Hz; target: carbon, nickel) in gaseous (0.1-6 MPa), liquid and supercritical CO2 (Tcrit: 304.1 K, Pcrit: 7.38 MPa). From shadowgraphs of PLA taken in gaseous, liquid and supercritical CO2, images of PLA in SCF showed characteristics similar to that of PLA in liquid. Compared to PLA in the gaseous and liquid states, optical emission spectra in SCF revealed enhanced interactions between plasma and solvent species, especially near the critical point. Owing to the high density fluctuation near the critical point, PLA in SCF is expected to lead to a better control of the synthesis of diamondoids and other nanomaterials.

  13. 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

  14. 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

  15. Supercritical fluid mixing in Diesel Engine Applications

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  16. 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

  17. 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.

  18. FINAL REPORT. MICELLE FORMATION AND SURFACE INTERACTIONS IN SUPERCRITICAL CO2: FUNDAMENTAL STUDIES FOR THE EXTRACTION OF ACTINIDES FROM CONTAMINATED SURFACES

    EPA Science Inventory

    The goal of this research was to build the fundamental understanding of microemulsion formation and mobility in supercritical CO2 necessary to develop an innovative extraction system for selectively removing metals (actinides) from contaminated surfaces. Supercritical CO2 has man...

  19. Applications of supercritical fluid extraction and chromatography in forensic science.

    PubMed

    Radcliffe, C; Maguire, K; Lockwood, B

    2000-07-01

    Supercritical fluid technology is a rapidly expanding analytical technique. Here we give a brief insight into the background of supercritical fluid technology and how supercritical fluid extraction and supercritical fluid chromatography work in analysis. The applications of these two techniques in forensic science are known to be important. The main area of forensic use of supercritical fluid technology is in the sample preparation and separation of drugs of abuse particularly opiates, cannabinoids, cocaine and sedatives. Supercritical fluid technology can be used for both time-of-death-related drug analysis and for obtaining information relating to long term drug abuse. We also give a review of the use of supercritical fluids in two other major forensic areas, fingerprinting and the extraction and separation of explosives from both bombing events and gunshot residues. Overall we show that supercritical fluid technology is fast becoming a major part of forensic investigations and that it is an invaluable analysis technique. PMID:10869681

  20. 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.

  1. Stable carbon isotope ratios as proxies for CO2 migration: An experimental approach with analogue fluids

    NASA Astrophysics Data System (ADS)

    Myrttinen, A.; Becker, V.; Mayer, B.; Barth, J. A.

    2012-12-01

    Stable carbon isotope ratios have proven to be highly sensitive tracers of CO2 migration in the subsurface, provided that the δ13C value of injected CO2 is distinct from that of baseline carbon in the reservoir and in shallow aquifers. This is of great importance for tracing the movement and the fate of injected CO2 in storage reservoirs where fluid and gas samples for chemical and isotope analyses can be obtained. One fundamental aspect that needs to be considered is carbon isotope fractionation between the various dissolved inorganic carbon (DIC) species and sub- or super-critical CO2. Such isotope fractionation may occur at various stages of CO2 migration including, the initial stages of injection during CO2 dissolution; during possible CO2 desiccation in pores; during CO2 migration within the reservoir or even during potential leakage into the near-surface environment. The magnitude and direction of carbon isotope fractionation (1000lnαDIC-CO2) between the DIC species and the injected CO2 depends highly on temperature and pH. At shallow depths, where temperatures are moderate and pH values are typically close to neutral, HCO3- is the dominant form of DIC. Carbon isotope fractionation between CO2 and DIC is therefore expected to reach ~ +10 ‰, resulting in a more positive δ13C value of DIC compared to that of the injected CO2. On the other hand, during injection, elevated temperatures and pH values of below 6 are usually observed. Here, H2CO3 is the dominant form of DIC and carbon isotope fractionation of close to -1 ‰ is expected. However, literature data on isotope fractionation values between H2CO3 and CO2 at temperatures above ˜ 60 °C are limited. In order to investigate the effects of pH and temperature on carbon isotope fractionation at various subsurface conditions, including elevated temperatures and pressures typical for CO2 reservoirs, laboratory experiments with analogue fluids were conducted within the framework of the CO2ISO-LABEL project

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  14. Supercritical fluid extraction and processing of foods

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Consumers are aware of the processing techniques used to manufacture food and health supplements and are concerned about the impact of those processes on their health and the environment. Processes that use supercritical fluids as an alternative to solvents that are used to extract nutrients and bio...

  15. 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

  16. 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

  17. Basalt Reactivity in the Presence of H2O-Saturated Supercritical CO2 Containing Gaseous Sulfur Compounds

    NASA Astrophysics Data System (ADS)

    Schaef, H. T.; McGrail, P.; Owen, A. T.

    2009-12-01

    Future impacts of climate change may be minimized by capture of emissions, primarily CO2 from fossil-fueled electric generating stations and subsequent sequestration in deep geologic formations. Injection of dry liquid CO2 into porous geologic reservoirs for long term storage is expected to eventually form a buoyant water-saturated bubble of supercritical fluid. Depending on purification processes and underground injection control regulations, the injected CO2 also could contain trace compounds associated with flue gas streams (SO2, N2, and O2). Once injected, the scCO2 will absorb water (1500 to 3000 ppmw) until becoming immobilized by reservoir trapping mechanisms. Reactivity of the water-bearing scCO2 with silicate minerals is relatively unknown and could have impacts on long term reservoir seal integrity and trapping by mineralization. To examine the reactivity of H2O-saturated scCO2, basalt experiments were conducted at pressures and temperatures relevant to geologic sequestration. Reaction products differed considerably depending on the gas mixtures used and type of basalt. In the presence of H2O-saturated CO2, the Newark Basin basalt reacted to produce secondary mineralization with needle-like morphologies and chemistries similar to aragonite. Exposing the same basalt to a CO2-H2S mixture (H2O saturated) produced two types of reaction products: carbonates in the form of small discrete nodules or needles and metallic-like circular areas similar in chemistry to pyrite and marcarsite. Tests conducted in the presence of CO2-SO2 produced the most extensive surface reaction products observed during the experiments. Some basalts were completely coated in white precipitate identified as a mixture of gypsum, sulfate bearing minerals (rozenite and melanterite), and a magnesium sulfate compound (MgSO4 ●5H2O). Hawaiian flow top basalts contained extensive reaction products including magnesium sulfate (MgSO4●6H2O), which formed on the large olivine crystals present

  18. 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

  19. 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

  20. 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

  1. 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.

  2. MICELLE FORMATION AND SURFACE INTERACTIONS IN SUPERCRITICAL CO2: FUNDAMENTAL STUDIES FOR THE EXTRACTION OF ACTINIDES FROM CONTAMINATED SURFACES

    EPA Science Inventory

    This research seeks to build the fundamental understanding of micelle formation and mobility in supercritical CO2, necessary to develop an innovative phase-transfer extraction system for selectively removing metals (actinides) from contaminated surfaces. We will extract metal ion...

  3. MICELLE FORMATION AND SURFACE INTERACTIONS IN SUPERCRITICAL CO2: FUNDAMENTAL STUDIES FOR THE EXTRACTION OF ACTINIDES FROM CONTAMINATED SURFACES

    EPA Science Inventory

    The goal of this research was to build a fundamental understanding of microemulsion formation and mobility in supercritical CO2 necessary to develop an innovative extraction system for selectively removing metals (actinides) from contaminated surfaces. The goals included (1) stud...

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

    DOE PAGESBeta

    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

  5. 3-D loaded scaffolds obtained by supercritical CO2 assisted process

    NASA Astrophysics Data System (ADS)

    Cardea, S.; Reverchon, E.

    2014-08-01

    In this work, a supercritical CO2 (SC-CO2) drying process for the formation of 3-D PVDF-HFP loaded scaffolds was tested. Experiments at pressures ranging between 150 and 250 bar and at temperatures ranging between 35 and 55°C were performed. The PVDF-HFP- acetone-ethanol solution at 15% w/w polymer was selected as the base case. The drug (amoxicillin) concentration was varied from 20 to 30% w/w with respect to PVDF-HFP. SC- CO2 drying process was confirmed to be a valid alternative to generate loaded structures; indeed, scaffolds characterized by nanometric networks (with mean pore diameter of about 300 nm) with a homogeneous drug distribution were obtained. Drug controlled release experiments were also performed and a quasi-zero order release kinetic was observed.

  6. SAXS investigation on aggregation phenomena in supercritical \\chem{CO2}

    NASA Astrophysics Data System (ADS)

    Celso, F. Lo; Triolo, A.; Triolo, F.; Donato, D. I.; Steinhart, M.; Kriechbaum, M.; Amenitsch, H.; Triolo, R.

    2002-06-01

    Synchrotron Small-Angle X-Ray scattering (SAXS) measurements on aggregate formation of a Polyvinyl acetate-b-Perfluoro octyl acrylate (PVAc-b-PFOA) block copolymer in supercritical CO{2} are here reported. Experiments were carried out for a series of different thermodynamic conditions, changing the solvent density by profiling both the pressure at constant temperature and the temperature at constant pressure. This block copolymer and in general fluorocarbon-hydrocarbon di-blocks form aggregates depending on the value of CO{2} density. A sharp transition between monomers dissolved as random coils and micelles characterized by a solvophilic shell and a solvophobic core occurs when the CO{2} density reaches a critical value. Results of critical micellization density (CMD) derived from pressure and temperature ramps experiment along with the comparison with previous SANS results are here reported to give additional experimental support to the solvent density-driven aggregation process.

  7. 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

  8. 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. PMID:21333587

  9. 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

  10. 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.

  11. 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.

    2013-01-01

    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.

  12. 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

  13. 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

  14. 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

  15. 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.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2005-10-01

    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.

  18. Characteristics of optical emission intensities and bubblelike phenomena induced by laser ablation in supercritical fluids

    NASA Astrophysics Data System (ADS)

    Takada, Noriharu; Machmudah, Siti; Goto, Hiroshi; Wahyudiono; Goto, Motonobu; Sasaki, Koichi

    2014-01-01

    We investigated the characteristics of laser ablation phenomena in supercritical fluids by optical emission and shadowgraph imaging. In comparison with laser ablation in liquid H2O, the optical emission of a laser ablation plasma produced in supercritical H2O had a longer lifetime and a larger transport length. It was found in supercritical CO2 that laser ablation plasmas with bright optical emissions were produced at a mass density of approximately 300 kg/m3. A clear correlation between the optical emission intensity and the density fluctuation was not observed in our experimental results, which were obtained in a regime deviated from the critical point. Bubblelike hollows were observed by shadowgraph imaging in both supercritical H2O and CO2. The dynamics of the bubblelike hollows were different from the dynamics of a cavitation bubble induced by laser ablation in a liquid medium but relatively similar to the dynamics of ambient gas in gas-phase laser ablation.

  19. A study of vortex breakdown in supercritical fluids

    NASA Astrophysics Data System (ADS)

    Crook, Loren C.

    The objective of this thesis is to evaluate the hydrodynamic stability theory of vortex breakdown by examining its presence in a swirling supercritical fluid jet. Supercritical fluids were chosen because they are technologically important, and because their strong density gradients near the critical point provide a self-excitable flow regime where hydrodynamic instabilities should be more easily identified. Computations were developed to provide flow conditions for experimental observation of vortex breakdown and to estimate hydrodynamic flow instabilities prior to testing. The RANS computations of an axial-plus-tangential air swirler were developed and verified as grid-independent and in agreement with experimental results reported in the literature. The computations also produced a correlation of momentum swirl number as a function of mass ratio (tangential/total) for estimating swirl number during experiments. Finally, the computations were extended to simulate supercritical CO2 in an axial-plus-tangential swirler that was compatible with the supercritical injection facility. Three mass flow ratio cases were investigated extensively: no-swirl (0%), low-swirl prior to breakdown (25%), and moderate swirl with breakdown (45%). (The three corresponding momentum swirl numbers for these mass flow ratios were 0.0, 0.30 and 0.80.) These three cases also served as the basis for the experimental portion of the work. Swirling supercritical fluid jets were observed in the injection facility using schlieren imaging for three separate swirl numbers. The Sobel method was used to locate the jet edges. The jets were characterized by their radii, including mean and standard deviation, and spreading angles as functions of swirl number and density ratio (2.3, 2.6, and 5.0). The swirl number was identified as the dominant parameter in determining the spreading angle and jet radius. Vortex breakdown was identified as the jet structure changed from straight edges to curved, signifying

  20. 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.

  1. 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.

  2. 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...

  3. 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.

  4. Application of supercritical CO2 and ionic liquids for the preparation of fluorinated nanocomposites.

    PubMed

    Livi, Sébastien; Duchet-Rumeau, Jannick; Gérard, Jean-François

    2012-03-01

    This work is focused on the tailoring of dispersions of layered silicates, such as MICA SOMASIF (ME-100) within a fluoride matrix (polytetrafluoroethylene) through two strategies: the physicochemical interactions between filler and matrix and the processing of materials. The interactions in these complex systems are modified by new environmentally friendly thermally stable surfactants. The ionic liquids used are based on alkyltriphenyl phosphonium and perfluorinated alkylpyridinium cations. The influences of the cation-anion combination and functionalization were investigated. The use of the supercritical carbon dioxide (ScCO(2)) as a solvent is relevant to generate structuring within the material based on ionic liquid phase separation. The tunability of ionic liquids and their combination with the supercritical carbon dioxide enables to design materials with optimized thermal and mechanical properties. PMID:22204975

  5. 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.

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

    NASA Astrophysics Data System (ADS)

    Abidoye, Luqman Kolawole; Das, Diganta Bhusan

    2015-10-01

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

  7. 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...

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

    PubMed Central

    Peet, Kyle C.

    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. PMID:25858826

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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

  14. 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. PMID:24801893

  15. [Efficiency of supercritical fluid extraction for the production of non-volatile terpenoids from Taraxaci radix].

    PubMed

    Kristó, T S; Terdy, P P; Simándi, B; Szöke, E; Lemberkovics, E; Kéry, A

    2001-10-01

    Supercritical fluid extraction (SFE) is an extraction technique which exploits the solvent properties of fluids above their critical point. As a result supercritical fluid extraction was used to gain various active substances from plants. The use of SFE to obtain bioactive substances from medicinal plants over the past twenty years has been proved to be a viable alternative for the extraction of natural compounds. Dandelion (Taraxacum officinale Wiggers et Webers, Asteraceae) is one of the best known European medicinal plants, not only as a traditional medicine but perspective raw material for modern phytopharmaceuticals. From the characteristic principles our attention has been directed to triterpenes and phytosterols with anti-inflammatory activity, which were extracted with supercritical carbon dioxide. Designed experiments were carried out to determine the optimal extraction parameters. The products obtained by supercritical fluids extraction were compared to extracts prepared by traditional extraction method (Soxhlet) with n-hexane and ethyl alcohol solvents. The content of triterpenes and sterols was monitored after saponification by thin layer chromatography-densitometry. The products gained by supercritical fluid extraction were different from the traditional ones both in their appearance and composition. Triterpenes and their esters were extracted quantitatively by supercritical fluid extraction using CO2 as solvent and the extraction dynamic for triterpenes and phytosterols was different. Triterpenes had a higher concentration in the SFE product then in the extracts prepared by traditional methods. PMID:11961900

  16. Forsterite [Mg2SiO4)] carbonation in wet supercritical CO2: an in situ high-pressure X-ray diffraction study.

    PubMed

    Todd Schaef, Herbert; McGrail, Bernard P; Loring, John L; Bowden, Mark E; Arey, Bruce W; Rosso, Kevin M

    2013-01-01

    Mechanisms controlling mineral stabilities in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss carbonation reactions occurring with forsterite (Mg(2)SiO(4)) exposed to variably wet supercritical CO(2) (scCO(2)). Transformation reactions were tracked by in situ high-pressure X-ray diffraction in the presence of scCO(2) containing dissolved water. Under modest pressures (90 bar) and temperatures (50 °C), scCO(2) saturated with water converted >70 wt % forsterite to a hydrated magnesium carbonate, nesquehonite (MgCO(3) · 3H(2)O), and magnesite (MgCO(3)) after 72 h. However, comparable tests with scCO(2) at only partial water saturation showed a faster carbonation rate but significantly less nesquehonite formation and no evidence of the anhydrous form (MgCO(3)). The presence and properties of a thin water film, observed by in situ infrared (IR) spectroscopy and with isotopically labeled oxygen ((18)O), appears to be critical for this silicate mineral to carbonate in low water environments. The carbonation products formed demonstrated by temperature and water-content dependence highlights the importance of these kinds of studies to enable better predictions of the long-term fate of geologically stored CO(2). PMID:22612304

  17. Evaluation of progesterone permeability from supercritical fluid processed dispersion systems.

    PubMed

    Falconer, James R; Wen, Jingyuan; Zargar-Shoshtari, Sara; Chen, John J; Farid, Mohammed; El Maghraby, Gamal M; Alany, Raid G

    2014-03-01

    The aim of this study was to investigate the permeability of unique dispersion systems prepared by supercritical fluid (SCF) processing, to deliver bioidentical progesterone (PGN) across mouse skin. Semisolid dispersions of PGN were made up of either polyethylene glycol (PEG) 400/4000, Gelucire 44/14, d-α-tocopheryl PEG 1000 succinate (TPGS), tanscutol P or myritol 318. SCF dispersion systems were compared with various control formulations; a market cream, aqueous suspension, and three conventionally prepared dispersions – comelted, cosolvent and physically mixed systems. The permeability coefficient in the absence or presence of a permeation enhancer was evaluated using ex vivo mouse skin. The permeation study results for the TPGS/myritol/transcutol P dispersion system prepared using supercritical carbon dioxide (SC-CO2) had a two-fold improvement in transdermal permeation over 24 h compared to the control formulation, 245.7 and 126 µg cm(-2), respectively (p value < 0.05). In this study, the skin integrity and morphology was also investigated for changes due to the formulation constituents using histological examination and Fourier transform infrared spectroscopy. The particles from the gas-saturated suspension method and SC-CO2 together with TPGS/myritol/transcutol P may offer potential advantages over the available cream on the market based on the vastly improved lag time and flux of PGN across the skin. PMID:23432633

  18. 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.

  19. Mixtures of SF6 CO2 as working fluids for geothermal power plants

    SciTech Connect

    Yin, Hebi; Sabau, Adrian S; Conklin, Jim; McFarlane, Joanna; Qualls, A L

    2013-01-01

    In this paper, supercritical/transcritical thermodynamic cycles using mixtures of SF6 CO2 as working fluids were investigated for geothermal power plants. The system of equations that described the thermodynamic cycle was solved using a Newton-Raphson method. This approach allows a high computational efficiency even when thermophysical properties of the working fluid depend strongly on the temperature and pressure. The thermophysical properties of the mixtures were obtained from National Institute of Standards and Technology (NIST) REFPROP software and constituent cubic equations. The local heat transfer coefficients in the heat exchangers were calculated based on the local properties of the working fluid, geothermal brine, and cooling water. The heat exchanger areas required were calculated. Numerical simulation results presented for different cycle configurations were used to assess the effects of the SF6 fraction in CO2, brine temperature, and recuperator size on the cycle thermal efficiency, and size of heat exchangers for the evaporator and condenser. Optimal thermodynamic cycle efficiencies were calculated to be approximately 13 and 15% mole content of SF6 in a CO2- SF6 mixture for a Brayton cycle and a Rankine cycle, respectively.

  20. 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.

  1. 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.

  2. Transport and relaxation processes in supercritical fluids

    NASA Astrophysics Data System (ADS)

    Jonas, J.

    1985-11-01

    Preparations for the study of naphthalene diffusion dissolved in the supercritical fluids carbon dioxide and ethylene have proceeded as follows. We plan to use the fixed field gradient NMR technique to monitor the diffusion of the dissolved naphthalene. However, the technique is not feasible in systems with spin-spin coupling among the nuclei of interest; unfortunately the protons on naphthalene exhibit this coupling. We thus intend to use totally deuterated naphthalene and monitor the deuterium signal, a nucleus whose coupling is negligible. We therefore have designed and built a new high pressure NMR probe for the measurement of deuterium. This probe is similar to the one used in the previous naphthalene solubility study, and accommodates the same supercritical sample cells. The probe is machined from Vespel SP-1 (a high temperature plastic), and houses a 17-1/2 turn solenoid NMR coil along with thermocouples located slightly above and below the sample area. The probe has been successfully tested to 2 kbar gas pressure. The data acquisition system for the NMR spectrometer used for supercritical fluid studies has been developed and described in this report.

  3. 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.

  4. 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.

  5. Bioethanol production from raffinate phase of supercritical CO2 extracted Stevia rebaudiana leaves.

    PubMed

    Coban, Isik; Sargin, Sayit; Celiktas, Melih Soner; Yesil-Celiktas, Ozlem

    2012-09-01

    The extracts of Stevia rebaudiana are marketed as dietary supplements and utilized as natural sweetening agent in food products. Subsequent to extraction on industrial scale, large quantities of solid wastes are produced. The aim of this study was to investigate the bioconversion efficiency of supercritical CO(2) extracted S. rebaudiana residues. Therefore, leaves were extracted with supercritical CO(2) and ethanol mixture in order to obtain glycosides, then the raffinate phase was hydrolyzed by both dilute acid and various concentrations of cellulase and β-glucosidase cocktail. The maximum yield of reducing sugars reached 25.67 g/L under the optimal conditions of enzyme pretreatment, whereas 32.00 g/L was reached by consecutive enzymatic and acid hydrolyses. Bioethanol yield (20 g/L, 2.0% inoculum, 2 days) based on the sugar consumed was 45.55% corresponding to a productivity of 0.19 kg/m(3)h which demonstrates challenges to be utilized as a potential feedstock for the production of bioethanol. PMID:22784953

  6. Supercritical fluids and their applications in biotechnology and related areas.

    PubMed

    Williams, John R; Clifford, Anthony A; al-Saidi, Salim H R

    2002-11-01

    This article serves as an overview, introducing the currently popular area of supercritical fluids (SFs) and their uses in biotechnology and related areas. It covers the fundamentals of supercritical science and moves on to the biotechnological and associated applications of these fluids. Subject areas covered include pure substances as supercritical fluids, the properties of supercritical fluids, organic cosolvents, solubility, and the following applications: extraction, chromatography, reactions, particle production, deposition, and the drying of biological specimens. Within each application, and where possible, the basic principles of the technique are given, as well as a description of the history, instrumentation, methodology, uses, problems encountered, and advantages over the traditional, nonsupercritical methods. PMID:12448881

  7. 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 (

  8. Supercritical fluid extraction of N-nitrosamines

    SciTech Connect

    Tewani, S.

    1993-01-01

    The detailed chemistry of N-nitrosamines including the mechanism of carcinogenicity, modes of formation, inhibition and destruction are discussed in detail. The occurrence and risk assessment of human exposure of these suspect cancer agents is described. The methods of isolation and analysis of N-nitrosamines are critically discussed with emphasis on Gas Chromatography (GC)-Electrochemical Detectors, GC-High Resolution Mass Spectrometry (GC-HRMS), GC-Thermal Energy Analyser (GC-TEA). The theoretical concepts of supercritical fluid extraction (SFE) are discussed. A comparison of physical and chemical properties of supercritical fluids (SF) with other phases is given. A comparison of static, dynamic, recirculating SFEs shows the versatility of this technique. The advantages over conventional methods such as Soxhlet extraction are discussed. The instrumentation and operational technique of a laboratory built supercritical fluid extractor is explained. A brief review of applications (industrial and analytical) of SFE is given. The evaluation of SFE for analytical sample preparation and analyses of volatile N-nitrosamines (VNAs), tobacco specific N-nitrosamines (TSNAs), and N-nitrosodiethanolamine (NDELA) from spiked matrices, tobacco and cutting fluids is presented. Experimental parameters such as pressure, temperature, equilibration time, collector materials, modifier are evaluated to optimize the recoveries. The extracts are analysed by GC-TEA which is already proven to be highly selective and sensitive to quantitation of N-nitrosamines. The extraction of VNAs in pure SF-CO[sub 2] is quantitative at moderate pressures and low temperatures. For the extraction of TSNAs and NDELA, it is imperative to have high pressures and presence of an additive ([approximately]10% methanol) to achieve satisfactory results. This study offers a simple, rapid, accurate and environmentally advantageous sample preparation technique for the estimation of N-nitrosamines at nanogram levels.

  9. Supercritical fluids: Reactions, materials and applications

    SciTech Connect

    Tumas, W.; Jacobson, G.B.; Josephsohn, N.S.; Brown, G.H.

    1999-04-09

    A number of important processes utilizing supercritical fluids have been either implemented or are emerging for extractions, separations and a wide range of cleaning applications. Supercritical fluids can be reasonable solvents yet share many of the advantages of gases including miscibility with other gases (i.e. hydrogen and oxygen), low viscosities and high diffusivities. Carbon dioxide has the further advantages of being nontoxic, nonflammable, inexpensive and currently unregulated. The use of compressed gases, either as liquids or supercritical fluids, as reaction media offers the opportunity to replace conventional hazardous solvents and also to optimize and potentially control the effect of solvent on chemical and material processing. The last several years has seen a significant growth in advances in chemical synthesis, catalytic transformations and materials synthesis and processing. The authors report on results from an exploratory program at Los Alamos National Laboratory aimed at investigating the use of dense phase fluids, particularly carbon dioxide, as reaction media for homogeneous, heterogeneous and phase-separable catalytic reactions in an effort to develop new, environmentally-friendly methods for chemical synthesis and processing. This approach offers the possibility of opening up substantially different chemical pathways, increasing selectivity at higher reaction rates, facilitating downstream separations and mitigating the need for hazardous solvents. Developing and understanding chemical and catalytic transformations in carbon dioxide could lead to greener chemistry at three levels: (1) Solvent replacement; (2) Better chemistry (e.g. higher reactivity, selectivity, less energy consumption); and (3) New chemistry (e.g. novel separations, use of COP{sub 2} as a C-1 source).

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  14. 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

  15. 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.

  16. 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. PMID:24328430

  17. 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. PMID:11743770

  18. 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

  19. Solute partial molal volumes in supercritical fluids

    SciTech Connect

    Eckert, C.A.; Ziger, D.H.; Johnston, K.P.; Kim, S.

    1986-06-05

    A novel technique is described for the measurement of the partial molal volume at infinite dilution of solutes in supercritical fluids. Results are reported for five systems from 2/sup 0/C above the solvent critical temperature up to 15/sup 0/C above, at pressures from just above the critical pressure to 350 bars. The solute partial molal volumes are small and positive at high pressures, but very large and negative in the highly compressible near-critical region. The results are interpreted in terms of solvent structure and intermolecular forces.

  20. 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

  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. 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.

  3. Chemical composition and antioxidant properties of candlenut oil extracted by supercritical CO2.

    PubMed

    Siddique, Bazlul Mobin; Ahmad, Anees; Alkarkhi, Abbas F M; Ibrahim, Mahamad Hakimi; K, Mohd Omar A

    2011-05-01

    Candlenut oil was extracted using supercritical CO(2) (SC-CO(2)) with an optimization of parameters, by the response surface methodology. The ground candlenut samples were treated in 2 different ways, that is, dried in either a heat oven (sample moisture content of 2.91%) or dried in a vacuum oven (sample moisture content of 1.98%), before extraction. An untreated sample (moisture content of 4.87%) was used as a control. The maximum percentage of oil was extracted from the heat-oven-dried sample (77.27%), followed by the vacuum-oven-dried sample (74.32%), and the untreated sample (70.12%). At an SC-CO(2) pressure of 48.26 Mpa and 60 min of extraction time, the optimal temperatures for extraction were found to be 76.4 °C, 73.9 °C, and 70.6 °C for the untreated, heat-oven-dried, and vacuum-oven-dried samples, respectively. The heat-oven-dried sample contains the highest percentage of linoleic acid, followed by the untreated and vacuum-oven-dried samples. The antiradical activity of candlenut oil corresponded to an IC(50) value of 30.37 mg/mL. PMID:22417332

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

    SciTech Connect

    Glezakou, Vassiliki Alexandra; McGrail, B. Peter

    2013-06-03

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

  5. 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. PMID:16431407

  6. 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

  7. 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.

  8. Supercritical fluid extraction of 5-hydroxymethyl-2-furaldehyde from raisins.

    PubMed

    Palma, M; Taylor, L T

    2001-02-01

    An extraction method based on supercritical CO(2) has been developed for the analysis of 5-hydroxymethyl-2-furaldehyde in raisins. To optimize extraction variables, a fractional factorial experimental design was applied. Six extraction variables were optimized. The organic modifier used for increasing the extraction fluid solvating power was the most important factor. Methanol as organic modifier produced 10-fold higher recoveries of 5-hydroxymethyl-2-furaldehyde than ethyl acetate. The efficiency of the organic modifier in the static extraction phase was compared with using it in the dynamic extraction phase. Repeatability of the analysis method was evaluated, which resulted in an RSD of <5%. 5-Hydroxymethyl-2-furaldehyde was quantified in raisins, and the concentration was found to be 0.128 mg/g of raisin. PMID:11262003

  9. Sequential fractionation of grape seeds into oils, polyphenols, and procyanidins via a single system employing CO2-based fluids.

    PubMed

    Ashraf-Khorassani, Mehdi; Taylor, Larry Thomas

    2004-05-01

    Pure supercritical CO(2) was used to remove >95% of the oil from the grape seeds. Subcritical CO(2) modified with methanol was used for the extraction of monomeric polyphenols, whereas pure methanol was used for the extraction of polyphenolic dimers/trimers and procyanidins from grape seed. At optimum conditions, 40% methanol-modified CO(2) removed >79% of catechin and epicatechin from the grape seed. This extract was light yellow in color, and no higher molecular weight procyanidins were detected. Extraction of the same sample after removal of the oils and polyphenols, but now under enhanced solvent extraction conditions using methanol as a solvent, provided a dark red solution shown via electrospray ionization HPLC-MS to contain a relatively high concentration of procyanidins. The uniqueness of the study is attested to by the use of CO(2)-based fluids and the employment of a single instrumental extraction system. PMID:15113138

  10. Experimental study of the hydrogeochemical properties of the Hontomin cap rock under CO2 supercritical conditions

    NASA Astrophysics Data System (ADS)

    Cama, Jordi; Soler, Josep M.; Davila, Gabriela; Luquot, Linda

    2013-04-01

    Gabriela Dávila, Linda Luquot, Jordi Cama and Josep M. Soler Departament de Geociències, Institut de Diagnosi Ambiental i Estudis de l'Aigua (IDAEA), CSIC, Barcelona 08034. The main cap rock for CO2 injection at the PDT Hontomin site (Spain) is a marly shale made up of calcite (56 %), quartz (21%), illite (17%) clinochlore (3%) and others (albite, gypsum, anhydrite, pyrite) (~3%). Contact with CO2-rich acid brines may induce the dissolution of these minerals. Since the brine contains sulfate, gypsum (or anhydrite at depth) may precipitate, which may coat the surface of the dissolving calcite grains and cause their passivation. These mineral reactions will also induce changes in porosity and permeability. Percolation laboratory experiments with Hontomin shale rock cores under controlled pCO2 (8 MPa) are being performed to quantify these processes. In mechanically fractured cores (7.5 mm in diameter and 18 mm in length), two synthetic brines (a sulfate-free solution and a version of the Hontomin formation brine (sulfate solution)) were injected into the rock at constant flow rates (0.2, 1 and 60 mL/h) under CO2 supercritical conditions (pCO2 = 8 MPa and T = 60 °C). As the pH of the injecting brines in equilibrium with a pCO2 of 8 MPa is acidic (~3), it was observed that in the case of the sulfate-free brine experiments, the main processes that yield variation in the hydrodynamic behavior of the fractured rock was the dissolution of calcite, Si-bearing minerals, clinochlore and pyrite. In the sulfate-rich brine experiments, the dissolution of calcite and Si-bearing minerals also occurred, together with gypsum precipitation in the experiments run at low flow rates. As a result, initial fracture permeability tends (i) to stabilize or increase when the cap rock interacts with the sulfate-free brine and (ii) to decrease as the rock interacts with the sulfate-rich brine. The interpretation (reactive transport modeling) of the changes in mineralogy and solution

  11. 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.

  12. 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.

  13. Extraction of atrazine and its metabolites using supercritical fluids and enhanced-fluidity liquids

    PubMed

    Shows; Olesik

    2000-09-01

    Supercritical fluid and enhanced-fluidity liquid extractions are performed on spiked sediment samples containing atrazine (ATRA) and five of its metabolites including desisopropyldesethylatrazine, desethylhydroxyatrazine (DEHA), desisopropylatrazine, desethylatrazine, and hydroxyatrazine (HA). The hydroxylated metabolites are of particular interest because of their increased water solubility and the fact that their high polarity makes them difficult to analyze. Soxhlet extractions using methanol are conducted for the purpose of comparison. Results of the extractions show that the hydroxy-containing metabolites of ATRA are not effectively extracted with supercritical CO2 alone. The solvating or desorbing power of carbon dioxide appears too low to extract HA and DEHA. The extraction recoveries of the hydroxylated metabolites increase when enhanced-fluidity liquid mixtures of methanol/CO2 are used, and these rates increase with the methanol concentration. Enhanced-fluidity ternary liquid mixtures of H2O/methanol/CO2 yield the best recoveries for these compounds. ATRA recoveries are equally effective when using supercritical CO2 or enhanced-fluidity mixtures. The other nonhydroxy-containing metabolites require the increased solvent strength of either large percentages of methanol in CO2 or ternary mixtures of H2O, methanol, and CO2 for high recoveries. Recoveries with enhanced-fluidity liquid ternary mixtures are better than the recoveries from Soxhlet for all the compounds in the study. PMID:11011724

  14. Formation of curcumin nanoparticles via solution-enhanced dispersion by supercritical CO2.

    PubMed

    Zhao, Zheng; Xie, Maobin; Li, Yi; Chen, Aizheng; Li, Gang; Zhang, Jing; Hu, Huawen; Wang, Xinyu; Li, Shipu

    2015-01-01

    In order to enhance the bioavailability of poorly water-soluble curcumin, solution-enhanced dispersion by supercritical carbon dioxide (CO2) (SEDS) was employed to prepare curcumin nanoparticles for the first time. A 2(4) full factorial experiment was designed to determine optimal processing parameters and their influence on the size of the curcumin nanoparticles. Particle size was demonstrated to increase with increased temperature or flow rate of the solution, or with decreased precipitation pressure, under processing conditions with different parameters considered. The single effect of the concentration of the solution on particle size was not significant. Curcumin nanoparticles with a spherical shape and the smallest mean particle size of 325 nm were obtained when the following optimal processing conditions were adopted: P = 20 MPa, T = 35°C, flow rate of solution = 0.5 mL·min(-1), concentration of solution = 0.5%. Fourier transform infrared (FTIR) spectroscopy measurement revealed that the chemical composition of curcumin basically remained unchanged. Nevertheless, X-ray powder diffraction (XRPD) and thermal analysis indicated that the crystalline state of the original curcumin decreased after the SEDS process. The solubility and dissolution rate of the curcumin nanoparticles were found to be higher than that of the original curcumin powder (approximately 1.4 μg/mL vs 0.2 μg/mL in 180 minutes). This study revealed that supercritical CO2 technologies had a great potential in fabricating nanoparticles and improving the bioavailability of poorly water-soluble drugs. PMID:25995627

  15. Formation of curcumin nanoparticles via solution-enhanced dispersion by supercritical CO2

    PubMed Central

    Zhao, Zheng; Xie, Maobin; Li, Yi; Chen, Aizheng; Li, Gang; Zhang, Jing; Hu, Huawen; Wang, Xinyu; Li, Shipu

    2015-01-01

    In order to enhance the bioavailability of poorly water-soluble curcumin, solution-enhanced dispersion by supercritical carbon dioxide (CO2) (SEDS) was employed to prepare curcumin nanoparticles for the first time. A 24 full factorial experiment was designed to determine optimal processing parameters and their influence on the size of the curcumin nanoparticles. Particle size was demonstrated to increase with increased temperature or flow rate of the solution, or with decreased precipitation pressure, under processing conditions with different parameters considered. The single effect of the concentration of the solution on particle size was not significant. Curcumin nanoparticles with a spherical shape and the smallest mean particle size of 325 nm were obtained when the following optimal processing conditions were adopted: P =20 MPa, T =35°C, flow rate of solution =0.5 mL·min−1, concentration of solution =0.5%. Fourier transform infrared (FTIR) spectroscopy measurement revealed that the chemical composition of curcumin basically remained unchanged. Nevertheless, X-ray powder diffraction (XRPD) and thermal analysis indicated that the crystalline state of the original curcumin decreased after the SEDS process. The solubility and dissolution rate of the curcumin nanoparticles were found to be higher than that of the original curcumin powder (approximately 1.4 μg/mL vs 0.2 μg/mL in 180 minutes). This study revealed that supercritical CO2 technologies had a great potential in fabricating nanoparticles and improving the bioavailability of poorly water-soluble drugs. PMID:25995627

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

    NASA Astrophysics Data System (ADS)

    Samuelson, Jon

    2013-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Samuelson, J. E.

    2012-12-01

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

  18. 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. PMID:24339322

  19. 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

  20. 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.

  1. 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

  2. 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...

  3. SUPERCRITICAL FLUID EXTRACTION OF TOXIC HEAVY METALS FROM SOLID AND AQUEOUS MATRICES

    SciTech Connect

    Wang, S; Lin, Yuehe; Wai, C M.

    2003-04-09

    The feasibility of using dithiocarbamate chelating agents or sulfur-containing organophosphorus reagents for the supercritical fluid extraction (SFE) of toxic heavy metals from solid and aqueous matrices is investigated. Effective extraction of heavy metal ions from both sand matrix and water samples was demonstrated by using supercritical CO2 containing dithiocarbamatechelating agents. A commercially available sulfur-containing organophosphorus reagent, Cyanex 302, was used for the extraction of toxic heavy metals from wood samples. The extraction profiles were initially rapid followed by a very low level of metal extraction, indicating that the process is limited to extraction of leachable toxic metals.

  4. 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

  5. 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

  6. Implementing stationary-phase optimized selectivity in supercritical fluid chromatography.

    PubMed

    Delahaye, Sander; Lynen, Frédéric

    2014-12-16

    The performance of stationary-phase optimized selectivity liquid chromatography (SOS-LC) for improved separation of complex mixtures has been demonstrated before. A dedicated kit containing column segments of different lengths and packed with different stationary phases is commercially available together with algorithms capable of predicting and ranking isocratic and gradient separations over vast amounts of possible column combinations. Implementation in chromatographic separations involving compressible fluids, as is the case in supercritical fluid chromatography, had thus far not been attempted. The challenge of this approach is the dependency of solute retention with the mobile-phase density, complicating linear extrapolation of retention over longer or shorter columns segments, as is the case in conventional SOS-LC. In this study, the possibilities of performing stationary-phase optimized selectivity supercritical fluid chromatography (SOS-SFC) are demonstrated with typical low density mobile phases (94% CO2). The procedure is optimized with the commercially available column kit and with the classical isocratic SOS-LC algorithm. SOS-SFC appears possible without any density correction, although optimal correspondence between prediction and experiment is obtained when isopycnic conditions are maintained. As also the influence of the segment order appears significantly less relevant than expected, the use of the approach in SFC appears as promising as is the case in HPLC. Next to the classical use of SOS for faster baseline separation of all solutes in a mixture, the benefits of the approach for predicting as wide as possible separation windows around to-be-purified solutes in semipreparative SFC are illustrated, leading to significant production rate improvements in (semi)preparative SFC. PMID:25393519

  7. A two-step supercritical fluid extraction of polycyclic aromatic hydrocarbons from roadside soil samples.

    PubMed

    Lojková, Lea; Sedláková, Jitka; Kubán, Vlastimil

    2005-11-01

    A two-step procedure for the supercritical fluid extraction (SFE) of polycyclic aromatic hydrocarbons from soil samples was developed. The procedure consists of a static supercritical fluid treatment in a closed extraction cell at a high temperature (T=250 or 340degreesC for 20 min) and an SFE with a solvent trapping. During the static phase, the sample is exposed to a supercritical organic solvent (methanol, toluene, dichloromethane, ACN, acetone, and hexane). The solvent penetrates particles of the matrix to substitute strongly bonded molecules and dissolves the analytes in the supercritical phase. At ambient temperature, supercritical fluids became liquid and lost their solvation abilities. Most of the analytes condense on the surface of the particles or on the extraction cell walls without forming strong bonds or penetrating deep into the matrix. Thus, the pretreatment liberates the analytes and they behave similar to those in freshly spiked samples. The common SFE with toluene-modified CO2 as an extraction fluid follows the static phase. With the use of the most suitable extraction phases (toluene, ACN), the extraction efficiency of the combined procedure is much higher (approximately100%). The results of the combined procedure are compared to the SFE procedure of the same untreated sample (difference less than 5%) and to the Soxhlet extraction. The extracts were analyzed using a GC with the flame ionization detection. PMID:16318201

  8. Brucite [Mg(OH 2)] carbonation in wet supercritical CO 2: An in situ high pressure X-ray diffraction study

    NASA Astrophysics Data System (ADS)

    Schaef, H. T.; Windisch, C. F.; McGrail, B. P.; Martin, P. F.; Rosso, K. M.

    2011-12-01

    Understanding mechanisms and kinetics of mineral carbonation reactions relevant to sequestering carbon dioxide as a supercritical fluid (scCO 2) 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 CO 2-bearing fluid. However, water-bearing scCO 2 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 scCO 2 was examined at pressure (82 bar) as a function of water concentration and temperature (50 and 75 °C). Exposing brucite to anhydrous scCO 2 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 [MgCO 3·3H 2O] within a few hours at 50 °C. By increasing water content to well above the saturation level of the scCO 2, complete conversion of brucite into nesquehonite was observed. Tests conducted at 75 °C resulted in the conversion of brucite into magnesite [MgCO 3] instead, apparently through an intermediate nesquehonite step. Raman spectroscopy applied to brucite reacted with 18O-labeled water in scCO 2 show it was incorporated into carbonate at a 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. 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

  10. 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.