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.

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

PubMed

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

2002-10-11

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

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

NASA Astrophysics Data System (ADS)

Alvarez, Guillermo A.; Baumanna, Wolfram

2005-02-01

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

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

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

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

2013-09-01

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

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

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

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

2013-02-01

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

Supercritical Fluid Fractionation of JP-8

DTIC Science & Technology

1991-12-26

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

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

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.

Supercritical Fluid Processing of Propellant Polymers

DTIC Science & Technology

1991-01-01

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

A biocompatible tissue scaffold produced by supercritical fluid processing for cartilage tissue engineering.

PubMed

Kim, Su Hee; Jung, Youngmee; Kim, Soo Hyun

2013-03-01

Supercritical fluids are used in various industrial fields, such as the food and medical industries, because they have beneficial physical and chemical properties and are also nonflammable and inexpensive. In particular, supercritical carbon dioxide (ScCO(2)) is attractive due to its mild critical temperature, pressure values, and nontoxicity. Poly(L-lactide-co-ɛ-caprolactone) (PLCL), which is a biocompatible, biodegradable, and very elastic polymer, has been used in cartilage tissue engineering. However, organic solvents, such as chloroform or dichloromethane, are usually used for the fabrication of a PLCL scaffold through conventional methods. This leads to a cytotoxic effect and long processing time for removing solvents. To alleviate these problems, supercritical fluid processing is introduced here. In this study, we fabricated a mechano-active PLCL scaffold by supercritical fluid processing for cartilage tissue engineering, and we compared it with a scaffold made by a conventional solvent-casting method in terms of physical and biological performance. Also, to examine the optimum condition for preparing scaffolds with ScCO(2), we investigated the effects of pressure, temperature, and the depressurization rate on PLCL foaming. The PLCL scaffolds produced by supercritical fluid processing had a homogeneously interconnected porous structure, and they exhibited a narrow pore size distribution. Also, there was no cytotoxicity of the scaffolds made with ScCO(2) compared to the scaffolds made by the solvent-pressing method. The scaffolds were seeded with chondrocytes, and they were subcutaneously implanted into nude mice for up to 4 weeks. In vivo accumulation of extracellular matrix of cell-scaffold constructs demonstrated that the PLCL scaffold made with ScCO(2) formed a mature and well-developed cartilaginous tissue compared to the PLCL scaffold formed by solvent pressing. Consequently, these results indicated that the PLCL scaffolds made by supercritical fluid

Synthesis of germanium nanocrystals in high temperature supercritical CO2

NASA Astrophysics Data System (ADS)

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

2005-07-01

Germanium nanocrystals were synthesized in supercritical (sc) CO2 by thermolysis of diphenylgermane (DPG) or tetraethylgermane (TEG) with octanol as a capping ligand at 500 °C and 27.6 MPa. The Ge nanocrystals were characterized with high resolution transmission electron microscopy (HRTEM), energy-dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD). On the basis of TEM, the mean diameters of the nanocrystals made from DPG and TEG were 10.1 and 5.6 nm, respectively. The synthesis in sc-CO2 produced much less organic contamination compared with similar reactions in organic supercritical fluids. When the same reaction of DPG with octanol was performed in the gas phase without CO2 present, bulk Ge crystals were formed instead of nanocrystals. Thus, the solvation of the hydrocarbon ligands by CO2 was sufficient to provide steric stabilization. The presence of steric stabilization in CO2 at a reduced temperature of 2.5, with a reduced solvent density of only 0.4, may be attributed to a reduction in the differences between ligand-ligand interactions and ligand-CO2 interactions relative to thermal energy.

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

PubMed

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

2013-10-01

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

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

PubMed

Lemasson, Elise; Bertin, Sophie; West, Caroline

2016-01-01

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

Supercritical fluid technology: concepts and pharmaceutical applications.

PubMed

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

2011-01-01

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

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

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

Rother, Gernot; Vlcek, Lukas; Gruszkiewicz, Miroslaw

2014-01-01

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

SUPERCRITICAL FLUID EXTRACTION OF POLYCYCLIC AROMATIC HYDROCARBON MIXTURES FROM CONTAMINATED SOILS

EPA Science Inventory

Highly contaminated (with PAHs) topsoils were extracted with supercritical CO₂ to determine the feasibility and mechanism of supercritical fluid extraction (SFE). Effect of SCF density, temperature, cosolvent type and amount, and of slurrying the soil with water were ...

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

PubMed

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

2018-04-01

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

Supercritical fluid extraction

DOEpatents

Wai, Chien M.; Laintz, Kenneth

1994-01-01

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

Supercritical 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.

Systematic investigations of peak deformations due to co-solvent adsorption in preparative supercritical fluid chromatography.

PubMed

Glenne, Emelie; Leek, Hanna; Klarqvist, Magnus; Samuelsson, Jörgen; Fornstedt, Torgny

2017-05-05

Strangely shaped overloaded bands were recently reported using a standard supercritical fluid chromatographic system comprising a diol column as the stationary phase and carbon dioxide with methanol as the mobile phase. Some of these overloaded elution profiles appeared strongly deformed and even had "anti-Langmuirian" shapes although their solute compounds had "Langmuirian" adsorption. To obtain a more complete understanding of the generality of these effects, the investigation was expanded to cover also other common co-solvents, such as ethanol, 2-propanol, and acetonitrile, as well as various stationary phase materials, such as silica, and 2-ethylpyridine. From this expanded study it could be confirmed that the effects of deformed overloaded solute band shapes, due to co-solvent adsorption, is general phenomena in supercritical fluid chromatographic. It could also be concluded that these effects as well as previously observed "solvent effects" or "plug effects" are entirely due to competition between the solute and solvent molecules for the adsorption sites on the stationary phase surface. Finally, guidelines were given for how to evaluate the risk of deformations occurring for a given solvent-column combination, based simply on testing retention times of solutes and co-solvent. Copyright © 2017 Elsevier B.V. All rights reserved.

Supercritical Fluid Extraction of Bioactive Compounds from Plant Materials.

PubMed

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

2017-11-01

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

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

PubMed

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

[Extraction of 10-Deacetyl Baccatin by Supercritical CO2 from Taxus yunnanensis Branches and Leaves].

PubMed

Tang, Yang-qin; Li, Hai-chi; Huang, Wen-jie; Xiong, Yan; Ge, Fa-huan

2015-04-01

To study the supercritical CO2 fluids extraction (SFE) method to extract the components from Taxus yunnanensis. Medicinal meterials were extracted by supercritical CO2, and then purified by industrial chromatography. Using the extraction yield of 10-DAB as the index,single factor test was carried out to investigate the effect of co-solvent, extraction time, extraction pressure, extraction temperature, pressure and temperature of separation kettle I. Then orthogonal experiment was used to optimize the best extraction condition. The suitable extraction condition was as follows: the ratio of co-solvent (80% ethanol) amount and the madicinal materials was 3: 1, Separation kettle I pressure was 14 MPa, separation kettle I temperature was 40 °C, extraction pressure was 25 MPa, extraction temperature was 60 T and extraction time was 90 min. The extract was separated by industrial chromatographic and then crystallized. The supercritical CO2 extraction and purification process of 10-DAB were simple and feasible.

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.

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.

Supercritical Fluid Chromatography/Fourier Transform Infrared Spectroscopy Of Food Components

NASA Astrophysics Data System (ADS)

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

1989-12-01

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

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

PubMed

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

2016-04-13

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

Supercritical CO2 uptake by nonswelling phyllosilicates

PubMed Central

Tokunaga, Tetsu K.; Ashby, Paul D.; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J.

2018-01-01

Interactions between supercritical (sc) CO2 and minerals are important when CO2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO2), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO2, can increase CO2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO2 uptake constitutes a previously unrecognized potential trapping mechanism. PMID:29339499

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

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 [MgCO

Triticonazole enantiomers: Separation by supercritical fluid chromatography and the effect of the chromatographic conditions.

PubMed

He, Jianfeng; Fan, Jun; Yan, Yilun; Chen, Xiaodong; Wang, Tai; Zhang, Yaomou; Zhang, Weiguang

2016-11-01

Enantiomeric pairs of triticonazole have been successfully separated by supercritical fluid chromatography coupled with a tris(3,5-dimethylphenylcarbamoyl) cellulose-coated chiral stationary phase in this work. The effects of co-solvent, dissolution solvent, flow rate, backpressure, and column temperature have been studied in detail with respect to retention, selectivity, and resolution of triticonazole. As indicated, the co-solvents mostly affected the retention factors and resolution, due to the different molecular structure and polarity. In addition, the dissolution solvents, namely, chloromethanes and alcohols, have been also important for enantioseparation because of the different interaction with stationary phase. Higher flow rate and backpressure led to faster elution of the triticonazole molecules, and the change of column temperature showed slight effect on the resolution of triticonazole racemate. Moreover, a comparative separation experiment between supercritical fluid chromatography and high performance liquid chromatography revealed that chiral supercritical fluid chromatography gave the 3.5 times value of R s /t R2 than high performance liquid chromatography, which demonstrated that supercritical fluid chromatography had much higher separation efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Comparison of Chemical Components of Essential Oil from Ocimum basilicum var. pilosum Extracted by Supercritical CO2 Fluid and Steam Distillation].

PubMed

Wang, Zhao-yu; Zheng, Jia-huan; Shi, Sheng-ying; Luo, Zhi-xiong; Ni, Shun-yu; Lin, Jing-ming

2015-11-01

To compare the chemical components of essential oil prepared by steam distillation extraction (SD) and supercritical CO2 fluid extraction (SFE-CO2) from Ocimum basilicum var. pilosum whole plant. The essential oil of Ocimum basilicum var. pilosum were extracted by SD and SFE-CO2. The chemical components of essential oil were separated and analyzed by gas chromatography-mass spectrometry( GC-MS). Their relative contents were determined by normalization of peak area. 40 and 42 compounds were detected in the essential oil prepared by SD and SFE-CO2 respectively. 25 compounds were common. Thereare significant differences of the chemical components between the Ocimum basilicum var. pilosum essential oil prepared by SD and thatby SFE-CO2. Different methods showed different extraction efficiency with a special compound. It might be a good idea to unite several methods in the modern traditional Chinese medicine industry.

Supercritical CO2 uptake by nonswelling phyllosilicates.

PubMed

Wan, Jiamin; Tokunaga, Tetsu K; Ashby, Paul D; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J

2018-01-30

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2 , can increase CO 2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism. Copyright © 2018 the Author(s). Published by PNAS.

Supercritical CO 2 uptake by nonswelling phyllosilicates

DOE PAGES

Wan, Jiamin; Tokunaga, Tetsu K.; Ashby, Paul D.; ...

2018-01-16

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubationmore » with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2, can increase CO 2 storage capacity by up to ~30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism.« less

Supercritical fluid processing: a new dry technique for photoresist developing

NASA Astrophysics Data System (ADS)

Gallagher-Wetmore, Paula M.; Wallraff, Gregory M.; Allen, Robert D.

1995-06-01

Supercritical fluid (SCF) technology is investigated as a dry technique for photoresist developing. Because of their unique combination of gaseous and liquid-like properties, these fluids offer comparative or improved efficiencies over liquid developers and, particularly carbon dioxide, would have tremendous beneficial impact on the environment and on worker safety. Additionally, SCF technology offers the potential for processing advanced resist systems which are currently under investigation as well as those that may have been abandoned due to problems associated with conventional developers. An investigation of various negative and positive photoresist systems is ongoing. Initially, supercritical carbon dioxide (SC CO2) as a developer for polysilane resists was explored because the exposure products, polysiloxanes, are generally soluble in this fluid. These initial studies demonstrated the viability of the SCF technique with both single layer and bilayer systems. Subsequently, the investigation focused on using SC CO2 to produce negative images with polymers that would typically be considered positive resists. Polymers such as styrenes and methacrylates were chemically modified by fluorination and/or copolymerization to render them soluble in SC CO2. Siloxane copolymers and siloxane-modified methacrylates were examined as well. The preliminary findings reported here indicate the feasibility of using SC CO2 for photoresist developing.

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.

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

PubMed

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

2008-01-01

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

High Materials Performance in Supercritical CO2 in Comparison with Atmospheric Pressure CO2 and Supercritical Steam

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

Holcomb, Gordon; Tylczak, Joseph; Carney, Casey

2017-02-26

This presentation covers environments (including advanced ultra-supercritical (A-USC) steam boiler/turbine and sCO2 indirect power cycle), effects of pressure, exposure tests, oxidation results, and mechanical behavior after exposure.

Relative permeabilities of supercritical CO2 and brine in carbon sequestration by a two-phase lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Xie, Jian.-Fei.; He, S.; Zu, Y. Q.; Lamy-Chappuis, B.; Yardley, B. W. D.

2017-08-01

In this paper, the migration of supercritical carbon dioxide (CO2) in realistic sandstone rocks under conditions of saline aquifers, with applications to the carbon geological storage, has been investigated by a two-phase lattice Boltzmann method (LBM). Firstly the digital images of sandstone rocks were reproduced utilizing the X-ray computed microtomography (micro-CT), and high resolutions (up to 2.5 μm) were applied to the pore-scale LBM simulations. For the sake of numerical stability, the digital images were "cleaned" by closing the dead holes and removing the suspended particles in sandstone rocks. In addition, the effect of chemical reactions occurred in the carbonation process on the permeability was taken into account. For the wetting brine and non-wetting supercritical CO2 flows, they were treated as the immiscible fluids and were driven by pressure gradients in sandstone rocks. Relative permeabilities of brine and supercritical CO2 in sandstone rocks were estimated. Particularly the dynamic saturation was applied to improve the reliability of the calculations of the relative permeabilities. Moreover, the effects of the viscosity ratio of the two immiscible fluids and the resolution of digital images on the relative permeability were systematically investigated.

Heat Transfer and Fluid Transport of Supercritical CO 2 in Enhanced Geothermal System with Local Thermal Non-equilibrium Model

DOE PAGES

Zhang, Le; Luo, Feng; Xu, Ruina; ...

2014-12-31

The heat transfer and fluid transport of supercritical CO 2 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 ofmore » volumetric 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

[Studies on technology of supercritical-CO2 fluid extraction for volatile oils and saikosaponins in Bupleurum chinense DC].

PubMed

Ge, F H; Li, Y; Xie, J M; Li, Q; Ma, G J; Chen, Y H; Lin, Y C; Li, X F

2000-03-01

To study the technology of supercritical-CO2 fluid extraction (SFE-CO2) for the volatile oils and saikosaponins in Bupleurum chinense. Exploring the effects of pressure, temperature, extraction time, flow rate of CO2 and entrainers on the yield of the oils and saikosaponin-contained extracts; determining the optimum conditions for SFE-CO2; analyzing the oils by GC/MS and comparing the technology of SFE-CO2 with that of traditional steam distillation. The optimum extraction conditions turned out to be--for volatile oils: pressure (EP) = 20 MPa, temperature (ET) = 30 degrees C, isolator I pressure (1P-I) = 12 MPa, temperature(1T-I) = 65 degrees C, isolator II pressure (1P-II) = 6 MPa, temperature (1T-II) = 40 degrees C, extraction time = 4 hours, and CO2 flow rate = 10-20 kg.(h.kg)-1 crude drug; for saikosaponins: EP = 30 MPa, ET = 65 degrees C, 1P I = 12 MPa, 1T I = 55 degrees C, 1P II = 6 MPa, 1T II = 43 degrees C, extraction time = 3 hours, entrainer = 60% ethanol, and CO2 flow rate = 20-25 kg.(h.kg)-1 crude drug. SFE-CO2 excels the traditional steam distillation in raising yield and reducing extraction time. The oils are composed of 22 constituents including caproaldehyde, and the saikosaponins can only be extracted with the help of entrainers under higher pressure and temperature.

Supercritical fluid chromatography

NASA Astrophysics Data System (ADS)

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

1992-03-01

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

Modeling Solvation in Supercritical CO2.

PubMed

Ingrosso, Francesca; Ruiz-López, Manuel F

2017-10-06

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

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

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

Kwak, Ja Hun; Hu, Jian Z.; Turcu, Romulus VF

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 scCO2more » 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.« less

Molecular Dynamic Simulation of Diffusion Coefficients for Alkanols in Supercritical CO2 1

NASA Astrophysics Data System (ADS)

Li, Zhiwei; Lai, Shuhui; Gao, Wei; Chen, Liuping

2018-07-01

The infinite dilution diffusion coefficients ( D 12) of methanol, ethanol, 1-propanol, 1-butanol and 1-pentanol in supercritical CO2 (scCO2) at 313.2 K and 10-16 MPa were simulated by molecular dynamics (MD) simulation. The microscopic structure was also analyzed by calculation of the radial distribution function, coordination number (CN) between the center mass of solute and solvent molecules, and the average number of hydrogen bonding of this system. In infinite dilute solution, the probability of forming hydrogen bond between alkanol molecules is greatly reduced relative to pure alkanol fluid, and the weak hydrogen bonds formed between alkanol and CO2 molecules. In general, this work provides a reliable simulation method for transfer properties of solutes in scCO2. The prediction data were provides for the design and development of chemical processing. The results are helpful for one to deeper understand the relationship between microscopic structures of fluid and its transfer properties.

Rapid Determination of Two Triterpenoid Acids in Chaenomelis Fructus Using Supercritical Fluid Extraction On-line Coupled with Supercritical Fluid Chromatography.

PubMed

Zhang, Xiaotian; Ji, Feng; Li, Yueqi; He, Tian; Han, Ya; Wang, Daidong; Lin, Zongtao; Chen, Shizhong

2018-01-01

In this study, an on-line supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC) method was developed for the rapid determination of oleanoic acid and ursolic acid in Chaenomelis Fructus. After optimization of the conditions, the two triterpenoid acids was obtained by SFE using 20% methanol as a modifier at 35°C in 8 min. They were resolved on a Shim-pack UC-X Diol column (4.6 × 150 mm, 3 μm) in 14 min (0 - 10 min, 5 - 10%; 10 - 14 min, 10% methanol in CO 2 ) with a backpressure of 15 MPa at 40°C. The on-line SFE-SFC method could be completed within 40 min (10.79 mg/g dry plant, R s = 2.36), while the ultrasound-assisted extraction and HPLC method required at least 90 min (3.55 mg/g dry plant, R s = 1.92). This on-line SFE-SFC method is powerful to simplify the pre-processing and quantitative analysis of natural products.

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

NASA Astrophysics Data System (ADS)

Asiaee, Alireza; Benjamin, Kenneth M.

2016-08-01

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

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

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

Asiaee, Alireza; Benjamin, Kenneth M., E-mail: kenneth.benjamin@sdsmt.edu

2016-08-28

For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (nomore » SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0–1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.« less

Advanced Thermal Storage for Central Receivers with Supercritical Coolants

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

Kelly, Bruce D.

2010-06-15

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

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

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

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

Gruszkiewicz, Miroslaw; Wesolowski, David J; Cole, David R

2011-01-01

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

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

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

Schaef, Herbert T.; Miller, Quin RS; Thompson, Christopher J.

2013-06-30

Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring between supercritical CO2 containing water and the silicate minerals forsterite (Mg2SiO4), wollastonite (CaSiO3), and enstatite (MgSiO3). This study utilizes newly developed in situ high pressure x-ray diffraction (HXRD) and in situ infra red (IR) to examine mineralmore » 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.« less

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

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

PubMed

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

2014-07-01

Benign prostatic hyperplasia (BPH) can lead to lower urinary tract symptoms. Rape pollen is an apicultural product that is composed of nutritionally valuable and biologically active substances. The aim of the present study was to investigate the protective effect of rape pollen supercritical CO 2 fluid extract (SFE-CO 2 ) 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-CO 2 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-CO 2 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-CO 2 treatment suppressed testosterone-induced BPH. These observations indicate that rape pollen SFE-CO 2 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-CO 2 extract may be a useful agent in BPH treatment.

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.

Benzil fluorescence and phosphorescence emissions: a pertinent probe for the kinematic behaviour and microheterogeneity of supercritical CO 2

NASA Astrophysics Data System (ADS)

Chattopadhyay, Nitin; Serpa, Carlos; Isilda Silva, M.; Arnaut, Luis G.; Formosinho, Sebastião J.

2001-10-01

The relative intensity (RI) of the phosphorescence and fluorescence from the relaxed trans-planar geometry of benzil has been studied as a function of pressure and temperature in supercritical carbon dioxide (SC-CO 2). The nature of the variation of RI with pressure and temperature is similar to that of the kinematic viscosity (KV) with the two said parameters. The experimental results have been interpreted in terms of microheterogeneity of the supercritical fluid (SCF).

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

NASA Astrophysics Data System (ADS)

Wei, Liang; Gao, Kewei; Li, Qian

2018-05-01

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

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...

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.

Oxy-combustor operable with supercritical fluid

DOEpatents

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

2017-04-04

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

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.

Particle seeding enhances interconnectivity in polymeric scaffolds foamed using supercritical CO(2).

PubMed

Collins, Niki J; Bridson, Rachel H; Leeke, Gary A; Grover, Liam M

2010-03-01

Foaming using supercritical CO(2) is a well-known process for the production of polymeric scaffolds for tissue engineering. However, this method typically leads to scaffolds with low pore interconnectivity, resulting in insufficient mass transport and a heterogeneous distribution of cells. In this study, microparticulate silica was added to the polymer during processing and the effects of this particulate seeding on the interconnectivity of the pore structure and pore size distribution were investigated. Scaffolds comprising polylactide and a range of silica contents (0-50 wt.%) were produced by foaming with supercritical CO(2). Scaffold structure, pore size distributions and interconnectivity were assessed using X-ray computed microtomography. Interconnectivity was also determined through physical measurements. It was found that incorporation of increasing quantities of silica particles increased the interconnectivity of the scaffold pore structure. The pore size distribution was also reduced through the addition of silica, while total porosity was found to be largely independent of silica content. Physical measurements and those derived from X-ray computed microtomography were comparable. The conclusion drawn was that the architecture of foamed polymeric scaffolds can be advantageously manipulated through the incorporation of silica microparticles. The findings of this study further establish supercritical fluid foaming as an important tool in scaffold production and show how a previous limitation can be overcome. Copyright 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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.

[Supercritical CO2 extraction and component analysis of Aesculus wilsonii seed oil].

PubMed

Chen, Guang-Yu; Shi, Zhao-Hua; Li, Hai-Chi; Ge, Fa-Huan; Zhan, Hua-Shu

2013-03-01

To research the optimal extraction process of supercritical CO2 extraction and analyze the component of the oil extracted from Aesculus wilsonii seed. Using the yield of Aesculus wilsonii seed oil as the index, optimized supercritical CO2 extraction parameter by orthogonal experiment methodology and analysed the compounds of Aesculus wilsonii seed oil by GC-MS. The optimal parameters of the supercritical CO2 extraction of the oil extracted from Aesculus wilsoniit seed were determined: the extraction pressure was 28 MPa and the temperature was 38 degrees C, the separation I pressure was 12 MPa and the temperature was 40 degrees C, the separation II pressure was 5 MPa and the temperature was 40 degrees C, the extraction time was 110 min. The average extraction rate of Aesculus wilsonii seed oil was 1.264%. 26 kinds of compounds were identified by GC-MS in Aesculus wilsonii seed oil extracted by supercritical CO2. The main components were fatty acids. Comparing with the petroleum ether extraction, the supercritical CO2 extraction has higher extraction rate, shorter extraction time, more clarity oil. The kinds of fatty acids with high amounts in Aesculus wilsonii seed oil is identical in general, the kinds of fatty acids with low amounts in Aesculus wilsonii seed oil have differences.

Feasibility of ion-pair/supercritical fluid extraction of an ionic compound--pseudoephedrine hydrochloride.

PubMed

Eckard, P R; Taylor, L T

1997-02-01

The supercritical fluid extraction (SFE) of an ionic compound, pseudoephedrine hydrochloride, from a spiked-sand surface was successfully demonstrated. The effect of carbon dioxide density (CO2), supercritical fluid composition (pure vs. methanol modified), and the addition of a commonly used reversed-phase liquid chromatographic ion-pairing reagent, 1-heptanesulfonic acid, sodium salt, on extraction efficiency was examined. The extraction recoveries of pseudoephedrine hydrochloride with the addition of the ion-pairing reagent from a spiked-sand surface were shown to be statistically greater than the extraction recoveries without the ion-pairing reagent with both pure and methanol-modified carbon dioxide.

Design of experimental setup for supercritical CO2 jet under high ambient pressure conditions

NASA Astrophysics Data System (ADS)

Shi, Huaizhong; Li, Gensheng; He, Zhenguo; Wang, Haizhu; Zhang, Shikun

2016-12-01

With the commercial extraction of hydrocarbons in shale and tight reservoirs, efficient methods are needed to accelerate developing process. Supercritical CO2 (SC-CO2) jet has been considered as a potential way due to its unique fluid properties. In this article, a new setup is designed for laboratory experiment to research the SC-CO2 jet's characteristics in different jet temperatures, pressures, standoff distances, ambient pressures, etc. The setup is composed of five modules, including SC-CO2 generation system, pure SC-CO2 jet system, abrasive SC-CO2 jet system, CO2 recovery system, and data acquisition system. Now, a series of rock perforating (or case cutting) experiments have been successfully conducted using the setup about pure and abrasive SC-CO2 jet, and the results have proven the great perforating efficiency of SC-CO2 jet and the applications of this setup.

Design of experimental setup for supercritical CO2 jet under high ambient pressure conditions.

PubMed

Shi, Huaizhong; Li, Gensheng; He, Zhenguo; Wang, Haizhu; Zhang, Shikun

2016-12-01

With the commercial extraction of hydrocarbons in shale and tight reservoirs, efficient methods are needed to accelerate developing process. Supercritical CO 2 (SC-CO 2 ) jet has been considered as a potential way due to its unique fluid properties. In this article, a new setup is designed for laboratory experiment to research the SC-CO 2 jet's characteristics in different jet temperatures, pressures, standoff distances, ambient pressures, etc. The setup is composed of five modules, including SC-CO 2 generation system, pure SC-CO 2 jet system, abrasive SC-CO 2 jet system, CO 2 recovery system, and data acquisition system. Now, a series of rock perforating (or case cutting) experiments have been successfully conducted using the setup about pure and abrasive SC-CO 2 jet, and the results have proven the great perforating efficiency of SC-CO 2 jet and the applications of this setup.

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...

A flow-through column electrolytic cell for supercritical fluid chromatography.

PubMed

Yamamoto, Kazuhiro; Ueki, Tatsuya; Higuchi, Naoyuki; Takahashi, Kouji; Kotani, Akira; Hakamata, Hideki

2017-10-01

A novel flow-through column electrolytic cell was proposed as a detector to obtain current signals for supercritical fluid chromatography. The electrochemical cell consisted of two electrodes and its holder, and a working and a counter electrode were fabricated from 192 carbon strings, which were composed of 400 carbon fibers of 10 μm in diameter filled into a heat-shrinkable tube. These electrodes were placed in the center of a holder made from polyether ether ketone blocks and they were separated by polytetrafluoroethylene membrane filters. To evaluate the sensitivity of this cell, a standard solution of ferrocene was injected into the supercritical fluid chromatography system connected to the electrolytic cell. The ferrocene was eluted through a silica gel column using a mixture of a mobile phase of supercritical CO 2 and a modifier of methanol containing ammonium acetate. The current peak area of ferrocene correlated to the ferrocene concentration in the range of 10-400 μmol/L (r = 0.999). Moreover, the limit of detection on the column estimated from a signal-to-noise ratio of 3 was 9.8  × 10 -13  mol. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supercritical carbon dioxide extraction of 2,4-dichlorophenol from food crop tissues.

PubMed

Thomson, C A; Chesney, D J

1992-04-15

Supercritical fluid extraction with carbon dioxide has been found to be effective for the isolation of residue levels (0.1-1 ppm) of 2,4-dichlorophenol from selected plant tissues. The 2,4-dichlorophenol residues were incompletely extracted with supercritical CO2 alone, since a substantial fraction of the 2,4-dichlorophenol was covalently attached to the plant matrix. An acid pretreatment procedure was developed to partially hydrolyze the plant tissue prior to extraction, releasing the bound 2,4-dichlorophenol residues. Steam distillation showed higher residue levels for field-treated straw samples. This is attributed to the greater degree of hydrolysis inherent in the steam distillation procedure. Supercritical CO2 extraction of field-treated seed samples showed higher levels of 2,4-dichlorophenol residues than did steam distillation. The supercritical fluid extractant was able to solvate 2,4-dichlorophenol residues in the interior of the seed and transport them to the surface for collection. The aqueous medium used in steam distillation was unable to penetrate the hydrophobic seed matrix to the same degree. While the actual extraction time experienced in supercritical fluid extraction was far less than that of steam distillation (45 min vs 6 h, respectively), the total sample preparation time was similar in both methods.

Rate variations of a hetero-Diels--Alder reaction in supercritical fluid CO{sub 2}

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

Thompson, R.L.; Glaeser, R.; Bush, D.

1999-11-01

The hetero-Diels-Alder reaction between anthracene and excess 4-phenyl-1,2,4-triazoline-3,5-dione has been investigated in supercritical CO{sub 2} at 40 C and pressures between 75 and 216 bar. Biomolecular reaction rate constants have been measured via fluorescence spectroscopy by following the decrease in anthracene concentration with reaction time. The reaction rate is elevated in the vicinity of the critical pressure. This difference is consistent with local composition enhancement and can be modeled with the Peng-Robinson equation of state.

Preparation of zein nanoparticles by using solution-enhanced dispersion with supercritical CO2 and elucidation with computational fluid dynamics

PubMed Central

Li, Sining; Zhao, Yaping

2017-01-01

Nanoparticles have attracted more and more attention in the medicinal field. Zein is a biomacromolecule and can be used as a carrier for delivering active ingredients to prepare controlled release drugs. In this article, we presented the preparation of zein nanoparticles by solution-enhanced dispersion by supercritical CO2 (SEDS) approach. Scanning electron microscopy and transmission electron microscopy were applied to characterize the size and morphology of the obtained particles. The nozzle structure and the CO2 flow rate greatly affected the morphology and the size of the particles. The size of zein was able to be reduced to 50–350 nm according to the different conditions. The morphologies of the resultant zein were either sphere or the filament network consisted of nanoparticles. The influence of the nozzle structure and the CO2 flow rate on the velocity field was elucidated by using computational fluid dynamics. The nozzle structure and the CO2 flow rate greatly affected the distribution of the velocity field. However, a similar velocity field could also be obtained when the nozzle structure or the CO2 flow rate, or both were different. Therefore, the influence of the nozzle structure and the CO2 flow rate on the size and morphology of the particles, can boil down to the velocity field. The results demonstrated that the velocity field can be a potential criterion for producing nanoparticles with controllable morphology and size, which is useful to scale-up the SEDS process. PMID:28496324

Coupled optical/thermal/fluid analysis and design requirements for operation and testing of a supercritical CO 2 solar receiver.

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

Khivsara, Sagar

Recent studies have evaluated closed-loop supercritical carbon dioxide (s-CO 2) Brayton cycles to be a higher energy-density system in comparison to conventional superheated steam Rankine systems. At turbine inlet conditions of 923K and 25 MPa, high thermal efficiency (~50%) can be achieved. Achieving these high efficiencies will make concentrating solar power (CSP) technologies a competitive alternative to current power generation methods. To incorporate a s-CO 2 Brayton power cycle in a solar power tower system, the development of a solar receiver capable of providing an outlet temperature of 923 K (at 25 MPa) is necessary. To satisfy the temperature requirementsmore » of a s-CO 2 Brayton cycle with recuperation and recompression, it is required to heat s-CO 2 by a temperature of ~200 K as it passes through the solar receiver. Our objective was to develop an optical-thermal-fluid model to design and evaluate a tubular receiver that will receive a heat input ~1 MWth from a heliostat field. We also undertook the documentation of design requirements for the development, testing and safe operation of a direct s-CO 2 solar receiver. The main purpose of this document is to serve as a reference and guideline for design and testing requirements, as well as to address the technical challenges and provide initial parameters for the computational models that will be employed for the development of s-CO 2 receivers.« less

Preparation of zein nanoparticles by using solution-enhanced dispersion with supercritical CO2 and elucidation with computational fluid dynamics.

PubMed

Li, Sining; Zhao, Yaping

2017-01-01

Nanoparticles have attracted more and more attention in the medicinal field. Zein is a biomacromolecule and can be used as a carrier for delivering active ingredients to prepare controlled release drugs. In this article, we presented the preparation of zein nanoparticles by solution-enhanced dispersion by supercritical CO 2 (SEDS) approach. Scanning electron microscopy and transmission electron microscopy were applied to characterize the size and morphology of the obtained particles. The nozzle structure and the CO 2 flow rate greatly affected the morphology and the size of the particles. The size of zein was able to be reduced to 50-350 nm according to the different conditions. The morphologies of the resultant zein were either sphere or the filament network consisted of nanoparticles. The influence of the nozzle structure and the CO 2 flow rate on the velocity field was elucidated by using computational fluid dynamics. The nozzle structure and the CO 2 flow rate greatly affected the distribution of the velocity field. However, a similar velocity field could also be obtained when the nozzle structure or the CO 2 flow rate, or both were different. Therefore, the influence of the nozzle structure and the CO 2 flow rate on the size and morphology of the particles, can boil down to the velocity field. The results demonstrated that the velocity field can be a potential criterion for producing nanoparticles with controllable morphology and size, which is useful to scale-up the SEDS process.

Separation of supercritical slab-fluids to form aqueous fluid and melt components in subduction zone magmatism.

PubMed

Kawamoto, Tatsuhiko; Kanzaki, Masami; Mibe, Kenji; Matsukage, Kyoko N; Ono, Shigeaki

2012-11-13

Subduction-zone magmatism is triggered by the addition of H(2)O-rich slab-derived components: aqueous fluid, hydrous partial melts, or supercritical fluids from the subducting slab. Geochemical analyses of island arc basalts suggest two slab-derived signatures of a melt and a fluid. These two liquids unite to a supercritical fluid under pressure and temperature conditions beyond a critical endpoint. We ascertain critical endpoints between aqueous fluids and sediment or high-Mg andesite (HMA) melts located, respectively, at 83-km and 92-km depths by using an in situ observation technique. These depths are within the mantle wedge underlying volcanic fronts, which are formed 90 to 200 km above subducting slabs. These data suggest that sediment-derived supercritical fluids, which are fed to the mantle wedge from the subducting slab, react with mantle peridotite to form HMA supercritical fluids. Such HMA supercritical fluids separate into aqueous fluids and HMA melts at 92 km depth during ascent. The aqueous fluids are fluxed into the asthenospheric mantle to form arc basalts, which are locally associated with HMAs in hot subduction zones. The separated HMA melts retain their composition in limited equilibrium with the surrounding mantle. Alternatively, they equilibrate with the surrounding mantle and change the major element chemistry to basaltic composition. However, trace element signatures of sediment-derived supercritical fluids remain more in the melt-derived magma than in the fluid-induced magma, which inherits only fluid-mobile elements from the sediment-derived supercritical fluids. Separation of slab-derived supercritical fluids into melts and aqueous fluids can elucidate the two slab-derived components observed in subduction zone magma chemistry.

Separation of supercritical slab-fluids to form aqueous fluid and melt components in subduction zone magmatism

PubMed Central

Kawamoto, Tatsuhiko; Kanzaki, Masami; Mibe, Kenji; Ono, Shigeaki

2012-01-01

Subduction-zone magmatism is triggered by the addition of H2O-rich slab-derived components: aqueous fluid, hydrous partial melts, or supercritical fluids from the subducting slab. Geochemical analyses of island arc basalts suggest two slab-derived signatures of a melt and a fluid. These two liquids unite to a supercritical fluid under pressure and temperature conditions beyond a critical endpoint. We ascertain critical endpoints between aqueous fluids and sediment or high-Mg andesite (HMA) melts located, respectively, at 83-km and 92-km depths by using an in situ observation technique. These depths are within the mantle wedge underlying volcanic fronts, which are formed 90 to 200 km above subducting slabs. These data suggest that sediment-derived supercritical fluids, which are fed to the mantle wedge from the subducting slab, react with mantle peridotite to form HMA supercritical fluids. Such HMA supercritical fluids separate into aqueous fluids and HMA melts at 92 km depth during ascent. The aqueous fluids are fluxed into the asthenospheric mantle to form arc basalts, which are locally associated with HMAs in hot subduction zones. The separated HMA melts retain their composition in limited equilibrium with the surrounding mantle. Alternatively, they equilibrate with the surrounding mantle and change the major element chemistry to basaltic composition. However, trace element signatures of sediment-derived supercritical fluids remain more in the melt-derived magma than in the fluid-induced magma, which inherits only fluid-mobile elements from the sediment-derived supercritical fluids. Separation of slab-derived supercritical fluids into melts and aqueous fluids can elucidate the two slab-derived components observed in subduction zone magma chemistry. PMID:23112158

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

PubMed

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

2012-10-01

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

Measurement of diffusion in fluid systems: Applications to the supercritical fluid region

NASA Astrophysics Data System (ADS)

Bruno, Thomas J.

1994-04-01

The experimental procedures that are applicable to the measurement of diffusion in supercritical fluid solutions are reviewed. This topic is of great importance to the proper design of advanced aircraft and turbine fuels, since the fuels on these aircraft may sometimes operate under supercritical fluid conditions. More specifically, we will consider measurements of the binary interaction diffusion coefficient D exp 12 of a solute (species 1) and the solvent (species 2). In this discussion, the supercritical fluid is species 2, and the solute, species 1, will be at a relatively low concentration, sometimes approaching infinite dilution. After a brief introduction to the concept of diffusion, we will discuss in detail the use of chromatographic methods, and then briefly treat light scattering, nuclear magnetic resonance spectra, and physical methods.

Electrodeposition of germanium from supercritical fluids.

PubMed

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

2012-01-28

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

Microfluidic study for investigating migration and residual phenomena of supercritical CO2 in porous media

NASA Astrophysics Data System (ADS)

Park, Gyuryeong; Wang, Sookyun; Lee, Minhee; Um, Jeong-Gi; Kim, Seon-Ok

2017-04-01

The storage of CO2 in underground geological formation such as deep saline aquifers or depleted oil and gas reservoirs is one of the most promising technologies for reducing the atmospheric CO2 release. The processes in geological CO2 storage involves injection of supercritical CO2 (scCO2) into porous formations saturated with brine and initiates CO2 flooding with immiscible displacement. The CO2 migration and porewater displacement within geological formations, and , consequentially, the storage efficiency are governed by the interaction of fluid and rock properties and are affected by the interfacial tension, capillarity, and wettability in supercritical CO2-brine-mineral systems. This study aims to observe the displacement pattern and estimate storage efficiency by using micromodels. This study aims to conduct scCO2 injection experiments for visualization of distribution of injected scCO2 and residual porewater in transparent pore networks on microfluidic chips under high pressure and high temperature conditions. In order to quantitatively analyze the porewater displacement by scCO2 injection under geological CO2 storage conditions, the images of invasion patterns and distribution of CO2 in the pore network are acquired through a imaging system with a microscope. The results from image analysis were applied in quantitatively investigating the effects of major environmental factors and scCO2 injection methods on porewater displacement process by scCO2 and storage efficiency. The experimental observation results could provide important fundamental information on capillary characteristics of reservoirs and improve our understanding of CO2 sequestration progress.

Mass balance of metal species in supercritical fluid extraction using sodium diethyldithiocarbamate and dibutylammonium dibutyldithiocarbamate.

PubMed

Wang, Joanna Shaofen; Chiu, Kong-Hwa

2006-03-01

The objective of this work is to track the amount of metal complexes distributed in the extraction cell, collection vial, and tubing used in supercritical fluid extraction (SFE) systems after progressive removal of metal ions in supercritical carbon dioxide (SC-CO2). Sodium diethyldithiocarbamate (NaDDC) and dibutylammonium dibutyldithiocarbamate (DBDC) ligands were used to form complexes with Cd, Cu, Pb, and Zn and CO(2)/5% methanol as a supercritical fluid. The mass balance of metal complexes were obtained before and after extraction, and metals in different locations in the system were flushed out using an organic solvent and nitric acid (HNO3). These results infer that the stability constant (beta) of the metal-ligand complex has a strong correlation with SFE. Because of the composition of the stainless-steel cell, Fe, Cr, and Ni or other trace elements in the cell might interfere with the mass balance of metal complexes in SFE due to an exchange mechanism taking place between the cell and the sample.

Au/Graphene Oxide Nanocomposite Synthesized in Supercritical CO2 Fluid as Energy Efficient Lubricant Additive.

PubMed

Meng, Yuan; Su, Fenghua; Chen, Yangzhi

2017-11-15

Au nanoparticles are successfully decorated onto graphene oxide (GO) sheets with the aid of supercritical carbon dioxide (ScCO 2 ) fluid. The synthesized nanocomposite (Sc-Au/GO) was characterized by X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), and transmission electron microscopy (TEM). The characterization results show that the Au nanoparticles are featured with face-centered cubic crystal structure and disperse well on the GO nanosheet surfaces with average diameters of 4-10 nm. The tribological behaviors of Sc-Au/GO as lubricating additive in PAO6 oil were investigated using a ball-on-disc friction tester, and a control experiment by respectively adding GO, nano-Au particles, and Au/GO produced in the absence of ScCO 2 was performed as well. It is found that Sc-Au/GO exhibits the best lubricating performances among all the samples tested. When 0.10 wt % Sc-Au/GO is dispersed into PAO6 oil, the friction coefficient and wear rate are respectively reduced by 33.6% and 72.8% as compared to that of the pure PAO6 oil, indicating that Sc-Au/GO is an energy efficient lubricant additive. A possible lubricating mechanism of Sc-Au/GO additive in PAO6 oil has been tentatively proposed on the basis of the analyzed results of the worn surface examined by scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS).

[Optimization for supercritical CO2 extraction with response surface methodology of Prunus armeniaca oil].

PubMed

Chen, Fei-Fei; Wu, Yan; Ge, Fa-Huan

2012-03-01

To optimize the extraction conditions of Prunus armeniaca oil by Supercritical CO2 extraction and identify its components by GC-MS. Optimized of SFE-CO extraction by response surface methodology and used GC-MS to analysis Prunus armeniaca oil compounds. Established the model of an equation for the extraction rate of Prunus armeniaca oil by supercritical CO2 extraction, and the optimal parameters for the supercritical CO2 extraction determined by the equation were: the extraction pressure was 27 MPa, temperature was 39 degrees C, the extraction rate of Prunus armeniaca oil was 44.5%. 16 main compounds of Prunus armeniaca oil extracted by supercritical CO2 were identified by GC-MS, unsaturated fatty acids were 92.6%. This process is simple, and can be used for the extraction of Prunus armeniaca oil.

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.

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

Advanced Supercritical Carbon Dioxide Brayton Cycle Development

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

Anderson, Mark; Sienicki, James; Moisseytsev, Anton

2015-10-21

Fluids operating in the supercritical state have promising characteristics for future high efficiency power cycles. In order to develop power cycles using supercritical fluids, it is necessary to understand the flow characteristics of fluids under both supercritical and two-phase conditions. In this study, a Computational Fluid Dynamic (CFD) methodology was developed for supercritical fluids flowing through complex geometries. A real fluid property module was implemented to provide properties for different supercritical fluids. However, in each simulation case, there is only one species of fluid. As a result, the fluid property module provides properties for either supercritical CO 2 (S-CO 2)more » or supercritical water (SCW). The Homogeneous Equilibrium Model (HEM) was employed to model the two-phase flow. HEM assumes two phases have same velocity, pressure, and temperature, making it only applicable for the dilute dispersed two-phase flow situation. Three example geometries, including orifices, labyrinth seals, and valves, were used to validate this methodology with experimental data. For the first geometry, S-CO 2 and SCW flowing through orifices were simulated and compared with experimental data. The maximum difference between the mass flow rate predictions and experimental measurements is less than 5%. This is a significant improvement as previous works can only guarantee 10% error. In this research, several efforts were made to help this improvement. First, an accurate real fluid module was used to provide properties. Second, the upstream condition was determined by pressure and density, which determines supercritical states more precise than using pressure and temperature. For the second geometry, the flow through labyrinth seals was studied. After a successful validation, parametric studies were performed to study geometric effects on the leakage rate. Based on these parametric studies, an optimum design strategy for the see-through labyrinth seals was

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

PubMed

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

2015-10-01

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

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

PubMed

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

2012-08-10

Supercritical fluid extraction (SFE) is an innovative, clean and environmental friendly technology with particular interest for the extraction of essential oil from plants and herbs. Supercritical CO(2) is selective, there is no associated waste treatment of a toxic solvent, and extraction times are moderate. Further, supercritical extracts were often recognized of superior quality when compared with those produced by hydro-distillation or liquid-solid extraction. This review provides a comprehensive and updated discussion of the developments and applications of SFE in the isolation of essential oils from plant matrices. SFE is normally performed with pure CO(2) or using a cosolvent; fractionation of the extract is commonly accomplished in order to isolate the volatile oil compounds from other co-extracted substances. In this review the effect of pressure, temperature and cosolvent on the extraction and fractionation procedure is discussed. Additionally, a comparison of the extraction yield and composition of the essential oil of several plants and herbs from Lamiaceae family, namely oregano, sage, thyme, rosemary, basil, marjoram and marigold, which were produced in our supercritical pilot-plant device, is presented and discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

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

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

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 temperaturemore » and pressure conditions of EGS reservoirs.« less

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

USGS Publications Warehouse

Freifeild, Barry M.; Trautz, Robert C.; Kharaka, Yousif K.; Phelps, Tommy J.; Myer, Larry R.; Hovorka, Susan D.; Collins, Daniel 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 CO2sequestration 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.

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

USGS Publications Warehouse

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

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.

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

PubMed

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

2009-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2010-01-01

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

Theoretical models for supercritical fluid extraction.

PubMed

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

2012-08-10

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

Supercritical Fluids Processing of Biomass to Chemicals and Fuels

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

Olson, Norman K.

2011-09-28

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

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.

Pore-scale observation and 3D simulation of wettability effects on supercritical CO2 - brine immiscible displacement in drainage

NASA Astrophysics Data System (ADS)

Hu, R.; Wan, J.; Chen, Y.

2016-12-01

Wettability is a factor controlling the fluid-fluid displacement pattern in porous media and significantly affects the flow and transport of supercritical (sc) CO2 in geologic carbon sequestration. Using a high-pressure micromodel-microscopy system, we performed drainage experiments of scCO2 invasion into brine-saturated water-wet and intermediate-wet micromodels; we visualized the scCO2 invasion morphology at pore-scale under reservoir conditions. We also performed pore-scale numerical simulations of the Navier-Stokes equations to obtain 3D details of fluid-fluid displacement processes. Simulation results are qualitatively consistent with the experiments, showing wider scCO2 fingering, higher percentage of scCO2 and more compact displacement pattern in intermediate-wet micromodel. Through quantitative analysis based on pore-scale simulation, we found that the reduced wettability reduces the displacement front velocity, promotes the pore-filling events in the longitudinal direction, delays the breakthrough time of invading fluid, and then increases the displacement efficiency. Simulated results also show that the fluid-fluid interface area follows a unified power-law relation with scCO2 saturation, and show smaller interface area in intermediate-wet case which suppresses the mass transfer between the phases. These pore-scale results provide insights for the wettability effects on CO2 - brine immiscible displacement in geologic carbon sequestration.

[Chemical constituents from supercritical CO2 extraction of Schisandra chinensis].

PubMed

Zhu, Hong-yan; Lin, Hai-cheng; Wang, Guo-li; Zhang, Lian-xue

2014-11-01

To study the chemical constituents from the supercritical CO2 extraction of Schisandra chinensis. The compounds were separated and purified by conventional column chromatography and their structures were identified by spectroscopic methods. Nine compounds were isolated from the supercritical CO2 extraction of Schisandra chinensis, and their structures were identified as chrysophanol(1),schisandrin B(2), β-sitosterol(3), schisandrin C(4),schisandrol A(5), angeloylgomisin H(6), daucosterol(7) 1, 5-dimethyl citrate (8), and shikimic acid (9). Compounds 1, 8 and 9 are isolated from Schisandra chinensis for the first time,and compound 1 as an anthraquinone is isolated from this genus for the first time.

Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O

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

Capobianco, Ryan; Gruszkiewicz, Miroslaw; Wesolowski, David J

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 densitiesmore » 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.« less

Research on the physical properties of supercritical CO2 and the log evaluation of CO2-bearing volcanic reservoirs

NASA Astrophysics Data System (ADS)

Pan, Baozhi; Lei, Jian; Zhang, Lihua; Guo, Yuhang

2017-10-01

CO2-bearing reservoirs are difficult to distinguish from other natural gas reservoirs during gas explorations. Due to the lack of physical parameters for supercritical CO2, particularly neutron porosity, at present a hydrocarbon gas log evaluation method is used to evaluate CO2-bearing reservoirs. The differences in the physical properties of hydrocarbon and CO2 gases have led to serious errors. In this study, the deep volcanic rock of the Songliao Basin was the research area. In accordance with the relationship between the density and acoustic velocity of supercritical CO2 and temperature and pressure, the regularity between the CO2 density and acoustic velocity, and the depth of the area was established. A neutron logging simulation was completed based on a Monte Carlo method. Through the simulation of the wet limestone neutron logging, the relationship between the count rate ratio of short and long space detectors and the neutron porosity was acquired. Then, the nature of the supercritical CO2 neutron moderation was obtained. With consideration given to the complexity of the volcanic rock mineral composition, a volcanic rock volume model was established, and the matrix neutron and density parameters were acquired using the ECS log. The properties of CO2 were applied in the log evaluation of the CO2-bearing volcanic reservoirs in the southern Songliao Basin. The porosity and saturation of CO2 were obtained, and a reasonable application was achieved in the CO2-bearing reservoir.

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

Chemical Reactions in Supercritical Carbon Dioxide

NASA Astrophysics Data System (ADS)

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

1998-12-01

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

Field-portable supercritical CO{sub 2} extractor

DOEpatents

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

1997-06-10

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

Field-portable supercritical CO.sub.2 extractor

DOEpatents

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

1997-01-01

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

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

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

Loring, John S.; Thompson, Christopher J.; Wang, Zheming

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.more » 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.« less

Use of liquid/supercritical CO2 extraction process for butanol recovery from fermentation broth

USDA-ARS?s Scientific Manuscript database

In order for butanol fermentation to be a viable option, it is essential to recover it from fermentation broth using economical alternate in-situ product recovery techniques such as liquid/supercritical CO2 extraction as compared to distillation. This technique (liquid CO2 extraction & supercritical...

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

NASA Astrophysics Data System (ADS)

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

1994-10-01

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

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...

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

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

Carmichael, Justin R; Rother, Gernot; Browning, Jim

2012-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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

PubMed

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

2013-03-01

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

Structural Evolution of Supercritical CO2 across the Frenkel Line.

PubMed

Bolmatov, Dima; Zav'yalov, D; Gao, M; Zhernenkov, Mikhail

2014-08-21

Here, we study structural properties of the supercritical carbon dioxide and discover the existence of persistent medium-range order correlations, which make supercritical carbon dioxide nonuniform and heterogeneous on an intermediate length scale. We report on the CO2 heterogeneity shell structure where, in the first shell, both carbon and oxygen atoms experience gas-like-type interactions with short-range order correlations while within the second shell, oxygen atoms essentially exhibit a liquid-like type of interactions due to localization of transverse-like phonon packets. Importantly, we highlight a catalytic role of atoms inside of the nearest-neighbor heterogeneity shell in providing a mechanism for diffusion and proving the existence of an additional thermodynamic boundary in the supercritical carbon dioxide on an intermediate length scale. Finally, we discuss important implications for answering the intriguing question whether Venus may have had CO2 oceans and urge for an experimental detection of this persistent local-order heterogeneity.

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

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

Fleming, Darryn D.; Holschuh, Thomas Vernon,; Conboy, Thomas M.

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 thatmore » 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.« less

Bio-oil production from biomass via supercritical fluid extraction

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

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

2016-04-18

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

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

Impact of CO2-solvent separators on the degradation of benzyl-2,3-dihydroxypiperidine-1-carboxylate during preparative supercritical fluid chromatographic (SFC) purification.

PubMed

Asokan, Kathiravan; Naidu, Harshavardhan; Madam, Ratalababu; Shaikh, Khaja Mohiuddin; Reddy, Manjunath; Kumar, Hemantha; Shirude, Pravin S; Rajendran, Muruganantham; Sarabu, Ramakanth; Wu, Dauh-Rurng; Bajpai, Lakshmikant; Zhang, Yingru

2017-12-29

During a preparative separation of the cis enantiomeric pair of benzyl-2,3-dihydroxypiperidine-1-carboxylate using supercritical-fluid chromatography (SFC) with methanol modifier, significant degradation of the products in the collected fractions was observed when a Waters SFC-350 ® (Milford, MA, USA) was used, but same was not observed when a Waters SFC-80q ® (Milford, MA, USA) was used. Through a systematic investigation, we discovered that the compound degraded over time under an acidic condition created by the formation of methyl carbonic acid from methanol and CO 2. The extent of the product degradation was dependent on the time and the concentration of CO 2 remained in the product fraction, which was governed by the efficiency of CO 2 -methanol separation during the fraction collection. Hence, we demonstrated that the different designs of CO 2 -solvent separator (high pressurized cyclone in Waters SFC-350 ® and low-pressurized vortexing separator in Waters SFC-80q ®® ) had a significant impact on the degradation of an acid-sensitive compound. The acidity caused by CO 2 in methanol was supported by diminished degradation after a nitrogen purging or after neutralizing the collected fractions with a base. Three different solutions to overcome the degradation problem of the acid sensitive compounds using SFC-350 ® with the high pressurized separator were investigated and demonstrated. The degraded products were isolated as four enantiomers and their relative stereochemistry were established based on 2D NMR data along with the plausible mechanism of degradation. Copyright © 2017 Elsevier B.V. All rights reserved.

Supercritical-fluid extraction and chromatography-mass spectrometry for analysis of mycotoxins

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

Smith, R.D.; Udseth, H.R.

1982-07-01

The use of direct supercritical-fluid injection-mass spectrometry for the rapid analysis of mycotoxins of the tricothecene group is demonstrated. A solution containing diacetoxyscirpenol or T-2 toxin is injected into a fluid consisting primarily of pentane or carbon dioxide and is rapidly brought to supercritical conditions. Direct injection of the fluid stream into a chemical ionization source allows thermally labile compounds to be analyzed. Under these conditions trichothecene mass spectra showing significant (M + 1)/sup +/ ions and distinctive fragmentation patterns are obtained. Detection limits are in the subnanogram range. Direct analysis from complex substrates using selective supercritical-fluid extraction is proposed.more » 4 figures.« less

Supercritical CO2 Extraction of Rice Bran Oil -the Technology, Manufacture, and Applications.

PubMed

Sookwong, Phumon; Mahatheeranont, Sugunya

2017-06-01

Rice bran is a good source of nutrients that have large amounts of phytochemicals and antioxidants. Conventional rice bran oil production requires many processes that may deteriorate and degrade these valuable substances. Supercritical CO 2 extraction is a green alternative method for producing rice bran oil. This work reviews production of rice bran oil by supercritical carbon dioxide (SC-CO 2 ) extraction. In addition, the usefulness and advantages of SC-CO 2 extracted rice bran oil for edible oil and health purpose is also described.

Instrumentation for analytical scale supercritical fluid chromatography.

PubMed

Berger, Terry A

2015-11-20

Analytical scale supercritical fluid chromatography (SFC) is largely a sub-discipline of high performance liquid chromatography (HPLC), in that most of the hardware and software can be used for either technique. The aspects that separate the 2 techniques stem from the use of carbon dioxide (CO2) as the main component of the mobile phase in SFC. The high compressibility and low viscosity of CO2 mean that pumps, and autosamplers designed for HPLC either need to be modified or an alternate means of dealing with compressibility needs to be found. The inclusion of a back pressure regulator and a high pressure flow cell for any UV-Vis detector are also necessary. Details of the various approaches, problems and solutions are described. Characteristics, such as adiabatic vs. isothermal compressibility, thermal gradients, and refractive index issues are dealt with in detail. Copyright © 2015 Elsevier B.V. All rights reserved.

Coiled tubing drilling with supercritical carbon dioxide

DOEpatents

Kolle , Jack J.

2002-01-01

A method for increasing the efficiency of drilling operations by using a drilling fluid material that exists as supercritical fluid or a dense gas at temperature and pressure conditions existing at a drill site. The material can be used to reduce mechanical drilling forces, to remove cuttings, or to jet erode a substrate. In one embodiment, carbon dioxide (CO.sub.2) is used as the material for drilling within wells in the earth, where the normal temperature and pressure conditions cause CO.sub.2 to exist as a supercritical fluid. Supercritical carbon dioxide (SC--CO.sub.2) is preferably used with coiled tube (CT) drilling equipment. The very low viscosity SC--CO.sub.2 provides efficient cooling of the drill head, and efficient cuttings removal. Further, the diffusivity of SC--CO.sub.2 within the pores of petroleum formations is significantly higher than that of water, making jet erosion using SC--CO.sub.2 much more effective than water jet erosion. SC--CO.sub.2 jets can be used to assist mechanical drilling, for erosion drilling, or for scale removal. A choke manifold at the well head or mud cap drilling equipment can be used to control the pressure within the borehole, to ensure that the temperature and pressure conditions necessary for CO.sub.2 to exist as either a supercritical fluid or a dense gas occur at the drill site. Spent CO.sub.2 can be vented to the atmosphere, collected for reuse, or directed into the formation to aid in the recovery of petroleum.

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).

Modeling of the Kinetics of Supercritical Fluid Extraction of Lipids from Microalgae with Emphasis on Extract Desorption

PubMed Central

Sovová, Helena; Nobre, Beatriz P.; Palavra, António

2016-01-01

Microalgae contain valuable biologically active lipophilic substances such as omega-3 fatty acids and carotenoids. In contrast to the recovery of vegetable oils from seeds, where the extraction with supercritical CO2 is used as a mild and selective method, economically viable application of this method on similarly soluble oils from microalgae requires, in most cases, much higher pressure. This paper presents and verifies hypothesis that this difference is caused by high adsorption capacity of microalgae. Under the pressures usually applied in supercritical fluid extraction from plants, microalgae bind a large fraction of the extracted oil, while under extremely high CO2 pressures their adsorption capacity diminishes and the extraction rate depends on oil solubility in supercritical CO2. A mathematical model for the extraction from microalgae was derived and applied to literature data on the extraction kinetics in order to determine model parameters. PMID:28773546

Transport relaxation processes in supercritical fluids

NASA Astrophysics Data System (ADS)

Jonas, J.

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

Evaluation of CO 2 -Fluid-Rock Interaction in Enhanced Geothermal Systems: Field-Scale Geochemical Simulations

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

Pan, Feng; McPherson, Brian J.; Kaszuba, John

Recent studies suggest that using supercritical CO 2 (scCO 2 ) instead of water as a heat transmission fluid in Enhanced Geothermal Systems (EGS) may improve energy extraction. While CO 2 -fluid-rock interactions at “typical” temperatures and pressures of subsurface reservoirs are fairly well known, such understanding for the elevated conditions of EGS is relatively unresolved. Geochemical impacts of CO 2 as a working fluid (“CO 2 -EGS”) compared to those for water as a working fluid (H 2 O-EGS) are needed. The primary objectives of this study are (1) constraining geochemical processes associated with CO 2 -fluid-rock interactions undermore » the high pressures and temperatures of a typical CO 2 -EGS site and (2) comparing geochemical impacts of CO 2 -EGS to geochemical impacts of H 2 O-EGS. The St. John’s Dome CO 2 -EGS research site in Arizona was adopted as a case study. A 3D model of the site was developed. Net heat extraction and mass flow production rates for CO 2 -EGS were larger compared to H 2 O-EGS, suggesting that using scCO 2 as a working fluid may enhance EGS heat extraction. More aqueous CO 2 accumulates within upper- and lower-lying layers than in the injection/production layers, reducing pH values and leading to increased dissolution and precipitation of minerals in those upper and lower layers. Dissolution of oligoclase for water as a working fluid shows smaller magnitude in rates and different distributions in profile than those for scCO 2 as a working fluid. It indicates that geochemical processes of scCO 2 -rock interaction have significant effects on mineral dissolution and precipitation in magnitudes and distributions.« less

Evaluation of CO 2 -Fluid-Rock Interaction in Enhanced Geothermal Systems: Field-Scale Geochemical Simulations

DOE PAGES

Pan, Feng; McPherson, Brian J.; Kaszuba, John

2017-01-01

Recent studies suggest that using supercritical CO 2 (scCO 2 ) instead of water as a heat transmission fluid in Enhanced Geothermal Systems (EGS) may improve energy extraction. While CO 2 -fluid-rock interactions at “typical” temperatures and pressures of subsurface reservoirs are fairly well known, such understanding for the elevated conditions of EGS is relatively unresolved. Geochemical impacts of CO 2 as a working fluid (“CO 2 -EGS”) compared to those for water as a working fluid (H 2 O-EGS) are needed. The primary objectives of this study are (1) constraining geochemical processes associated with CO 2 -fluid-rock interactions undermore » the high pressures and temperatures of a typical CO 2 -EGS site and (2) comparing geochemical impacts of CO 2 -EGS to geochemical impacts of H 2 O-EGS. The St. John’s Dome CO 2 -EGS research site in Arizona was adopted as a case study. A 3D model of the site was developed. Net heat extraction and mass flow production rates for CO 2 -EGS were larger compared to H 2 O-EGS, suggesting that using scCO 2 as a working fluid may enhance EGS heat extraction. More aqueous CO 2 accumulates within upper- and lower-lying layers than in the injection/production layers, reducing pH values and leading to increased dissolution and precipitation of minerals in those upper and lower layers. Dissolution of oligoclase for water as a working fluid shows smaller magnitude in rates and different distributions in profile than those for scCO 2 as a working fluid. It indicates that geochemical processes of scCO 2 -rock interaction have significant effects on mineral dissolution and precipitation in magnitudes and distributions.« less

Extraction of nobiletin from Citrus Unshiu peels by supercritical fluid and its CRE-mediated transcriptional activity.

PubMed

Oba, Chisato; Ota, Masaki; Nomura, Koichiro; Fujiwara, Hironori; Takito, Jiro; Sato, Yoshiyuki; Ohizumi, Yasushi; Inomata, Hiroshi

2017-04-15

Polymethoxyflavone (PMF) is one of bioactive compounds in Citrus Unshiu and included mainly in the peels rather than the fruits, seeds and leaves. Supercritical CO 2 extraction is one candidate for selective extraction of polymethoxyflavone and in this study, supercritical CO 2 extraction with/without ethanol entrainer from Citrus Unshiu peels was examined at a temperature of 333K and a pressure of 30MPa. CRE (cyclic AMP response element)-mediated transcriptional assay was examined by using the extracts from supercritical fluid extraction. The results showed that extracts including nobiletin increased with increasing ethanol concentration in supercritical CO 2 and the elapsed extraction time. Extracts at ethanol concentration of 5 mol% showed high CRE-mediated transcription activity. This can be caused by activity of the extract including nobiletin in addition to the other methoxylated flavonoid species such as tangeretin. Extracts at ethanol concentration of 50% showed the highest CRE-mediated transcription activity, which can be attributed to flavonoid glycoside such as hesperidin. From our investigations, flavonoid glycoside can be one of promoters of CRE-mediated transcription activity. Copyright © 2017 Elsevier GmbH. All rights reserved.

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

PubMed

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

2018-01-01

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

Effect of sub- and supercritical CO2 treatment on the properties of Pseudomonas cepacia lipase.

PubMed

Chen, Dawei; Zhang, Houjin; Xu, Jing; Yan, Yunjun

2013-07-10

In this work, we have investigated the influences of sub- and supercritical CO2 treatment on the properties of Pseudomonas cepacia lipase (PCL), including its esterification and transesterification activities, structural changes and stability. Results demonstrated that exposure time to subcritical CO2 treatment had a negative effect on PCL transesterification activity whereas exposure time to supercritical CO2 treatment had a positive effect. But generally, most compressed treatments significantly enhanced PCL esterification activity. Conformational analysis by FT-IR and fluorescence emission spectra revealed that enhanced activities after supercritical CO2 treatment were correlated with the secondary and tertiary structural changes of PCL. Secondary structure changes also appeared to be responsible for enhancement of PCL activities by subcritical CO2 treatment. Compared to native PCL, treated PCL's esterification activity significantly decreased in hydrophilic organic media, while transesterification activity significantly increased in tert-amyl alcohol and acetone. After supercritical treatment, the thermal stability of PCL significantly decreased in esterification reactions, however, there was no significant difference in transesterification reactions. Copyright © 2013 Elsevier Inc. All rights reserved.

Supercritical Fluid Extraction of Pyrrolidine Alkaloid from Leaves of Piper amalago L.

PubMed Central

Filho, L. C.; Faiões, V. S.; Cunha-Júnior, E. F.; Torres-Santos, E. C.; Cortez, D. A. G.

2017-01-01

Supercritical fluid extraction was used to extract the alkaloid N-[7-(3′,4′-methylenedioxyphenyl)-2(Z),4(Z)-heptadienoyl]pyrrolidine from leaves of Piper amalago L. A three-level orthogonal array design matrix, OAD OA9(34), was used for optimization of the parameters of supercritical extraction of the alkaloid, employing supercritical carbon dioxide: extraction time (20, 40, and 60 min), temperature (40, 50, and 60°C), pressure (150, 200, and 250 bar), and the use of cosolvents (ethanol, methanol, and propyleneglycol). All parameters had significant effect on the alkaloid yield. The alkaloid yield after 60 min of extraction without cosolvents at 9 different conditions (32) in terms of temperature (40, 50, and 60°C) and pressure (150, 200, and 250 bar) was also evaluated. The optimal yield (≈3.8 mg g−1) was obtained with supercritical CO2 + methanol (5% v : v) at 40°C and 200 bar for 60 min of extraction. PMID:28539966

The effects of ultrasonic agitation on supercritical CO2 copper electroplating.

PubMed

Chuang, Ho-Chiao; Yang, Hsi-Min; Wu, Guan-Lin; Sánchez, Jorge; Shyu, Jenq-Huey

2018-01-01

Applying ultrasound to the electroplating process can improve mechanical properties and surface roughness of the coating. Supercritical electroplating process can refine grain to improve the surface roughness and hardness. However, so far there is no research combining the above two processes to explore its effect on the coating. This study aims to use ultrasound (42kHz) in supercritical CO 2 (SC-CO 2 ) electroplating process to investigate the effect of ultrasonic powers and supercritical pressures on the properties of copper films. From the results it was clear that higher ultrasonic irradiation resulted in higher current efficiency, grain refinement, higher hardness, better surface roughness and higher internal stress. SEM was also presented to verify the correctness of the measured data. The optimal parameters were set to obtain the deposit at pressure of 2000psi and ultrasonic irradiation of 0.157W/cm 3 . Compared with SC-CO 2 electroplating process, the current efficiency can be increased from 77.57% to 93.4%, the grain size decreases from 24.34nm to 22.45nm, the hardness increases from 92.87Hv to 174.18Hv, and the surface roughness decreases from 0.83μm to 0.28μm. Therefore, this study has successfully integrated advantages of ultrasound and SC-CO 2 electroplating, and proved that applied ultrasound to SC-CO 2 electroplating process can significantly improve the mechanical properties of the coating. Copyright © 2017 Elsevier B.V. All rights reserved.

Supercritical and Transcritical Real-Fluid Mixing in Diesel Engine Applications

DTIC Science & Technology

2015-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

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

NASA Astrophysics Data System (ADS)

Hu, R.; Wan, J.

2015-12-01

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

Forsterite [Mg 2 SiO 4 )] Carbonation in Wet Supercritical CO 2 : An in Situ High-Pressure X-ray Diffraction Study

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

Todd Schaef, Herbert; McGrail, Bernard P.; Loring, John L.

2013-01-02

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 with forsterite (Mg2SiO4) exposed to wet supercritical CO2. Forsterite was selected as it is an important olivine group mineral present in igneous and mafic rocks and has been the subject of a large number of aqueous dissolutionmore » studies that can be compared with non-aqueous fluid tests in this study. Transformation reactions were examined by in situ high pressure x-ray diffraction in the presence of supercritical carbon dioxide (scCO2) containing dissolved water at conditions relevant to carbon sequestration. Under modest pressures (90 bar) and temperatures (50°C), scCO2 saturated with water was found to convert >70 wt% forsterite to a hydrated magnesium carbonate, nesquehonite (MgCO3 •3H2O) and magnesite (MgCO3), after 72 hours of reaction. However, comparable tests with scCO2 at only partial water saturation (82%) showed a significantly slower carbonation rate with only ~30-39 wt% conversion to nesquehonite and no evidence of the anhydrous form (MgCO3). Further decreases in water content of the scCO2 continued to reduce the extent of carbonation, until a critical moisture threshold (~30%) was crossed where forsterite no longer reacted in the presence of the wet scCO2 to form crystalline carbonates. Increasing the temperature to 75°C produced anhydrous magnesium carbonate, magnesite (MgCO3), preceded by the intermediate phase, hydromagnesite [Mg(CO3)4(OH)2 •4H2O]. Measurements conducted during in situ IR experiments at 50°C and 30% saturation identified the presence of an amorphous

Fluidized-Bed Heat Transfer Modeling for the Development of Particle/Supercritical-CO2 Heat Exchanger

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

Ma, Zhiwen; Martinek, Janna G

Concentrating solar power (CSP) technology is moving toward high-temperature and high-performance design. One technology approach is to explore high-temperature heat-transfer fluids and storage, integrated with a high-efficiency power cycle such as the supercritical carbon dioxide (s-CO2) Brayton power cycle. The s-CO2 Brayton power system has great potential to enable the future CSP system to achieve high solar-to-electricity conversion efficiency and to reduce the cost of power generation. Solid particles have been proposed as a possible high-temperature heat-transfer medium that is inexpensive and stable at high temperatures above 1,000 degrees C. The particle/heat exchanger provides a connection between the particles andmore » s-CO2 fluid in the emerging s-CO2 power cycles in order to meet CSP power-cycle performance targets of 50% thermal-to-electric efficiency, and dry cooling at an ambient temperature of 40 degrees C. The development goals for a particle/s-CO2 heat exchanger are to heat s-CO2 to =720 degrees C and to use direct thermal storage with low-cost, stable solid particles. This paper presents heat-transfer modeling to inform the particle/s-CO2 heat-exchanger design and assess design tradeoffs. The heat-transfer process was modeled based on a particle/s-CO2 counterflow configuration. Empirical heat-transfer correlations for the fluidized bed and s-CO2 were used in calculating the heat-transfer area and optimizing the tube layout. A 2-D computational fluid-dynamics simulation was applied for particle distribution and fluidization characterization. The operating conditions were studied from the heat-transfer analysis, and cost was estimated from the sizing of the heat exchanger. The paper shows the path in achieving the cost and performance objectives for a heat-exchanger design.« less

Pushing the speed limit in enantioselective supercritical fluid chromatography.

PubMed

Regalado, Erik L; Welch, Christopher J

2015-08-01

Chromatographic enantioseparations on the order of a few seconds can be achieved by supercritical fluid chromatography using short columns packed with chiral stationary phases. The evolution of 'world record' speeds for the chromatographic separation of enantiomers has steadily dropped from an industry standard of 20-40 min just two decades ago, to a current ability to perform many enantioseparations in well under a minute. Improvements in instrument and column technologies enabled this revolution, but the ability to predict optimal separation time from an initial method development screening assay using the t(min cc) predictor greatly simplifies the development and optimization of high-speed chiral chromatographic separations. In this study, we illustrate how the use of this simple tool in combination with the workhorse technique of supercritical fluid chromatography on customized short chiral columns (1-2 cm length) allows us to achieve ultrafast enantioseparations of pharmaceutically relevant compounds on the 5-20 s scale, bringing the technique of high-throughput enantiopurity analysis out of the specialist realm and into the laboratories of most researchers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antimicrobial activity and composition profile of grape (Vitis vinifera) pomace extracts obtained by supercritical fluids.

PubMed

Oliveira, Daniela A; Salvador, Ana Augusta; Smânia, Artur; Smânia, Elza F A; Maraschin, Marcelo; Ferreira, Sandra R S

2013-04-10

The possibility of increasing the aggregated value of the huge amount of residues generated by wineries around the world foment studies using the grape pomace - the residue from the wine production, composed by seed, skin and stems - to obtain functional ingredients. Nowadays, consumers in general prefer natural and safe products mainly for food and cosmetic fields, where the supercritical fluid extraction is of great importance due to the purity of the extracts provided. Therefore, the objective of this work is to evaluate the global extraction yield, the antimicrobial activity and the composition profile of Merlot and Syrah grape pomace extracts obtained by supercritical CO2 (SC-CO2) and CO2 added with co-solvent at pressures up to 300 bar and temperatures of 50 and 60 °C. The results were compared with the ones obtained by Soxhlet and by ultrasound-assisted leaching extraction methods. The main components from the extracts, identified by HPLC, were gallic acid, p-OH-benzoic acid, vanillic acid and epicatechin. The antibacterial and antifungal activities of the extracts were evaluated using four strains of bacteria (Staphylococcus aureus, Bacillus cereus, Escherichia coli and Pseudomonas aeruginosa) and three fungi strains (Candida albicans, Candida parapsilosis, Candida krusei). Despite lower extraction yield results, the supercritical fluid extracts presented the highest antimicrobial effectiveness compared to the other grape pomace extracts due to the presence of antimicrobial active compounds. Syrah extracts were less efficient against the microorganisms tested and Merlot extracts were more active against Gram-positive bacteria. Copyright © 2012 Elsevier B.V. All rights reserved.

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

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

Schaef, Herbert T.; Windisch, Charles F.; McGrail, B. Peter

2011-11-01

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

Preparation and characterisation of hydrocortisone particles using a supercritical fluids extraction process.

PubMed

Velaga, Sitaram P; Ghaderi, Raouf; Carlfors, Johan

2002-01-14

Crystallisation and subsequent milling of pharmaceutical powders by traditional methods often cause variations in physicochemical properties thereby influencing bioavailability of the formulation. Crystallisation of drug substances using supercritical fluids (SFs) offers some advantages over existing traditional methods in controlling particle characteristics. The novel particle formation method, solution enhanced dispersion by supercritical (SEDS) fluids was used for the preparation of hydrocortisone (HC) particles. The influence of processing conditions on the solid-state properties of the particles was studied. HC, an anti-inflammatory corticosteroid, particles were prepared from acetone and methanol solutions using the SEDS process. The solutions were dispersed with supercritical CO(2), acting as an anti-solvent, through a specially designed co-axial nozzle into a pressured vessel maintained at a specific constant temperature and pressure. The temperatures and pressures studied were 40-90 degrees C and 90-180 bar, respectively. The relative flow rates of drug solution to CO(2) were varied between 0.002 and 0.03. Solid-state characterisation of particles included differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD), solubility studies and scanning electron microscopy (SEM) examination. The aerodynamic properties of SEDS prepared particles were determined by a multistage liquid impinger (MLI). Particles produced from acetone solutions were crystalline needles, melting at 221+/-2 degrees C. Their morphology was independent of processing conditions. With methanol solutions, particles were flakes or needles depending on the processing temperature and pressure. This material melted at 216+/-1 degrees C, indicating a different crystal structure from the original material, in agreement with observed differences in the position and intensity of the XRPD peaks. The simulated lung deposition, using the MLI, for HC powder was improved after SEDS

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

PubMed

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

2016-10-17

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

Eliminating glutaraldehyde from crosslinked collagen films using supercritical CO2.

PubMed

Casali, Dominic M; Yost, Michael J; Matthews, Michael A

2018-01-01

Collagen has received considerable attention as a biomaterial for tissue engineering because of its low immunogenicity, controllable biodegradation, and ability to influence cell growth and proliferation. Frequently, collagen scaffolds require crosslinking to improve mechanical strength, requiring agents like glutaraldehyde that have high residual cytotoxicity. A novel method for extracting residual glutaraldehyde from crosslinked collagen films with supercritical carbon dioxide (CO 2 ) is presented. CO 2 is a nontoxic, nonflammable substance that is relatively inert and can be used to process biomaterials at mild pressures and physiologic temperatures. In this work, it was first determined that type I collagen is chemically compatible with both liquid and supercritical CO 2 . Treated collagen showed minimal changes in physicochemical properties as determined by differential scanning calorimetry, gel electrophoresis, and circular dichroism. CO 2 was subsequently used to extract residual glutaraldehyde from crosslinked collagen films. Glutaraldehyde concentration was reduced by over 95%, from over 20 ppm before treatment to about 1 ppm, in only 1 h. CO 2 treatment caused negligible alteration of thermal stability but did significantly increase film stiffness and tensile strength. However, these changes were minor compared to heat-based removal of glutaraldehyde. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 86-94, 2018. © 2017 Wiley Periodicals, Inc.

Design of an efficient space constrained diffuser for supercritical CO2 turbines

NASA Astrophysics Data System (ADS)

Keep, Joshua A.; Head, Adam J.; Jahn, Ingo H.

2017-03-01

Radial inflow turbines are an arguably relevant architecture for energy extraction from ORC and supercritical CO 2 power cycles. At small scale, design constraints can prescribe high exit velocities for such turbines, which lead to high kinetic energy in the turbine exhaust stream. The inclusion of a suitable diffuser in a radial turbine system allows some exhaust kinetic energy to be recovered as static pressure, thereby ensuring efficient operation of the overall turbine system. In supercritical CO 2 Brayton cycles, the high turbine inlet pressure can lead to a sealing challenge if the rotor is supported from the rotor rear side, due to the seal operating at rotor inlet pressure. An alternative to this is a cantilevered layout with the rotor exit facing the bearing system. While such a layout is attractive for the sealing system, it limits the axial space claim of any diffuser. Previous studies into conical diffuser geometries for supercritical CO 2 have shown that in order to achieve optimal static pressure recovery, longer geometries of a shallower cone angle are necessitated when compared to air. A diffuser with a combined annular-radial arrangement is investigated as a means to package the aforementioned geometric characteristics into a limited space claim for a 100kW radial inflow turbine. Simulation results show that a diffuser of this design can attain static pressure rise coefficients greater than 0.88. This confirms that annular-radial diffusers are a viable design solution for supercritical CO2 radial inflow turbines, thus enabling an alternative cantilevered rotor layout.

METHOD FOR THE SUPERCRITICAL FLUID EXTRACTION OF SOILS/SEDIMENTS

EPA Science Inventory

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

Analysis of new psychoactive substances in human urine by ultra-high performance supercritical fluid and liquid chromatography: Validation and comparison.

PubMed

Borovcová, Lucie; Pauk, Volodymyr; Lemr, Karel

2018-05-01

New psychoactive substances represent serious social and health problem as tens of new compounds are detected in Europe annually. They often show structural proximity or even isomerism, which complicates their analysis. Two methods based on ultra high performance supercritical fluid chromatography and ultra high performance liquid chromatography with mass spectrometric detection were validated and compared. A simple dilute-filter-and-shoot protocol utilizing propan-2-ol or methanol for supercritical fluid or liquid chromatography, respectively, was proposed to detect and quantify 15 cathinones and phenethylamines in human urine. Both methods offered fast separation (<3 min) and short total analysis time. Precision was well <15% with a few exceptions in liquid chromatography. Limits of detection in urine ranged from 0.01 to 2.3 ng/mL, except for cathinone (5 ng/mL) in supercritical fluid chromatography. Nevertheless, this technique distinguished all analytes including four pairs of isomers, while liquid chromatography was unable to resolve fluoromethcathinone regioisomers. Concerning matrix effects and recoveries, supercritical fluid chromatography produced more uniform results for different compounds and at different concentration levels. This work demonstrates the performance and reliability of supercritical fluid chromatography and corroborates its applicability as an alternative tool for analysis of new psychoactive substances in biological matrixes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advanced Stimulated Scattering Measurements in Supercritical Fluids

DTIC Science & Technology

2006-09-01

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

Supercritical CO{sub 2} mediated synthesis and catalytic activity of graphene/Pd nanocomposites

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

Tang, Lulu; Nguyen, Van Hoa; Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang

2015-11-15

Highlights: • RGO/Pd composite was efficiently prepared via a facile method in supercritical CO{sub 2}. • Graphene sheets were coated uniformly with Pd nanoparticles with a size of ∼8 nm. • Composites exhibited excellent catalytic activity in the Suzuki reaction even after 10 cycles. - Abstract: Graphene sheets were decorated with palladium nanoparticles using a facile and efficient method in supercritical CO{sub 2}. The nanoparticles were formed on the graphene sheets by the simple hydrogen reduction of palladium(II) hexafluoroacetylacetonate precursor in supercritical CO{sub 2}. The product was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electronmore » microscopy, and X-ray photoelectron spectroscopy. Highly dispersed nanoparticles with various sizes and shapes adhered well to the graphene sheets. The composites showed high catalytic activities for the Suzuki reaction under aqueous and aerobic conditions within 5 min. The effects of the different Pd precursor loadings on the catalytic activities of the composites were also examined.« less

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.

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

Investigation of Mineral Transformations in Wet Supercritical CO2 by Electron Microscopy

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

Arey, Bruce W.; Kovarik, Libor; Wang, Zheming

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 lessmore » 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

[Optimization for supercritical CO2 extraction with response surface methodology and component analysis of Sapindus mukorossi oil].

PubMed

Wu, Yan; Xiao, Xin-yu; Ge, Fa-huan

2012-02-01

To study the extraction conditions of Sapindus mukorossi oil by Supercritical CO2 Extraction and identify its components. Optimized SFE-CO2 Extraction by response surface methodology and used GC-MS to analysie Sapindus mukorossi oil compounds. Established the model of an equation for the extraction rate of Sapindus mukorossi oil by Supercritical CO2 Extraction, and the optimal parameters for the Supercritical CO2 Extraction determined by the equation were: the extraction pressure was 30 MPa, temperature was 40 degrees C; The separation I pressure was 14 MPa, temperature was 45 degrees C; The separation II pressure was 6 MPa, temperature was 40 degrees C; The extraction time was 60 min and the extraction rate of Sapindus mukorossi oil of 17.58%. 22 main compounds of Sapindus mukorossi oil extracted by supercritical CO2 were identified by GC-MS, unsaturated fatty acids were 86.59%. This process is reliable, safe and with simple operation, and can be used for the extraction of Sapindus mukorossi oil.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Supercritical fluid chromatography approach for a sustainable manufacture of new stereoisomeric anticancer agent.

PubMed

Ghinet, Alina; Zehani, Yasmine; Lipka, Emmanuelle

2017-10-25

Two routes aimed at the manufacture of unprecedented stereoisomeric combretastatin A-4 analogue were described: flash chromatography vs supercritical fluid chromatography. The latter has many advantages over liquid chromatography and was therefore chosen for the small scale separation of methyl 1-[(3-hydroxy-4-methoxyphenyl) (3,4,5-trimethoxyphenyl)methyl]-5-oxo-l-prolinate 5, with potential antitumoral activity. After a screening of six different polysaccharide based chiral stationary phases and four co-solvents, the percentage of co-solvent, the flow-rate and the outlet pressure were optimized through a design of experiments (DoE). The preparation of 50mg of each stereoisomer was achieved successfully on a Chiralpak AD-H with isopropanol as a co-solvent. Productivity (kkd), solvent usage and environmental factor (E Factor) were calculated. Flash chromatography and supercritical fluid chromatography approaches were compared in terms of yield and purity of each stereoisomer manufactured. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

Optimization of process parameters for supercritical fluid extraction of cholesterol from whole milk powder using ethanol as co-solvent.

PubMed

Dey Paul, Indira; Jayakumar, Chitra; Niwas Mishra, Hari

2016-12-01

In spite of being highly nutritious, the consumption of milk is hindered because of its high cholesterol content, which is responsible for numerous cardiac diseases. Supercritical carbon dioxide using ethanol as co-solvent was employed to extract cholesterol from whole milk powder (WMP). This study was undertaken to optimize the process parameters of supercritical fluid extraction (SCFE), viz. extraction temperature, pressure and volume of ethanol. The cholesterol content of WMP was quantified using high-performance liquid chromatography. The impact of the extraction conditions on the fat content (FC), solubility index (SI) and lightness (L*) of the SCFE-treated WMP were also investigated. The process parameters were optimized using response surface methodology. About 46% reduction in cholesterol was achieved at the optimized conditions of 48 °C, 17 MPa and 31 mL co-solvent; flow rate of expanded CO 2 , static time and dynamic time of extraction were 6 L min -1 , 10 min and 80 min respectively. The treated WMP retained its FC, SI, and L* at moderate limits of 183.67 g kg -1 , 96.3% and 96.90, respectively. This study demonstrated the feasibility of ethanol-modified SCFE of cholesterol from WMP with negligible changes in its physicochemical properties. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Fingerprints of flower absolutes using supercritical fluid chromatography hyphenated with high resolution mass spectrometry.

PubMed

Santerre, Cyrille; Vallet, Nadine; Touboul, David

2018-06-02

Supercritical fluid chromatography hyphenated with high resolution mass spectrometry (SFC-HRMS) was developed for fingerprint analysis of different flower absolutes commonly used in cosmetics field, especially in perfumes. Supercritical fluid chromatography-atmospheric pressure photoionization-high resolution mass spectrometry (SFC-APPI-HRMS) technique was employed to identify the components of the fingerprint. The samples were separated with a porous graphitic carbon (PGC) Hypercarb™ column (100 mm × 2.1 mm, 3 μm) by gradient elution using supercritical CO 2 and ethanol (0.0-20.0 min (2-30% B), 20.0-25.0 min (30% B), 25.0-26.0 min (30-2% B) and 26.0-30.0 min (2% B)) as mobile phase at a flow rate of 1.5 mL/min. In order to compare the SFC fingerprints between five different flower absolutes: Jasminum grandiflorum absolutes, Jasminum sambac absolutes, Narcissus jonquilla absolutes, Narcissus poeticus absolutes, Lavandula angustifolia absolutes from different suppliers and batches, the chemometric procedure including principal component analysis (PCA) was applied to classify the samples according to their genus and their species. Consistent results were obtained to show that samples could be successfully discriminated. Copyright © 2018 Elsevier B.V. All rights reserved.

Supercritical Fluid Facilitated Growth of Copper and Aluminum Oxide Nanoparticles

ERIC Educational Resources Information Center

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

2005-01-01

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

Supercritical fluid 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. Copyright © 2014 Elsevier B.V. All rights reserved.

Molecular Gibbs Surface Excess and CO2-Hydrate Density Determine the Strong Temperature- and Pressure-Dependent Supercritical CO2-Brine Interfacial Tension.

PubMed

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

2017-06-29

In CO 2 geological storage, the interfacial tension (IFT) between supercritical CO 2 and brine is critical for the storage capacitance design to prevent CO 2 leakage. IFT relies not only on the interfacial molecule properties but also on the environmental conditions at different storage sites. In this paper, supercritical CO 2 -NaCl solution systems are modeled at 343-373 K and 6-35 MPa under the salinity of 1.89 mol/L using molecular dynamics simulations. After computing and comparing the molecular density profile across the interface, the atomic radial distribution function, the molecular orientation distribution, the molecular Gibbs surface excess (derived from the molecular density profile), and the CO 2 -hydrate number density under the above environmental conditions, we confirm that only the molecular Gibbs surface excess of CO 2 molecules and the CO 2 -hydrate number density correlate strongly with the temperature- and pressure-dependent IFTs. We also compute the populations of two distinct CO 2 -hydrate structures (T-type and H-type) and attribute the observed dependence of IFTs to the dominance of the more stable, surfactant-like T-type CO 2 -hydrates at the interface. On the basis of these new molecular mechanisms behind IFT variations, this study could guide the rational design of suitable injecting environmental pressure and temperature conditions. We believe that the above two molecular-level metrics (Gibbs surface excess and hydrate number density) are of great fundamental importance for understanding the supercritical CO 2 -water interface and engineering applications in geological CO 2 storage.

10 MW Supercritical CO2 Turbine Test

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

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 MWemore » 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

Multivessel supercritical fluid extraction of food items in Total Diet Study.

PubMed

Hopper, M L; King, J W; Johnson, J H; Serino, A A; Butler, R J

1995-01-01

An off-line, large capacity, multivessel supercritical fluid extractor (SFE) was designed and constructed for extraction of large samples. The extractor can simultaneously process 1-6 samples (15-25 g) by using supercritical carbon dioxide (SC-CO2), which is relatively nontoxic and nonflammable, as the solvent extraction medium. Lipid recoveries for the SFE system were comparable to those obtained by blending or Soxhlet extraction procedures. Extractions at 10,000 psi, 80 degrees C, expanded gaseous CO2 flow rates of 4-5 L/min (35 degrees C), and 1-3 h extraction times gave reproducible lipid recoveries for pork sausage (relative standard deviation [RSD], 1.32%), corn chips (RSD, 0.46%), cheddar cheese (RSD, 1.14%), and peanut butter (RSD, 0.44%). In addition, this SFE system gave reproducible recoveries (> 93%) for butter fortified with cis-chlordane and malathion at the 100 ppm and 0.1 ppm levels. Six portions each of cheddar cheese, saltine crackers, sandwich cookies, and ground hamburger also were simultaneously extracted with SC-CO2 and analyzed for incurred pesticide residues. Results obtained with this SFE system were reproducible and comparable with results from organic-solvent extraction procedures currently used in the Total Diet Study; therefore, use and disposal of large quantities of organic solvents can be eliminated.

Particle Formation and Product Formulation Using Supercritical Fluids.

PubMed

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

2015-01-01

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

Combination of supercritical CO2 and vacuum distillation for the fractionation of bergamot oil.

PubMed

Fang, Tao; Goto, Motonobu; Sasaki, Mitsuru; Hirose, Tsutomu

2004-08-11

Supercritical CO2 can be used to separate oxygenated compounds from essential oils. This technique still cannot replace vacuum distillation as an industrial process because of low recoveries and inconsistent results. In the present work, a comparison between the two methods was made in terms of composition, recovery, and color. Vacuum distillation and supercritical CO2 are complementary processes for producing high quality oxygenated compounds with high recovery rates. The former is more suitable for removing monoterpenes at low fraction temperatures (< or =308 K), and the latter is more suitable for separating oxygenated compounds from pigments and waxes. Consequently, the two methods were combined. For supercritical CO2 fractionation, the parameters of pressure, temperature gradient, and the ratio of solvent to feed were investigated for the fractionation of oxygenated compounds with high recoveries (> or =85%) and without other macromolecules, such as pigments and waxes.

Computational fluid dynamics study of viscous fingering in supercritical fluid chromatography.

PubMed

Subraveti, Sai Gokul; Nikrityuk, Petr; Rajendran, Arvind

2018-01-26

Axi-symmetric numerical simulations are carried out to study the dynamics of a plug introduced through a mixed-stream injection in supercritical fluid chromatographic columns. The computational fluid dynamics model developed in this work takes into account both the hydrodynamics and adsorption equilibria to describe the phenomena of viscous fingering and plug effect that contribute to peak distortions in mixed-stream injections. The model was implemented into commercial computational fluid dynamics software using user-defined functions. The simulations describe the propagation of both the solute and modifier highlighting the interplay between the hydrodynamics and plug effect. The simulated peaks showed good agreement with experimental data published in the literature involving different injection volumes (5 μL, 50 μL, 1 mL and 2 mL) of flurbiprofen on Chiralpak AD-H column using a mobile phase of CO 2 and methanol. The study demonstrates that while viscous fingering is the main source of peak distortions for large-volume injections (1 mL and 2 mL) it has negligible impact on small-volume injections (5 μL and 50 μL). Band broadening in small-volume injections arise mainly due to the plug effect. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Ultra-high performance supercritical fluid chromatography of lignin-derived phenols from alkaline cupric oxide oxidation.

PubMed

Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta; Turner, Charlotta

2016-08-01

Traditional chromatographic methods for the analysis of lignin-derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra-high performance supercritical fluid chromatography method with a diode array detector for the analysis of major lignin-derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5-2.5 μM, a limit of quantification of 2.5-5.0 μM, and a dynamic range of 5.0-2.0 mM (R(2) > 0.997). The new ultra-high performance supercritical fluid chromatography method was also applied for the qualitative and quantitative analysis of lignin-derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercritical fluid chromatography is a fast and reliable technique for the analysis of lignin-derived phenols in complex environmental samples. © 2016 The Authors, Journal of Separation Science Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supercritical fluid processing: opportunities for new resist materials and processes

NASA Astrophysics Data System (ADS)

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

1996-05-01

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

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.

Structural behavior of supercritical fluids under confinement

NASA Astrophysics Data System (ADS)

Ghosh, Kanka; Krishnamurthy, C. V.

2018-01-01

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

Structural behavior of supercritical fluids under confinement.

PubMed

Ghosh, Kanka; Krishnamurthy, C V

2018-01-01

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

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.

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

Exploring a novel preparation method of 1D metal organic frameworks based on supercritical CO2.

PubMed

López-Periago, A; Vallcorba, O; Frontera, C; Domingo, C; Ayllón, J A

2015-04-28

The preparation of copper(II) one-dimensional MOFs using an eco-efficient method is reported here. This method is based exclusively on using supercritical CO2 as a solvent, without the addition of any other additive or co-solvent. Neutral acetylacetonate copper complexes and two linear linkers, namely, the bidentate 4,4'-bipyridine and 4,4'-trimethylenedipyridine molecules, were reacted under compressed CO2 at 60 °C and 20 MPa for periods of 4 or 24 h. The success achieved in the synthesis of the different studied 1D-MOFs was related to the solubility of the reagents in supercritical CO2. The reaction yield of the synthesized coordination polymers via the supercritical route was close to 100% because both the reactants were almost completely depleted in the performed experiments.

Widom Lines in Binary Mixtures of Supercritical Fluids.

PubMed

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

2017-06-08

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

High Density Thermal Energy Storage with Supercritical Fluids

NASA Technical Reports Server (NTRS)

Ganapathi, Gani B.; Wirz, Richard

2012-01-01

A novel approach to storing thermal energy with supercritical fluids is being investigated, which if successful, promises to transform the way thermal energy is captured and utilized. The use of supercritical fluids allows cost-affordable high-density storage with a combination of latent heat and sensible heat in the two-phase as well as the supercritical state. This technology will enhance penetration of several thermal power generation applications and high temperature water for commercial use if the overall cost of the technology can be demonstrated to be lower than the current state-of-the-art molten salt using sodium nitrate and potassium nitrate eutectic mixtures.

The effect of two gases forming supercritical fluids (Xe and CO 2) on the spectral characteristics and analytical capabilities of microwave induced plasmas

NASA Astrophysics Data System (ADS)

Montes-Bayón, M.; Camuña-Aguilar, F.; Pereiro, R.; Sánchez-Uria, J. E.; Sanz-Medel, A.

1996-06-01

A comparative study of the effect of CO 2 and Xe added along with the plasma gas to He and Ar microwave induced plasmas (MIPs), simulating possible conditions to be used when a MIP is employed as specific detector for supercritical fluid chromatography (SFC), has been carried out. The proportions of CO 2 and Xe to the plasma gas investigated are comparable to the typical percentages used for SFC-MIP couplings. The study has been performed with two different MIP systems: an atmospheric pressure discharge held in a Beenakker cavity TM 010 and a reduced pressure surfatron-MIP. The influence of CO 2 and Xe addition on the spectrochemical properties of the discharge has been studied by using the atomic emission of mercury and some typical non-metals (chlorine, carbon and sulfur) at different wavelengths (atomic and ionic lines). Results showed that ion line emission intensities are always reduced more significantly than atom line emissions by both dopant gases on study, whatever the pressure. In general terms, however, the effect of adding Xe is less severe, both for atom and ion lines, than that of CO 2; in most cases the detection limits (DLs) observed are better for Xe than for CO 2 as dopant gas. In fact, the DLs obtained for the selected lines of mercury measured were practically unaltered by the addition of 0.2% Xe to atmospheric pressure Ar or He MIPs. CO 2 addition (0.2%) produced about 1.5 times worsening of the observed DLs for mercury. For non-metal analyses better DLs were also obtained, in general terms, with Xe than with CO 2 as dopant gas.

A combinational supercritical CO2 system for nanoparticle preparation of indomethacin.

PubMed

Tozuka, Yuichi; Miyazaki, Yuta; Takeuchi, Hirofumi

2010-02-15

An improved system using both supercritical antisolvent precipitation and rapid expansion from supercritical to aqueous solution (RESAS) was proposed to overcome the problem of low solubility of medicinal substances in scCO(2). When the ethanol solution with IMC was sprayed into the vessel purged with scCO(2), no precipitation of IMC was observed if the CO(2) pressure was more than 15MPa at 40 degrees C. This indicates that very small droplets of the ethanol solution with IMC could disperse in the high pressure CO(2). After expansion into distilled water using an RESAS device, this same solution, in CO(2) at high pressure, produced submicron particles of IMC. For the pharmaceutical application, the IMC suspension was freeze-dried and re-dispersed to the aqueous media. SEM images of freeze-dried sample showed that the suspension was composed of submicron particles with 300-500 nm. Although the average particle size of re-dispersed IMC related significantly to the pressure and temperature in the vessel on scCO(2) processing, the freeze-dried sample of the IMC suspension after the treatment shows good redispersibility as a nanosuspension. This apparatus is found to be a promising way to produce fine crystals of IMC with a high yield. Copyright 2009 Elsevier B.V. All rights reserved.

Large Eddy Simulation of Supercritical CO2 Through Bend Pipes

NASA Astrophysics Data System (ADS)

He, Xiaoliang; Apte, Sourabh; Dogan, Omer

2017-11-01

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

Study of sulfur bonding on gallium arsenide (100) surfaces using supercritical fluid extraction

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

Cabauy, P.; Darici, Y.; Furton, K.G.

1995-12-01

In the last decades Gallium Arsenide (GaAs) has been considered the semiconductor that will replace silicon because of its direct band gap and high electron mobility. Problems with GaAs Fermi level pinning has halted its widespread use in the electronics industry. The formation of oxides on GaAs results in a high density of surface states that effectively pin the surface Fermi level at the midgap. Studies on sulfur passivation have eliminated oxidation and virtually unpinned the Fermi level on the GaAs surface. This has given rise to interest in sulfur-GaAs bonds. In this presentation, we will discuss the types ofmore » sulfur bonds extracted from a sulfur passivated GaAs (100) using Supercritical Fluid (CO2) Extraction (SFE). SFE can be a valuable tool in the study of chemical speciations on semiconductor surfaces. The variables evaluated to effectively study the sulfur species from the GaAs surface include passivation techniques, supercritical fluid temperatures, densities, and extraction times.« less

Supercritical fluid extraction of bi & multi-layer graphene sheets from graphite by using exfoliation technique

NASA Astrophysics Data System (ADS)

Xavier, Gauravi; Dave, Bhoomi; Khanna, Sakshum

2018-05-01

In recent times, researchers have turned to explore the possibility of using Supercritical Fluid (SCFs) system to penetrate into the inert-gaping of graphite and exfoliate it into a number of layer graphene sheets. The supercritical fluid holds excellent wetting surfaces with low interfacial tension and high diffusion coefficients. Although SCFs exfoliation approach looks promising to developed large scale & low-cost graphene sheet but has not received much attention. To arouse interest and reflection on this approach, this review is organized to summarize the recent progress in graphene production by SCF technology. Here we present the simplest route to obtained layers of graphene sheets by intercalating and exfoliating graphite using supercritical CO2 processing. The layers graphene nano-sheets were collected in dichloromethane (DCM) solution which prevents the restocking of sheets. The obtained graphene sheets show the desired characteristics and thus can be used in physical, chemical and biological sciences. Thus this method provides an effortless and eco-friendly approach for the synthesis of layers of graphene sheets.

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

PubMed

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

2014-02-01

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

Supercritical Fluid Extraction of Toxic Heavy Metals and Uranium from Acidic Solutions with Sulfur-Containing Organophosphorus Reagents

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

Lin, Yuehe; Liu, Chongxuan; Wu, Hong

2003-03-02

The feasibility of using sulfur-containing organophosphorus reagents for the chelation-supercritical fluid extraction (SFE) of toxic heavy metals and uranium from acidic media was investigated. The SFE experiments were conducted in a specially-designed flow-through liquid extractor. Effective extraction of the metal ions from various acidic media was demonstrated. The effect of ligand concentration in supercritical CO{sub 2} on the kinetics of metal extraction was studied. A simplified model is used to describe the extraction kinetics and the good agreement of experimental data with the equilibrium-based model is achieved.

Optimization and characterization of condensation nucleation light scattering detection coupled with supercritical fluid chromatography

NASA Astrophysics Data System (ADS)

Yang, Shaoping

This dissertation is an investigation of two aspects of coupling condensation nucleation light scattering detection (CNLSD) with supercritical fluid chromatography (SFC). In the first part, it was demonstrated that CNLSD was compatible with packed column SFC using either pure CO2 or organic solvent modified CO2 as mobile phases. Factors which were expected to affect the interface between SFC and CNLSD were optimized for the detector to reach low detection limits. With SFC using pure CO2 as mobile phase, the detection limit of CNLSD with SFC was observed to be at low nanogram levels, which was at the same level of flame ionization detection (FID) coupled with SFC. For SFC using modified CO2 as mobile phase, detection limits at the picogram level were observed for CNLSD at optimal conditions, which were at least ten times lower than those reached by evaporative light scattering detection. In the second part, particle size distributions of aerosols produced from rapid expansion of supercritical solutions were measured with a scanning mobility particle sizer. The effect of the factors, which were investigated in the first part for their effects on signal intensities and signal to noise ratios (S/N), on particle size distributions (PSDs) of both analyte and background were investigated. Whenever possible, both particle sizes and particle number obtained from PSDs were used to explain the optimization results. In general, PSD data support the observations made in the first part. The detection limits of CNLSD obtained were much higher than predicted. PSDs did not provide direct explanation of this problem. The amount of analyte deposited in the transport tubing, evaporated to gas phase, and condensed to form particles was determined experimentally. Almost no analyte was found in the gas phase. Less than 3% was found in the particle forms. The vast majority of analyte was lost in the transport tubing, especially in the short distance after supercritical fluid expansion. A

Methods for producing films using supercritical fluid

DOEpatents

Yonker, Clement R.; Fulton, John L.

2004-06-15

A method for forming a continuous film on a substrate surface that involves depositing particles onto a substrate surface and contacting the particle-deposited substrate surface with a supercritical fluid under conditions sufficient for forming a continuous film from the deposited particles. The particles may have a mean particle size of less 1 micron. The method may be performed by providing a pressure vessel that can contain a compressible fluid. A particle-deposited substrate is provided in the pressure vessel and the compressible fluid is maintained at a supercritical or sub-critical state sufficient for forming a film from the deposited particles. The T.sub.g of particles may be reduced by subjecting the particles to the methods detailed in the present disclosure.

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

Surface properties of poly(acrylonitrile) (PAN) precipitation polymerized in supercritical CO2 and the influence of the molecular weight.

PubMed

Shen, Qing; Gu, Qing-Feng; Hu, Jian-Feng; Teng, Xin-Rong; Zhu, Yun-Feng

2003-11-15

In this paper, the surface properties, e.g., the total surface free energy and the related Lifshitz-van der Waals and Lewis acid-base components, of polyacrylonitrile (PAN) precipitation polymerized in supercritical CO(2) have been characterized. Moreover, the influence of molecular weight varying has been also investigated. Results show that the surface properties of PAN resulting from supercritical CO(2) are different from those obtained by the conventional method. Of these data, one important finding is that the supercritical CO(2) PAN seems to decrease the surface free energy with the increased molecular weight. Based on previous recorded NMR spectra of this PAN and especially compared to commercial PAN, such phenomena are discussed and ascribed to an increase of the H-bonds and a reduction of the isotacticity in the supercritical CO(2) condition for PAN.

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

PubMed

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

2010-09-15

Evidences indicating the presence of phase transformations in the mixed cholesteryl benzoate (CBE) and cholesteryl butyrate (CBU) under the supercritical CO(2) pressurization, by means of differential scanning calorimetry (DSC) and X-ray diffraction (XRD), are presented in this work. These include (1) the DSC heating curve of pure CBU; (2) the DSC heating curves of CBU/CBE mixtures; (3) the XRD spectra of pure CBU; (4) the XRD spectra of CBU/CBE mixtures; (5) CBU and CBE are miscible in either solid phase or liquid phase over the whole composition range. As a result of the presence of these phase transformations induced by pressurization, it could be deduced that a solid solution of the CBU/CBE mixture might have formed at the interfaces under supercritical conditions, subsequently influencing their dissolving behaviors in supercritical CO(2). Copyright 2010 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

Evaluation of supercritical CO2 dried cellulose aerogels as nano-biomaterials

NASA Astrophysics Data System (ADS)

Lee, Sinah; Kang, Kyu-Young; Jeong, Myung-Joon; Potthast, Antje; Liebner, Falk

2017-10-01

Cellulose is the renewable, biodegradable and abundant resource and is suggested as an alternative material to silica due to the high price and environmental load of silica. The first step for cellulose aerogel production is to dissolve cellulose, and hydrated calcium thiocyanate molten salt is one of the most effective solvents for preparing porous material. Cellulose aerogels were prepared from dissolved cellulose samples of different degree of polymerization (DP) and drying methods, and tested with shrinkage, density and mechanical strength. Supercritical CO2 dried cellulose aerogels shrank less compared to freeze-dried cellulose aerogels, whereas the densities were increased according to the DP increases in both cellulose aerogels. Furthermore, scanning electron microscope (SEM) images showed that the higher DP cellulose aerogels were more uniform with micro-porous structure. Regarding the mechanical strength of cellulose aerogels, supercritical CO2 dried cellulose aerogels with higher molecular weight were much more solid.

Effect of combined treatment with supercritical CO2 and rosemary on microbiological and physicochemical properties of ground pork stored at 4°C.

PubMed

Huang, Shirong; Liu, Bin; Ge, Du; Dai, Jiehui

2017-03-01

The effect of combined treatment with supercritical CO 2 (2000psi, 35°C for 2h) and rosemary powder (2.5% and 5.0% (w/w)) on microbiological and physicochemical properties of ground pork stored at 4°C was investigated. The changes in total viable count, pH, total volatile base nitrogen (TVB-N), lipid oxidation and instrumental color (CIE L ⁎ , a ⁎ , b ⁎ ) were analyzed during a week period of refrigerated storage. It was found that microbial populations were reduced by supercritical CO 2 treatment, with the more pronounced effect being achieved by combined treatment with supercritical CO 2 and 5.0g rosemary powder/100g meat. Supercritical CO 2 treatment for 2h could accelerate lipid oxidation of ground pork during refrigerated storage, whereas combination with rosemary can significantly slow down the increase of oxidation rate. Combined treatment of supercritical CO 2 and rosemary significantly increased L ⁎ and b ⁎ values of the ground pork, while the a ⁎ , pH and TVB-N value were not affected as compared to the treatment with supercritical CO 2 alone. The results of this study indicate that combined treatment of supercritical CO 2 and rosemary may be useful in the meat industry to enhance the storage stability of ground pork treated with long time exposure of supercritical CO 2 during refrigerated storage. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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

2012-05-01

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

On-line supercritical fluid extraction-supercritical fluid chromatography-mass spectrometry of polycyclic aromatic hydrocarbons in soil.

PubMed

Wicker, A Paige; Carlton, Doug D; Tanaka, Kenichiro; Nishimura, Masayuki; Chen, Vivian; Ogura, Tairo; Hedgepeth, William; Schug, Kevin A

2018-06-01

On-line supercritical fluid extraction - supercritical fluid chromatography - mass spectrometry (SFE-SFC-MS) has been applied for the determination of polycyclic aromatic hydrocarbons (PAHs) in soil. The purpose of this study was to develop and validate the first on-line SFE-SFC-MS method for the quantification of PAHs in various types of soil. By coupling the sample extraction on-line with chromatography and detection, sample preparation is minimized, diminishing sample loss and contamination, and significantly decreasing the required extraction time. Parameters for on-line extraction coupled to chromatographic analysis were optimized. The method was validated for concentrations of 10-1500 ng of PAHs per gram of soil in Certified Reference Material (CRM) sediment, clay, and sand with R 2  ≥ 0.99. Limits of detection (LOD) were found in the range of 0.001-5 ng/g, and limits of quantification (LOQ) in the range of 5-15 ng/g. The method developed in this study can be effectively applied to the study of PAHs in the environment, and may lay the foundation for further applications of on-line SFE-SFC-MS. Copyright © 2018 Elsevier B.V. All rights reserved.

Chemical Composition Analysis of Extracts from Ficus Hirta Using Supercritical Fluid

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Supercritical CO2/Co-solvents Extraction of Porogen and Surfactant to Obtain

NASA Astrophysics Data System (ADS)

Lubguban, Jorge

2005-03-01

A method of pore generation by supercritical CO2 (SCCO2)/co-solvents extraction for the preparation of nanoporous organosilicate thin films for ultralow dielectric constant materials is investigated. A nanohybrid film was prepared from poly (propylene glycol) (PPG) and poly(methylsilsesquioxane) (PMSSQ) whereby the PPG porogen are entrapped within the crosslinked PMSSQ matrix. Another set of thin films was produced by liquid crystal templating whereby non-ionic (polyoxyethylene 10 stearyl ether) (Brij76) and ionic (cetyltrimethylammonium bromide) (CTAB) surfactant were used as sacrificial templates in a tetraethoxy silane (TEOS) and methyltrimethoxy silane (MTMS) based matrix. These two types of films were treated with SCCO2/co-solvents to remove porogen and surfactant templates. As a comparison, porous structures generated by thermal decomposition were also evaluated. It is found that SCCO2/co-solvents treatment produced closely comparable results with thermal decomposition. The results were evident from Fourier Transform Infrared (FT- IR) spectroscopy and optical constants data obtained from variable angle spectroscopic ellipsometry (VASE).

Phytochemical profile, antioxidant and antimicrobial activity of extracts obtained from erva-mate (Ilex paraguariensis) fruit using compressed propane and supercritical CO2.

PubMed

Fernandes, Ciro E F; Scapinello, Jaqueline; Bohn, Aline; Boligon, Aline A; Athayde, Margareth L; Magro, Jacir Dall; Palliga, Marshall; Oliveira, J Vladimir; Tres, Marcus V

2017-01-01

Traditionally, Ilex paraguariensis leaves are consumed in tea form or as typical drinks like mate and terere, while the fruits are discarded processing and has no commercial value. The aim of this work to evaluate phytochemical properties, total phenolic compounds, antioxidant and antimicrobial activity of extracts of Ilex paraguariensis fruits obtained from supercritical CO 2 and compressed propane extraction. The extraction with compressed propane yielded 2.72 wt%, whereas with supercritical CO 2 1.51 wt% was obtained. The compound extracted in larger amount by the two extraction solvents was caffeine, 163.28 and 54.17 mg/g by supercritical CO 2 and pressurized propane, respectively. The antioxidant activity was more pronounced for the supercritical CO 2 extract, with no difference found in terms of minimum inhibitory concentration for Staphylococcus aureus for the two extracts and better results observed for Escherichia coli when using supercritical CO 2 .

The latent heat of vaporization of supercritical fluids

NASA Astrophysics Data System (ADS)

Banuti, Daniel; Raju, Muralikrishna; Hickey, Jean-Pierre; Ihme, Matthias

2016-11-01

The enthalpy of vaporization is the energy required to overcome intermolecular attractive forces and to expand the fluid volume against the ambient pressure when transforming a liquid into a gas. It diminishes for rising pressure until it vanishes at the critical point. Counterintuitively, we show that a latent heat is in fact also required to heat a supercritical fluid from a liquid to a gaseous state. Unlike its subcritical counterpart, the supercritical pseudoboiling transition is spread over a finite temperature range. Thus, in addition to overcoming intermolecular attractive forces, added energy simultaneously heats the fluid. Then, considering a transition from a liquid to an ideal gas state, we demonstrate that the required enthalpy is invariant to changes in pressure for 0 < p < 3pcr . This means that the classical pressure-dependent latent heat is merely the equilibrium part of the phase transition. The reduction at higher pressures is compensated by an increase in a nonequilibrium latent heat required to overcome residual intermolecular forces in the real fluid vapor during heating. At supercritical pressures, all of the transition occurs at non-equilibrium; for p -> 0 , all of the transition occurs at equilibrium.

Time-Resolved and Operando XAS Studies on Heterogeneous Catalysts - From the Gas Phase Towards Reactions in Supercritical Fluids

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

Grunwaldt, Jan-Dierk; Baiker, Alfons

2007-02-02

x-ray absorption spectroscopy is a well-suited technique to uncover the structure of heterogeneous catalysts under reaction conditions. Different aspects of in situ cell design suitable for dynamic and catalytic studies are discussed. In addition, criteria are presented that allow estimating the influence external and internal mass transfer. Starting with studies on gas-solid reactions, including structure-activity relationships, this concept is extended to liquid-solid reactions, reactions at high pressure and in supercritical fluids. The following examples are discussed in more detail: partial oxidation of methane over Pt-Rh/Al2O3, reduction of a Cu/ZnO catalyst, alcohol oxidation over Bi-promoted Pd/Al2O3 in liquid phase and overmore » Pd/Al2O3 in supercritical CO2, and batch reactions (e.g. CO2-fixation over zinc-based catalysts)« less

Supercritical fluids in separation science--the dreams, the reality and the future.

PubMed

Smith, R M

1999-09-24

The last 20 years have seen an intense interest in the use of supercritical fluids in separation science. This started with the introduction of commercial instruments first for packed and then for capillary chromatography and it looked as if this would be a technique to rival gas-liquid chromatography and HPLC. The activity developed quite rapidly into packed column supercritical fluid separations then into supercritical fluid extraction. However, in recent years there has been a decline in publications. These later techniques continue to be used but are now principally applied to a limited group of applications where they offer significant advantages over alternative techniques. This review looks back over this period and analyses how these methods were developed and the fluids, detectors and applications that were examined. It suggests why many of the initial applications have vanished and why the initial apparent promise was not fulfilled. The rise and fall of supercritical fluids represents a lesson in the way analysts approach new techniques and how we might view other new separation developments at the end of this millennium. The review looks forward to the future of supercritical fluids and their role at the end of the first century of separation science. Probably the most important idea that supercritical fluids have brought to separation science is a recognition that there is unity in the separation methods and that a continuum exists from gases to liquids.

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...

Single-anchor support and supercritical CO2 drying enable high-precision microfabrication of three-dimensional structures.

PubMed

Maruo, Shoji; Hasegawa, Takuya; Yoshimura, Naoki

2009-11-09

In high-precision two-photon microfabrication of three-dimensional (3-D) polymeric microstructures, supercritical CO(2) drying was employed to reduce surface tension, which tends to cause the collapse of micro/nano structures. Use of supercritical drying allowed high-aspect ratio microstructures, such as micropillars and cantilevers, to be fabricated. We also propose a single-anchor supporting method to eliminate non-uniform shrinkage of polymeric structures otherwise caused by attachment to the substrate. Use of this method permitted frame models such as lattices to be produced without harmful distortion. The combination of supercritical CO(2) drying and the single-anchor supporting method offers reliable high-precision microfabrication of sophisticated, fragile 3-D micro/nano structures.

Formation of indomethacin-saccharin cocrystals using supercritical fluid technology.

PubMed

Padrela, Luis; Rodrigues, Miguel A; Velaga, Sitaram P; Matos, Henrique A; de Azevedo, Edmundo Gomes

2009-08-12

The main objective of the present work is to check the feasibility of supercritical fluid (SCF) technologies in the screening and design of cocrystals (novel crystalline solids). The cocrystal formation tendencies in three different SCF techniques, focusing on distinct supercritical fluid properties - solvent, anti-solvent and atomization enhancer - were investigated. The effect of processing parameters on the cocrystal formation behaviour and particle properties in these techniques was also studied. A recently reported indomethacin-saccharin (IND-SAC) cocrystalline system was our model system. A 1:1 molar ratio of indomethacin (gamma-form) and saccharin was used as a starting material. The SCF techniques employed in the study include the CSS technique (cocrystallization with supercritical solvent), the SAS technique (supercritical anti-solvent), and the AAS technique (atomization and anti-solvent). The resulting cocrystalline phase was identified using differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier transform-Raman (FT-Raman). The particle morphologies and size distributions were determined using scanning electron microscopy (SEM) and aerosizer, respectively. The pure IND-SAC cocrystals were obtained from SAS and AAS processes, whilst partial to no cocrystal formation occurred in the CSS process. However, no remarkable differences were observed in terms of cocrystal formation at different processing conditions in SAS and AAS processes. Particles from CSS processes were agglomerated and large, whilst needle-to-block-shaped and spherical particles were obtained from SAS and AAS processes, respectively. The particle size distribution of these particles was 0.2-5microm. Particulate IND-SAC cocrystals with different morphologies and sizes (nano-to-micron) were produced using supercritical fluid techniques. This work demonstrates the potential of SCF technologies as screening methods for cocrystals with possibilities for particle

Extraction of metals using supercritical fluid and chelate forming legand

DOEpatents

Wai, Chien M.; Laintz, Kenneth E.

1998-01-01

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

Extraction of metals using supercritical fluid and chelate forming ligand

DOEpatents

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

1998-03-24

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

Identification of critical process variables affecting particle size following precipitation using a supercritical fluid.

PubMed

Sacha, Gregory A; Schmitt, William J; Nail, Steven L

2006-01-01

The critical processing parameters affecting average particle size, particle size distribution, yield, and level of residual carrier solvent using the supercritical anti-solvent method (SAS) were identified. Carbon dioxide was used as the supercritical fluid. Methylprednisolone acetate was used as the model solute in tetrahydrofuran. Parameters examined included pressure of the supercritical fluid, agitation rate, feed solution flow rate, impeller diameter, and nozzle design. Pressure was identified as the most important process parameter affecting average particle size, either through the effect of pressure on dispersion of the feed solution into the precipitation vessel or through the effect of pressure on solubility of drug in the CO2/organic solvent mixture. Agitation rate, impeller diameter, feed solution flow rate, and nozzle design had significant effects on particle size, which suggests that dispersion of the feed solution is important. Crimped HPLC tubing was the most effective method of introducing feed solution into the precipitation vessel, largely because it resulted in the least amount of clogging during the precipitation. Yields of 82% or greater were consistently produced and were not affected by the processing variables. Similarly, the level of residual solvent was independent of the processing variables and was present at 0.0002% wt/wt THF or less.

Supercritical fluid chromatography with photodiode array detection for pesticide analysis in papaya and avocado samples.

PubMed

Pano-Farias, Norma S; Ceballos-Magaña, Silvia G; Gonzalez, Jorge; Jurado, José M; Muñiz-Valencia, Roberto

2015-04-01

To improve the analysis of pesticides in complex food matrices with economic importance, alternative chromatographic techniques, such as supercritical fluid chromatography, can be used. Supercritical fluid chromatography has barely been applied for pesticide analysis in food matrices. In this paper, an analytical method using supercritical fluid chromatography coupled to a photodiode array detection has been established for the first time for the quantification of pesticides in papaya and avocado. The extraction of methyl parathion, atrazine, ametryn, carbofuran, and carbaryl was performed through the quick, easy, cheap, effective, rugged, and safe methodology. The method was validated using papaya and avocado samples. For papaya, the correlation coefficient values were higher than 0.99; limits of detection and quantification ranged from 130-380 and 220-640 μg/kg, respectively; recovery values ranged from 72.8-94.6%; precision was lower than 3%. For avocado, limit of detection values were ˂450 μg/kg; precision was lower than 11%; recoveries ranged from 50.0-94.2%. Method feasibility was tested for lime, banana, mango, and melon samples. Our results demonstrate that the proposed method is applicable to methyl parathion, atrazine, ametryn, and carbaryl, toxics pesticides used worldwide. The methodology presented in this work could be applicable to other fruits. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Ab initio molecular dynamics study of fluid H2O-CO2 mixture in broad pressure-temperature range

NASA Astrophysics Data System (ADS)

Fu, Jie; Zhao, Jijun; Plyasunov, Andrey V.; Belonoshko, Anatoly B.

2017-11-01

Properties of H2O and CO2 fluid and their mixtures under extreme pressures and temperatures are poorly known yet critically important in a number of applications. Several hundreds of first-principles molecular dynamics (FPMD) runs have been performed to obtain the pressure-volume-temperature (P-V-T) data on supercritical H2O, CO2, and H2O-CO2 mixtures. The pressure-temperature (P-T) range are from 0.5 GPa to 104 GPa (48.5 GPa for CO2) and from 600 K to 4000 K. Based on these data, we evaluate several existing equations of state (EOS) for the fluid H2O, CO2, and H2O-CO2 mixture. The results show that the EOS for H2O from Belonoshko et al. [Geochim. Cosmochim. Acta 55, 381-387; Geochim. Cosmochim. Acta 55, 3191-3208; Geochim. Cosmochim. Acta 56, 3611-3626; Comput. Geosci. 18, 1267-1269] not only can be used in the studied P-T range but also is accurate enough to be used for prediction of P-V-T data. In addition, IAPWS-95 EOS for H2O shows excellent extrapolation behavior beyond 1.0 GPa and 1273 K. However, for the case of CO2, none of the existing EOS produces data in agreement with the FPMD results. We created new EOS for CO2. The precision of the new EOS is tested by comparison to the calculated P-V-T data, fugacity coefficient of the CO2 fluid derived from high P-T experimental data as well as to the (very scarce) experimental volumetric data in the high P-T range. On the basis of our FPMD data we created a new EOS for H2O-CO2 mixture. The new EOS for the mixture is in reasonable agreement with experimental data.

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

ERIC Educational Resources Information Center

Palmieri, Margo D.

1988-01-01

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

Solvation of Esters and Ketones in Supercritical CO2.

PubMed

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

2016-02-04

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.

Solid-state chemistry and particle engineering with supercritical fluids in pharmaceutics.

PubMed

Pasquali, Irene; Bettini, Ruggero; Giordano, Ferdinando

2006-03-01

The present commentary aims to review the modern and innovative strategies in particle engineering by the supercritical fluid technologies and it is principally concerned with the aspects of solid-state chemistry. Supercritical fluids based processes for particle production have been proved suitable for controlling solid-state, morphology and particle size of pharmaceuticals, in some cases on an industrial scale. Supercritical fluids should be considered in a prominent position in the development processes of drug products for the 21st century. In this respect, this innovative technology will help in meeting the more and more stringent requirements of regulatory authorities in terms of solid-state characterisation and purity, and environmental acceptability.

Reducing oyster-associated bacteria levels using supercritical fluid CO2 as an agent of warm pasteurization.

PubMed

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

2010-03-31

An innovative approach to Post-Harvest Processing (PHP) of oysters is introduced focusing on the effects of supercritical carbon dioxide (scCO(2)) on bacterial contaminants trapped in the digestive system of oysters. Oysters were exposed to scCO(2) under two conditions: (1) 100 bar and 37 degrees C for 30 min and (2) 172 bar and 60 degrees C for 60 min. Using FDA standard guidelines for food analysis, variations in the Aerobic Plate Count (APC) were assessed. It was established that exposing oysters to CO(2) at 100 bar and 37 degrees C for 30 min and at 172 bar and 60 degrees C for 60 min induced 2-log and 3-log reductions in the APC respectively. The decrease in the microbial load as a result of treatment with scCO(2) 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 degrees C for 60 min; this was not the case for oysters treated at 100 bar and 37 degrees C for 30 min. 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 scCO(2) on several bacterial isolates, including a referenced ATCC strain of a non-pathogenic Vibrio (Vibrio fischeri) 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. fischeri. Copyright 2009 Elsevier B.V. All rights reserved.

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

Supercritical fluid extraction and direct fluid injection mass spectrometry for the determination of trichothecene mycotoxins in wheat samples

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

Kalinoski, H.T.; Udseth, H.R.; Wright, B.W.

1986-10-01

The application of on-line supercritical fluid extraction with chemical ionization mass spectrometry and collision induced dissociation tandem mass spectrometry for the rapid identification of parts-per-million levels of several trichothecene mycotoxins is demonstrated. Supercritical carbon dioxide is shown to allow identification of mycotoxins with minimum sample handling in complex natural matrices (e.g., wheat). Tandem mass spectrometry techniques are employed for unambiguous identification of compounds of varying polarity, and false positives from isobaric compounds are avoided. Capillary column supercritical fluid chromatography-mass spectrometry of a supercritical fluid extract of the same sample was also performed and detection limits in the parts-per-billion range appearmore » feasible.« less

Supercritical Fluid Extraction and Separation of Uranium from Other Actinides

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

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 uraniummore » 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.« less

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

The research interests lie in a deeper understanding of the mechanisms of diffusion and nucle-ation of organic solutes in near-and supercritical state of a solvent, which count as important means of mass transfer in the process engineering industry. The use of supercritical fluids in industrial processes, such as extraction and particle handling, has become a more and more popular method. Take a closer look at the two processes one would find that there are obviously two sub-processes involved in each of the process, namely the diffusion/nucleation as well as a phase transition procedure. Because of the operational limitations in the practice, this phase transition can-not be neglected. So it is also included in the theoretical approach. Classically to deduce conclusions from experiment results, mathematical/physical models outlining property changes and summarizing characteristics of the two processes are expected. In order to become an insight of these phenomena from the origin, and also to serve as a fundamental attribute for the numerical simulation later, the theories of statistical thermodynamics are adopted here as a proper means to describe the behaviors of the two processes. As the diffusion coefficients of the samples in our case are only of an order of approx. 10-8m2s-1, it can be assumed that the processes are in equilibrium (local changes are neglectably small), a model can be built on a general macroscopic approach for equilibrium systems, namely the Boltzmann-Gibbs distri-bution. And some rather general methods e.g. linear response theory can be applied. But as the transfer phenomena are genuinely not equilibrium systems, from this aspect a model can also be built based on the microscopic description -the kinetic theory of the behaviors of the particles of this non-equilibrium system. The characteristics under compensated gravity are also to be considered in the models. The differences and constraints between the models are to be compared and

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.

Disintegration of fluids under supercritical conditions from mixing layer studies

NASA Technical Reports Server (NTRS)

Okong'o, N.; Bellan, J.

2003-01-01

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

Experimental investigation of CO2-brine-rock interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers

USGS Publications Warehouse

Rosenbauer, R.J.; Koksalan, T.; Palandri, J.L.

2005-01-01

Deep-saline aquifers are potential repositories for excess CO2, currently being emitted to the atmosphere from anthropogenic activities, but the reactivity of supercritical CO2 with host aquifer fluids and formation minerals needs to be understood. Experiments reacting supercritical CO2 with natural and synthetic brines in the presence and absence of limestone and plagioclase-rich arkosic sandstone showed that the reaction of CO2-saturated brine with limestone results in compositional, mineralogical, and porosity changes in the aquifer fluid and rock that are dependent on initial brine composition, especially dissolved calcium and sulfate. Experiments reacting CO2-saturated, low-sulfate brine with limestone dissolved 10% of the original calcite and increased rock porosity by 2.6%. Experiments reacting high-sulfate brine with limestone, both in the presence and absence of supercritical CO2, were characterized by the precipitation of anhydrite, dolomitization of the limestone, and a final decrease in porosity of 4.5%. However, based on favorable initial porosity changes of about 15% due to the dissolution of calcite, the combination of CO2 co-injection with other mitigation strategies might help alleviate some of the well-bore scale and formation-plugging problems near the injection zone of a brine disposal well in Paradox Valley, Colorado, as well as provide a repository for CO2. Experiments showed that the solubility of CO2 is enhanced in brine in the presence of limestone by 9% at 25 ??C and 6% at 120 ??C and 200 bar relative to the brine itself. The solubility of CO2 is enhanced also in brine in the presence of arkosic sandstone by 5% at 120 ??C and 300 bar. The storage of CO 2 in limestone aquifers is limited to only ionic and hydraulic trapping. However, brine reacted with supercritical CO2 and arkose yielded fixation and sequestration of CO2 in carbonate mineral phases. Brine desiccation was observed in all experiments containing a discrete CO2 phase

Supercritical fluid technology: a promising approach in pharmaceutical research.

PubMed

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

2013-02-01

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

Non-equilibrium condensation of supercritical carbon dioxide in a converging-diverging nozzle

NASA Astrophysics Data System (ADS)

Ameli, Alireza; Afzalifar, Ali; Turunen-Saaresti, Teemu

2017-03-01

Carbon dioxide (CO2) is a promising alternative as a working fluid for future energy conversion and refrigeration cycles. CO2 has low global warming potential compared to refrigerants and supercritical CO2 Brayton cycle ought to have better efficiency than today’s counter parts. However, there are several issues concerning behaviour of supercritical CO2 in aforementioned applications. One of these issues arises due to non-equilibrium condensation of CO2 for some operating conditions in supercritical compressors. This paper investigates the non-equilibrium condensation of carbon dioxide in the course of an expansion from supercritical stagnation conditions in a converging-diverging nozzle. An external look-up table was implemented, using an in-house FORTRAN code, to calculate the fluid properties in supercritical, metastable and saturated regions. This look-up table is coupled with the flow solver and the non-equilibrium condensation model is introduced to the solver using user defined expressions. Numerical results are compared with the experimental measurements. In agreement with the experiment, the distribution of Mach number in the nozzle shows that the flow becomes supersonic in upstream region near the throat where speed of sound is minimum also the equilibrium reestablishment occurs at the outlet boundary condition.

Oxidation of alloys for energy applications in supercritical CO 2 and H 2O

DOE PAGES

Holcomb, Gordon R.; Carney, Casey; Doğan, Ömer N.

2016-03-19

To facilitate development of supercritical CO 2 (sCO 2) power plants, a comparison of the oxidation behavior of austenitic stainless steels and Ni-base alloys in sH 2O and sCO 2 were made. Experiments were conducted at 730 °C/207 bar (sCO 2) and 726 °C/208 bar (sH 2O). Ni-base alloys in sCO 2 did not exhibit much change with pressure. Ni-base alloys in sH 2O had an increase in corrosion rate and the log of the parabolic rate constant was proportional to pressure. Lastly, fine-grain austenitic stainless steels in sCO 2 and sH 2O were both less protective with pressure asmore » the dense protective chromia scale was replaced with faster growing Fe-oxide rich scales.« less

Electrochemical Reduction of Protic Supercritical CO2 on Copper Electrodes.

PubMed

Melchaeva, Olga; Voyame, Patrick; Bassetto, Victor Costa; Prokein, Michael; Renner, Manfred; Weidner, Eckhard; Petermann, Marcus; Battistel, Alberto

2017-09-22

The electrochemical reduction of carbon dioxide is usually studied in aqueous solutions under ambient conditions. However, the main disadvantages of this method are high hydrogen evolution and low faradaic efficiencies of carbon-based products. Supercritical CO 2 (scCO 2 ) can be used as a solvent itself to suppresses hydrogen evolution and tune the carbon-based product yield; however, it has received little attention for this purpose. Therefore, the focus of this study was on the electrochemical reduction of scCO 2 . The conductivity of scCO 2 was increased through the addition of supporting electrolyte and a cosolvent (acetonitrile). Furthermore, the addition of protic solutions of different pH to scCO 2 was investigated. 1 m H 2 SO 4 , trifluoroethanol, H 2 O, KOH, and CsHCO 3 solutions were used to determine the effect on current density, faradaic efficiency, and selectivity of the scCO 2 reduction. The reduction of scCO 2 to methanol and ethanol are reported for the first time. However, methane and ethylene were not observed. Additionally, corrosion of the Cu electrode was noticed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

Hartmann, Anja; Ganzera, Markus

2015-11-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-09-01

. Total dissolved solids increase with reaction progress, mostly due to dissolution of calcite with an accompanying increase in dissolved bicarbonate. The Madison Limestone is a natural example of the thermodynamic end point that similar fluid-rock systems will develop following emplacement of a supercritical CO 2-sulfur mixture and is a natural analog for geologic carbon-sulfur co-sequestration.

Discovering geothermal supercritical fluids: a new frontier for seismic exploration.

PubMed

Piana Agostinetti, Nicola; Licciardi, Andrea; Piccinini, Davide; Mazzarini, Francesco; Musumeci, Giovanni; Saccorotti, Gilberto; Chiarabba, Claudio

2017-11-06

Exploiting supercritical geothermal resources represents a frontier for the next generation of geothermal electrical power plant, as the heat capacity of supercritical fluids (SCF),which directly impacts on energy production, is much higher than that of fluids at subcritical conditions. Reconnaissance and location of intensively permeable and productive horizons at depth is the present limit for the development of SCF geothermal plants. We use, for the first time, teleseismic converted waves (i.e. receiver function) for discovering those horizons in the crust. Thanks to the capability of receiver function to map buried anisotropic materials, the SCF-bearing horizon is seen as the 4km-depth abrupt termination of a shallow, thick, ultra-high (>30%) anisotropic rock volume, in the center of the Larderello geothermal field. The SCF-bearing horizon develops within the granites of the geothermal field, bounding at depth the vapor-filled heavily-fractured rock matrix that hosts the shallow steam-dominated geothermal reservoirs. The sharp termination at depth of the anisotropic behavior of granites, coinciding with a 2 km-thick stripe of seismicity and diffuse fracturing, points out the sudden change in compressibility of the fluid filling the fractures and is a key-evidence of deep fluids that locally traversed the supercritical conditions. The presence of SCF and fracture permeability in nominally ductile granitic rocks open new scenarios for the understanding of magmatic systems and for geothermal exploitation.

A supercritical-CO2 extract of Ganoderma lucidum spores inhibits cholangiocarcinoma cell migration by reversing the epithelial-mesenchymal transition.

PubMed

Li, Lian; Guo, Hui-Jun; Zhu, Ling-Yan; Zheng, Limin; Liu, Xin

2016-05-15

Ganoderma lucidum (G. lucidum) is an oriental medical mushroom that has been widely used in Asian countries for centuries to prevent and treat different diseases, including cancer. The objective of this study was to investigate the effect of A supercritical-CO2 extract of G. lucidum spores on the transforming growth factor beta 1 (TGF-β1)-induced epithelial-mesenchymal transition (EMT) of cholangiocarcinoma cells. This was an in vitro study with human cholangiocarcinoma TFK-1 cells treated with varying concentrations of G. lucidum. A supercritical-CO2 extract of G. lucidum spores (GLE) was obtained from completely sporoderm-broken germinating G. lucidum spores by supercritical fluid carbon dioxide (SCF-CO2) extraction. GLE pre-incubated with human cholangiocarcinoma TFK-1 cells prior to TGF-β1 treatment (2ng/ml) for 48h. Changes in EMT markers were analyzed by western blotting and immunofluorescence. The formation of F-actin stress fibers was assessed via immunostaining with phalloidin and examined using confocal microscopy. Additionally, the effect of the GLE on TGF-β1-induced migration was investigated by a Boyden chamber assay. TGF-β1-induced reduction in E-cadherin expression was associated with a loss of epithelial morphology and cell-cell contact. Concomitant increases in N-cadherin and Fibronectin were evident in predominantly elongated fibroblast-like cells. The GLE suppressed the TGF-β1-induced morphological changes and the changes in cadherin expression, and also inhibited the formation of F-actin stress fibers, which are a hallmark of EMT. The GLE also inhibited TGF-β1-induced migration of TFK-1 cells. Our findings provide new evidence that GLE suppress cholangiocarcinoma migration in vitro through inhibition of TGF-β1-induced EMT. The GLE may be clinically applied in the prevention and/or treatment of cancer metastasis. Copyright © 2016. Published by Elsevier GmbH.

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

PubMed

Taguchi, Kaori; Fukusaki, Eiichiro; Bamba, Takeshi

2014-10-03

Chromatography techniques usually use a single state in the mobile phase, such as liquid, gas, or supercritical fluid. Chromatographers manage one of these techniques for their purpose but are sometimes required to use multiple methods, or even worse, multiple techniques when the target compounds have a wide range of chemical properties. To overcome this challenge, we developed a single method covering a diverse compound range by means of a "unified" chromatography which completely bridges supercritical fluid chromatography and liquid chromatography. In our method, the phase state was continuously changed in the following order; supercritical, subcritical and liquid. Moreover, the gradient of the mobile phase starting at almost 100% CO2 was replaced with 100% methanol at the end completely. As a result, this approach achieved further extension of the polarity range of the mobile phase in a single run, and successfully enabled the simultaneous analysis of fat- and water-soluble vitamins with a wide logP range of -2.11 to 10.12. Furthermore, the 17 vitamins were exceptionally separated in 4min. Our results indicated that the use of dense CO2 and the replacement of CO2 by methanol are practical approaches in unified chromatography covering diverse compounds. Additionally, this is a first report to apply the novel approach to unified chromatography, and can open another door for diverse compound analysis in a single chromatographic technique with single injection, single column and single system. Copyright © 2014. Published by Elsevier B.V.

A high-pressure atomic force microscope for imaging in supercritical carbon dioxide

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

Lea, Alan S.; Higgins, Steven R.; Knauss, Kevin G.

2011-04-26

A high-pressure atomic force microscope (AFM) that enables in-situ, atomic scale measurements of topography of solid surfaces in contact with supercritical CO2 (scCO2) fluids has been developed. This apparatus overcomes the pressure limitations of the hydrothermal AFM and is designed to handle pressures up to 100 atm at temperatures up to ~ 350 K. A standard optically-based cantilever deflection detection system was chosen. When imaging in compressible supercritical fluids such as scCO2, precise control of pressure and temperature in the fluid cell is the primary technical challenge. Noise levels and imaging resolution depend on minimization of fluid density fluctuations thatmore » change the fluid refractive index and hence the laser path. We demonstrate with our apparatus in-situ atomic scale imaging of a calcite (CaCO3) mineral surface in scCO2; both single, monatomic steps and dynamic processes occurring on the (10¯14) surface are presented. This new AFM provides unprecedented in-situ access to interfacial phenomena at solid-fluid interfaces under pressure.« less

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.

In Situ Natural Abundance 17 O and 25 Mg NMR Investigation of Aqueous Mg(OH) 2 Dissolution in the Presence of Supercritical CO 2

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

Hu, Mary Y.; Deng, Xuchu; Thanthiriwatte, K. Sahan

We report the development of an in situ high pressure NMR capability that permits natural abundance 17O and 25Mg NMR characterization of dissolved species in aqueous solution and in the presence of supercritical CO 2 fluid (scCO 2). The dissolution of Mg(OH) 2 (brucite) in a multiphase water/scCO 2 fluid at 90 atm pressure and 50 C was studied in situ, with relevance to geological carbon sequestration. 17O NMR spectra allowed identification and distinction of various fluid species including dissolved CO 2 in the H 2O-rich phase, scCO 2, aqueous H 2O, and HCO 3 -. The widely separated spectralmore » peaks for various species can all be observed both dynamically and quantitatively at concentrations of as low as 20 mM. Measurement of the concentrations of these individual species also allows an in situ estimate of the hydrogen ion concentration, or pCH + values, of the reacting solutions. The concentration of Mg 2+ can be observed by natural abundance 25Mg NMR at a concentration as low as 10 mM. Quantum chemistry calculations of the NMR chemical shifts on cluster models aided in the interpretation of the experimental results. Evidence for the formation of polymeric Mg 2+ clusters at high concentrations in the H 2O-rich phase, a possible critical step needed for magnesium carbonate formation, was found. The approach and findings enable insight into metal carbonation reactions associated with geological carbon sequestration that cannot be probed by ex situ methods.« less

Supercritical fluids crystallization of budesonide and flunisolide.

PubMed

Velaga, Sitaram P; Berger, Rolf; Carlfors, Johan

2002-10-01

Budesonide and flunisolide anhydrate were crystallized using the solution enhanced dispersion by supercritical fluids (SEDS) technique. The aim was to investigate the possibility of preparing different pure polymorphs. 0.25% w/v solutions of each drug were prepared from acetone and methanol. Operating conditions were 40-80 degrees C and 80-200 bars. The flow rate of drug solution was 0.3 mL/min and that of CO2 was 9-25 mL/min. Sample characterizations included differential scanning calorimetry, X-ray powder diffraction, variable temperature X-ray diffraction, scanning electron microscopy, and solubility studies. The particle morphology of budesonide was dependent on the nature of the solvent. SEDS processing of flunisolide with acetone at 100 bars resulted in the formation of polymorphic mixtures at 80 degrees C and a new polymorph III at 60 C and 40 degrees C. With methanol at 100 bars another new polymorph IV was formed with different particle morphology at 80 degrees C and a polymorphic mixture at 60 degrees C. Using the SEDS, microparticles of crystalline budesonide were prepared and new polymorphs of flunisolide were produced. Particle characteristics were controlled by the temperature, pressure and relative flow rates of drug solution and CO2.

Solvation and Evolution Dynamics of an Excess Electron in Supercritical CO2

NASA Astrophysics Data System (ADS)

Wang, Zhiping; Liu, Jinxiang; Zhang, Meng; Cukier, Robert I.; Bu, Yuxiang

2012-05-01

We present an ab initio molecular dynamics simulation of the dynamics of an excess electron solvated in supercritical CO2. The excess electron can exist in three types of states: CO2-core localized, dual-core localized, and diffuse states. All these states undergo continuous state conversions via a combination of long lasting breathing oscillations and core switching, as also characterized by highly cooperative oscillations of the excess electron volume and vertical detachment energy. All of these oscillations exhibit a strong correlation with the electron-impacted bending vibration of the core CO2, and the core-switching is controlled by thermal fluctuations.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Experimental investigation of supercritical CO 2 trapping mechanisms at the Intermediate Laboratory Scale in well-defined heterogeneous porous media

DOE PAGES

Trevisan, Luca; Pini, Ronny; Cihan, Abdullah; ...

2014-12-31

The heterogeneous nature of typical sedimentary formations can play a major role in the propagation of the CO 2 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 themore » migration and trapping of supercritical CO 2 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 CO 2 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

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. Copyright © 2011 Elsevier B.V. All rights reserved.

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

PubMed

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

2016-09-13

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

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

PubMed

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

2018-05-18

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

Pulsed Laser Ablation Synthesis of Diamond Molecules in Supercritical Fluids

NASA Astrophysics Data System (ADS)

Nakahara, Sho; Stauss, Sven; Miyazoe, Hiroyuki; Shizuno, Tomoki; Suzuki, Minoru; Kataoka, Hiroshi; Sasaki, Takehiko; Terashima, Kazuo

2010-09-01

Nanocarbon materials have been synthesized by pulsed laser ablation (532 nm; 52 J/cm2; 7 ns; 10 Hz) of highly oriented pyrolytic graphite in adamantane-dissolved supercritical xenon at a temperature T = 290.2 K and pressure p = 5.86 MPa. Micro-Raman spectroscopy of the products revealed the presence of hydrocarbons possessing sp3 hybridized bonds also found in diamond structures. The synthesis of diamantane was confirmed by gas chromatography-mass spectrometry. The same measurements also indicate the possible synthesis of other diamondoids up to octamantane. Thus, laser ablation in supercritical fluids is proposed as one practical method of synthesizing diamondoids.

Determination of arsenic species in solid matrices utilizing supercritical fluid extraction coupled with gas chromatography after derivatization with thioglycolic acid n-butyl ester.

PubMed

Wang, Zhifeng; Cui, Zhaojie

2016-12-01

A method using derivatization and supercritical fluid extraction coupled with gas chromatography was developed for the analysis of dimethylarsinate, monomethylarsonate and inorganic arsenic simultaneously in solid matrices. Thioglycolic acid n-butyl ester was used as a novel derivatizing reagent. A systematic discussion was made to investigate the effects of pressure, temperature, flow rate of the supercritical CO 2 , extraction time, concentration of the modifier, and microemulsion on extraction efficiency. The application for real environmental samples was also studied. Results showed that thioglycolic acid n-butyl ester was an effective derivatizing reagent that could be applied for arsenic speciation. Using methanol as modifier of the supercritical CO 2 can raise the extraction efficiency, which can be further enhanced by adding a microemulsion that contains Triton X-405. The optimum extraction conditions were: 25 MPa, 90°C, static extraction for 10 min, dynamic extraction for 25 min with a flow rate of 2.0 mL/min of supercritical CO 2 modified by 5% v/v methanol and microemulsion. The detection limits of dimethylarsinate, monomethylarsonate, and inorganic arsenic in solid matrices were 0.12, 0.26, and 1.1 mg/kg, respectively. The optimized method was sensitive, convenient, and reliable for the extraction and analysis of different arsenic species in solid samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Materials, Turbomachinery and Heat Exchangers for Supercritical CO2 Systems

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

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-temperaturemore » 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

Experimental Insights into Multiphase (H2O-CO2) Fluid-Rock Interactions in Geothermal Systems

NASA Astrophysics Data System (ADS)

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

2012-12-01

Integrated hydrothermal experiments and geochemical modeling elucidate fluid-rock interactions and reaction pathways in both natural and anthropogenic systems, including enhanced geothermal systems (EGS) in which CO2 is introduced as a working fluid. Experiments are conducted in rocker bombs and flexible Au-Ti reaction cells. Individual experiments require one to three months to complete; intensive in-situ fluid/gas sampling gauges reaction progress. Investigation of granitic reservoirs and associated vein minerals are broadly based on the Roosevelt Hot Springs thermal area, Utah, USA. The granite consists of subequal amounts of quartz, perthitic K-feldspar (~25% wt% albite and 75% wt% K-feldspar), and oligoclase (An23), and 4 wt% Fe-rich biotite. Vein minerals include epidote and chlorite (clinochlore). Experiments are conducted at 250°C and 25 to 45 MPa. Each experiment uses mineral powders (75 wt% of rock mass, ground to <45 um) to increase reactivity and also mineral pieces (0.1-0.7 cm in size) to promote petrologic evaluation of mineral reactions. The water (I ≈ 0.1 molal) initially contains millimolal quantities of SiO2, Al, Ca, Mg, K, SO4, and HCO3 and is designed to be saturated with all of the minerals present at the start of each experiment. Excess CO2 is injected to saturate the water and maintain an immiscible supercritical fluid phase. The entire evolutionary path of the natural system is not replicated at laboratory scales. Instead, experiments define a segment of the reaction path and, in combination with geochemical modeling, provide clear trajectories towards equilibrium. Reaction of granite+water yields illite+zeolite; smectite subsequently precipitates in response to CO2 injection. Reaction of granite+epidote+water yields illite+zeolite+smectite; zeolite does not precipitate after CO2 is injected. Water in all experiments become saturated with chalcedony. Carbonate minerals do not precipitate but are predicted as final equilbrium products

Supercritical Fluid Extraction of Metal Chelate: A Review.

PubMed

Ding, Xin; Liu, Qinli; Hou, Xiongpo; Fang, Tao

2017-03-04

Supercritical fluid extraction (SFE), as a new green extraction technology, has been used in extracting various metal species. The solubilities of chelating agents and corresponding metal chelates are the key factors which influence the efficiency of SFE. Other main properties of them such as stability and selectivity are also reviewed. The extraction mechanisms of mainly used chelating agents are explained by typical examples in this paper. This is the important aspect of SFE of metal ions. Moreover, the extraction efficiencies of metal species also depend on other factors such as temperature, pressure, extraction time and matrix effect. The two main complexation methods namely in-situ and on-line chelating SFE are described in detail. As an efficient chelating agent, tributyl phosphate-nitric acid (TBP-HNO 3 ) complex attracts much attention. The SFE of metal ions, lanthanides and actinides as well as organometallic compounds are also summarized. With the proper selection of ligands, high efficient extraction of metal species can be obtained. As an efficient sample analysis method, supercritical fluid chromatography (SFC) is introduced in this paper. Recently, the extraction method combining ionic liquids (ILs) with supercritical fluid has been becoming a novel technology for treating metal ions. The kinetics related to SFE of metal species is discussed with some specific examples.

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

PubMed

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

2015-02-01

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

Essential oil composition of Valeriana officinalis L. roots cultivated in Iran. Comparative analysis between supercritical CO2 extraction and hydrodistillation.

PubMed

Safaralie, Asghar; Fatemi, Shohreh; Sefidkon, Fatemeh

2008-02-08

The composition of essential oil extracted from Valeriana officinalis L. roots growing wild in Iran was studied by hydrodistillation and supercritical CO2 extraction. Forty-seven components representing 89.3% and 35 constituents varying from 86.1% to 95.1% of the oil obtained by hydrodistillation and supercritical CO2 were identified, respectively. The major components in the extracted oil from supercritical CO2 were isovaleric acid (18.7-41.8%), valerenic acid (8.2-11.8%), acetoxyvaleranone (5.6-9.6%), (Z)-valernyl acetate (4.5-6.5%), bornyl acetate (2.3-7.7%) and valerenol (3.7-5.2%), whereas by hydrodistillation were bornyl acetate (11.6%), valerenic acid (8.0%), (Z)-valernyl acetate (7.9%) and acetoxyvaleranone (7.6%). The analysis of the extracts was performed by capillary GC and GC/MS.

Phytosterols and their extraction from various plant matrices using supercritical carbon dioxide: a review.

PubMed

Uddin, Md Salim; Sarker, Md Zaidul Islam; Ferdosh, Sahena; Akanda, Md Jahurul Haque; Easmin, Mst Sabina; Bt Shamsudin, Siti Hadijah; Bin Yunus, Kamaruzzaman

2015-05-01

Phytosterols provide important health benefits: in particular, the lowering of cholesterol. From environmental and commercial points of view, the most appropriate technique has been searched for extracting phytosterols from plant matrices. As a green technology, supercritical fluid extraction (SFE) using carbon dioxide (CO2) is widely used to extract bioactive compounds from different plant matrices. Several studies have been performed to extract phytosterols using supercritical CO2 (SC-CO2) and this technology has clearly offered potential advantages over conventional extraction methods. However, the efficiency of SFE technology fully relies on the processing parameters, chemistry of interest compounds, nature of the plant matrices and expertise of handling. This review covers SFE technology with particular reference to phytosterol extraction using SC-CO2. Moreover, the chemistry of phytosterols, properties of supercritical fluids (SFs) and the applied experimental designs have been discussed for better understanding of phytosterol solubility in SC-CO2. © 2014 Society of Chemical Industry.

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

PubMed

Kalani, Mahshid; Yunus, Robiah

2012-01-01

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

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

PubMed Central

Kalani, Mahshid; Yunus, Robiah

2012-01-01

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

Novel micronisation β-carotene using rapid expansion supercritical solution with co-solvent

NASA Astrophysics Data System (ADS)

Kien, Le Anh

2017-09-01

Rapid expansion of supercritical solution (RESS) is the most common approach of pharmaceutical pacticle forming methods using supercritical fluids. The RESS method is a technology producing a small solid product with a very narrow particle size distribution, organic solvent-free particles. This process is also simple and easy to control the operating parameters in comparision with other ways based on supercritical techniques. In this study, β-carotene, a strongly colored red-orange pigment abundant in plants and fruits, has been forming by RESS. In addition, the size and morphology effect of four different RESS parameters including co-solvent, extraction temperature, and extraction pressure and expansion nozzle temperature has surveyed. The particle size distribution has been determined by using laser diffraction experiment. SEM has conducted to analyze the surface structure, DSC and FTIR for thermal and chemical structure analysis.

Towards Overhauser DNP in supercritical CO(2).

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. Copyright © 2016 Elsevier Inc. All rights reserved.

Supercritical fluid processing of drug nanoparticles in stable suspension.

PubMed

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

2007-07-01

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

Forensic applications of supercritical fluid chromatography - mass spectrometry.

PubMed

Pauk, Volodymyr; Lemr, Karel

2018-06-01

Achievements of supercritical fluid chromatography with mass spectrometric detection made in the field of forensic science during the last decade are reviewed. The main topics include analysis of traditional drugs of abuse (e.g. cannabis, methamphetamine) as well as new psychoactive substances (synthetic cannabinoids, cathinones and phenethylamines), doping agents (anabolic steroids, stimulants, diuretics, analgesics etc.) and chemical warfare agents. Control of food authenticity, detection of adulteration and identification of toxic substances in food are also pointed out. Main aspects of an analytical workflow, such as sample preparation, separation and detection are discussed. A special attention is paid to the performance characteristics and validation parameters of supercritical fluid chromatography-mass spectrometric methods in comparison with other separation techniques. Copyright © 2018 Elsevier B.V. All rights reserved.

Summary of the research and development effort on the supercritical CO2 cycle

NASA Astrophysics Data System (ADS)

Fraas, A. P.

1981-06-01

The supercritical CO2 cycle has the advantage over a conventional closed cycle gas turbine in that the compression work phase of the cycle can be carried out close to the critical point and hence aerodynamic losses in the compressor are reduced and the cycle efficiency increased for a given turbine inlet temperature. However, the practicable turbine inlet temperature is reduced by permissible stresses in the heater tubes because the peak pressure in the cycle must be approx. 260 atm in order to have the compression process take place close to the critical point of the working fluid. The high system pressure also makes the capital cost of the heat exchangers and gas piping higher than that for a conventional closed cycle gas turbine. Further, the waste heat from the cycle must be rejected at too low a temperature for it to be useful for industrial process heat or for district heating systems.

Analysis of non-phthalates plasticizers on porous graphitic carbon by supercritical fluid chromatography using evaporative light scattering detection.

PubMed

Vaccher, Claude; Decaudin, Bertrand; Sautou, Valérie; Lecoeur, Marie

2014-09-12

The analysis of several plasticizers, widely used in the production of medical devices, was investigated on porous graphitic carbon (PGC) stationary phase in supercritical fluid chromatography (SFC) with an evaporative light scattering detector (ELSD). Due to strong interaction of compounds with the PGC support, solvents of strong eluotropic strength were added to the CO2 supercritical fluid. The effect of alkyl chain (pentane, hexane, heptane) and chlorinated (CH2Cl2, CHCl3, CCl4) solvents was studied on the retention and on the ELSD detection of plasticizers. A co-solvent mixture composed of CHCl3/heptane, eluted under gradient mode, allowed a significant improvement of the ELSD response compared to the use of each solvent individually. Then, a central composite design (CCD) was implemented to optimize both the separation and the detection of plasticizers. The parameters involved were the outlet pressure, the gradient slope, the co-solvent composition and the drift tube temperature of the ELSD. After optimization, baseline separation of plasticizers was achieved in 7min and best signal-to-noise ratios were obtained with outlet pressure and drift tube temperature of ELSD set at 200bar and 31°C, respectively. The co-solvent mixture was also composed of CHCl3/heptane (35/65 v/v) and a gradient from 15 to 60% of co-solvent in 2.2min was employed. The results demonstrated that CCD is a powerful tool for the optimization of SFC/ELSD method and the response surface model analysis can provide statistical understandings of the significant factors required to achieve optimal separation and ELSD sensitivity. Copyright © 2014 Elsevier B.V. All rights reserved.

The Influence of Fracturing Fluids on Fracturing Processes: A Comparison Between Water, Oil and SC-CO2

NASA Astrophysics Data System (ADS)

Wang, Jiehao; Elsworth, Derek; Wu, Yu; Liu, Jishan; Zhu, Wancheng; Liu, Yu

2018-01-01

Conventional water-based fracturing treatments may not work well for many shale gas reservoirs. This is due to the fact that shale gas formations are much more sensitive to water because of the significant capillary effects and the potentially high contents of swelling clay, each of which may result in the impairment of productivity. As an alternative to water-based fluids, gaseous stimulants not only avoid this potential impairment in productivity, but also conserve water as a resource and may sequester greenhouse gases underground. However, experimental observations have shown that different fracturing fluids yield variations in the induced fracture. During the hydraulic fracturing process, fracturing fluids will penetrate into the borehole wall, and the evolution of the fracture(s) then results from the coupled phenomena of fluid flow, solid deformation and damage. To represent this, coupled models of rock damage mechanics and fluid flow for both slightly compressible fluids and CO2 are presented. We investigate the fracturing processes driven by pressurization of three kinds of fluids: water, viscous oil and supercritical CO2. Simulation results indicate that SC-CO2-based fracturing indeed has a lower breakdown pressure, as observed in experiments, and may develop fractures with greater complexity than those developed with water-based and oil-based fracturing. We explore the relation between the breakdown pressure to both the dynamic viscosity and the interfacial tension of the fracturing fluids. Modeling demonstrates an increase in the breakdown pressure with an increase both in the dynamic viscosity and in the interfacial tension, consistent with experimental observations.

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.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

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. Copyright © 2012 Elsevier Ltd. All rights reserved.

Removal of common organic solvents from aqueous waste streams via supercritical C02 extraction: a potential green approach to sustainable waste management in the pharmaceutical industry.

PubMed

Leazer, Johnnie L; Gant, Sean; Houck, Anthony; Leonard, William; Welch, Christopher J

2009-03-15

Supercritical CO2 extraction of aqueous streams is a convenient and effective method to remove commonly used solvents of varying polarities from aqueous waste streams. The resulting aqueous layers can potentially be sewered; whereas the organic layer can be recovered for potential reuse. Supercritical fluid extraction (SFE) is a technology that is increasingly being used in commercial processes (1). Supercritical fluids are well suited for extraction of a variety of media, including solids, natural products, and liquid products. Many supercritical fluids have low critical temperatures, allowing for extractions to be done at modestly low temperatures, thus avoiding any potential thermal decomposition of the solutes under study (2). Furthermore, the CO2 solvent strength is easily tuned by adjusting the density of the supercritical fluid (The density is proportional to the pressure of the extraction process). Since many supercritical fluids are gases at ambient temperature, the extract can be concentrated by simply venting the reaction mixture to a cyclone collection vessel, using appropriate safety protocols.

Role of modifiers for analytical-scale supercritical fluid extraction of environmental samples

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

Langenfeld, J.J.; Hawthorne, S.B.; Miller, D.J.

1994-03-15

Supercritical fluid extraction (SFE) using eight different CO[sub 2] + organic modifier mixtures and one ternary mixture (CO[sub 2] + methanol/toluene) at two different concentrations (1 and 10% v/v) was performed on two certified reference materials including polychlorinated biphenyls (PCBs) from river sediment and polycyclic aromatic hydrocarbons (PAHs) from urban air particulate matter. The modifier identity was more important than modifier concentration for increasing extraction efficiencies. Acidic/basic modifiers including methanol, acetic acid, and aniline greatly enhanced the extraction of PCBs. Low molecular weight PAHs were best extracted with modifiers including aniline, acetic acid, acetonitrile, methanol/toluene, hexane, and diethylamine. In contrast,more » modifiers capable of dipole-induced dipole interactions and [pi]-[pi] interactions such as toluene, diethylamine, and methylene chloride were the best modifiers to use for SFE of high molecular weight PAHs from air particulates. 37 refs., 6 tabs.« less

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

Intermolecular interactions and the thermodynamic properties of supercritical fluids.

PubMed

Yigzawe, Tesfaye M; Sadus, Richard J

2013-05-21

The role of different contributions to intermolecular interactions on the thermodynamic properties of supercritical fluids is investigated. Molecular dynamics simulation results are reported for the energy, pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, Joule-Thomson coefficient, and speed of sound of fluids interacting via both the Lennard-Jones and Weeks-Chandler-Andersen potentials. These properties were obtained for a wide range of temperatures, pressures, and densities. For each thermodynamic property, an excess value is determined to distinguish between attraction and repulsion. It is found that the contributions of intermolecular interactions have varying effects depending on the thermodynamic property. The maxima exhibited by the isochoric and isobaric heat capacities, isothermal compressibilities, and thermal expansion coefficient are attributed to interactions in the Lennard-Jones well. Repulsion is required to obtain physically realistic speeds of sound and both repulsion and attraction are necessary to observe a Joule-Thomson inversion curve. Significantly, both maxima and minima are observed for the isobaric and isochoric heat capacities of the supercritical Lennard-Jones fluid. It is postulated that the loci of these maxima and minima converge to a common point via the same power law relationship as the phase coexistence curve with an exponent of β = 0.32. This provides an explanation for the terminal isobaric heat capacity maximum in supercritical fluids.

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

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

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

2013-01-01

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

Growth and Morphology of Supercritical Fluids Studied in Microgravity on Mir

NASA Technical Reports Server (NTRS)

Wilkinson, R. Allen

2000-01-01

The Growth and Morphology of Supercritical Fluids (GMSF) is an international experiment facilitated by the NASA Glenn Research Center at Lewis Field and under the guidance of U.S. principal investigator Professor John Hegseth of the University of New Orleans and three French coinvestigators Daniel Beysens, Yves Garrabos, and Carole Chabot. In early 1999, GMSF experiments were operated for 20 days on the Russian Space Station Mir. Mir astronauts performed experiments One through Seven, which spanned the three science themes of near-critical phase separation rates, interface dynamics in near-critical boiling, and measurement of the spectrum of density fluctuation length scales very close to the critical point. The fluids used were pure CO2 or SF6. Three of the five thermostats used could adjust the sample volume with the scheduled crew time. Such a volume adjustment enabled variable sample densities around the critical density as well as pressure steps (as distinct from the usual temperature steps) to be applied to the sample.

Chemical composition of Juniperus communis L. fruits supercritical CO2 extracts: dependence on pressure and extraction time.

PubMed

Barjaktarović, Branislava; Sovilj, Milan; Knez, Zeljko

2005-04-06

Ground fruits of the common juniper (Juniperus communis L.), with a particle size range from 0.250-0.400 mm, forming a bed of around 20.00 +/- 0.05 g, were extracted with supercritical CO(2) at pressures of 80, 90, and 100 bars and at a temperature of 40 degrees C. The total amount of extractable substances or global yield (mass of extract/mass of raw material) for the supercritical fluid extraction process varied from 0.65 to 4.00% (wt). At each investigated pressure, supercritical CO(2) extract fractions collected in successive time intervals over the course of the extraction were analyzed by capillary gas chromatography, using flame ionization (GC-FID) and mass spectrometric detection (GC-MS). More than 200 constituents were detected in the extracts, and the contents of 50 compounds were reported in the work. Dependence of the percentage yields of monoterpene, sesquiterpene, oxygenated monoterpene, and oxygenated sesquiterpene hydrocarbon groups on the extraction time was investigated, and conditions that favored the yielding of each terpene groups were emphasized. At all pressures, monoterpene hydrocarbons were almost completely extracted from the berries in the first 0.6 h. It was possible to extract oxygenated monoterpenes at 100 bar in 0.5 h and at 90 bar in 1.2 h. Contrary to that, during an extraction period of 4 h at 80 bar, it was possible to extract only 75% of the maximum yielded value of oxygenated monoterpene at 100 bar. Intensive extraction of sesquiterpenes could be by no means avoided at any pressure, but at the beginning of the process (the first 0.5 h) at 80 bar, they were extracted about 8 and 3 times slower than at 100 and 90 bar, respectively. Oxygenated sesquiterpenes were yielded at fast, constant extraction rates at 100 and 90 bar in 1.2 and 3 h, respectively. This initial fast extraction period was consequently followed by much slower extraction of oxygenated sesquiterpenes.

[Study on condition for extraction of arctiin from fruits of Arctium lappa using supercritical fluid extraction].

PubMed

Dong, Wen-hong; Liu, Ben

2006-08-01

To study the feasibility of supercritical fluid extraction (SFE) for arctiin from the fruits of Arctium lappa. The extracts were analyzed by HPLC, optimum extraction conditions were studied by orthogonal tests. The optimal extraction conditions were: pressure 40 MPa, temperature 70 degrees C, using methanol as modifier carrier at the rate of 0.55 mL x min(-1), static extraction time 5 min, dynamic extraction 30 min, flow rate of CO2 2 L x min(-1). SFE has the superiority of adjustable polarity, and has the ability of extracting arctiin.

Supercritical fluid extraction and bioactivity of cedarwood oil

USDA-ARS?s Scientific Manuscript database

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

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

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

USGS Publications Warehouse

Kolak, Jonathan J.; Burruss, Robert A.

2014-01-01

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

Preparation of Active Proteins, Vaccines and Pharmaceuticals as Fine Powders using Supercritical or Near-Critical Fluids

PubMed Central

Villa, Joseph A.; Huang, Edward T. S.; Yang, Tzung-Horng; Carpenter, John F.; Sievers, Robert E.

2008-01-01

Supercritical or near-critical fluid processes for generating microparticles have enjoyed considerable attention in the past decade or so, with good success for substances soluble in supercritical fluids or organic solvents. In this review, we survey their application to the production of protein particles. A recently developed process known as CO2-assisted nebulization with a Bubble Dryer® (CAN-BD) has been demonstrated to have broad applicability to small-molecule as well as macromolecule substances (including therapeutic proteins). The principles of CAN-BD are discussed as well as the stabilization, micronization and drying of a wide variety of materials. More detailed case studies are presented for three proteins, two of which are of therapeutic interest: anti-CD4 antibody (rheumatoid arthritis), α1-antitrypsin (cystic fibrosis and emphysema), and trypsinogen (a model enzyme). Dry powders were formed in which stability and activity are maintained and which are fine enough to be inhaled and reach the deep lung. Enhancement of apparent activity after CAN-BD processing was also observed in some formulation and processing conditions. PMID:18581212

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

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

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

Chang, Chun; Zhou, Quanlin; Kneafsey, Timothy J.

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-analogue 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. Highmore » 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

Supercritical Fluid Spray Application Process for Adhesives and Primers

DTIC Science & Technology

2003-03-01

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

Extraction fatty acid as a source to produce biofuel in microalgae Chlorella sp. and Spirulina sp. using supercritical carbon dioxide

NASA Astrophysics Data System (ADS)

Tai, Do Chiem; Hai, Dam Thi Thanh; Vinh, Nguyen Hanh; Phung, Le Thi Kim

2016-06-01

In this research, the fatty acids of isolated microalgae were extracted by some technologies such as maceration, Soxhlet, ultrasonic-assisted extraction and supercritical fluid extraction; and analyzed for biodiesel production using GC-MS. This work deals with the extraction of microalgae oil from dry biomass by using supercritical fluid extraction method. A complete study at laboratory of the influence of some parameters on the extraction kinetics and yields and on the composition of the oil in terms of lipid classes and profiles is proposed. Two types of microalgae were studied: Chlorella sp. and Spirulina sp. For the extraction of oil from microalgae, supercritical CO2 (SC-CO2) is regarded with interest, being safer than n-hexane and offering a negligible environmental impact, a short extraction time and a high-quality final product. Whilst some experimental papers are available on the supercritical fluid extraction (SFE) of oil from microalgae, only limited information exists on the kinetics of the process. These results demonstrate that supercritical CO2 extraction is an efficient method for the complete recovery of the neutral lipid phase.

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

PubMed

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

2016-04-07

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

Investigation on the supercritical CO(2) extraction of the volatile constituents from Juniperus communis obtained under different treatments of the "berries" (cones).

PubMed

Chatzopoulou, Paschalina; de Haan, Andre; Katsiotis, Stavros T

2002-09-01

The present investigation reports the experimental data a) from the recovery and the composition of the extract under super critical fluid extraction from Juniperus communis L. "berries" (cones), and b) their comparison with those of the essential oil obtained by hydrodistillation. For the extraction of the juniper oil different values of temperature and pressure were applied; furthermore, the degree of comminution of the plant material was also considered - a) integral "berries" and b) comminuted "berries". The quality of the oil recovered from the "berries" by supercritical carbon dioxide extraction was found to be highly dependent on the applied conditions. The comminution affected greatly the oil recovery and consequently the final composition of the extracts. Significant differences were recorded between the supercritical CO(2) extract and the distilled oil, the latter being more enriched in monoterpenoid hydrocarbons.

Evaluation of an amide-based stationary phase for supercritical fluid chromatography

PubMed Central

Borges-Muñoz, Amaris C.; Colón, Luis A.

2017-01-01

A relatively new stationary phase containing a polar group embedded in a hydrophobic backbone (i.e., ACE® C18-amide) was evaluated for use in supercritical fluid chromatography. The amide-based column was compared with columns packed with bare silica, C18 silica, and a terminal-amide silica phase. The system was held at supercritical pressure and temperature with a mobile phase composition of CO2 and methanol as cosolvent. The linear solvation energy relationship model was used to evaluate the behavior of these stationary phases, relating the retention factor of selected probes to specific chromatographic interactions. A five-component test mixture, consisting of a group of drug-like molecules was separated isocratically. The results show that the C18-amide stationary phase provided a combination of interactions contributing to the retention of the probe compounds. The hydrophobic interactions are favorable; however, the electron donating ability of the embedded amide group shows a large positive interaction. Under the chromatographic conditions used, the C18-amide column was able to provide baseline resolution of all the drug-like probe compounds in a text mixture, while the other columns tested did not. PMID:27396487

Supercritical fluid extraction and processing of foods

USDA-ARS?s Scientific Manuscript database

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...

Essential oils (EOs), pressurized liquid extracts (PLE) and carbon dioxide supercritical fluid extracts (SFE-CO2) from Algerian Thymus munbyanus as valuable sources of antioxidants to be used on an industrial level.

PubMed

Bendif, Hamdi; Adouni, Khaoula; Miara, Mohamed Djamel; Baranauskienė, Renata; Kraujalis, Paulius; Venskutonis, Petras Rimantas; Nabavi, Seyed Mohammad; Maggi, Filippo

2018-09-15

The aim of this study was to demonstrate the potential of extracts from Algerian Thymus munbyanus as a valuable source of antioxidants for use on an industrial level. To this end, a study was conducted on the composition and antioxidant activities of essential oils (EOs), pressurized liquid extracts (PLE) and supercritical fluid extracts (SFE-CO 2 ) obtained from Thymus munbyanus subsp. coloratus (TMC) and subsp. munbyanus (TMM). EOs and SFE-CO 2 extracts were analysed by GC-FID and GC×GC-TOFMS revealing significant differences. A successive extraction of the solid SFE-CO 2 residue by PLE extraction with solvents of increasing polarity such as acetone, ethanol and water, was carried out. The extracts were evaluated for total phenolic content by Folin-Ciocalteu assay, while the antioxidant power was assessed by DPPH, FRAP, and ORAC assays. SFE-CO 2 extracts were also analysed for their tocopherol content. The antioxidant activity of PLE extracts was found to be higher than that of SFE-CO 2 extracts, and this increased with solvent polarity (water > ethanol > acetone). Overall, these results support the use of T. munbyanus as a valuable source of substances to be used on an industrial level as preservative agents. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

PubMed Central

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

2005-01-01

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

Dynamics, thermodynamics and structure of liquids and supercritical fluids: crossover at the Frenkel line

NASA Astrophysics Data System (ADS)

Fomin, Yu D.; Ryzhov, V. N.; Tsiok, E. N.; Proctor, J. E.; Prescher, C.; Prakapenka, V. B.; Trachenko, K.; Brazhkin, V. V.

2018-04-01

We review recent work aimed at understanding dynamical and thermodynamic properties of liquids and supercritical fluids. The focus of our discussion is on solid-like transverse collective modes, whose evolution in the supercritical fluids enables one to discuss the main properties of the Frenkel line separating rigid liquid-like and non-rigid gas-like supercritical states. We subsequently present recent experimental evidence of the Frenkel line showing that structural and dynamical crossovers are seen at a pressure and temperature corresponding to the line as predicted by theory and modelling. Finally, we link dynamical and thermodynamic properties of liquids and supercritical fluids by the new calculation of liquid energy governed by the evolution of solid-like transverse modes. The disappearance of those modes at high temperature results in the observed decrease of heat capacity.

Synthesis of N-vinylpyrrolidone modified acrylic acid copolymer in supercritical fluids and its application in dental glass-ionomer cements.

PubMed

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

2008-07-01

Compressed fluids such as supercritical CO(2) offer marvellous opportunities for the synthesis of polymers, particularly in applications in medicine and dentistry. It has several advantages in comparison to conventional polymerisation solvents, such as enhanced kinetics and simplified solvent removal process. In this study, poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone) (PAA-IA-NVP), a modified glass-ionomer polymer, was synthesised in supercritical CO(2) (sc-CO(2)) and methanol as a co-solvent. The synthesised polymer was characterized by (1)H-NMR, Raman and FT-IR spectroscopy and viscometry. The molecular weight of the final product was also measured using static light scattering method. The synthesised polymers were subsequently used in several glass ionomer cement formulations (Fuji II commercial GIC) in which mechanical strength (compressive strength (CS), diametral tensile strength (DTS) and biaxial flexural strength (BFS)) and handling properties (working and setting time) of the resulting cements were evaluated. The polymerisation reaction in sc-CO(2)/methanol was significantly faster than the corresponding polymerisation reaction in water and the purification procedures were simpler for the former. Furthermore, glass ionomer cement samples made from the terpolymer prepared in sc-CO(2)/methanol exhibited higher CS and DTS and comparable BFS compared to the same polymer synthesised in water. The working properties of glass ionomer formulations made in sc-CO(2)/methanol were comparable and in selected cases better than the values of those made from polymers synthesised in water.