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Sample records for supercritical fluids reactions

  1. Supercritical Fluid Reactions for Coal Processing

    SciTech Connect

    Charles A. Eckert

    1997-11-01

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

  2. Supercritical fluid reactions for coal processing

    SciTech Connect

    Eckert, C.A.

    1997-04-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The Diels-Alder reaction of anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) was chosen as the model system and was investigated in supercritical carbon dioxide. Kinetic data has been previously collected for pure CO{sub 2} at pressures between the critical pressure of CO{sub 2} (73.8 bar) and 216 bar. This data is now being used to construct mathematical forms which can model these pressure induced kinetic changes. One promising avenue of investigation involves treating the supercritical medium as a dense gas, which allows a kinetic model based on high reference pressure fugacity coefficients to be derived.

  3. Supercritical Fluid Reactions for Coal Processing

    SciTech Connect

    Eckert, Charles A

    1997-07-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The Diels-Alder reaction of anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) was chosen as the model system and was investigated in supercritical carbon dioxide. Kinetic data have been previously collected for pure CO2 at 40C and pressures between the critical pressure of CO2 (73.8 bar) and 216 bar. These data support the theory of local density enhancements suggested in the literature. Data taken at 50C and pressures ranging from 70 bar to 195 bar are currently reported; they do not exhibit the molecular clustering evident closer to the critical temperature. The data taken at 40C are now being used to construct mathematical forms which can model these pressure-induced kinetic changes. One promising avenue of investigation involves treating the supercritical medium as a dense gas, which allows a kinetic model based on high reference pressure fugacity coefficients to be derived.

  4. Supercritical fluids: Reactions, materials and applications

    SciTech Connect

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

    1999-04-09

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

  5. Asphaltene reaction via supercritical fluid extraction

    SciTech Connect

    Deo, M.D.; Hanson, F.V.

    1993-01-01

    Supercritical fluid extraction (SFE) of bitumen was carried out in a continuous extractor using propane as the solvent at several temperatures and pressures. The asphaltene contents of the residual fractions in the extractor were compared to the asphaltene content of the original bitumen. Asphaltenes were defined as pentane insolubles in this study. It was found that the absolute asphaltene content of the residual fractions exceeded the asphaltene content of the original bitumen. Even when the asphaltene content was prorated by the weight percent of the residual material, it was found to be higher than the original asphaltene content. The data established that the types of compounds separating as asphaltenes changed as the nature of the mixture was altered by SFE. The data also indicated that it may be inappropriate to perform asphaltene material balances to assess the amount of precipitate. The original asphaltene content of a bitumen that is undergoing compositional changes in a sequence of operations may not be an accurate measure of the precipitating tendency of the bitumen in production and processing operations. The asphaltene content of the residual material varied depending on the extraction conditions and was as much as 3--5 times the original asphaltene content. The asphaltene content of the residual material was a maximum at the most efficient extraction condition which was in the vicinity of the critical temperature of propane. The H/C atomic ratio of the residual fractions was lower compared to the original bitumen, indicating that the ratio of polar to nonpolar compounds may also be important from precipitation considerations. Saturate and aromatic compounds were preferentially extracted and the ratio of asphaltenes to resins increased in the residual fractions relative to the original bitumen.

  6. Asphaltene reaction via supercritical fluid extraction

    SciTech Connect

    Deo, M.D.; Hanson, F.V.

    1993-03-01

    Supercritical fluid extraction (SFE) of bitumen was carried out in a continuous extractor using propane as the solvent at several temperatures and pressures. The asphaltene contents of the residual fractions in the extractor were compared to the asphaltene content of the original bitumen. Asphaltenes were defined as pentane insolubles in this study. It was found that the absolute asphaltene content of the residual fractions exceeded the asphaltene content of the original bitumen. Even when the asphaltene content was prorated by the weight percent of the residual material, it was found to be higher than the original asphaltene content. The data established that the types of compounds separating as asphaltenes changed as the nature of the mixture was altered by SFE. The data also indicated that it may be inappropriate to perform asphaltene material balances to assess the amount of precipitate. The original asphaltene content of a bitumen that is undergoing compositional changes in a sequence of operations may not be an accurate measure of the precipitating tendency of the bitumen in production and processing operations. The asphaltene content of the residual material varied depending on the extraction conditions and was as much as 3--5 times the original asphaltene content. The asphaltene content of the residual material was a maximum at the most efficient extraction condition which was in the vicinity of the critical temperature of propane. The H/C atomic ratio of the residual fractions was lower compared to the original bitumen, indicating that the ratio of polar to nonpolar compounds may also be important from precipitation considerations. Saturate and aromatic compounds were preferentially extracted and the ratio of asphaltenes to resins increased in the residual fractions relative to the original bitumen.

  7. Fatty and resin acid analysis in tall oil products via supercritical fluid extraction-supercritical fluid reaction using enzymatic catalysis.

    PubMed

    Taylor, S L; King, J W

    2001-07-01

    Supercritical fluid extraction (SFE) is combined with supercritical fluid reaction (SFR) in an analytical mode to assess tall oil products for their fatty or resin acid content or both. The SFR consists of an inline enzymatically catalyzed reaction in which a lipase transesterifies specific lipids with methanol. The SFE-SFR sequence is conducted employing commercially available extractors using supported lipases in the extraction cell to form methyl esters. In this study, six different commercially available lipases are screened for activity. The SFE-SFR extracts are analyzed by capillary gas chromatography and supercritical fluid chromatography and then compared with tall oil products derivatized by conventional chemical derivatization techniques.

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

    SciTech Connect

    Eckert, C.A.

    1996-11-01

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

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

    SciTech Connect

    Eckert, C.A.

    1996-10-01

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

  10. Supercritical fluid reactions for coal processing. Quarterly report, July 1--September 30, 1996

    SciTech Connect

    Eckert, C.A.

    1996-12-31

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

  11. Super acid catalysis in supercritical fluid reaction media for the formation of linear alkyl benzenes.

    PubMed

    Harmer, Mark A; Hutchenson, Keith W

    2002-01-07

    High catalytic activity is demonstrated for the formation of linear alkylbenzenes using a perfluorosulfonic acid catalyst in supercritical fluid reaction media: enhanced alkylation activity is observed in fluoroform (CHF3) compared to carbon dioxide.

  12. Supercritical fluid reactions for coal processing. Quarterly technical progress report, April 1, 1995--June 30, 1995

    SciTech Connect

    Eckert, C.A.

    1995-10-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which closely resemble the organic sulfur and nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal desulfurization and denitrogenation. Diels-Alder reactions involving such compounds have been extensively studied and characterized in liquids. However, there is very little understanding of such reactions in SCF`s. We are developing an approach which will allow optimum design of coal desulfurization and denitrogenation processes.

  13. Supercritical fluid reactions for coal processing. Quarterly progress report, January 1, 1995--March 31, 1995

    SciTech Connect

    Eckert, C.A.

    1995-08-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which closely resemble the organic sulfur and nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal desulfurization and denitrogenation. Diels-Alder reactions involving such compounds have been extensively studied and characterized in liquids. However, there is very little understanding of such reactions in SCF`S. We are developing an approach which will allow optimum design of coal desulfurization and denitrogenation processes.

  14. Interfacing supercritical fluid reaction apparatus with on-line liquid chromatography: monitoring the progress of a synthetic organic reaction performed in supercritical fluid solution.

    PubMed

    Ramsey, Edward D; Li, Ben; Guo, Wei; Liu, Jing Y

    2015-04-03

    An interface has been developed that connects a supercritical fluid reaction (SFR) vessel directly on-line to a liquid chromatograph. The combined SFR-LC system has enabled the progress of the esterification reaction between phenol and benzoyl chloride to synthesize phenyl benzoate in supercritical fluid carbon dioxide solution to be dynamically monitored. This was achieved by the periodic SFR-LC analysis of samples directly withdrawn from the esterification reaction mixture. Using the series of SFR-LC analysis results obtained for individual esterification reactions, the reaction progress profile for each esterification reaction was obtained by expressing the measured yield of phenyl benzoate as a function of reaction time. With reaction temperature fixed at 75°C, four sets (n=3) of SFR-LC reaction progress profiles were obtained at four different SFR pressures ranging from 13.79 to 27.58 MPa. The maximum SFR yield obtained for phenyl benzoate using a standard set of reactant concentrations was 85.2% (R.S.D. 4.2%) when the reaction was performed at 13.79 MPa for 90 min. In comparison, a phenyl benzoate yield of less than 0.3% was obtained using the same standard reactant concentrations after 90 min reaction time at 75°C using either: heptane, ethyl acetate or acetonitrile as conventional organic reaction solvents.

  15. Supercritical fluid reactions for coal processing. Quarterly progress report, October 1, 1996--December 31, 1996

    SciTech Connect

    Eckert, C.A.

    1994-09-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The Diels - Alder reaction of anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) was chosen as the model system and was investigated in supercritical carbon dioxide. During this quarter, measurement of the density dependence of the kinetic rate constant for PTAD and anthracene in supercritical solvents was continued. Having completed studies of rates versus density in pure CO{sub 2} at 40C, attention was focused on CO{sub 2}/Cosolvent mixtures. Experiments were performed using binary mixtures of CO{sub 2} and either chloroform or acetone as cosolvent. Cosolvent concentrations were varied between 0.00826 mol/L and 0.0826 mol/L. The cosolvents produced no significant change in the rate constant over that of pure CO{sub 2} at these concentrations.

  16. Applications of supercritical fluids.

    PubMed

    Brunner, Gerd

    2010-01-01

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

  17. Supercritical fluid reactions for coal processing. Quarterly progress report, October 1, 1995--December 31, 1995

    SciTech Connect

    Eckert, C.A.

    1995-12-31

    The goal of this work is to design benign solvent/cosolvent systems for reactions which will achieve optimum desulfurization and/or denitrogenation in the pre-treatment of coal or coal liquids. Supercritical fluids present excellent opportunities for the pre- treatment of coal, hence we shall utilize supercritical fluids (SCF) as a reaction medium. The specific objectives of this work are three fold. The first objective is the quantification of the intermolecular interactions affecting reaction transition states in SCF`s via kinetic measurements using well characterized Diels-Alder reactions. The second objective is the characterization of the thermodynamics of the reacting systems. From the thermodynamics of the reacting species detailed information about the transition state may be determined. The third objective is the development of molecular level mathematical models using the results from the first two objectives. The models shall be developed using both an equation of state approach and linear solvation energy relationships with solvatochromic parameters. During this quarter, the solubility of the nitrogen bearing dienophile 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) has been measured as a function of pressure at 40 C, with the exception of points at 2500 psig and 3000 psig. When collection of these last points has been accomplished, the collection of all preliminary data needed to begin kinetic studies of the Diels-Alder reaction between PTAD and anthracene at 40 C in supercritical CO{sub 2} will be complete.

  18. Supercritical fluid reactions for coal processing. Quarterly progress report, July 1, 1995--September 30, 1995

    SciTech Connect

    Eckert, C.A

    1995-12-31

    The goal of this work is to design benign solvent/cosolvent systems for reactions which will achieve optimum desulfurization and/or denitrogenation in the pre-treatment of coal or coal liquids. Supercritical fluids present excellent opportunities for the pretreatment of coal, hence we shall utilize supercritical fluids as a reaction medium. A number of possible Diels-Alder reactive systems involving anthracene (diene) in supercritical solvent were proposed at the outset of research. Scouting experiments designed to select out the optimum reactive system from among the candidate dienophiles and solvents have been completed. The nitrogen bearing compound 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) has demonstrated superior reactivity and sensitivity to cosolvent additions and has been selected as dienophile. A convenient half-life of reaction between PTAD and anthracene is obtained at temperatures in the neighborhood of 50{degree}C. Carbon dioxide has been selected as the solvent because of its convenient critical properties, and also to optimize the safety of the experiments. In the process of completing these scouting experiments, the experimental apparatus that will be used to obtain kinetic data for calculation of partial molar volumes of the reaction transition state has also been optimized.

  19. Electrodeposition from supercritical fluids.

    PubMed

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

    2014-05-28

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

  20. 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.

  1. 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

  2. Electrochemistry in supercritical fluids.

    PubMed

    Branch, Jack A; Bartlett, Philip N

    2015-12-28

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

  3. PULSE RADIOLYSIS IN SUPERCRITICAL RARE GAS FLUIDS

    SciTech Connect

    HOLROYD,R.

    2007-01-01

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

  4. Water-gas shift reaction on alumina-supported Pt-CeOx catalysts prepared by supercritical fluid deposition

    DOE PAGES

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

    2016-08-25

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

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

    SciTech Connect

    Thompson, R.L.; Glaeser, R.; Bush, D.; Liotta, C.L.; Eckert, C.A.

    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.

  6. Supercritical fluids cleaning

    SciTech Connect

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

    1991-01-01

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

  7. Supercritical fluids cleaning

    NASA Astrophysics Data System (ADS)

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

    1991-04-01

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

  8. Corrosion in supercritical fluids

    SciTech Connect

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

    1996-05-01

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

  9. How does the critical point change during a chemical reaction in supercritical fluids? A study of the hydroformylation of propene in supercritical CO(2).

    PubMed

    Ke, J; Han, B; George, M W; Yan, H; Poliakoff, M

    2001-04-25

    An understanding of homogeneous catalysis in supercritical fluids requires a knowledge of the phase behavior and the variation in critical point as the reaction proceeds. In this paper, the critical temperatures, T(c) and pressures, P(c), have been measured for a considerable number of mixtures representing the various stages of the hydroformylation reaction of propene in supercritical CO(2) and different reactant concentrations. Critical point data have also been measured for all of the binary mixtures of the components (CO(2), H(2), CO, propene, n- and isobutyraldehyde) which are not available from the literature or can be deduced from published data. We use the stoichiometry of the reacting system to simplify greatly the phase behavior problem by defining a path through the otherwise multidimensional "phase space". Satisfactory modeling of the data (0.3% in T(c) and 3.0% in P(c)) has been achieved using the Peng-Robinson equation of state and ignoring all binary interactions which do not involve CO(2). The model is used to explore the strategies needed to avoid phase separation in continuous and batch reactions. At a given temperature, a batch reactor may need to be run under much higher pressures than a flow reactor if single-phase conditions are to be preserved throughout the course of the reaction. Most of the critical point data were measured acoustically, but a selection of points were validated using more traditional view-cell procedures.

  10. Using supercritical fluids to refine hydrocarbons

    SciTech Connect

    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.

  11. Laser flash photolysis investigations of diffusion-controlled reactions in supercritical fluids

    SciTech Connect

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

    1993-05-27

    Laser flash photolysis has been used to investigate the triplet-triplet annihilation (TTA) process of benzophenone (Ph[sub 2]C=O) and the self-termination reaction of benzyl radical (PhCH[sub 2]) in supercritical CO[sub 2] and ethane. Kinetic measurements were performed at various pressures above the critical pressure along two isotherms, one close to the critical temperature of the solutions (35[degrees]C) and one further removed (50[degrees]C). The second-order rate constants obtained indicate that each reaction occurs at the diffusion limit when spin statistical factors are considered. No evidence of enhanced cage effects due to supercritical solvent clustering about diffusive encounter pairs or enhanced solute/solute interactions were observed in these experiments. Additionally, the photocleavage of dibenzyl ketone and the rate constants for decarbonylation of phenylacetyl radical (PhCH[sub 2]CO) have been examined under the above conditions and do not show any anomalous behavior or cage effects. 37 refs., 8 figs.

  12. 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.

  13. Supercritical fluid technology

    SciTech Connect

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

    1985-01-01

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

  14. Optimization of a supercritical fluid extraction/reaction methodology for the analysis of castor oil using experimental design.

    PubMed

    Turner, Charlotta; Whitehand, Linda C; Nguyen, Tasha; McKeon, Thomas

    2004-01-14

    The aim of this work was to optimize a supercritical fluid extraction (SFE)/enzymatic reaction process for the determination of the fatty acid composition of castor seeds. A lipase from Candida antarctica (Novozyme 435) was used to catalyze the methanolysis reaction in supercritical carbon dioxide (SC-CO(2)). A Box-Behnken statistical design was used to evaluate effects of various values of pressure (200-400 bar), temperature (40-80 degrees C), methanol concentration (1-5 vol %), and water concentration (0.02-0.18 vol %) on the yield of methylated castor oil. Response surfaces were plotted, and these together with results from some additional experiments produced optimal extraction/reaction conditions for SC-CO(2) at 300 bar and 80 degrees C, with 7 vol % methanol and 0.02 vol % water. These conditions were used for the determination of the castor oil content expressed as fatty acid methyl esters (FAMEs) in castor seeds. The results obtained were similar to those obtained using conventional methodology based on solvent extraction followed by chemical transmethylation. It was concluded that the methodology developed could be used for the determination of castor oil content as well as composition of individual FAMEs in castor seeds.

  15. 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.

  16. Supercritical Fluids Processing of Biomass to Chemicals and Fuels

    SciTech Connect

    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 to the use of water as a supercritical fluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”

  17. 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.

  18. 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.

  19. Mass spectrometry with direct supercritical fluid injection

    SciTech Connect

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

    1983-12-01

    Direct fluid injection mass spectrometry utilizes supercritical fluids for solvation and transfer of materials to a mass spectrometer chemical ionization (CI) source. Available data suggest that any material soluble in a supercritical fluid is transferred efficiently to the ionization region. Mass spectra are presented for mycotoxins of the trichothecene group obtained by use of supercritical carbon dioxide with isobutane as the CI reagent gas. Direct fluid injection MS/MS is also illustrated for major ions in the isobutane chemical ionization of T-2 toxin. The effect of pressure and temperature upon solubility in supercritical fluids is described and illustrated for diacetoxycirpenol. A potential method is also demonstrated for on-line fraction during MS analysis using pressure to control supercritical fluid solubility. Mass spectra are also presented for polar compounds, using supercritical ammonia, and the extension to complex mixtures is described. The fundamental basis and experimental requirements of the direct fluid injection process are discussed. 34 references, 11 figures, 1 table.

  20. Mass spectrometry with direct supercritical fluid injection

    SciTech Connect

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

    1983-12-01

    Direct fluid injection mass spectrometry utilizes supercritical fluids for solvation and transfer of materials to a mass spectrometer chemical ionization (CI) source. Available data suggest that any material soluble in a supercritical fluid is transferred efficiently to the ionization region. Mass spectra are presented for mycotoxins of the trichothecene group obtained by use of supercritical carbon dioxide with isobutane as the CI reagent gas. Direct fluid injection MS/MS is also illustrated for major ions in the isobutane chemical ionization of T-2 toxin. The effect of pressure and temperature upon solubility in supercritical fluids is described and illustrated for diacetoxyscirpenol. A potential method is also demonstrated for ''on-line fractionation'' during MS analysis using pressure to control supercritical fluid solubility. Mass spectra are also presented for polar compounds, using supercritical ammonia, and the extension to complex mixtures is described. The fundamental basis and experimental requirements of the direct fluid injection process are discussed. 1 figure, 11 tables.

  1. Chemical deposition methods using supercritical fluid solutions

    DOEpatents

    Sievers, Robert E.; Hansen, Brian N.

    1990-01-01

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

  2. Water-gas shift reaction on alumina-supported Pt-CeOx catalysts prepared by supercritical fluid deposition

    SciTech Connect

    Deal, Jacob W.; Le, Phong; Corey, C. Blake; More, Karren; West, Christy Wheeler

    2016-08-25

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

  3. Water-gas shift reaction on alumina-supported Pt-CeOx catalysts prepared by supercritical fluid deposition

    SciTech Connect

    Deal, Jacob W.; Le, Phong; Corey, C. Blake; More, Karren; West, Christy Wheeler

    2016-08-25

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

  4. 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

  5. Lipidomics by Supercritical Fluid Chromatography.

    PubMed

    Laboureur, Laurent; Ollero, Mario; Touboul, David

    2015-06-17

    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.

  6. High-temperature and high-pressure cell for kinetic measurements of supercritical fluids reactions with the use of ultraviolet-visible spectroscopy

    NASA Astrophysics Data System (ADS)

    Gorbaty, Yuri E.; Venardou, Eleni; Garcia-Verdugo, Eduardo; Poliakoff, Martyn

    2003-06-01

    A high-temperature high-pressure ultraviolet-visible (UV-Vis) cell is described. The cell has been designed specifically for use with the UV spectrophotometer Hewlett-Packard 8453 but it could work up to 780 K at 100 MPa with any other UV-Vis spectrophotometer, as well as for near infrared (NIR) experiments. Three features of the cell make it convenient for experiments with supercritical fluids: the possibility to choose an optimal path length, the presence of three interchangeable ports into the cell, and a movable thermocouple in the working zone of the cell. The cell has been used to study a range of chemical reactions in water under near-critical and supercritical conditions, as well as for measuring the kinetics of such reactions. Some examples illustrating the performance of the cell are given.

  7. Using supercritical fluids to refine hydrocarbons

    DOEpatents

    Yarbro, Stephen Lee

    2014-11-25

    This is a method to reactively refine hydrocarbons, such as heavy oils with API gravities of less than 20.degree. and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure using a selected fluid at supercritical conditions. The reaction portion of the method delivers lighter weight, more volatile hydrocarbons to an attached contacting device that operates in mixed subcritical or supercritical modes. This separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques. This method produces valuable products with fewer processing steps, lower costs, increased worker safety due to less processing and handling, allow greater opportunity for new oil field development and subsequent positive economic impact, reduce related carbon dioxide, and wastes typical with conventional refineries.

  8. Oxidation catalysis in a supercritical fluid medium

    SciTech Connect

    Dooley, K.M.; Knopf, F.C.

    1986-01-01

    The supercritical fluid (SCF) extraction technique was extended by its application to SCF-solid catalyzed reactions that otherwise take place in a two-fluid-phase reactor. Using CO/sub 2/ as a solvent, an alkylaromatic hydrocarbon such as toluene was contacted with air in the presence of solid metal redox or acid catalysts, and underwent partial oxidation to benzaldehyde, benzyl alcohol, and cresols. This process should result in more rapid rates of mass transfer and intrinsic reaction than is customary for such reactions at conventional conditions, and more efficient quenching of the oxidation at the desired products; in addition it should allow an easier product separation and a decrease in reaction temperature that will improve the yield to desired products.

  9. Direct supercritical fluid extraction from water

    SciTech Connect

    Brewer, S.E.; Kruus, P.

    1993-12-01

    This paper describes the development of apparatus suitable for direct supercritical fluid extraction of organics from water. Results are presented for the extraction of pentachlorophenol present in water at concentrations of the order of 0.1 ppm. The effect of changes in apparatus design and supercritical fluid flow rate on recovery are discussed.

  10. Biocatalytic Processing Polymers in Supercritical Fluids

    DTIC Science & Technology

    1994-01-01

    Russell, A.J and Beckman, E.J. (1991) Appl. Bioch . Biotech., 31, 197-211. Enzyme activity in supercritical fluids. 22. *Russell, A.J and Beckman, E.J...S., Jacob , J., Beckman, E.J. and Russell, A.J. (1991) Enz. Microb. Technol., 13, 519. Biocatalytic synthesis of acrylates in supercritical fluids. 24

  11. Supercritical fluids for reaction and extraction of coal and heavy oils. Third quarterly progress report, March 1-May 31, 1982

    SciTech Connect

    Gopal, J.S.; Holder, G.D.; Deshpande, G.V.

    1982-06-01

    The experimental unit for the coal-water experiments has been erected. Some modifications in the inlet and outlet ports of the autoclave have been made. The tranfer lines have been kept to a minimum to avoid any temperature gradients and refluxing of water in the lines. The system has been leak tested and is found to be in proper operating condition. Samples of brown coal have been received and the coal has been crushed and ground under adequate precautionary measures to a desirable particle size. It has been planned to initially carry out the experiments with a coal sample in the -100 mesh range. Major changes in the experimental set-up to study the solubility of solids in supercritical fluids have been made. Two equilibrium cells will be used instead of an autoclave. A metered supply of the supercritical fluid phase will be provided to the two cells and the extracted sample will be collected in a suitable solvent for chromatographic analysis.

  12. Electrodeposition of metals from supercritical fluids.

    PubMed

    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

    2009-09-01

    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.

  13. 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

  14. 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.

  15. Supercritical fluid thermodynamics for coal processing

    SciTech Connect

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

    1988-09-15

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

  16. 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.

  17. Supercritical hydrogenation and acid-catalysed reactions "without gases".

    PubMed

    Hyde, Jason R; Poliakoff, Martyn

    2004-07-07

    The high temperature catalytic decomposition of HCO2H and HCO2Et are used to generate the high pressure H2 and the supercritical fluids needed for micro-scale hydrogenation of organic compounds; our approach overcomes the problems and limitations of handling high pressure gases on a small-scale and opens the way to the widespread use of continuous supercritical reactions in the laboratory.

  18. Thermochromic shifts in supercritical fluids

    SciTech Connect

    Yonker, C.R.; Smith, R.D. )

    1989-02-23

    Thermochromic shifts of organic solute molecules in supercritical CO{sub 2} under conditions of both constant pressure and density are compared to previous studies of solvatochromic shifts at isothermal conditions. Similar solvatochromic and thermochromic shifts are seen as a function of density for supercritical CO{sub 2}. At constant density a small thermochromic shift ({approx}400 cm{sup {minus}1}) for supercritical CO{sub 2} was seen for both 2-nitroanisole and 4-ethylnitrobenzene. The excited-state dipole moments for 2-nitroanisole, as calculated from the thermochromic and solvatochromic data, were in agreement.

  19. 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

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

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1998-12-31

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

  1. Model studies using supercritical carbon dioxide fluid (SF CO{sub 2}) as a reaction medium for radiotracer synthesis and purification

    SciTech Connect

    Ferrieri, R.A.; Fowler, J.S.; Wolf, A.P.

    1994-05-01

    Supercritical fluids (SFs) have found widespread use in the analytical field as solvents for compound purification, and initial results on their use for radiotracer synthesis have been reported. SF`s possess the unique feature that their solvating strength can be altered drastically through small changes in pressure and temperature of the fluid within the supercritical regime. We have modified a SF chromatograph to allow us to investigate its use in radiotracer synthesis and purification. The solubility of several PET radiotracers was measured in SF CO{sub 2} at 5000 psi and 55{degrees}C and showed the following: raclopride, 68 {mu}g/mL{sup 2}; (L)-deprenyl, 85 {mu}g/mL; flumazenil, 61 {mu}g/mL; (-)cocaine, 108 {mu}g/mL; ritalin, 45 {mu}g/Ml; and cogentin, 250 {mu}g/mL. Analytical separations were achieved on 30 to 50 {mu}g amounts of (L)-deprenyl (3.9 min RT) and nor-deprenyl (4.7 min RT), as well as raclopride (10.8 min RT) and nor-raclopride (10.3 min RT) using 250 mm x 4.5 mm i.d. Ultracarb 5 ODS (30), and 75 mm x 4.5 mm i.d. silica columns, respectively, and pure SF CO{sub 2} as the mobile phase. Model studies on simple N-alkylation reactions were also carried out using pur SF CO{sub 2} as the reaction medium on a modified alumina support. (L)-Deprenyl was synthesized from only 100 {mu}g of the starting labelling substrate using 500 mg of alumina impregnated with triphenylphosphine diiodide (20% by wt.) and maintained at 170{degrees}C. The methylating agent, methyl iodide, was generated in situ from methanol, but was always present in excess of the substrate. Studies are in progress to reduce methanol amounts. Pressure studies of SF CO{sub 2} ranging from 3000 to 6000 psi showed an 80% increase in the methylation reaction relative to the amount of starting substrate suggesting an effect of the fluid density. Temperature was also a critical parameter here as the reaction did not proceed at 80{degrees}C for similiar pressures.

  2. 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.

  3. 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.

  4. Supercritical fluid mixing in Diesel Engine Applications

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  5. 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.

  6. Determination of solvation kinetics in supercritical fluids. Project summary, August 15, 1993--May 3, 1994

    SciTech Connect

    Bright, F.V.

    1994-08-01

    This project is directed on determining effects of supercritical fluids on salvation and chemical reactions. Sub-projects are: understanding the effects of neat and entrainer-modified supercritical fluids on solute-fluid interactions; determining the influence of supercritical fluids on energetics and dynamics of solute conformation; and probing effects of continuous phase density on internal dynamics of reverse micelles formed in supercritical fluids. In order to follow these fast molecular-level processes, modern picosecond in-situ optical spectroscopy is being used. To date this work has: helped define how ``diffusion controlled`` reactions proceed in supercritical fluids; determined how and on what time scale entrainers preferentially solvate solutes in the near-critical region; shown that the conformation (i.e., reactivity) of flexible solutes can be altered easily with fluid density; shown how lateral diffusion within reverse micelles (formed in supercritical alkanes) is affected by the continuous phase density; and begun to probe how the conformation of polymers can be controlled with supercritical fluids. This is leading to a better molecular-level understanding of the chemistry of supercritical fluids.

  7. The Effect of Supercritical Fluids on Solid Acid Catalyst Alkylation

    SciTech Connect

    Ginosar, Daniel Michael; Thompson, David Neil; Burch, Kyle Coates; Zalewski, D. J.

    2002-05-01

    The alkylation of isobutane with trans-2-butene was explored over six solid acid catalysts in the liquid, near-critical liquid, and supercritical regions through the addition of an inert cosolvent to the reaction feed mixture. The addition of supercritical cosolvents did not result in sustained catalytic alkylation activity. A modest improvement in product yield was obtained with the addition of methane in the modified-liquid region; however, catalyst longevity and product selectivity were decreased compared to cosolvent-free liquid conditions. This paper describes the catalyst screening and selection process, an exploration of catalyst performance with varying concentrations of methane, and an examination of the effects of seven supercritical fluids on catalyst performance. The catalysts included two zeolites, two sulfated metal oxides, and two Nafion catalysts. Three hydrocarbons, two fluorocarbons, carbon dioxide, and sulfur hexafluoride were explored as inert cosolvents added to the reaction mixture.

  8. Organic syntheses employing supercritical carbon dioxide as a reaction solvent

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  9. Organic syntheses employing supercritical carbon dioxide as a reaction solvent

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  10. Supercritical fluid carbon dioxide cleaning of plutonium parts

    SciTech Connect

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

    1993-09-01

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

  11. 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...

  12. Analytical supercritical fluid extraction of adsorbent materials

    SciTech Connect

    Wright, B.W.; Wright, C.W.; Gale, R.W.; Smith, R.D.

    1987-01-01

    The use of supercritical fluids for the analytical extraction of semivolatile and higher molecular weight materials from various adsorbent and particulate matrices was investigated. Instrumentation was designed to allow gram quantities of the matrix to be extracted at pressures up to 400 bar and temperatures to 235 /sup 0/C with collection of the effluent in a sealed liquid-nitrogen-cooled flask. Carbon dioxide, isobutane, and methanol modified (20 mol %) carbon dioxide fluid systems were evaluated and compared to liquid Soxhlet extraction. Supercritical fluid extraction (SFE) provided very rapid (approx. =30 min) extraction with comparable efficiency to the Soxhlet methods, and both more rapid and more efficient extractions appear feasible. The more polar carbon dioxide-methanol fluid system gave higher extraction efficiencies for the more polar adsorbates and the isobutane system was more efficient for the higher molecular weight and less polar compounds.

  13. Determination of diffusion coefficients for supercritical fluids.

    PubMed

    Medina, Ignacio

    2012-08-10

    A review of the diffusion coefficients for solutes in supercritical fluids as reported in the literature is presented together with the correlation methods applied by the authors for modeling the experimentally determined data. Supercritical carbon dioxide has been the preferred solvent in most of the systems investigated, although other solvents at elevated pressure have also been used. The influence of pressure, temperature, density, and viscosity on the binary diffusion coefficients is discussed, and some general trends have been established. A number of experimental methods for determining diffusion coefficients in supercritical fluids have been reported in the literature. The methods are described, their advantages and disadvantages are discussed and some examples of their application are given. Predictive equations based on the Stokes-Einstein model, the Rough-Hard-Sphere theory, and other methods for the calculation of diffusion coefficients in supercritical fluids at infinite dilution are reviewed. The review also looks at the ternary systems reported in the literature. The latter are discussed in terms of temperature, pressure, the type of modifier employed, amount of modifier, and solute-modifier interactions. Several equations have been proposed for correlating and predicting the diffusion coefficients in ternary systems. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. 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.

  15. Low temperature extraction and upgrading of oil sands and bitumen in supercritical fluid mixtures.

    PubMed

    Brough, Sarah A; Riley, Sandra H; McGrady, G Sean; Tanhawiriyakul, Supaporn; Romero-Zerón, Laura; Willson, Christopher D

    2010-07-21

    Preliminary results are reported for the extraction and catalytic hydrocracking of Alberta bitumen and oil sands using supercritical fluid mixtures; high levels of extraction and upgrading were attained using reaction conditions significantly milder than those previously reported.

  16. Synthesis of an excellent electrocatalyst for oxygen reduction reaction with supercritical fluid: Graphene cellular monolith with ultrafine and highly dispersive multimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhou, Yazhou; Cheng, Xiaonong; Yen, Clive H.; Wai, Chien M.; Wang, Chongmin; Yang, Juan; Lin, Yuehe

    2017-04-01

    Graphene cellular monolith (GCM) can be used as an excellent support for nanoparticles in widespread applications. However, it's still a great challenge to deposit the desirable nanoparticles in GCM that have small size, controllable structure, composition, and high dispersion using the current methods. Here we demonstrate a green, efficient and large-scale method to address this challenge using supercritical fluid (SCF). By this superior method, graphene hydrogel can be transferred into GCM while being deposited with ultrafine and highly dispersive nanoparticles. Specifically, the bimetallic PtFe/GCM and the trimetallic PtFeCo/GCM catalysts are successfully synthesized, and their electrocatalytic performances toward oxygen reduction reaction (ORR) are also studied. The resultant PtFe/GCM shows the significant enhancement in ORR activity, including a factor of 8.47 enhancement in mass activity (0.72 A mgPt-1), and a factor of 7.67 enhancement in specific activity (0.92 mA cm-2), comparing with those of the commercial Pt/C catalyst (0.085 A mgPt-1, 0.12 mA cm-2). Importantly, by introducing the Co, the trimetallic PtFeCo/GCM exhibits the further improved ORR activities (1.28 A mgPt-1, 1.80 mA cm-2). The high ORR activity is probably attributed to the alloying structure, ultrafine size, highly dispersive, well-defined, and a better interface with 3D porous graphene support.

  17. Supercritical fluid thermodynamics for coal processing

    SciTech Connect

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

    1990-01-01

    Because of their unusual solvating and mass transfer properties, supercritical fluids show potential for a variety of coal processing applications. We have established a database of coal model compound equilibria; to add to this database, we have developed and are testing techniques of measuring entrainer effects on solubility rapidly. In addition, we have used fluorescence spectroscopy to study the nature of entrainer effects on a molecular level. The solubility and spectroscopic measurements are being used in the development of an equation of state that includes both physical and chemical interactions; we are currently testing the equation. The equation of state will be used to predict solubility behavior so systems can be designed for the processing of coal with supercritical fluids. 3 figs.

  18. 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...binder application, some costs for coffee decaffeination for a plant producing 50,000,000 lbs/yr are related. No absolute figures have been published...figure is based on the retail price difference between Maxwell House (the supercritical fluid coffee decaffeinator ) and Sanka brand coffee. For 13 oz of

  19. 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.

  20. Anomalous sorption of supercritical fluids on polymer thin films.

    PubMed

    Wang, Xiaochu; Sanchez, Isaac C

    2006-10-24

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

  1. Application of supercritical fluid extraction in biotechnology.

    PubMed

    Khosravi-Darani, K; Vasheghani-Farahani, E

    2005-01-01

    In the present paper recent investigations on the applications of supercritical fluid extraction (SCE) from post fermentation biomass or in situ extraction of inhibitory fermentation products as a promising method for increasing the yield of extraction have been reviewed. Although supercritical CO2 (SC-CO2) is unfriendly, or even toxic, for some living cells and precludes direct fermentation in dense CO2, it does not rule out other useful applications for in situ extraction of inhibitory fermentation products and fractional extraction of biomass constituents. This technique is a highly desirable method for fractional extraction of biomass constituents, and intracellular metabolites due to the potential of system modification by physical parameters and addition of co-solvents to selectively extract compounds of different polarity, volatility and hydrophilicity without any contamination.

  2. Supercritical fluid extraction of N-nitrosamines

    SciTech Connect

    Tewani, S.

    1993-01-01

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

  3. Biodiesel production from various oils under supercritical fluid conditions by Candida antartica lipase B using a stepwise reaction method.

    PubMed

    Lee, Jong Ho; Kwon, Cheong Hoon; Kang, Jeong Won; Park, Chulhwan; Tae, Bumseok; Kim, Seung Wook

    2009-05-01

    In this study, we evaluate the effects of various reaction factors, including pressure, temperature, agitation speed, enzyme concentration, and water content to increase biodiesel production. In addition, biodiesel was produced from various oils to establish the optimal enzymatic process of biodiesel production. Optimal conditions were determined to be as follows: pressure 130 bar, temperature 45 degrees C, agitation speed 200 rpm, enzyme concentration 20%, and water contents 10%. Among the various oils used for production, olive oil showed the highest yield (65.18%) upon transesterification. However, when biodiesel was produced using a batch system, biodiesel conversion yield was not increased over 65%; therefore, a stepwise reaction was conducted to increase biodiesel production. When a reaction medium with an initial concentration of methanol of 60 mmol was used and adjusted to maintain this concentration of methanol every 1.5 h during biodiesel production, the conversion yield of biodiesel was 98.92% at 6 h. Finally, reusability was evaluated using immobilized lipase to determine if this method was applicable for industrial biodiesel production. When biodiesel was produced repeatedly, the conversion rate was maintained at over 85% after eight reuses.

  4. Supercritical Fluid Infusion of Iron Additives in Polymeric Matrices

    NASA Technical Reports Server (NTRS)

    Nazem, Negin; Taylor, Larry T.

    1999-01-01

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

  5. 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.

  6. Supercritical fluid thermodynamics from equations of state

    NASA Astrophysics Data System (ADS)

    Giovangigli, Vincent; Matuszewski, Lionel

    2012-03-01

    Supercritical multicomponent fluid thermodynamics are often built from equations of state. We investigate mathematically such a construction of a Gibbsian thermodynamics compatible at low density with that of ideal gas mixtures starting from a pressure law. We further study the structure of chemical production rates obtained from nonequilibrium statistical thermodynamics. As a typical application, we consider the Soave-Redlich-Kwong cubic equation of state and investigate mathematically the corresponding thermodynamics. This thermodynamics is then used to study the stability of H2-O2-N2 mixtures at high pressure and low temperature as well as to illustrate the role of nonidealities in a transcritical H2-O2-N2 flame.

  7. Supercritical fluid chromatography in food analysis.

    PubMed

    Bernal, José L; Martín, María T; Toribio, Laura

    2013-10-25

    In the last years, supercritical fluid chromatography (SFC) has increased its acceptance between scientists. The unique selectivity, short analysis times, low consumption of organic solvents as well as the improvements in instrumentation have contributed to expand its use. These characteristics make SFC a powerful tool when food analysis requires individualized evaluation of several compounds in very complex samples. In this work, the advantages and main applications of SFC in food analysis are reviewed, focusing special attention onto analytical and preparative separations. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. Supercritical fluid extraction: Recent advances and applications.

    PubMed

    Herrero, Miguel; Mendiola, Jose A; Cifuentes, Alejandro; Ibáñez, Elena

    2010-04-16

    Among the different extraction techniques used at analytical and preparative scale, supercritical fluid extraction (SFE) is one of the most used. This review covers the most recent developments of SFE in different fields, such as food science, natural products, by-product recovery, pharmaceutical and environmental sciences, during the period 2007-2009. The revision is focused on the most recent advances and applications in the different areas; among them, it is remarkable the strong impact of SFE to extract high value compounds from food and natural products but also its increasing importance in areas such as heavy metals recovery, enantiomeric resolution or drug delivery systems.

  9. Facile reaction/extraction of coal with supercritical fluids. Quarterly technical progress report, January 1-March 31, 1984

    SciTech Connect

    Venier, C. G.; Squires, T. G.

    1984-04-20

    Arylmethyl phenyl ethers undergo competing reactions when treated with Lewis acids in benzene solvent. Apparently, benzene is insufficiently reactive to compete with intramolecular (intrapolymer) nucleophiles and, consequently, no increase in solubility accompanies the cleavages of ether links upon addition of benzene. When better nucleophiles, naphthalene and phenanthene, are provided, carbonium ions generated from ether cleavages are capped and the product is lower in molecular weight and more soluble. It is worth noting that the naphthalene (k/sub rel/ = 300) is nearly as good a trap as the phenol (k/sub rel/ = 450). Since hydroxylic solvents will level the acid strength of BF/sub 3/ to that of ROBF/sub 3//sup -/H/sup +/ and hydrocarbons would not, the acid-catalyzed bond cleavages necessary for unlinking coal may in fact be faster in BF/sub 3/-arene than in BF/sub 3/-phenol. While we have not yet extended these results to coals, we believe that the combination of a relatively mild Lewis acid catalyst, BF/sub 3/, with a good carbonium ion trap, naphthalene, will allow selective cleavage and capping of aryl alkyl ether bonds. 3 references, 2 figures, 3 tables.

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

    SciTech Connect

    Durak, Halil

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

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

    NASA Astrophysics Data System (ADS)

    Durak, Halil

    2016-04-01

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

  12. Welding immiscible polymers with a supercritical fluid.

    PubMed

    Wang, Xiaochu; Sanchez, Isaac C

    2007-11-20

    Polymer adhesion between two immiscible polymers is usually poor because there is little interpenetration of one polymer into the other at the interface. Increasing the width of the interfacial zone can enhance adhesion and mechanical properties. In principle, this can be accomplished by exposing heterogeneous polymer materials to a high-pressure fluid. The fluid can act as a common solvent and promote interpenetration. It also increases chain mobility at the interface, which helps to promote "welding" of the two polymers. A combination of the gradient theory of inhomogeneous systems and the Sanchez-Lacombe equation of state was used to investigate this phenomenon, especially the effect of the high compressibility of supercritical (SC) fluid on the compatibilization of two incompatible polymers. We calculate the interfacial density profile, interfacial thickness, and interfacial tension between the two polymers with and without the SC fluid. We find that the interfacial tension is decreased and the interfacial thickness is increased with high-pressure SC fluid for the ternary systems we have investigated. As the critical point is approached and the SC compressibility becomes large, no enhancement or deleterious effects on compatibilization were observed.

  13. Supercritical fluid extraction of Beauvericin from maize.

    PubMed

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

    2004-02-27

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

  14. Transport and relaxation processes in supercritical fluids

    NASA Astrophysics Data System (ADS)

    Jonas, J.

    Main emphasis was on design and testing of different modifications of the NMR solubility probe equipped with mixing. A new solution of the difficult problem of mixing in NMR probe at high pressure was proposed which should open new directions in supercritical fluid research. Experiments on supercritical CO2 were performed to examine collision induced scattering. The theoretical analysis of the data for SF6 and CH4 was completed, and the manuscript should be submitted for publication within the next grant period. The naphthalene/carbon dioxide solubility determination without mixing was initiated as described in the previous report. The first measurements were at 55 C and cover a range of pressures from 120 bar to 320 bar. The results are compared to the solubility data of Paulaitis, et al., and Reid, et al. Unfortunately, the data seems to be about 40% low at the higher pressures caused by diffusion of the naphthalene out of the sample cell while the equilibrium solubility is being obtained. This problem should be overcome with further sample cell design changes.

  15. Recovery of Minerals in Martian Soils Via Supercritical Fluid Extraction

    NASA Astrophysics Data System (ADS)

    Debelak, Kenneth A.; Roth, John A.

    2001-03-01

    We are investigating the use of supercritical fluids to extract mineral and/or carbonaceous material from Martian surface soils and its igneous crust. Two candidate supercritical fluids are carbon dioxide and water. The Martian atmosphere is composed mostly of carbon dioxide (approx. 95.3%) and could therefore provide an in-situ source of carbon dioxide. Water, although present in the Martian atmosphere at only approx. 0.03%, is also a candidate supercritical solvent. Previous work done with supercritical fluids has focused primarily on their solvating properties with organic compounds. Interestingly, the first work reported by Hannay and Hogarth at a meeting of the Royal Society of London in 1879 observed that increasing or decreasing the pressure caused several inorganic salts e.g., cobalt chloride, potassium iodide, and potassium bromide, to dissolve or precipitate in supercritical ethanol. In high-pressure boilers, silica, present in most boiler feed waters, is dissolved in supercritical steam and transported as dissolved silica to the turbine blades. As the pressure is reduced the silica precipitates onto the turbine blades eventually requiring the shutdown of the generator. In supercritical water oxidation processes for waste treatment, dissolved salts present a similar problem. The solubility of silicon dioxide (SiO2) in supercritical water is shown. The solubility curve has a shape characteristic of supercritical systems. At a high pressure (greater than 1750 atmospheres) increasing the temperature results in an increase in solubility of silica, while at low pressures, less than 400 atm., the solubility decreases as temperature increases. There are only a few studies in the literature where supercritical fluids are used in extractive metallurgy. Bolt modified the Mond process in which supercritical carbon monoxide was used to produce nickel carbonyl (Ni(CO)4). Tolley and Tester studied the solubility of titanium tetrachloride (TiCl4) in supercritical CO2

  16. Use of supercritical fluid solution expansion processes for drug delivery, particle synthesis, and thin film deposition

    SciTech Connect

    Hybertson, B.M.

    1992-01-01

    Properties of the gases and aerosols resulting from the expansion of supercritical fluid solutions were studied. Film deposition, particle formation, and drug delivery processes using supercritical fluids were developed. Thin films of palladium, copper, aluminum, silver, and silicon dioxide were deposited by a method called supercritical fluid transport-chemical deposition (SFT-CD). In each case, a precursor compound was dissolved in a supercritical fluid and the solution was allowed to expand through a restrictor nozzle into a reaction chamber at subcritical pressure, resulting in the formation of aerosol particles of the precursor. A chemical reaction was induced to occur at the surface of a substrate, resulting in deposition of a thin film. Micron-sized particles of aluminum fluoride and copper oxide were synthesized by a method called supercritical fluid transport-chemical formation of particles (SFT-CFP). The process was similar to that in SFT-CD, but the chemical reactions were induced to occur in the gas phase instead of at a substrate surface, resulting in the formation of fine particles. A new method of pulmonary drug delivery called supercritical fluid drug delivery (SFDD) was conceived and demonstrated. In SFDD a drug compound is dissolved in a supercritical fluid, and the solution is allowed to expand through a restrictor nozzle. The resultant aerosol is directly inhaled by a human or animal subject and the fine drug particles are deposited in the lungs. Menthol, vanillin, camphor, cholesterol, Sudan III, and Oil Blue N were used as model drug compounds for SFDD. Delivery of [alpha]-tocopherol to rat lung tissue was demonstrated, with observed increases of 80-290% above background levels.

  17. 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.

  18. Recovery of Alkylation Activity in Deactivated USY Catalyst Using Supercritical Fluids: A Comparison of Light Hydrocarbons

    SciTech Connect

    Daniel M. Ginosar; David N. Thompson; Kyle C. Burch

    2004-05-01

    Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical fluids (SCF). A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical fluids over the catalyst bed. A comparison of reactivation fluids on catalyst activity recovery is reported. Fluids examined included helium, propane, n-butane, isobutane, n-pentane, and isopentane. Phases studied included gas, liquid, and supercritical. As much as 82% of the fresh catalyst activity was recovered when employing supercritical isobutane. The ability of the fluid to facilitate a hydride reaction with the adsorbed deactivating high-molecular weight carbocations was indicated as an important property necessary to attain high levels of catalyst activity recovery. Activity recovery utilizing supercritical fluids that enhance reactivation by both reacting with and desorbing fouling compounds appears to be a promising technique to advance solid catalyst alkylation.

  19. Fluid dynamic effects on precision cleaning with supercritical fluids

    SciTech Connect

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

    1994-06-01

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

  20. Supercritical fluid extraction (SFE) for determination of metalworking fluid aerosols.

    PubMed

    Brudin, Stella; Hjalmarsson, Theres; Ljungkvist, Göran; Mathiasson, Lennart; Lillienberg, Linnéa

    2006-07-01

    A common methodology for analyzing metalworking fluid (MWF) aerosols in workplace air is based on gravimetry before and after organic solvent extraction of the MWFs from a suitable collection filter. Because MWFs have different chemical and physical properties, various mixtures of organic solvents have been used to extract the MWFs from their collection device. An alternative to organic solvents, used in the work presented in this article, is the use of a supercritical fluid. The efficiency of supercritical fluid extraction (SFE) was investigated by weighing conditioned filters before and after extraction of samples spiked with MWFs at different concentrations using the American Society for Testing and Materials method. For three common straight oil MWFs spiked on filters, supercritical carbon dioxide gave recoveries of 92-101% with a low standard deviation (0.2-1.9%). For semisynthetic MWFs, carbon dioxide had to be mixed with methanol to obtain recoveries above 80%. With the optimized method using 7% methanol in carbon dioxide, the 10 investigated MWFs could be extracted in 30 min with a recovery of 90-98%. The amount of MWFs spiked on the filters varied between 0.10-1.65 mg. In Sweden, the limit value for MWFs is 1 mg/m3. Thus, our spike level is in the range of 10-200% of the limit value if sampling for 8 hours with 2 L/min. The use of SFE methodology results in small volume extracts (3 mL) with concentrations at such high levels that analysis of chemical components in the MWF can be carried out without further volume reduction.

  1. Ceramic powder synthesis in supercritical fluids

    SciTech Connect

    Adkins, C.L.J.; Russick, E.M.; Cesarano, J; Tadros, M.E.; Voigt, J.A.

    1996-04-01

    Gas-phase processing plays an important role in the commercial production of a number of ceramic powders. These include titanium dioxide, carbon black, zinc oxide, and silicon dioxide. The total annual output of these materials is on the order of 2 million tons. The physical processes involved in gas-phase synthesis are typical of those involved in solution -phase synthesis: chemical reaction kinetics, mass transfer, nucleation, coagulation, and condensation. This report focuses on the work done under a Laboratory-Directed Research and Development (LDRD) project that explored the use of various high pressure techniques for ceramic powder synthesis. Under this project, two approaches were taken. First, a continuous flow, high pressure water reactor was built and studied for powder synthesis. And second, a supercritical carbon dioxide static reactor, which was used in conjunction with surfactants, was built and used to generate oxide powders.

  2. Supercritical Fluid Extraction of Aflatoxin B 1 from Soil

    EPA Science Inventory

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

  3. Mini-review: green sustainable processes using supercritical fluid carbon dioxide.

    PubMed

    Ramsey, Edward; Sun, Qiubai; Zhang, Zhiqiang; Zhang, Chongmin; Gou, Wei

    2009-01-01

    Environmentally benign carbon dioxide offers significant potential in its supercritical fluid phase to replace current reliance on a range of hazardous, relatively expensive and environmentally damaging organic solvents that are used on an extensive global basis. The unique combination of the physical properties of supercritical fluids are being exploited and further researched to continue the development and establishment of high efficiency, compact plant to provide energy and water efficient manufacturing processes. This mini-review is focused on the use and potential applications of supercritical fluid carbon dioxide for a selected range of key and emerging industrial processes as a sustainable alternative to totally eliminate or greatly reduce the requirement of numerous conventional organic solvents. Examples of the industries include: chemical extraction and purification, synthetic chemical reactions including polymerization and inorganic catalytic processes. Biochemical reactions involving enzymes, particle size engineering, textile dyeing and advanced material manufacture provide further illustrations of vital industrial activities where supercritical fluid technology processes are being implemented or developed. Some aspects relating to the economics of sustainable supercritical fluid carbon dioxide processes are also considered.

  4. 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.

  5. 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.

  6. Anomalous change in the dynamics of a supercritical fluid.

    PubMed

    Han, Sungho

    2011-11-01

    We perform molecular dynamics simulations to investigate dynamical properties of a supercritical Lennard-Jones fluid. We find that in the supercritical region there is a short-ranged deviation in dynamic character. We further find that this anomalous change is associated with the presence of the Widom line, the locus of specific heat maxima, of the liquid-vapor phase transition. The salient change in dynamics is consistent with a crossover in the correlation of the diffusion coefficient with the excess entropy. Our results lead to an interpretation that, even though a supercritical fluid excludes a singularity, its dynamical properties can be significantly affected by the existence of thermodynamic response maxima.

  7. Derivatization reactions of carbamate pesticides in supercritical carbon dioxide.

    PubMed

    King, Jerry W; Zhang, Zhouyao

    2002-09-01

    Supercritical fluid carbon dioxide (SC-CO(2)) has been used to dissolve derivatizing agents (e.g. heptafluorobutyric anhydride, HFBA, and pyridine), which also act as a modifier in the fluid phase, for simultaneous extraction and derivatization of carbamates from the sample matrix. The derivatized carbamate pesticides (carbaryl, 3-hydroxycarbofuran, carbofuran, aldicarb, methiocarb) were then analyzed by GC-ECD or GC-MS with excellent sensitivity. Extraction and conversion of the carbamates was complete, as indicated by HPLC with post-column hydrolysis and o-phthalaldehyde derivatization then fluorescence detection. GC-MS (ion trap) was also used to confirm the formation of the carbamate derivatives. Compared with the same HFBA reaction in an organic solvent the derivatization reaction time was considerably shorter in SC-CO(2.) The described approach, combining both extraction and derivatization, simplifies the analysis of carbamate pesticides and eliminates the use of organic solvents associated with the derivatization step.

  8. Particle Formation by Supercritical Fluid Extraction and Expansion Process

    PubMed Central

    Zhou, Junbo; Li, Haiting; Quan, Can

    2013-01-01

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

  9. A man-portable supercritical fluid extractor

    SciTech Connect

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

    1995-02-01

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

  10. A man-portable supercritical fluid extractor

    SciTech Connect

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

    1995-12-31

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

  11. Plasmas in High-Density Medium - Supercritical fluid plasma and Cryogenic plasma

    NASA Astrophysics Data System (ADS)

    Terashima, Kazuo

    2011-10-01

    Recently, there has been a lot of attention to plasmas in high-density medium as novel plasmas from the views points of not only pure sciences but also various technologies. In this talk, two topics, supercritical fluid plasma and cryogenic plasma, will be discussed. First, plasmas generated in supercritical fluids (supercritical fluid plasma) provide a new reaction field that combines the high reactivity of plasmas with the unique characteristics of supercritical fluids, i.e. molecular clustering and density fluctuations near the critical point. An overview of the earliest studies on plasmas generated in supercritical fluids to recent advances in the field, including synthesis of novel nanomaterials such as highly-order diamondoid (diamond molecules), will be given. Second, continuing to thermal plasma (gas temperature Tg higher than a few thousands to millions of K) and low temperature plasma (Tg ranging from a few hundreds to thousands of K), plasma in a third range of gas temperatures (Tg lower than 300 K) is called cryogenic plasma (or cryoplasma) to distinguish it from thermal and low-temperature plasmas. In our group, the gas temperature of the plasma can be continuously controlled below room temperature (RT) down to a cryogenic temperature such as the boiling point of helium (4 K). In addition to the diagnostics, the application of cryogenic plasma to nanoporous material processing (low damage ashing of low-k materials) will be discussed. This work was supported financially in part by Grants-in-Aid.

  12. Application of Supercritical Fluids to Solid Acid Catalyst Alkylation and Regeneration

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; David N. Thompson; Kyle C. Burch

    2007-05-01

    Supercritical fluid (SCF) regeneration is a promising alternative method for regenerating solid catalysts deactivated by carbonaceous deposits. The unique solvent and transport properties of SCFs such as solvent strength similar to liquids and transport properties similar to gases make them highly suitable for extraction of fouling materials from porous heterogeneous catalysts. A brief review of the research work performed at the Idaho National Laboratory (INL) on the application of supercritical fluids to both isobutane/butene alkylation reaction and solid acid catalyst regeneration is presented in this contribution.

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

    PubMed

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

    2014-02-01

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

  14. 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.

  15. 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.

  16. Thermal analysis of turbulent flow of a supercritical fluid

    NASA Technical Reports Server (NTRS)

    Yamane, E.

    1979-01-01

    The influence of the large variation of thermodynamics and transport properties near the pseudocritical temperature on the heat transfer coefficient of supercritical fluid in turbulent flow was studied. The formation of the characteristics peak in the heat transfer coefficient vs. bulk temperature curve is described, and the necessity of the fluid element at pseudocritical temperature located in the buffer layer is discussed.

  17. 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.

  18. Geological controls on supercritical fluid resources in volcanic geothermal systems

    NASA Astrophysics Data System (ADS)

    Scott, S. W.; Driesner, T.; Weis, P.

    2014-12-01

    Large-scale fluid convection in conventional volcanic geothermal systems is driven by the hydrothermal cooling of shallow intrusions. Recently, there has been increased interest in tapping supercritical fluid resources in volcanic geothermal systems, since such fluid reservoirs could provide a roughly order-of-magnitude greater potential for electricity production than conventional geothermal wells drilled to temperatures of 250-300 °C. The potential of supercritical geothermal reservoirs was demonstrated in 2010, when the Iceland Deep Drilling Project (IDDP) drilled into liquid magma at 2 km depth and encountered an overlying permeable, high-temperature (~450 °C) fluid reservoir capable of more than ~30 MWe of electricity production. However, a conceptual model describing the main factors governing the extent and structure of target reservoirs has remained elusive. Here, we present the first systematic investigation of the role of rock permeability, the brittle-ductile transition temperature, and the depth of magma chamber emplacement on the development of supercritical fluid reservoirs. We use the numerical modeling code CSMP++ to model two-phase flow of compressible water around an initially elliptical, 900 °C intrusion. Our models indicate that potentially exploitable supercritical fluid resources are an integral part of many magma-driven geothermal systems. Hotter and more extensive reservoirs are promoted by a brittle-ductile transition temperature higher than ~400 °C, an intrusion depth less than 3 km, and a host rock permeability of 10-14 to 10-15 m2. The systematic dependence of the size, location and hydrologic behavior of supercritical reservoirs on these factors aids the development of exploration models for different volcanic settings. In addition, by serving as the main agents of heat transfer at the interface of an intrusion and the overlying hydrothermal system, supercritical fluid reservoirs play a decisive role in determining the overall

  19. Research and development opportunities in supercritical fluid technology: Final report

    SciTech Connect

    Not Available

    1989-08-01

    On December 2, 1988, the US Department of Energy (DOE) held a workshop on supercritical fluid technology. The purpose of this workshop was to elicit research ideas from participants representing government, industry, and academia. A special concern was to determine the appropriate level of involvement for DOE and other organizations in order to develop commercial supercritical fluid technology. Group presentations and a general discussion were held to summarize the results. Comments on the general roles of DOE and industry in supercritical fluid R D included: some industries (e.g., food processing) are already researching this technology; DOE should cooperate with industry in attempting to demonstrate this technology; and direct support of private-sector projects by DOE should be encouraged. It was also noted that productivity benefits may outweigh energy conservation benefits in some application areas. 1 fig., 5 tabs.

  20. Preparation of drug delivery systems using supercritical fluid technology.

    PubMed

    Kompella, U B; Koushik, K

    2001-01-01

    Small changes in temperature and pressure near the critical region induce dramatic changes in the density and solubility of supercritical fluids, thereby facilitating the use of environmentally benign agents such as CO2 for their solvent and antisolvent properties in processing a wide variety of materials. While supercritical fluid technologies have been in commercial use in the food and chromatography industries for several years, only recently has this technology made inroads in the formulation of drug delivery systems. This review summarizes some of the recent applications of supercritical fluid technology in the preparation of drug delivery systems. Drugs containing polymeric particles, plain drug particles, solute-containing liposomes, and inclusion complexes of drug and carrier have been formulated using this technology. Also, polymer separation using this technology is enabling the selection of a pure fraction of a polymer, thereby allowing a more precise control of drug release from polymeric delivery systems.

  1. Biocatalytic synthesis of acrylates in supercritical fluids: tuning enzyme activity by changing pressure.

    PubMed Central

    Kamat, S V; Iwaskewycz, B; Beckman, E J; Russell, A J

    1993-01-01

    Supercritical fluids are a unique class of nonaqueous media in which biocatalytic reactions can occur. The physical properties of supercritical fluids, which include gas-like diffusivities and liquid-like densities, can be predictably controlled with changing pressure. This paper describes how adjustment of pressure, with the subsequent predictable changes of the dielectric constant and Hildebrand solubility parameter for fluoroform, ethane, sulfur hexafluoride, and propane, can be used to manipulate the activity of lipase in the transesterification of methylmethacrylate with 2-ethyl-1-hexanol. Of particular interest is that the dielectric constant of supercritical fluoroform can be tuned from approximately 1 to 8, merely by increasing pressure from 850 to 4000 psi (from 5.9 to 28 MPa). The possibility now exists to predictably alter both the selectivity and the activity of a biocatalyst merely by changing pressure. Images Fig. 6 PMID:8464910

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

    PubMed

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

    2014-01-07

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

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

    SciTech Connect

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

    2014-01-07

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

  4. 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)

  5. 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)

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Transport and relaxation processes in supercritical fluids. Technical progress report

    SciTech Connect

    Jonas, J.

    1986-01-01

    We have tested our improved NMR method for determining diffusion coefficients using a sample of H/sub 2/O. We obtain the literature value for D to within the error of the experiment (+- 3%). A manuscript on the method is in preparation. This NMR diffusion experiment now allows us to obtain diffusion data for the naphthalene-CO/sub 2/ system. Spin echo modulation is no longer a problem, so we may monitor the proton NMR signal from naphthalene which has the necessary sensitivity to obtain diffusion data. Diffusion measurements are now in progress. These are the first NMR diffusion measurements on a solid-supercritical fluid system. We have recently been testing the feasibility of obtaining high resolution sulfur-33 NMR spectra of solids containing sulfur dissolved in supercritical fluids. Typically sulfur linewidths in these molecules are very large (greater than 10kHz) when dissolved in liquid solution. However, the viscosity of a supercritical fluid is much less than that of a simple liquid, and thus a sulfur containing compound dissolved in a supercritical fluid should have a greatly narrowed linewidth. This would allow the characterization of sulfur containing coal liquids, for example. We have investigated the system dibenzothiophene-supercritical ethylene in this way. Unfortunately, the NMR sensitivity of /sup 33/S is quite poor, and the signal to noise ratios were not sufficient to obtain the spectrum. We now plan to use the supercritical solvent xenon, which is known to be an excellent solvent. This solvent should give greater solubilities so that the problems of sensitivity can be overcome.

  12. Stationary phases for packed-column supercritical fluid chromatography.

    PubMed

    Poole, Colin F

    2012-08-10

    The properties of silica-based, chemically bonded, packed column stationary phases used in supercritical fluid chromatography are described with a focus on column design and retention mechanisms. Supercritical fluid chromatography has benefited substantially from innovations in column design for liquid chromatography even if the separation conditions employed are generally quite different. The mobile phase composition and column operating conditions play an interactive role in modifying selectivity in supercritical fluid chromatography by altering analyte solubility in the mobile phase and through selective solvation of the stationary phase resulting in a wider range and intensity of intermolecular interactions with the analyte. The solvation parameter model is used to identify the main parameters that affect retention in supercritical fluid chromatography using carbon dioxide-methanol as a mobile phase and as a basis for column characterization to facilitate the identification of stationary phases with different separation characteristics for method development. As a caution it is pointed out that these column characterization methods are possibly a product of both the stationary phase chemistry and the column operating conditions and are suitable for use only when columns of similar design and with similar operating conditions are used.

  13. Determination of thermodynamic properties by supercritical fluid chromatography.

    PubMed

    Roth, Michal

    2004-05-28

    This survey attempts to summarise thermodynamic applications of supercritical fluid chromatography (SFC) with an emphasis on the results published during the last 10 years. In addition to a review of thermodynamic measurements by SFC, it contains brief sections on instrumental considerations and on the sources of auxiliary information needed when processing the retention data.

  14. Method for nucleic acid isolation using supercritical fluids

    SciTech Connect

    Nivens, David E.; Applegate, Bruce M.

    1999-01-01

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

  15. Method for nucleic acid isolation using supercritical fluids

    DOEpatents

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

    1999-07-13

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

  16. 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.

  17. [Determination of caffeine in teas by supercritical fluid chromatography].

    PubMed

    Guo, Ya-dong

    2002-01-01

    A rapid supercritical fluid chromatographic method for the determination of caffeine in tea is described. It is shown that a mobile phase of carbon dioxide, modified with 5% methanol achieved excellent results. The method is simple in the sample preparation. Other components contained in the sample do not interfere the measurement. It can be used to determine caffeine in tea rapidly.

  18. Supercritical fluid chromatography for lipid analysis in foodstuffs.

    PubMed

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

    2017-01-01

    The task of lipid analysis has always challenged separation scientists, and new techniques in chromatography were often developed for the separation of lipids; however, no single technique or methodology is yet capable of affording a comprehensive screening of all lipid species and classes. This review acquaints the role of supercritical fluid chromatography within the field of lipid analysis, from the early developed capillary separations based on pure CO2 , to the most recent techniques employing packed columns under subcritical conditions, including the niche multidimensional techniques using supercritical fluids in at least one of the separation dimensions. A short history of supercritical fluid chromatography will be introduced first, from its early popularity in the late 1980s, to the sudden fall and oblivion until the last decade, experiencing a regain of interest within the chromatographic community. Afterwards, the subject of lipid nomenclature and classification will be briefly dealt with, before discussing the main applications of supercritical fluid chromatography for food analysis, according to the specific class of lipids.

  19. 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.

  20. Biodiesel synthesis from Calophyllum inophyllum oil with different supercritical fluids.

    PubMed

    Lamba, Neha; Gupta, Kaveri; Modak, Jayant M; Madras, Giridhar

    2017-10-01

    Biodiesel or fatty acid methyl esters (FAMEs) is primarily synthesized using edible vegetable oils and methanol with a catalyst. However, in the present study, FAMEs were synthesized from a non-edible oil (Calophyllum inophyllum also called as sura honne, Punnagam, Alexandrian Laurel) in different supercritical fluids: methanol (MeOH), methyl tert-butyl ether (MTBE), methyl acetate (MeOAc) and dimethyl carbonate (DMC) non-catalytically. Reactions were performed from 523K to 673K at 30MPa with a molar ratio of 40:1 with times varying from 3min to 3h. Conversions higher than 80% were obtained within 30min for oil reaction with MeOH and DMC at 623K and conversions of 60% and 70% were obtained at 673K with MeOAc and MTBE, respectively. Pseudo first order kinetics was used to obtain the rate constants and the activation energies followed the order: EMeOH

  1. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, October 1, 1993--December 31, 1993

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1993-12-31

    Objectives for the first quarter for Task A, Diffusion Coefficients of F-T Products in Supercritical Fluids, were to measure diffusion coefficients of 1-tetradecene in subcritical propane and the diffusion coefficients of 1-octene and 1-tetradecene in subcritical propane and the diffusion coefficients of 1-octene and 1-tetradecene in subcritical and supercritical ethane. We planned to use ethane as a solvent because its lower critical temperature enabled measurements without modification of the existing unit. Our objective was to investigate the behavior of the diffusion coefficients in crossing from subcritical to supercritical conditions. Objectives for Task B, Fischer Tropsch reaction related studies, were: (1) to install and test the temperature probe and the flammable gas detector: (2) to conduct Fischer-Tropsch experiments at baseline conditions and at a high pressure in order to test the newly constructed fixed bed reactor assembly. Accomplishments and problems, are presented.

  2. 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

  3. Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

    NASA Astrophysics Data System (ADS)

    Olanrewaju, Kazeem Bode

    The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

  4. Behavior of Supercritical Fluids across the "Frenkel Line".

    PubMed

    Bryk, T; Gorelli, F A; Mryglod, I; Ruocco, G; Santoro, M; Scopigno, T

    2017-09-29

    The "Frenkel line" (FL), the thermodynamic locus where the time for a particle to move by its size equals the shortest transverse oscillation period, has been proposed as a boundary between recently discovered liquid-like and gas-like regions in supercritical fluids. We report a simulation study of isothermal supercritical neon in a range of densities intersecting the FL. Specifically, structural properties and single-particle and collective dynamics are scrutinized to unveil the onset of any anomalous behavior at the FL. We find that (i) the pair distribution function smoothly evolves across the FL displaying medium-range order, (ii) low-frequency transverse excitations are observed below the "Frenkel frequency", and (iii) the high-frequency shear modulus does not vanish even for low-density fluids, indicating that positive sound dispersion characterizing the liquid-like region of the supercritical state is unrelated to transverse dynamics. These facts critically undermine the definition of the FL and its significance for any relevant partition of the supercritical phase.

  5. Statistical mechanical description of supercritical fluid extraction and retrograde condensation

    NASA Astrophysics Data System (ADS)

    Park, S. J.; Kwak, T. Y.; Mansoori, G. A.

    1987-07-01

    The phenomena of supercritical fluid extraction (SFE) and its reverse effect, which is known as retrograde condensation (RC), have found new and important applications in industrial separation of chemical compounds and recovery and processing of natural products and fossil fuels. Full-scale industrial utilization of SFE/RC processes requires knowledge about thermodynamic and transport characteristics of the asymmetric mixtures involved and the development of predictive modeling and correlation techniques for performance of the SFE/RC system under consideration. In this report, through the application of statistical mechanical techniques, the reasons for the lack of accuracy of existing predictive approaches are described and they are improved. It is demonstrated that these techniques also allow us to study the effect of mixed supercritical solvents on the solubility of heavy solutes (solids) at different compositions of the solvents, pressures, and temperatures. Fluid phase equilibrium algorithms based on the conformal solution van der Waals mixing rules and different equations of state are presented for the prediction of solubilities of heavy liquid in supercritical gases. It is shown that the Peng-Robinson equation of state based on conformal solution theory can predict solubilites of heavy liquid in supercritical gases more accurately than the van der Waals and Redlich-Kwong equations of state.

  6. 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.

  7. Intermolecular interactions and the thermodynamic properties of supercritical fluids

    NASA Astrophysics Data System (ADS)

    Yigzawe, Tesfaye M.; Sadus, Richard J.

    2013-05-01

    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.

  8. 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.

  9. 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.

  10. 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.

  11. Solubilities in supercritical fluids: the application of chromatographic measurement methods

    SciTech Connect

    Smith, R.D.; Udseth, H.R.; Wright, B.W.; Yonker, C.R.

    1987-01-01

    New methods are described for the measurement of the solubilities of solids in supercritical fluids. These methods utilize instrumentation developed for capillary supercritical fluid chromatography consisting of deactivated, small diameter, fused silica tubing, coupled with detection methods based upon on flame ionization and mass spectrometric detectors. The methods involve (a) direct solubility determination where the fused silica capillary is used as an equilibrium cell, and (b) a pressure of threshold solubility technique which resembles chromatography and uses a programmed pressure increase and sensitive detection to determine the onset of solute migration. Results are also presented which suggest that solubilities can be determined, within certain limitations, from actual chromatographic experiments. The methods are illustrated using aromatic hydrocarbons and complex mycotoxins of the trichothecene group.

  12. Micronization processes with supercritical fluids: fundamentals and mechanisms.

    PubMed

    Martín, A; Cocero, M J

    2008-02-14

    Supercritical fluid techniques for materials precipitation have been proposed as an alternative to conventional precipitation processes as they allow to improve the performance of these processes in terms of reduction of particle size and control of morphology and particle size distribution, without degradation or contamination of the product. These techniques have received much attention during the last years, and their feasibility and performance have been experimentally demonstrated for many substances. One of the main pending tasks is the development of a systematic procedure for the design and scale-up of these processes. This requires not only empirical knowledge, but also information about the fundamentals of the process. This work aims to review the published literature dealing with a fundamental investigation or modeling of supercritical fluid precipitation processes.

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

    SciTech Connect

    Campbell, R.M.

    1987-01-01

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

  14. Supercritical fluid extraction of all-trans-lycopene from tomato.

    PubMed

    Gómez-Prieto, M Salud; Caja, M Mar; Herraiz, Marta; Santa-María, Guillermo

    2003-01-01

    A procedure is proposed for the supercritical fluid extraction of all-trans-lycopene from tomato using carbon dioxide at 40 degrees C without modifier. The present method minimizes the risk of degradation via isomerization and oxidation of health-promoting ingredients, such as lycopene. The effect of different experimental variables on the solvating power of the supercritical fluid was evaluated in terms of both the selectivity achievable in the process and the yield of the extraction of all-trans-lycopene. Satisfactory separations of the all-trans-lycopene isomers from the cis counterparts were achieved using a C(30) column. The obtained extract contained 88% all-trans-lycopene and 12% cis-lycopene.

  15. Antioxidant effects of supercritical fluid garlic extracts in sunflower oil.

    PubMed

    Bravi, Elisabetta; Perretti, Giuseppe; Falconi, Caterina; Marconi, Ombretta; Fantozzi, Paolo

    2017-01-01

    Lipid oxidation causes changes in quality attributes of vegetable oils. Synthetic antioxidants have been used to preserve oils; however, there is interest in replacing them with natural ones. Garlic and its thiosulfinate compound allicin are known for their antioxidant activities. This study assesses a novel formulation, the supercritical fluid extract of garlic, on sunflower oil oxidation during an accelerated shelf-life test. Three quality parameters (free acidity, peroxide values, and p-anisidine values) were evaluated in each of the six oil samples. The samples included sunflower oil alone, sunflower oil supplemented with BHT, the undiluted supercritical fluid extract of garlic, and sunflower oils supplemented with three levels of garlic extract. The oils were also investigated for their antioxidant properties using the DPPH and the FRAP assays. The results were compared with the effect of the synthetic BHT. Our results underlined that the highest level of garlic extract may be superior, or at least comparable, with BHT in preserving sunflower oil. The oxidative degradation of oily samples can be limited by using supercritical fluid extract of garlic as it is a safe and an effective natural antioxidant formulation. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  16. 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-HNO3) 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.

  17. Application of Fokker-Planck-Kramers equation treatment for short-time dynamics of diffusion-controlled reaction in supercritical Lennard-Jones fluids over a wide density range.

    PubMed

    Ibuki, Kazuyasu; Ueno, Masakatsu

    2006-04-07

    The validity of a Fokker-Planck-Kramers equation (FPKE) treatment of the rate of diffusion-controlled reaction at short times [K. Ibuki and M. Ueno, J. Chem. Phys. 119, 7054 (2003)] is tested in a supercritical Lennard-Jones fluid over a wide density range by comparing it with the Langevin dynamics and molecular dynamics simulations and other theories. The density n range studied is 0.323n(c)< or =n< or =2.58n(c) and the temperature 1.52T(c), where n(c) and T(c) are the critical density and temperature, respectively. For the rate of bimolecular reactions, the transition between the collision-limited and diffusion-limited regimes is expected to take place in this density range. The simulations show that the rate constant decays with time extensively at high densities, and that the magnitude of decay decreases gradually with decreasing density. The decay profiles of the rate constants obtained by the simulations are reproduced reasonably well by the FPKE treatment in the whole density range studied if a continuous velocity distribution is used in solving the FPKE approximately. If a discontinuous velocity distribution is used instead of the continuous one, the FPKE treatment leads to a rate constant much larger than the simulation results at medium and low densities. The rate constants calculated from the Smoluchowski-Collins-Kimball (SCK) theory based on the diffusion equation are somewhat smaller than the simulation results in medium and low densities when the intrinsic rate constant is chosen to adjust the steady state rate constant in the low density limit to that derived by the kinetic collision theory. The discrepancy is relatively small, so that the SCK theory provides a useful guideline for a qualitative discussion of the density effect on the rate constant.

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

    SciTech Connect

    1995-12-01

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

  19. 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

  20. Mass spectrometer sampling of supercritical water-oxidation reactions

    SciTech Connect

    Miller, D.R.; Maharrey, S.

    1995-03-01

    Supercritical water is a useful medium for oxidation of toxic hydrocarbons because under such conditions hydrocarbons and oxidizers are dissolved into a single phase, diffusivities are high, the combustion is complete, and it occurs at relatively low temperatures. There is a large literature on the thermodynamics, kinetics, and applications of supercritical water oxidation. Supercritical fluids have also been used as solvent carriers in chromatography and the interface of the column output to mass spectrometers has been investigated by many researchers. In the present investigation the authors seek to operate a micro-reactor in which supercritical water oxidation kinetics can be examined and for which the output flow can be injected directly into a mass spectrometer system. The motivation for this approach was the microjet burner utilized by Groeger and Fenn for combustion studies. Water is one of the more difficult supercritical solvents to interface with the mass spectrometer, compared with CO{sub 2} for example, because the pressures and temperatures are of order 30MPa and 500{degrees}C, and because the large water throughput must be removed by the vacuum pumps. They have fabricated supercritical nozzles from both stainless steel and from quartz capillary tubing. Despite the fact that supercritical water can dissolve quartz in the ppm range they have been able to operate quartz capillary reactors and nozzles in excess of 20hrs without any measurable degradation in performance. Because these nozzles are much easier to fabricate, especially to diameters below 0.004cm, they have been recently using them exclusively. This variable nozzle diameter is important because it permits us to vary the range of residence times in the reactor. The converging nozzle length is less than two capillary diameters, so the flow time through the nozzle is very short compared with the residence time in the reactor.

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

    PubMed

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

    2011-01-01

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

  2. Microbial Inactivation by Ultrasound Assisted Supercritical Fluids

    NASA Astrophysics Data System (ADS)

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

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

  3. 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.

  4. Viral inactivation of human bone tissue using supercritical fluid extraction.

    PubMed

    Fages, J; Poirier, B; Barbier, Y; Frayssinet, P; Joffret, M L; Majewski, W; Bonel, G; Larzul, D

    1998-01-01

    A new bone tissue process using supercritical carbon dioxide fluid extraction (SFE) has been evaluated for its ability to inactivate or eliminate viruses. Four viruses, human immunodeficiency virus type 1 (HIV-1), Sindbis virus, polio Sabin type I virus, and pseudorabies virus (PRV), were exposed to four different processing steps. In addition to supercritical CO2, hydrogen peroxide, sodium hydroxide, and ethanol treatments were evaluated. The mean cumulated reduction factors (log10) for the four viruses exposed to these four steps were > 14.2 for HIV-1, > 18.2 for Sindbis virus, > 24.4 for poliovirus, and > 17.6 for PRV. The mean reduction factors obtained by the supercritical fluid extraction alone were > 4.0, > 4.3, > 6.6, and > 4.0, respectively. These results demonstrate that the SFE process is effective in inactivating viruses on human femoral heads, and provides a level of inactivation similar to that obtained by traditional cleaning methods. It is proposed that CO2 SFE be incorporated as a routine step in the processing of bone allografts for transplantation either to replace or supplement existing procedures.

  5. 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.

  6. 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.

  7. Selective extraction of strontium with supercritical fluid carbon dioxide

    PubMed Central

    Kulyako, Yurii; Yak, Hwa-Kwang; Chen, Xiaoyuan; Lee, Suh-Jane

    2010-01-01

    Strontium (Sr2+) can be selectively extracted from aqueous solutions into supercritical fluid CO2 at 60 °C and 100 atm with dicyclohexano-18-crown-6 (DC18C6) using CF3(CF2)6CO2− (PFOA−) or CF3(CF2)6CF2SO3− (PFOSA−) as a counter anion; at a mole ratio of Sr2+ : DC18C6 : PFOA− = 1:10:50, the extraction of Sr (5.6 × 10−5 M) from water at pH 3 is near quantitative whereas Ca2+ and Mg2+ at equal concentration are only extracted to a level of 7 and 1%, respectively; PFOSA− is an effective counter anion for selective extraction of Sr2+ from 1.3 M HNO3 with DC18C6 in supercritical CO2. PMID:21394239

  8. Solute nucleation and growth in supercritical fluid mixtures

    SciTech Connect

    Smedley, G.T.; Rawlins, W.T.; Oakes, D.B.

    1996-06-05

    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 A nucleation process in supercritical fluids to aid in the evaluation and development of existing rheoretical 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 {approx}1 followed by a rapid recompression to a less supersaturated state that effectively terminates nucleation while permitting growth 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 CO{sub 2} have been completed.

  9. Modeling of supercritical fluid extraction from herbaceous matrices

    SciTech Connect

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

    1993-11-01

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

  10. Carbon dioxide-based supercritical fluids as IC manufacturing solvents

    SciTech Connect

    Rubin, J.B.; Davenhall, L.B.; Taylor, C.M.V.; Sivils, L.D.; Pierce, T.; Tiefert, K.

    1999-05-11

    The production of integrated circuits (IC's) involves a number of discrete steps which utilize hazardous or regulated solvents and generate large waste streams. ES&H considerations associated with these chemicals have prompted a search for alternative, more environmentally benign solvent systems. An emerging technology for conventional solvent replacement is the use of supercritical fluids based on carbon dioxide (CO{sub 2}). Research work, conducted at Los Alamos in conjunction with the Hewlett-Packard Company, has lead to the development of a CO{sub 2}-based supercritical fluid treatment system for the stripping of hard-baked photoresists. This treatment system, known as Supercritical CO{sub 2} Resist Remover, or CORR, uses a two-component solvent composed of a nonhazardous, non-regulated compound, dissolved in supercritical CO{sub 2}. The solvent/treatment system has been successfully tested on metallized Si wafers coated with negative and positive photoresist, the latter both before and after ion-implantation. A description of the experimental data will be presented. Based on the initial laboratory results, the project has progressed to the design and construction of prototype, single-wafer photoresist-stripping equipment. The integrated system involves a closed-loop, recirculating cycle which continuously cleans and regenerates the CO{sub 2}, recycles the dissolved solvent, and separates and concentrates the spent resist. The status of the current design and implementation strategy of a treatment system to existing IC fabrication facilities will be discussed. Additional remarks will be made on the use of a SCORR-type system for the cleaning of wafers prior to processing.

  11. Fischer-Tropsch synthesis in supercritical reaction media

    SciTech Connect

    Subramaniam, B.

    1992-10-01

    The goal of this research is to thoroughly investigate the feasibility of using supercritical fluid (SCF) solvent medium for carrying out Fischer-Tropsch (FT) synthesis. Research will address the systematic experimental investigations of FT synthesis over supported Fe and Co catalysts in a CSTR and in a fixed-bed reactor at typical synthesis temperatures (240-260[degrees]C). The SCF medium to be employed is n-Hexane (P[sub c] = 29.7 bar; [Tc] = 233.7[degrees]C), while n-Hexadecane will be employed as the liquid reaction medium. Overall conversion, product distribution and catalyst deactivation will be measured in each case for various feed H[sub 2]/CO ratios ranging from 0.5 to 2. Product analyses will be carried out using GC/TCD, GC/FID and GC/MS systems. The fresh and used catalysts will be characterized with respect to active metal dispersion, surface area and pore size distribution.

  12. MOLECULAR DESIGN OF COLLOIDS IN SUPERCRITICAL FLUIDS

    SciTech Connect

    Keith P. Johnston

    2009-04-06

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

  13. 2DCOR-GC: an application of the generalized two-dimensional correlation analysis as a route to optimization of continuous flow supercritical fluid reactions.

    PubMed

    Hyde, Jason R; Bourne, Richard A; Noda, Isao; Stephenson, Phil; Poliakoff, Martyn

    2004-11-01

    A new approach for optimization and monitoring of continuous reactions has been developed using 2D correlation methods for the analysis of GC data (2DCOR-GC). 2DCOR-GC maps are obtained following perturbation of the system that allow the effect of changing reaction parameters such as time, temperature, pressure, or concentration to be both monitored and sequenced with regard to changes in the raw GC data. In this paper, we describe the application of the 2DCOR-GC technique to monitoring the reverse water-gas shift reaction in scCO(2). 2DCOR-GC is combined with FT-IR data to validate the methodology. We also report the application of 2DCOR-GC to probe the mechanism of the alkylation of m-cresol with isopropyl alcohol in scCO(2) using Nafion SAC-13 as the catalyst. These results identify coeluting peaks that could easily be missed without exhaustive method development.

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

    SciTech Connect

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

    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 appear feasible.

  15. Growth of nanostructured polycrystalline cerium oxide through a solvothermal precipitation using near-supercritical fluids.

    PubMed

    Lee, Jongmin; Ahn, Jae-Pyoung; Kim, Sang Woo

    2010-01-01

    Well-crystallized cerium dioxide with cubic phase were formed and self-assembly grown to nanofibers or nanosheets via a solvothermal precipitation from near-supercritical fluids without any help of metal catalysts or capping agents. The self-assembly attachment process without any preferred or selective orientation dominated the growth of the polycrystalline nanofibers or nanosheets consisting of grains of approximately 3 nm to which are formed by the coalescence of the single crystalline cerium oxide seeds. The growth is attributed to be driven by phase separation due to partial compatibility between ethyl alcohol and supercritical carbon dioxide fluid during the precipitation reaction, not by different surface energies or defects. With increasing temperature, the nanofibers with a weblike network structure were formed and then fused to large spherical particles. As a result, the polycrystalline fibers or sheets consisting of pure cerium dioxide phase were produced by the solvothermal reaction with an aid of the supercritical carbon dioxide from the alcoholic metal salt solution.

  16. Facile reaction/extraction of coal with supercritical fluids. Quarterly technical progress report, April 1, 1983-June 30, 1983. [In Benzene

    SciTech Connect

    Venier, C.G.; Squires, T.G.

    1983-09-01

    In summary, model studies have provided the following information. An aprotic solvent will be required for both transalkylation and ionic hydrogenation; a non-nucleophilic solvent will be required for ionic hydrogenation; intromolecular reaction will occur in the reactions of phenyl ethers; and in an aromatic solvent, arylation (transalkylation) occurs in preference to ionic hydrogenation. Model studies of the ionic hydrogenation were continued using a copolymer of 1,4-bis(bromomethyl)naphthalene and hydroquinone to mimic the solid, insoluble nature of coal. The results are shown. Infrared spectra of products in experiments 1 and 4 are virtually indistinguishable and indicate that none of the original polymer remains. This establishes that the reaction takes essentially the same course in the presence and absence of triethylsilane. However, the solubilities of the products in the presence and absence of triethylsilane is dramatically different. Since solubility is a sensitive function of molecular weight for oligomeric systems, the solubility of the attempted ionic hydrogenation product signals its lower molecular weight. This indicates that hydride has indeed captured enough of the benzylic cations to change the physical properties of the product. Changes in acid strength indicate that stronger acids lead to more solubility (lower molecular weight) in the presence of the same molar ratio of hydride source. Experiments show that increasing hydride concentration beyond six equivalents only slightly increases the solubility of the product. Using these results as a basis, we will next perform both the transalkylation and ionic hydrogenation of coal.

  17. Reactions of inorganic nitrogen species in supercritical water

    SciTech Connect

    Dell`Orco, P.C.

    1994-12-31

    Redox reactions of nitrate salts with NH3 and methanol were studied in near-critical and supercritical water at 350 to 530 C and constant pressure of 302 bar. Sodium nitrate decomposition reactions were investigated at similar conditions. Reactions were conducted in isothermal tubular reactor under plug flow. For kinetic modeling, nitrate and nitrite reactants were lumped into an NO{sub x}{sup -} reactant; kinetic expressions were developed for MNO{sub 3}/NH{sub 4}X and sodium nitrate decomposition reactions. The proposed elementary reaction mechanism for MNO{sub 3}/NH{sub 4}X reaction indicated that NO{sub 2} was the primary oxidizing species and that N{sub 2}/N{sub 2}O selectivities could be determined by the form of MNO{sub 3} used. This suggest a nitrogen control strategy for use in SCWO (supercritical water oxidation) processes; nitrate or NH3 could be used to remove the other, at reaction conditions far less severe than required by other methods. Reactions of nitrate with methanol indicated that nitrate was a better oxidant than oxygen in supercritical water. Nitrogen reaction products included NH3 and nitrite, while inorganic carbon was the major carbon reaction product. Analysis of excess experiments indicated that the reaction at 475 C was first order in methanol concentration and second order in NO{sub x}{sup -} concentration. In order to determine phase regimes for these reactions, solubility of sodium nitrate was determined for some 1:1 nitrate electrolytes. Solubilities were measured at 450 to 525 C, from 248 to 302 bar. A semi-empirical solvation model was shown to adequately describe the experimental sodium nitrate solubilities. Solubilities of Li, Na, and K nitrates revealed with cations with smaller ionic radii had greater solubilities with nitrate.

  18. Computational Fluid Dynamics Analysis of Canadian Supercritical Water Reactor (SCWR)

    NASA Astrophysics Data System (ADS)

    Movassat, Mohammad; Bailey, Joanne; Yetisir, Metin

    2015-11-01

    A Computational Fluid Dynamics (CFD) simulation was performed on the proposed design for the Canadian SuperCritical Water Reactor (SCWR). The proposed Canadian SCWR is a 1200 MW(e) supercritical light-water cooled nuclear reactor with pressurized fuel channels. The reactor concept uses an inlet plenum that all fuel channels are attached to and an outlet header nested inside the inlet plenum. The coolant enters the inlet plenum at 350 C and exits the outlet header at 625 C. The operating pressure is approximately 26 MPa. The high pressure and high temperature outlet conditions result in a higher electric conversion efficiency as compared to existing light water reactors. In this work, CFD simulations were performed to model fluid flow and heat transfer in the inlet plenum, outlet header, and various parts of the fuel assembly. The ANSYS Fluent solver was used for simulations. Results showed that mass flow rate distribution in fuel channels varies radially and the inner channels achieve higher outlet temperatures. At the outlet header, zones with rotational flow were formed as the fluid from 336 fuel channels merged. Results also suggested that insulation of the outlet header should be considered to reduce the thermal stresses caused by the large temperature gradients.

  19. Chiral separation of some triazole pesticides by supercritical fluid chromatography.

    PubMed

    Toribio, L; del Nozal, M J; Bernal, J L; Jiménez, J J; Alonso, C

    2004-08-13

    The enantiomeric separation of six triazole pesticides: cyproconazole, propiconazole, diniconazole, hexaconazole, tebuconazole and tetraconazole, using supercritical fluid chromatography and the Chiralpak AD column, is presented in this work. The effect of different organic modifiers such as methanol, ethanol and 2-propanol on the retention and resolution was studied as well as the presence of additives in the mobile phase. The results obtained were highly successful, all the compounds were enantiomerically separated and in most of the cases the analysis time was close to 10 min. The type of organic modifier that provided the best results depended on the compound.

  20. Hydroetching of high surface area ceramics using moist supercritical fluids

    DOEpatents

    Fryxell, Glen; Zemanian, Thomas S.

    2004-11-02

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

  1. Ideality contours and thermodynamic regularities in supercritical molecular fluids

    NASA Astrophysics Data System (ADS)

    Desgranges, Caroline; Margo, Abigail; Delhommelle, Jerome

    2016-08-01

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

  2. Separations of petroleum products involving supercritical fluid chromatography.

    PubMed

    Thiébaut, Didier

    2012-08-24

    This paper gives a survey of the most attractive trends and applications of supercritical fluid chromatography in the petroleum industry: simulated distillation, group-type analysis and related applications including the implementation of multidetection in a so-called "hypernated" system, as well as the hyphenation to GC×GC for improved group-type separation, SFC×GC and first promising SFC×SFC results. Some specific technical information related to the use of capillary columns or conventional packed columns in combination with FID (or detectors that require decompression and in some instances splitting of the mobile phase prior detection) is also provided.

  3. Supercritical fluid removal of hydrocarbons adsorbed on wide pore zeolite catalysts

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; Kyle C. Burch

    2005-06-01

    The effect of zeolite pore structure on coke removal by supercritical fluid regeneration (SFR) was studied on a series of wide pore zeolite catalysts, which included acidic Y, beta, L, and mordenite zeolites. Catalyst samples were deactivated under liquid phase isobutane/butene alkylation reaction conditions and treated under flowing supercritical isobutane for 60 min. The chemical nature of the species remaining on the catalyst surface before and after SFR was analyzed by temperature-programmed oxidation (TPO), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and ultraviolet-visible (UV-Vis) spectroscopy. Zeolite pore structure played an important role not only in hydrocarbon deposition during alkylation but also in hydrocarbon transformation and removal during SFR. During SFR, the formation of unsaturated cyclic or polycyclic compounds, which likely affects catalyst long-term activity after cyclic alkylation/SFR treatments, was hindered on beta zeolites and favored on catalysts containing periodic expansions or cages, such as Y and L zeolites.

  4. Supercritical fluid extraction of particulate and adsorbent materials. Part 2. Final report, February 1985-January 1986

    SciTech Connect

    Wright, B.W.; Smith, R.D.

    1987-12-01

    The physical properties of supercritical fluids allow similar solvent strengths as liquids, but with higher diffusion coefficients, lower viscosities, and an extended temperature range that provides the potential for more-rapid and efficient extraction rates than possible with liquids. The report describes expanded studies conducted to evaluate the applicability and efficiency of analytical supercritical fluid extraction and related methodologies. These studies included the development of quantitative off-line supercritical fluid extraction methodology and a comparison to traditional Soxhlet extraction, the development and evaluation of on-line supercritical fluid extraction-gas chromatography for combined sample preparation and analysis, and direct supercritical fluid extraction-mass spectrometry for the monitoring of specific extraction profiles as a function of time. The sample matrices included an air particulate sample and XAD-2 resin, polyurethane foam, and Spherocarb adsorbents that were spiked with various model compounds. Carbon dioxide, isobutane, and methanol modified (20 mole %) carbon dioxide were utilized as supercritical fluid systems. Related studies on the evaluation of the quantitative analysis capability of a fluorescence detection supercritical fluid chromatography method and the development of viable solute focusing methods for capillary supercritical fluid chromatography were also conducted.

  5. 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.

  6. Concerning the Role of Supercritical Carbon Dioxide in SN 1 Reactions.

    PubMed

    Qiao, Yun X; Theyssen, Nils; Eifert, Tobias; Liauw, Marcel A; Franciò, Giancarlo; Schenk, Karolin; Leitner, Walter; Reetz, Manfred T

    2017-03-17

    A series of SN 1-type reactions has been studied under various conditions to clarify the role of supercritical carbon dioxide (scCO2 ) as reaction medium for this kind of transformations. The application of scCO2 did not result in higher yields in any of the experiments in comparison to those under neat conditions or in the presence of other inert compressed gases. High-pressure UV/Vis spectroscopic measurements were carried out to quantify the degree of carbocation formation of a highly SN 1-active alkyl halide as a function of the applied solvent. No measureable concentration of carbocations could be detected in scCO2 , just like in other low polarity solvents. Taken together, these results do not support the previously claimed activating effect via enhanced SN 1 ionization due to the quadrupolar moment of the supercritical fluid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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.

  8. 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

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

    PubMed

    Sikin, Adi Md; Rizvi, Syed S H

    2011-09-01

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

  10. 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.

  11. Dynamics of chelation-supercritical fluid extraction from wood fibers.

    PubMed

    Al-Jabari, Maher

    2004-06-01

    The dynamics of supercritical fluid extraction (SFE) of the metal content of wood fibers chelated with lithium bis(trifluoroethyl) dithiocarbamate (FDDC) by supercritical (SF) CO2 was investigated experimentally by monitoring the spectra of the eluted metal complex as a function of time. The characteristic shape of the dynamic SFE curve was determined mainly by the flow conditions in the extraction vessel, the mass transfer resistance in the SF phase, and the solubility. High extraction yields of metal content were obtained in two-stage extraction including static (batch) and dynamic (semi-batch) stages. Increasing the length of the static stage increased the rate of dynamic elution of metal complex until it approached the dynamics of fluid displacement for a continuous stirred tank reactor (CSTR). In such cases, increasing the flow rate had no effect on the dynamic extraction curve when it was plotted using dimensionless time. Efficient chelation-SFE from wood fibers was obtained at a pressure of 20.3 MPa and with a static time of 30 min.

  12. Supercritical fluid and Soxhlet extractions of organics from sediments

    SciTech Connect

    Riley, R.G.; Sklarew, D.S.; Ozanich, R.M.; Lee, R.N.; Amonette, J.E.; Wright, B.W.

    1995-10-01

    The authors evaluated solvent consumption, atmospheric emissions, and waste generation as factors contributing to environmental, safety, and health issues associated with the extraction of organic materials from sediments when commercially available supercritical fluid extraction (SFE) and Soxhlet extraction systems are used. They found that the Soxhlet system used 10 times as much solvent as the SFE system and released about 6 times the volume of solvent into the atmosphere. Although the total volume of solvent released was much greater for Soxhlet than for SFE extractions, the mean concentration of solvent in the exhaust air from operation of SFE was about 10 times higher because the SFE extraction was much quicker (40 min vs. 18--24 h). As a consequence, operation of Soxhlet or SFE systems under conditions that do not control vapor releases could lead to air concentrations that exceed threshold limit values (TLVs) provided as guidelines for industrial exposure. The releases at facility stacks could also exceed the ambient air concentration limits for hazardous chemicals. Soxhlet systems produced significant liquid waste and some solid hazardous waste. Although components of the SFE process did not produce any liquid waster, they did produce solid waste that may be hazardous unless the solvent modifiers are carefully selected and their concentrations controlled in the supercritical fluid.

  13. 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.

  14. Frenkel line and solubility maximum in supercritical fluids.

    PubMed

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

    2015-01-01

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

  15. Physical properties of rocks and aqueous fluids at conditions simulating near- and supercritical reservoirs

    NASA Astrophysics Data System (ADS)

    Kummerow, Juliane; Raab, Siegfried

    2016-04-01

    The growing interest in exploiting supercritical geothermal reservoirs calls for a thorough identification and understanding of physico-chemical processes occuring in geological settings with a high heat flow. In reservoir engineering, electrical sounding methods are common geophysical exploration and monitoring tools. However, a realistic interpretation of field measurements is based on the knowledge of both, the physical properties of the rock and those of the interacting fluid at defined temperature and pressure conditions. Thus, laboratory studies at simulated in-situ conditions provide a link between the field data and the material properties in the depth. The physico-chemical properties of fluids change dramatically above the critical point, which is for pure water 374.21 °C and 221.2 bar. In supercritical fluids mass transfer and diffusion-controlled chemical reactions are enhanced and cause mineral alterations. Also, ion mobility and ion concentration are affected by the change of physical state. All this cause changes in the electrical resistivity of supercritical fluids and may have considerable effects on the porosity and hydraulic properties of the rocks they are in contact with. While there are some datasets available for physical and chemical properties of water and single component salt solutions above their critical points, there exist nearly no data for electrical properties of mixed brines, representing the composition of natural geothermal fluids. Also, the impact of fluid-rock interactions on the electrical properties of multicomponent fluids in a supercritical region is scarcely investigated. For a better understanding of fluid-driven processes in a near- and supercritical geological environment, in the framework of the EU-funded FP7 program IMAGE we have measured (1) the electrical resistivity of geothermal fluids and (2) physical properties of fluid saturated rock samples at simulated in-situ conditions. The permeability and electrical

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

    SciTech Connect

    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. 4 figures.

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

    NASA Astrophysics Data System (ADS)

    1994-03-01

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

  18. New topic of supercritical fluids: local activity coefficients of supercritical solvent and cosolvent around solute.

    PubMed

    Hou, Minqiang; Zhang, Xiaogang; Han, Buxing; Song, Jiyuan; Liu, Gang; Zhang, Zhaofu; Zhang, Jianling

    2008-03-14

    The study of inhomogeneity in supercritical fluids (SCFs) is of great importance. In this work, we propose the concept of local activity coefficients in supercritical (SC) solutions, which link thermodynamics and inhomogeneity in SC systems. The local activity coefficients of CO(2)+acetonitrile+phenol blue and CO(2)+acetic acid+phenol blue systems are investigated at 308.15 K in critical region and outside critical region. To do this, the local compositions of CO(2)+acetonitrile and CO(2)+acetic acid mixed solvents around phenol blue are first estimated using UV-visible spectroscopy. Then it is considered that there exist bulk phase and local phase around phenol blue in the systems. The activity coefficients of CO(2) and the cosolvents (acetonitrile or acetic acid) in bulk phase are calculated using Peng-Robinson equation of state. The local activity coefficients of CO(2) and the cosolvents are then calculated on the basis of thermodynamic principles. It is demonstrated that in the critical region the local activity coefficients differ from bulk activity coefficients significantly and are sensitive to pressure. This can explain many unusual phenomena in SC systems in critical region thermodynamically.

  19. New topic of supercritical fluids: Local activity coefficients of supercritical solvent and cosolvent around solute

    NASA Astrophysics Data System (ADS)

    Hou, Minqiang; Zhang, Xiaogang; Han, Buxing; Song, Jiyuan; Liu, Gang; Zhang, Zhaofu; Zhang, Jianling

    2008-03-01

    The study of inhomogeneity in supercritical fluids (SCFs) is of great importance. In this work, we propose the concept of local activity coefficients in supercritical (SC) solutions, which link thermodynamics and inhomogeneity in SC systems. The local activity coefficients of CO2+acetonitrile+phenol blue and CO2+aceticacid+phenol blue systems are investigated at 308.15K in critical region and outside critical region. To do this, the local compositions of CO2+acetonitrile and CO2+acetic acid mixed solvents around phenol blue are first estimated using UV-visible spectroscopy. Then it is considered that there exist bulk phase and local phase around phenol blue in the systems. The activity coefficients of CO2 and the cosolvents (acetonitrile or acetic acid) in bulk phase are calculated using Peng-Robinson equation of state. The local activity coefficients of CO2 and the cosolvents are then calculated on the basis of thermodynamic principles. It is demonstrated that in the critical region the local activity coefficients differ from bulk activity coefficients significantly and are sensitive to pressure. This can explain many unusual phenomena in SC systems in critical region thermodynamically.

  20. Selective chelation and extraction of lanthanides and actinides with supercritical fluids

    SciTech Connect

    Brauer, R.D.; Carleson, T.E.; Harrington, J.D.; Jean, F.; Jiang, H.; Lin, Y.; Wai, C.M.

    1994-01-01

    This report is made up of three independent papers: (1) Supercritical Fluid Extraction of Thorium and Uranium with Fluorinated Beta-Diketones and Tributyl Phosphate, (2) Supercritical Fluid Extraction of Lanthanides with Beta-Diketones and Mixed Ligands, and (3) A Group Contribution Method for Predicting the Solubility of Solid Organic Compounds in Supercritical Carbon Dioxide. Experimental data are presented demonstrating the successful extraction of thorium and uranium using fluorinated beta-diketones to form stable complexes that are extracted with supercritical carbon dioxide. The conditions for extracting the lanthanide ions from liquid and solid materials using supercritical carbon dioxide are presented. In addition, the Peng-Robison equation of state and thermodynamic equilibrium are used to predict the solubilities of organic solids in supercritical carbon dioxide from the sublimation pressure, critical properties, and a centric factor of the solid of interest.

  1. 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

  2. Nanoparticles synthesis using supercritical fluid technology - towards biomedical applications.

    PubMed

    Byrappa, K; Ohara, S; Adschiri, T

    2008-02-14

    Supercritical fluid (SCF) technology has become an important tool of materials processing in the last two decades. Supercritical CO(2) and H(2)O are extensively being used in the preparation of a great variety of nanomaterials. The greatest requirement in the application of nanomaterials is its size and morphology control, which determine the application potential of the nanoparticles, as their properties vary significantly with size. Although significance of SCF technology has been described earlier by various authors, the importance of this technology for the fabrication of inorganic and hybrid nanomaterials in biomedical applications has not been discussed thoroughly. This review presents the nanomaterial preparation systematically using SCF technology with reference to the processing of biomedical materials. The basic principles of each one of the processes have been described in detail giving their merits and perspectives. The actual experimental data and results have been discussed in detail with respect to the selected nanomaterials for biomedical applications. The SCF synthesis of nanoparticles like phosphors, magnetic materials, carbon nanotubes, etc. have been discussed as they have potential applications in bio-imaging, hyperthermia, cancer therapy, neutron capture therapy, targeted drug delivery systems and so on. The more recent approach towards the in situ surface modification, dispersibility, single nanocrystal formation, and morphology control of the nanoparticles has been discussed in detail.

  3. Operation and performance of the Supercritical Fluids Reactor (SFR)

    SciTech Connect

    Hanush, R.G.; Rice, S.F.; Hunter, T.B.; Aiken, J.D.

    1995-11-01

    The Supercritical Fluids Reactor (SFR) at Sandia National Laboratories, CA has been developed to examine and solve engineering, process, and fundamental chemistry issues regarding the development of supercritical water oxidation (SCWO). This report details the experimental apparatus, procedures, analytical methods used in these experiments, and performance characteristics of the reactor. The apparatus consists of pressurization, feed, preheat, reactor, cool down, and separation subsystems with ancillary control and data acquisition hardware and software. Its operating range is from 375 - 650{degrees} at 3250 - 6300 psi with resident times from 0.09 to 250 seconds. Procedures required for experimental operations are described. They include maintenance procedures conducted between experiments, optical alignment for acquisition of spectroscopic data, setup of the experiment, reactor start up, experimental operations, and shutdown of apparatus. Analytical methods used are Total Organic Carbon analysis, Gas Chromatography, ion probes, pH probes, turbidity measurements and in situ Raman spectroscopy. Experiments conducted that verify the accuracy of measurement and sampling methods are described.

  4. Supercritical fluid chromatography for the separation of isoflavones.

    PubMed

    Ganzera, Markus

    2015-03-25

    The first protocol for the analysis of isoflavones by supercritical fluid chromatography is reported. Optimum results were obtained on an Acquity UPC(2) BEH 1.7 μm column, using a solvent gradient of supercritical carbon dioxide and methanol (with phosphoric acid as additive) for elution. The method enables the baseline separation of nine isoflavones (aglyca and glycosides) in 8 min, and is suitable for their quantitative determination in dietary supplements containing soy (Glycine max), red glover (Trifolium pratense) and kudzu (Pueraria lobata). Method validation confirmed that the assay is selective, linear (R(2)≥0.9994), accurate (recovery rates from 97.6 to 102.4%), as well as precise on the short- and long-term level (intra-day precision ≤2.1%), and shows an on-column detection limit of 0.2 ng and below. This, together with an excellent performance shown in the analysis of real samples, indicates that SFC is well suited for the fast and accurate determination of isoflavones in complex matrices. Disadvantages compared to the established approaches were not observed, so that SFC has to be considered in this case as an (at least) equivalent analytical alternative.

  5. Diffusion-controlled reactions in supercritical CHF[sub 3] and CO[sub 2]/acetonitrile mixtures

    SciTech Connect

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

    1993-10-20

    We present results of the triplet-triplet annihilation (TTA) process of benzophenone (Ph[sub 2]C = O) and the self-termination reaction of benzyl radical (PhCH[sub 2]) to investigate the possibility of diffusion-controlled processes being hindered or enhanced in supercritical fluids (SCFs) or fluid mixtures. However, both reactions occur essentially at the diffusion-control limit in supercritical fluoroform (CHF[sub 3]) and carbon dioxide (CO[sub 2]) doped with 1 mol % acetonitrile (CH[sub 3]CN) when spin statistical factors are taken into account. The reaction kinetics were measured by laser flash photolysis at various pressures above the critical pressure along three isotherms. This study corroborates our earlier report of these reactions in supercritical CO[sub 2] and ethane (C[sub 2]H[sub 6]). In all of the fluids and fluid mixture, the locally higher density of the solvent around the solutes in no way enhances or slows the bimolecular annihilation or termination reaction. In addition, there is no evidence of enhanced solute-solute interaction. Finally, we studied the photocleavage of dibenzyl ketone (DBK) and the subsequent decarbonylation of the phenylacetyl radical (PhCH[sub 2]CO) and did not observe any enhanced cage effects or anomalous behavior due to the increased local density. 54 refs., 6 figs.

  6. Processing energetic materials with supercritical fluid precipitation techniques

    NASA Astrophysics Data System (ADS)

    Essel, Jonathan

    Research has shown that nano-sized particles of explosives have a reduced sensitivity to impact and shock. Nano-sized energetic particles have also shown promise in improving the performance of propellants and explosives. Therefore, a method to produce nano-sized explosive particles could be ideal for sensitivity and performance reasons. Supercritical fluid precipitation has been shown to produce nano-sized explosive particles effectively. This research explores the feasibility of processing energetic materials using three different supercritical fluid precipitation techniques. The first technique is called the Rapid Expansion of a Supercritical Solution (RESS). The RESS process dissolves a solute in a supercritical fluid and then rapidly expands the resulting solution through a nozzle to produce small (nano-sized) and uniform particles from a high degree of supersaturation. The second technique is the Rapid Expansion of a Supercritical Solution into a Liquid Solvent (RESOLV) Process. This process is similar to the RESS process except the supercritical solution is expanded into a liquid and dispersant solution to reduce particle agglomeration and to reduce the size of the particles further. The final technique investigated is the Rapid Expansion of a Supercritical Solution with a Nonsolute (RESS-N) process in which the precipitating solute is used to encapsulate or coat a nonsoluble substance by heterogeneous nucleation. This works takes both a theoretical an empirical approach. On the theoretical side, a numerical code that accounts for nucleation and condensation in the RESS process was written in FORTRAN to predict how altering pre-expansion pressures and pre-expansion temperatures in the RESS process could affect the final particle size of the produced RDX. It was determined that pre-expansion temperature had a marginal impact on final particle size but higher pre-expansion pressures were beneficial in forming smaller particles. Also, a software program called

  7. Structural changes in supercritical fluids at high pressures

    NASA Astrophysics Data System (ADS)

    Santoro, Mario; Gorelli, Federico A.

    2008-06-01

    The structure of an archetypal model simple fluid system as argon has been investigated by x-ray diffraction at high pressures and room and high temperatures. Despite the markedly supercritical conditions (T=2 4Tc,P>102Pc) , the structure factor S(Q) is very similar, close to the melting line, to that observed in the liquid phase, thereby assessing a liquidlike structure with high atomic correlation, as proposed in a recent inelastic experiment. On the other hand, the S(Q) continuously changes upon approaching the extrapolation of the liquid-gas coexistence line in the (P/Pc,T/Tc) plane, ultimately exhibiting low atomic correlation, which reasonably indicates intermediate character between liquid and gas. The analysis of the S(Q) s based on the hard-sphere model shows that the changes are driven by the decrease in the packing fraction and the increase in the nearest-neighbor distance with decreasing pressure.

  8. Comprehensive Review of Applicable Supercritical Fluid Extraction Research

    SciTech Connect

    Harvey, Scott; Wright, Cherylyn W.; Wright, Bob W.

    2001-09-10

    This comprehensive supercritical fluid extraction (SFE) literature review is divided into three major sections. The first section describes the electronic literature search details including the abstract service used and the different topics searched. This section also contains an overview of the seven search topics that yielded relevant references along with a brief synopsis of the most significant literature citations. These seven groupings are (1) chemical warfare agents; (2) explosives; (3) hazardous chemicals; (4) poisons, toxins and mycotoxins; (5) toxic (lethal) chemical and toxicants; (6) pesticides in soil; and (7) pesticides from plant and animal tissues. The second section contains tables of each of these groupings. Each of the seven tables contains entries for individual literature citations listed along with the specific compounds or compound classes that are addressed. The third section refers to the abstracts used in the literature search.

  9. PAH desorption from river floodplain soils using supercritical fluid extraction.

    PubMed

    Yang, Yi; Cajthaml, Tomás; Hofmann, Thilo

    2008-12-01

    Sequential supercritical fluid extraction (SFE) was performed in order to estimate desorption of PAHs from river floodplain soils which contain coal and coal-derived particles. Original soils, soils' light fractions (rho<2 g cm(-3)), and <63 microm fractions were studied for PAHs' desorption kinetics. Desorption data were successfully described using a two-site model. Desorption rate constants were one order of magnitude lower than those of "slow" and "very slow" desorption rates from other studies. This suggests very slow and extremely slow desorption. Estimated time scales releasing 99% of total extractable contaminants ranged from decades for 2-4-ring PAHs and hundreds of years for 5-6-ring PAHs. We demonstrate that, despite high soil PAH concentrations which are due to coal and coal-derived particles, the general environmental risk is reduced by the very slow and extremely slow desorption rates.

  10. Enantiomeric composition studies in Lavandula species using supercritical fluids.

    PubMed

    Flores, Gema; Blanch, Gracia Patricia; Ruiz del Castillo, Maria Luisa; Herraiz, Marta

    2005-11-01

    Characteristic aroma compounds in plants and essential oils of Lavandula from different varieties were examined. The study of the qualitative and quantitative composition of the major volatile components was faced by developing a method based on the use of supercritical fluid extraction-GC-MS (SFE-GC-MS). The optimization of a variety of parameters affecting SFE extraction enabled RSDs from three replicates lower than 2% to be achieved. Equally, recoveries of up to 59% were obtained by applying the proposed method. The use of multidimensional GC was necessary to enantiomerically resolve the target compounds. The obtained results showed enantiomeric purities >90% for all studied compounds in all varieties considered, proving the natural invariability of the enantiomeric composition of the compounds of interest. This information can be useful in authenticity studies as well as in selecting natural sources of enantiomerically pure compounds.

  11. Enantioselective supercritical fluid chromatography using ristocetin A chiral stationary phases.

    PubMed

    Svensson, L A; Owens, P K

    2000-06-01

    Racemic mixtures of five acidic drugs have been successfully separated by supercritical fluid chromatography (SFC) using macrocyclic antibiotic chiral stationary phases (CSPs). A ristocetin A CSP has been prepared 'in-house' and effectively applied in packed capillary SFC to separate the enantiomers of dichlorprop (R(s) = 1.4), ketoprofen (R(s) = 0.9) and warfarin (R(s) = 0.9). The commercial ristocetin A CSP (Chirobiotic R) was subsequently studied in packed column SFC with similar results where the enantiomers of warfarin (R(s) = 2.2), coumachlor (R(s) = 2.5) and thalidomide (R(s) = 0.6) were separated. Interestingly, differences were observed between the two differently immobilised CSPs where the enantiomers of dichlorprop and ketoprofen, which were separated on the 'in-house' CSP, could not be separated on the commercial phase.

  12. Volume-energy parameters for heat transfer to supercritical fluids

    NASA Technical Reports Server (NTRS)

    Kumakawa, A.; Niino, M.; Hendricks, R. C.; Giarratano, P. J.; Arp, V. D.

    1986-01-01

    Reduced Nusselt numbers of supercritical fluids from different sources were grouped by several volume-energy parameters. A modified bulk expansion parameter was introduced based on a comparative analysis of data scatter. Heat transfer experiments on liquefied methane were conducted under near-critical conditions in order to confirm the usefulness of the parameters. It was experimentally revealed that heat transfer characteristics of near-critical methane are similar to those of hydrogen. It was shown that the modified bulk expansion parameter and the Gibbs-energy parameter grouped the heat transfer data of hydrogen, oxygen and methane including the present data on near-critical methane. It was also indicated that the effects of surface roughness on heat transfer were very important in grouping the data of high Reynolds numbers.

  13. Supercritical fluid extraction of plant flavors and fragrances.

    PubMed

    Capuzzo, Andrea; Maffei, Massimo E; Occhipinti, Andrea

    2013-06-19

    Supercritical fluid extraction (SFE) of plant material with solvents like CO₂, propane, butane, or ethylene is a topic of growing interest. SFE allows the processing of plant material at low temperatures, hence limiting thermal degradation, and avoids the use of toxic solvents. Although today SFE is mainly used for decaffeination of coffee and tea as well as production of hop extracts on a large scale, there is also a growing interest in this extraction method for other industrial applications operating at different scales. In this review we update the literature data on SFE technology, with particular reference to flavors and fragrance, by comparing traditional extraction techniques of some industrial medicinal and aromatic crops with SFE. Moreover, we describe the biological activity of SFE extracts by describing their insecticidal, acaricidal, antimycotic, antimicrobial, cytotoxic and antioxidant properties. Finally, we discuss the process modelling, mass-transfer mechanisms, kinetics parameters and thermodynamic by giving an overview of SFE potential in the flavors and fragrances arena.

  14. 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 ...

  15. SUPERCRITICAL FLUID EXTRACTION OF POLYCYCLIC AROMATIC HYDROCARBON MIXTURES FROM CONTAMINATED SOILS

    EPA Science Inventory

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

  16. Supercritical Fluid Extraction and Chromatography Using a Lee Scientific Series 600 SFE/SFC System

    DTIC Science & Technology

    1992-05-01

    Dioxide and Ethylene. Journal of Chemical Engineering Data , 26:47. Lee, M.L. and K.E. Markides 1987 Chromatography with Supercritical Fluids. Science...Publishers, Stoneham, MA. McHugh, M.A., and M.E. Paulaitis 1980 Solid Solubilities of Naphthalene and Biphenyle in Supercritical Carbon Dioxide. Journal of Chemical Engineering Data , 25

  17. Silica-promoted Diels-Alder reactions in carbon dioxide from gaseous to supercritical conditions

    SciTech Connect

    Weinstein, R.D.; Renslo, A.R.; Danheiser, R.L.; Tester, J.W.

    1999-04-15

    Amorphous fumed silica (SiO{sub 2}) was shown to increase yields and selectivities of several Diels-Alder reactions in gaseous and supercritical CO{sub 2}. Pressure effects on the Diels-Alder reaction were explored using methyl vinyl ketone and penta-1,3-diene at 80 C. The selectivity of the reaction was not affected by pressure/density. As pressure was increased, the yield decreased. At the reaction temperature, adsorption isotherms at various pressures were obtained for the reactants and the Diels-Alder adduct. As expected when pressure is increased, the ratio of the amount of reactants adsorbed to the amount of reactants in the fluid phase decreases, thus causing the yield to decrease. The Langmuir adsorption model fit the adsorption data. The Langmuir equilibrium partitioning constants all decreased with increasing pressure. The effect of temperature on adsorption was experimentally determined and traditional heats of adsorption were calculated. However, since supercritical CO{sub 2} is a highly compressible fluid, it is logical to examine the effect of temperature at constant density. In this case, entropies of adsorption were obtained. The thermodynamic properties that influence the real enthalpy and entropy of adsorption were derived. Methods of doping the silica and improving yields and selectivities were also explored.

  18. Practical development of continuous supercritical fluid process using high pressure and high temperature micromixer

    NASA Astrophysics Data System (ADS)

    Kawasaki, Shin-Ichiro; Sue, Kiwamu; Ookawara, Ryuto; Wakashima, Yuichiro; Suzuki, Akira

    2015-12-01

    In the synthesis of metal oxide fine particles by continuous supercritical hydrothermal method, the particle characteristics are greatly affected by not only the reaction conditions (temperature, pressure, residence time, concentration, etc.), but also the heating rate from ambient to reaction temperature. Therefore, the heating method by direct mixing of starting solution at room temperature with supercritical water is a key technology for the particle production having smaller size and narrow distribution. In this paper, mixing engineering study through comparison between conventional T-shaped mixers and recently developed swirl mixers was carried out in the hydrothermal synthesis of NiO nanoparticles from Ni(NO3)2 aqueous solution at 400 °C and 30 MPa. Inner diameter in the mixers and total flow rates were varied. Furthermore, the heating rate was calculated by computational fluid dynamics (CFD) simulation. Relationship between the heating rate and the average particle size were discussed. It was clarified that the miniaturization of mixer inner diameter and the use of the swirl flow were effective for improving mixing performance and contributed to produce small and narrow distribution particle under same experimental condition of flow rate, temperature, pressure, residence time, and concentration of the starting materials. We have focused the mixer optimization due to a difference in fluid viscosity.

  19. Cryogenic fluid dynamics of pressure swirl injectors at supercritical conditions

    NASA Astrophysics Data System (ADS)

    Zong, Nan; Yang, Vigor

    2008-05-01

    A comprehensive numerical analysis has been conducted to explore the development of liquid-oxygen (LOX) flow in pressure swirl injectors operating at supercritical pressures. The model is based on full-conservation laws and accommodates real-fluid thermodynamics and transport phenomena over the entire range of fluid states of concern. Three different flow regimes with distinct characteristics, the developing, stationary, and accelerating regimes, are identified within the injector. Results are compared to predictions from classical hydrodynamics theories to acquire direct insight into the flow physics involved. In addition, various flow dynamics are investigated by means of the spectral and proper-orthogonal-decomposition techniques. The interactions between the hydrodynamic instabilities in the LOX film and acoustic oscillations in the gaseous core are clearly observed and studied. The influences of flow conditions (mass flowrate, swirl strength of the injected fluid, and ambient pressure) and injector geometry (injector length and tangential entry location) on the injector flow behavior are systematically characterized in terms of the LOX film thickness and spreading angle. The axial and azimuthal momentum exchange and loss mechanisms are also examined.

  20. Functional properties of spice extracts obtained via supercritical fluid extraction.

    PubMed

    Leal, Patrícia F; Braga, Mara E M; Sato, Daisy N; Carvalho, João E; Marques, Marcia O M; Meireles, M Angela A

    2003-04-23

    In the present study the antioxidant, anticancer, and antimycobacterial activities of extracts from ginger (Zingiber officinale Roscoe), rosemary (Rosmarinus officinalis L.), and turmeric (Curcuma longa L.) were evaluated. The extracts were obtained using supercritical CO(2) with and without ethanol and/or isopropyl alcohol as cosolvent. The extracts' antioxidant power was assessed using the reaction between beta-carotene and linolenic acid, the antimycobacterial activity against M. tuberculosis was measured by the MABA test, and their anticancer action was tested against nine human cancer ancestries: lung, breast, breast resistant, melanoma, colon, prostate, leukemia, and kidney. The rosemary extracts exhibited the strongest antioxidant and the lowest antimycobacterial activities. Turmeric extracts showed the greatest antimycobacterial activity. Ginger and turmeric extracts showed selective anticancer activities.

  1. Supercritical (and Subcritical) Fluid Behavior and Modeling: Drops, Streams, Shear and Mixing Layers, Jets and Sprays

    NASA Technical Reports Server (NTRS)

    Bellan, J.

    1999-01-01

    A critical review of recent investigations in the real of supercritical (and subcritical) fluid behavior is presented with the goal of obtaining a perspective on the peculiarities of high pressure observations.

  2. Supercritical fluid extraction of sulphamethazine and its metabolites from meat tissues.

    PubMed

    Din, N; Bartle, K D; Clifford, A A; McCormack, A; Castle, L

    1997-01-01

    An investigation is reported of factors affecting the supercritical fluid extraction of sulphamethazine and five of its metabolites from spiked meat (swine liver and kidney). The addition of the polar modifier methanol to the carbon dioxide extracting fluid was found to generally enhance recoveries under subcritical and supercritical conditions. Recoveries of the ionic metabolites were increased by up to 72% when employing tetramethylammonium hydroxide for ion pairing in situ with the supercritical fluid extraction. Extraction efficiency is demonstrated to be dependent on the matrix. Extractions of the less polar compounds from the kidney are more successful than from the liver, which corresponds to their partitioning into the supercritical fluid and/or the greater fraction of highly extractable fatty materials. The kidney was more retentive than liver for the relatively more polar compounds, which suggests that the liver offers a less polar environment under the same extraction conditions.

  3. Optimized Supercritical Fluid Refrigeration Cycle for Venus Lander Payload Electronics Active Cooling

    NASA Astrophysics Data System (ADS)

    Anderson, K. R.; McNamara, C.; Gatti, A.; Guererro, J.

    2017-05-01

    This paper presents an active electronics thermal control system allowing for continuous operation of instruments for Venus lander missions. The thermal control system uses supercritical fluids cascaded and optimized for minimum compressor power.

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

    PubMed

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

    2013-10-01

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

  5. Supercritical fluid precipitation of recombinant human immunoglobulin from aqueous solutions.

    PubMed

    Nesta, D P; Elliott, J S; Warr, J P

    2000-02-20

    Supercritical carbon dioxide was used as an antisolvent for producing recombinant human immunoglobulin G (rIgG) particulate powders. Liquid carbon dioxide (CO(2)) was premixed with ethanol to create a single-phase, modified supercritical fluid (SCF). The modified SCF was then vigorously mixed with a pharmaceutically acceptable, aqueous formulation of rIgG, and the mixture was immediately atomized into a pressurized vessel where rapid expansion of the modified SCF extracted the aqueous phase, resulting in precipitation of the protein powder. The process was reproducible, and resulting powder products were characterized by their aqueous solubilities, and the spectroscopic profile, molecular integrity, and antigen binding activity of the individual soluble fractions. Molecular integrity was assessed via size-exclusion high-performance liquid chromatography (SEC), whereas antigen binding activity was determined using an enzyme-linked immunosorbent assay (ELISA). Attempts to characterize particle size and morphology were confounded due to the extremely deliquescent nature of the powders, causing them to absorb moisture rapidly and become gummy. Operational conditions were optimized to a point which yielded powders that were completely soluble, and had ultraviolet (UV) spectroscopic and SEC profiles indistinguishable from those of the reference standard starting solution from which the powders were derived. Antigen binding activities of the powders, however, were

  6. Integral equations for the microstructures of supercritical fluids

    SciTech Connect

    Lee, L.L.; Cochran, H.D.

    1993-11-01

    Molecular interactions and molecular distributions are at the heart of the supercritical behavior of fluid mixtures. The distributions, i.e. structure, can be obtained through any of the three routes: (1) scattering experiments, (2) Monte Carlo or molecular dynamics simulation, and (3) integral equations that govern the relation between the molecular interactions u(r) and the probability distributions g{sub ij}(r). Most integral equations are based on the Ornstein-Zernike relation connecting the total correlation to the direct correlation. The OZ relation requires a {open_quotes}closure{close_quotes} equation to be solvable. Thus the Percus-Yevick, hypernetted chain, and mean spherical approximations have been proposed. The authors outline the numerical methods of solution for these integral equations, including the Picard, Labik-Gillan, and Baxter methods. Solution of these equations yields the solvent-solute, solvent-solvent, and solute-solute pair correlation functions (pcf`s). Interestingly, these pcf`s exhibit characteristical signatures for supercritical mixtures that are classified as {open_quotes}attractive{close_quotes} or {open_quotes}repulsive{close_quotes} in nature. Close to the critical locus, the pcf shows enhanced first neighbor peaks with concomitant long-range build-ups (sic attractive behavior) or reduced first peaks plus long-range depletion (sic repulsive behavior) of neighbors. For ternary mixtures with entrainers, there are synergistic effects between solvent and cosolvent, or solute and cosolute. These are also detectable on the distribution function level. The thermodynamic consequences are deciphered through the Kirkwood-Buff fluctuation integrals (G{sub ij}) and their matrix inverses: the direct correlation function integrals (DCFI`s). These quantities connect the correlation functions to the chemical potential derivatives (macroscopic variables) thus acting as {open_quotes}bridges{close_quotes} between the two Weltanschauungen.

  7. Supercritical fluid extraction of particulate and adsorbent materials. Report for February 1984-January 1985

    SciTech Connect

    Wright, B.W.; Smith, R.D.

    1986-03-01

    The report is a summary of work performed by PNL on the extraction of semivolatile organic materials (SVOCs), for example, polynuclear aromatic compounds, from various adsorbents and environmental matrices, using supercritical fluids (SCFs) as extractants. The results of the work show that supercritical fluids are effective extractants for many SVOCs, and are often competitive with conventional Soxhlet extraction. Advantages of SCFs over conventional methods include higher extraction efficiency, more rapid extraction, and reduced decomposition of thermally labile compounds.

  8. Analysis of semi-volatile organic compounds using supercritical fluid methodologies

    SciTech Connect

    Wright, B.W.; Chess, E.K.; Yonker, C.R.; Smith, R.D.

    1985-06-01

    This study demonstrates the applicability of supercritical fluid chromatography (SFC) and analytical supercritical fluid extraction (SFE) for the analysis of semi-volatile compounds. Mixtures of nitro-polycyclic aromatic hydrocarbons that are not ammenable to gas chromatography were separated using SFC with tentative compound identifications made by SFC-MS. Comparisons of analytical SFE of XAD-2 resin and NBS Urban Dust (SRM 1649) to conventional Soxhlet extraction are also discussed.

  9. Precipitation of microsize organic particles from supercritical fluids

    SciTech Connect

    Chang, C.J.; Randolph, A.D. )

    1989-11-01

    The precipitation of organic particles from supercritical fluids (SF) by expansion (SFX) has become an interesting alternative to milling without thermal decomposition. The authors report how through the rapid expansion process, a dramatic change of the solute supersaturation ratio was created causing subsequent precipitation with a narrow particle-size distribution. It was found that {beta}-carotene precipitates from SF ethylene and ethane have the feed material crystallinity. However, SF CO{sub 2} reacted with {beta}-carotene and did not give characteristic {beta}-carotene X-ray spectra. The mean particle sizes of these precipitates were in the submicron range (ca 0.3 {mu}m). Increased solubility was obtained by addition of toluene as cosolvent in SF ethylene. It was found that the mean size of {beta}-carotene particles, generally remained unchanged if the toluene concentration was less than 1 1/2 mol %. The SFX process appears to be in a single fluid phase when up to 1 1/2 mol % toluene cosolvent is used.

  10. Supercritical fluid thermodynamics for coal processing. Final report, September 15, 1988--September 14, 1991

    SciTech Connect

    van Swol, F.; Eckert, C.A.

    1988-09-15

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

  11. Fundamental kinetics and mechanistic pathways for oxidation reactions in supercritical water

    NASA Technical Reports Server (NTRS)

    Webley, Paul A.; Tester, Jefferson W.

    1988-01-01

    Oxidation of the products of human metabolism in supercritical water has been shown to be an efficient way to accomplish the on-board water/waste recycling in future long-term space flights. Studies of the oxidation kinetics of methane to carbon dioxide in supercritical water are presented in this paper in order to enhance the fundamental understanding of the oxidation of human waste compounds in supercritical water. It is concluded that, although the elementary reaction models remain the best hope for simulating oxidation in supercritical water, several modifications to existing mechanisms need to be made to account for the role of water in the reaction mechanism.

  12. Fundamental kinetics and mechanistic pathways for oxidation reactions in supercritical water

    NASA Technical Reports Server (NTRS)

    Webley, Paul A.; Tester, Jefferson W.

    1988-01-01

    Oxidation of the products of human metabolism in supercritical water has been shown to be an efficient way to accomplish the on-board water/waste recycling in future long-term space flights. Studies of the oxidation kinetics of methane to carbon dioxide in supercritical water are presented in this paper in order to enhance the fundamental understanding of the oxidation of human waste compounds in supercritical water. It is concluded that, although the elementary reaction models remain the best hope for simulating oxidation in supercritical water, several modifications to existing mechanisms need to be made to account for the role of water in the reaction mechanism.

  13. Micro-scale methods for characterization of supercritical fluid extraction and fractionation processes. [Trichothecene mycotoxins

    SciTech Connect

    Smith, R.D.; Wright, B.W.; Udseth, H.R.

    1984-11-01

    The development of new supercritical fluid extraction and fractionation processes requires exploration of wide ranges of fluid temperature and pressure. As the fluid phase becomes more complex, conventional methods become inadequate unless augmented by increasingly sophisticated analytical instrumentation. In addition to chemical complexity, analysis is often hindered by characteristics of the analyte which makes supercritical fluid extraction desirable (e.g., thermal lability). Micro-scale methods are described which address these problems while providing the additional benefits of speed, reduced cost, greatly reduced sample and solvent consumption, and safety. Techniques are described in which the fluid phase from micro-scale (0.005 to 5 ml) high pressure cells is sampled and analyzed in either continuous or periodic modes. The methods developed in our laboratory utilize capillary supercritical fluid chromatography and direct fluid injection-mass spectrometry (or their combination), in addition to conventional analytical techniques, for the characterization of complex supercritical fluid mixtures. The application of these methods to various extraction and fractionation processes involving CO/sub 2/ and NH/sub 3/, solubility studies of simple and complex mixtures, and the study of rapid chemical processes in supercritical water is described. New methods for the automated examination of extraction processes using capillary chromatography are also described and their initial application illustrated.

  14. Large-eddy simulation of supercritical fluid flow and combustion

    NASA Astrophysics Data System (ADS)

    Huo, Hongfa

    The present study focuses on the modeling and simulation of injection, mixing, and combustion of real fluids at supercritical conditions. The objectives of the study are: (1) to establish a unified theoretical framework that can be used to study the turbulent combustion of real fluids; (2) to implement the theoretical framework and conduct numerical studies with the aim of improving the understanding of the flow and combustion dynamics at conditions representative of contemporary liquid-propellant rocket engine operation; (3) to identify the key design parameters and the flow variables which dictate the dynamics characteristics of swirl- and shear- coaxial injectors. The theoretical and numerical framework is validated by simulating the Sandia Flame D. The calculated axial and radial profiles of velocity, temperature, and mass fractions of major species are in reasonably good agreement with the experimental measurements. The conditionally averaged mass fraction profiles agree very well with the experimental results at different axial locations. The validated model is first employed to examine the flow dynamics of liquid oxygen in a pressure swirl injector at supercritical conditions. Emphasis is placed on analyzing the effects of external excitations on the dynamic response of the injector. The high-frequency fluctuations do not significantly affect the flow field as they are dissipated shortly after being introduced into the flow. However, the lower-frequency fluctuations are amplified by the flow. As a result, the film thickness and the spreading angle at the nozzle exit fluctuate strongly for low-frequency external excitations. The combustion of gaseous oxygen/gaseous hydrogen in a high-pressure combustion chamber for a shear coaxial injector is simulated to assess the accuracy and the credibility of the computer program when applied to a sub-scale model of a combustor. The predicted heat flux profile is compared with the experimental and numerical studies. The

  15. Dehydroxyl effect of Sn-doped silicon oxide resistance random access memory with supercritical CO2 fluid treatment

    NASA Astrophysics Data System (ADS)

    Tsai, Tsung-Ming; Chang, Kuan-Chang; Chang, Ting-Chang; Syu, Yong-En; Liao, Kuo-Hsiao; Tseng, Bae-Heng; Sze, Simon M.

    2012-09-01

    The tin-doped can supply conduction path to induce resistance switching behavior. However, the defect of tin-doped silicon oxide (Sn:SiOx) increased the extra leakage path lead to power consumption and joule heating degradation. In the study, supercritical CO2 fluids treatment was used to improve resistive switching property. The current conduction of high resistant state in post-treated Sn:SiOx film was transferred to Schottky emission from Frenkel-Poole due to the passivation effect. The molecular reaction model is proposed that the defect was passivated through dehydroxyl effect of supercritical fluid technology, verified by material analyses of x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy.

  16. BEHAVIOR OF EXCESS ELECTRONS IN SUPERCRITICAL FLUIDS - ELECTRON ATTACHMENT

    SciTech Connect

    NISHIKAWA,M.; HOLROYD,R.A.; ITOH,K.

    1999-07-01

    The behavior of excess electrons in supercritical ethane was investigated by measuring mobility and reaction rates. Mobilities were measured by means of a time-of-flight method at 306--320K as a function of pressure. Mobility values decreased at all temperatures with increasing pressure, but showed a small minimum or a shoulder at the pressure where the compressibility {chi}{sub T} has a peak. Electron attachment to CO{sub 2}, NO, pyrimidine and C{sub 2}F{sub 4} over the same temperature range was studied as a function of pressure. Both attachment rate constants k{sub a} for NO and C{sub 2}F{sub 4}, and equilibrium constants K({double_bond}k{sub a}/k{sub d}) for CO{sub 2} and pyrimidine increased sharply at pressures of {chi}{sub T} peaks. Activation volumes V{sub a}* and reaction volumes {Delta}V{sub r} are very large and negative in the critical region. The volume change is mainly due to electrostriction around ions formed. The results are compared to volume changes predicted by, a compressible continuum model.

  17. [Study on ingredients of essential oils of Curcuma wenyujin extracted by supercritical-CO2 fluid extraction and steam distillation].

    PubMed

    Li, Hong-Xia; Yang, Tie-Yao; Yang, Tian-Liang; Ge, Fa-Huan; Pan, Wei-San; Yang, Xing-Gang; Chen, Ji-Min

    2006-09-01

    To compare the ingredients of essential oils of Curcuma wenyujin extracted by supercritical-CO2 fluid extraction and by steam distillation. GC-MS was applied in this experiment. The ingredients and physical and chemical properties of essential oils of C. wenyujin extracted by supercritical-CO2 fluid extraction and by steam distillation are similar. Supercritical-CO2 fluid extraction is better than steam distillation in extraction time, power consumption, recovery and purity.

  18. Supercritical-Fluid Extraction of Oil From Tar Sands

    NASA Technical Reports Server (NTRS)

    Compton, L. E.

    1982-01-01

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

  19. Supercritical-Fluid Extraction of Oil From Tar Sands

    NASA Technical Reports Server (NTRS)

    Compton, L. E.

    1982-01-01

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

  20. Supercritical fluid extraction of lycopene from tomato processing byproducts.

    PubMed

    Rozzi, N L; Singh, R K; Vierling, R A; Watkins, B A

    2002-04-24

    Tomato seeds and skins acquired from the byproduct of a local tomato processing facility were studied for supercritical fluid extraction (SFE) of phytochemicals. The extracts were analyzed for lycopene, beta-carotene, alpha-carotene, alpha-tocopherol, gamma-tocopherol, and delta-tocopherol content using high-performance liquid chromatography-electrochemical detection and compared to a chemically extracted control. SFEs were carried out using CO(2) at seven temperatures (32-86 degrees C) and six pressures (13.78-48.26 MPa). The effect of CO(2) flow rate and volume also was investigated. The results indicated that the percentage of lycopene extracted increased with elevated temperature and pressure until a maximum recovery of 38.8% was reached at 86 degrees C and 34.47 MPa, after which the amount of lycopene extracted decreased. Conditions for the optimum extraction of lycopene from 3 g of raw material were determined to be 86 degrees C, 34.47 MPa, and 500 mL of CO(2) at a flow rate of 2.5 mL/min. These conditions resulted in the extraction of 61.0% of the lycopene (7.19 microg lycopene/g).

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

    SciTech Connect

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

    2014-06-01

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

  2. Supercritical fluid extraction of free amino acids from broccoli leaves.

    PubMed

    Arnáiz, E; Bernal, J; Martín, M T; Nozal, M J; Bernal, J L; Toribio, L

    2012-08-10

    The extraction of free amino acids (AAs) from broccoli leaves using supercritical fluid extraction (SFE) with CO(2) modified with methanol, is presented in this work. The effect of the different variables was studied, showing the percentage of methanol a strong influence on the extraction. The best results in terms of extraction yield were obtained at 250 bar, 70°C, 35% methanol as organic modifier, a flow rate of 2 mL/min, and 5 min and 30 min as static and dynamic extraction times, respectively. The extraction yield obtained with the SFE method was comparable to that obtained employing conventional solvent extraction with methanol-water (70:30) and minor than using water, but the relative proportion of the AAs in the extracts was very different. For example, the use of SFE allowed the enrichment in proline and glutamine of the extracts. The selected conditions were applied to obtain SFE extracts of broccoli leaves from different varieties (Naxos, Nubia, Marathon, Parthenon and Viola). The highest levels of AAs were found in the SFE extracts from the Nubia variety.

  3. Determination of adsorption isotherms in supercritical fluid chromatography.

    PubMed

    Enmark, Martin; Forssén, Patrik; Samuelsson, Jörgen; Fornstedt, Torgny

    2013-10-18

    In this study we will demonstrate the potential of modern integrated commercial analytical SFC-systems for rapid and reliable acquisition of thermodynamic data. This will be done by transferring the following adsorption isotherm determination methods from liquid chromatography (LC) to supercritical fluid chromatography (SFC): Elution by Characteristic Points (ECP), the Retention Time Method (RTM), the Inverse Method (IM) and the Perturbation Peak (PP) method. In order to transfer these methods to SFC in a reliable, reproducible way we will demonstrate that careful system verification using external sensors of mass flow, temperature and pressure are needed first. The adsorption isotherm data generated by the different methods were analyzed and compared and the adsorption isotherms ability to predict new experimental elution profiles was verified by comparing experiments with simulations. It was found that adsorption isotherm data determined based on elution profiles, i.e., ECP, IM and RTM, were able to accurately predict overloaded experimental elution profiles while the more tedious and time-consuming PP method, based on small injections on concentration plateaus, failed in doing so.

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

    PubMed

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

    2016-02-20

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

  5. Update on Area Production in Mixing of Supercritical Fluids

    NASA Technical Reports Server (NTRS)

    Okongo, Nora; Bellan, Josette

    2003-01-01

    The focus of this research is on supercritical C7H16/N2 and O2/H2 mixing layers undergoing transitions to turbulence. The C7H16/N2 system serves as a simplified model of hydrocarbon/air systems in gas-turbine and diesel engines; the O2/H2 system is representative of liquid rocket engines. One goal of this research is to identify ways of controlling area production to increase disintegration of fluids and enhance combustion in such engines. As used in this research, "area production" signifies the fractional rate of change of surface area oriented perpendicular to the mass-fraction gradient of a mixing layer. In the study, a database of transitional states obtained from direct numerical simulations of the aforementioned mixing layers was analyzed to investigate global layer characteristics, phenomena in regions of high density-gradient magnitude (HDGM), irreversible entropy production and its relationship to the HDGM regions, and mechanisms leading to area production.

  6. Supercritical fluid molecular spray thin films and fine powders

    DOEpatents

    Smith, Richard D.

    1988-01-01

    Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. The solvent is vaporized and pumped away. Solution pressure is varied to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solution temperature is varied in relation to formation of a two-phase system during expansion to control porosity of the film or powder. A wide variety of film textures and powder shapes are produced of both organic and inorganic compounds. Films are produced with regular textural feature dimensions of 1.0-2.0 .mu.m down to a range of 0.01 to 0.1 .mu.m. Powders are formed in very narrow size distributions, with average sizes in the range of 0.02 to 5 .mu.m.

  7. Supercritical fluid molecular spray film deposition and powder formation

    DOEpatents

    Smith, Richard D.

    1986-01-01

    Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. Upon expansion and supersonic interaction with background gases in the low pressure region, any clusters of solvent are broken up and the solvent is vaporized and pumped away. Solute concentration in the solution is varied primarily by varying solution pressure to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solvent clustering and solute nucleation are controlled by manipulating the rate of expansion of the solution and the pressure of the lower pressure region. Solution and low pressure region temperatures are also controlled.

  8. 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.

  9. Gene Delivery Nanoparticles Fabricated by Supercritical Fluid Extraction of Emulsions

    PubMed Central

    Mayo, Aaron S.; Ambati, Balamurali K.; Kompella, Uday B.

    2010-01-01

    Non-viral polymeric gene delivery systems offer increased protection from nuclease degradation, enhanced plasmid DNA (pDNA) uptake, and controlled dosing to sustain the duration of pDNA administration. Such gene delivery systems can be formulated from biocompatible and biodegradable polymers such as poly (d,l-lactic-co-glycolic) acid (PLGA). Experimental loading of hydrophilic macromolecules such as pDNA is low in polymeric particles. The study purpose was to develop a supercritical fluid extraction of emulsions (SFEE) process based on CO2 for preparing pEGFP-PLGA nanoparticles with high plasmid loading and loading efficiency. Another objective was to determine the efficacy of pFlt23k, an anti-angiogenic pDNA capable of inhibiting vascular endothelial growth factor (VEGF) secretion, following nanoparticle formation using the SFEE process. Results indicated that the SFEE process allows high actual loading of pDNA (19.7% w/w), high loading efficiency (> 98%), and low residual solvents (< 50 ppm), due to rapid particle formation from efficient solvent removal provided by the SFEE process. pFlt23K-PLGA nanoparticles were capable of in vitro transfection, significantly reducing secreted VEGF from human lung alveolar epithelial cells (A549) under normoxic and hypoxic conditions. pFlt23K-PLGA nanoparticles did not exhibit cytotoxicity and are of potential value in treating neovascular disorders wherein VEGF levels are elevated. PMID:20025945

  10. Supercritical fluid thermodynamics for coal processing: Quarterly progress report, September 15, 1988--December 31, 1988

    SciTech Connect

    Eckert, C.A.

    1988-01-01

    Because of their unusual solvating and mass transfer properties, supercritical fluids show potential for a variety of coal processing applications. To establish a database of coal model compound equilibria, this quarter we have measured the solubility of 5,6-dimethyl-benzimidazole and anthraquinone in supercritical butane. In addition, we have used fluorescence spectroscopy to study the nature of the intermolecular interactions in the systems of pyrene and naphthalene in supercritical CO/sub 2/, C/sub 2/H/sub 4/, and CF/sub 3/H. The spectroscopy measurements are being used to guide the development of an equation of state that can be used to predict the solubility behavior so systems can be designed for the processing of coal with supercritical fluids. 4 figs.

  11. Simultaneous deactivation and coating of porous silica particles for microcolumn supercritical fluid chromatography

    SciTech Connect

    Payne, K.M.; Tarbet, B.J.; Bradshaw, J.S.; Markides, K.E.; Lee, M.L. )

    1990-07-15

    A new method for the simultaneous deactivation and coating of porous silica particles for supercritical fluid chromatography (SFC) has been developed. This method is based on a dehydrocondensation reaction between polymeric silicon hydride reagents and the silanol groups on the surface of the particles. The procedure produces a less active surface than conventional silica packings, which results in less adsorption and improved peak shapes for polar analytes. In SFC, more polar analytes can be chromatographed without the need for mobile phase modifiers. Furthermore, the sensitive and universal flame ionization detector (FID) can be used, since modifiers are not necessary. To avoid splitting of the column effluent before FID detection, packed capillary columns were utilized in this study. The ability to use packed capillary columns for the analysis of polar compounds, while at the same time allowing the use of a wide range of detection methods, serves to expand the number of useful applications for packed column SFC.

  12. Purification method development for chiral separation in supercritical fluid chromatography with the solubilities in supercritical fluid chromatographic mobile phases.

    PubMed

    Gahm, Kyung H; Tan, Helming; Liu, Jodi; Barnhart, Wesley; Eschelbach, John; Notari, Steve; Thomas, Samuel; Semin, David; Cheetham, Janet

    2008-04-14

    A comprehensive approach was applied to develop a chiral purification method for an analyte that was found to be unusually difficult to scale-up in supercritical fluid chromatography (SFC). This was performed by studying major factors such as the solubility of an analyte in SFC mobile phases, impurity profiles, and cycle time. For this case study, the solubility in SFC mobile phase was measured by a packed column technique, coupled with a novel trapping mechanism to enhance measurement precision in SFC conditions. The solubility studies in SFC mobile phases suggested a couple of possible SFC mobile phases, in which the analyte would potentially be most soluble. The SFC methods were developed to purify a sample containing 15% of an impurity, after considering impurity profiles and cycle times of several potential methods in addition to SFC mobile phase solubility. An equal volume mixture of acetonitrile and ethanol was chosen for the final purification method, since this mixture demonstrated the relatively high SFC solubility among all solvent combinations with enhanced resolution between the analyte and the impurity as well as the shortest run time. The solubility of the compound was also determined in various organic solvents using a high throughput solubility screening system to better understand relative change of solubility from neat solution to SFC mobile phases.

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

    SciTech Connect

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

    2013-02-01

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

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

    SciTech Connect

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

    2013-07-01

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

  15. A Supercritical Fluid Chromatography/Tandem Mass Spectrometry Method for the Simultaneous Quantification of Metformin and Gliclazide in Human Plasma

    PubMed Central

    Agrawal, Y. K.; Gogoi, P. J.; Manna, K.; Bhatt, H. G.; Jain, V. K.

    2010-01-01

    Present study reports the development and validation of a simultaneous estimation of metformin and gliclazide in human plasma using supercritical fluid chromatography followed by tandem mass spectrometry. Acetonitrile:water (80:20) mixture was used as a mobile phase along with liquid CO2 in supercritical fluid chromatography and phenformin as an internal standard. The modified plasma samples were analyzed by electro-spray ionization method in selective reaction monitoring mode in tandem mass spectrometry. Supercritical fluid chromatographic separation was performed using nucleosil C18 containing column as a stationary phase. The separated products were identified by characteristic peaks and specific fragments peaks in tandem mass spectrometry as m/z 130 to 86 for metformin, m/z 324 to 110 for gliclazide and m/z 206 to 105 for phenformin. The present method was found linear in the concentration ranges of 6.0-3550 ng/ml and 7.5-7500 ng/ml for metformin and gliclazide, respectively. Pharmacokinetic study was performed after an oral administration of dispersible tablets containing 500 mg of metformin and 80 mg of gliclazide using same techniques. PMID:20582190

  16. Extraction and recovery of polycyclic aromatic hydrocarbons from environmental solids using supercritical fluids

    SciTech Connect

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

    1987-07-01

    The use of supercritical fluids for the extraction and recovery of polycyclic aromatic hydrocarbons (PAH) from environmental solids has been developed and tested by using urban dust, fly ash, and river sediment. Supercritical N/sub 2/O and 5% methanol modifier gave the best recoveries of PAH from all three samples when compared to supercritical CO/sub 2/ with 5% methanol, N/sub 2/O, CO/sub 2/, and ethane. Quantitative recovery of PAH from National Bureau of Standards SRM 1649 (urban dust) and of deuteriated PAH spikes (phenanthrene-d/sub 10/, pyrene-d/sub 10/, and perylene-d/sub 12/) from the river sediment was obtained with supercritical fluid extractions in as little as 30 min. In most cases, 30-60 min extractions of the river sediment and fly ash with supercritical N/sub 2/O/5% methanol gave better recovery of the deuteriated PAH spikes than the recoveries obtained by using 4 h of sonication or 8 h of Soxhlet extraction with either benzene or methylene chloride. Supercritical fluid extractions yield good PAH recoveries, require only small amounts of sample, minimize analyte concentration steps, and are simple and rapid to perform.

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

    DTIC Science & Technology

    2007-11-02

    Tucker, manuscript in preparation. “Examination of Nonequilibrium Solvent Effects on an SN2 Reaction in Supercritical Water,” R. Behera, B...DATES COVERED Final: 7/1/99 - 12/31/02 4. TITLE AND SUBTITLE Development of theoretical methods for predicting solvent effects on reactions ...computational methods for predicting how reaction rate constants will vary with thermodynamic condition in supercritical water (SCW). Towards this

  18. Thermal induced flow oscillations in heat exchangers for supercritical fluids

    NASA Technical Reports Server (NTRS)

    Friedly, J. C.; Manganaro, J. L.; Krueger, P. G.

    1972-01-01

    Analytical model has been developed to predict possible unstable behavior in supercritical heat exchangers. From complete model, greatly simplified stability criterion is derived. As result of this criterion, stability of heat exchanger system can be predicted in advance.

  19. 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.

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

    PubMed

    Asiaee, Alireza; Benjamin, Kenneth M

    2016-08-28

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

  1. Supercritical Fluid Particle Design of DPI Formulations (Review).

    PubMed

    Sun, Yongda

    2015-01-01

    Pulmonary drug delivery (PDD) with dry powder inhaler (DPI) has rapidly developed for the treatment of local and systemic diseases, which targets the delivery of fine drug particles into the deep lung surface by combining technologies of fine drug particle formulation, small dose packaging and suitable inhaler, where by each contributes to the overall aerodynamic performance. The basic requirements of DPI formulation are an excellent aerodynamic performance, including particle size distribution within 1-5 μm, suitable morphology and electrostatic charge, low surface energy, high deposition rate and long shelf life stability. The strategy of DPI formulation is shifting from carrier-based to carrier free, from single drug to drug combination, from microparticles to nanoparticles and from small molecules to biomacromolecules. Making such DPI formulation is a big challenge for conventional pharmaceutical techniques. Fortunately, an emerging technology of supercritical fluid particle design (SCF PD) provides a powerful platform for DPI formulation since it runs single step operation at near ambient temperature to minimize the potential damage of delicate active ingredients and to ensure the consistency of the DPI formulation. Combining with our research experiences in DPI formulation of budesonide and recombinant human insulin, this review focus on the most recent development of DPI formulation using SCF PD technology, which can well control and tune the particle size, morphology and surface properties through different design routes (nanoparticles or microparticles, polymorphic particles, composite particles and bio-drug particles), and hence enable prominent enhancement aerodynamic performance and pulmonary deposition of such inhaled dry powders. Also considered within this review is the progress of the industrialization of SCF PD processes for DPI formulation.

  2. Impact of injection solvents on supercritical fluid chromatography.

    PubMed

    Abrahamsson, Victor; Sandahl, Margareta

    2013-09-06

    Even though there has been a rapid development in instrumentation and applications of supercritical fluid chromatography (SFC), relatively little is known about retention mechanisms compared to high-performance liquid chromatography (HPLC). Much effort has been made to characterize the influence of injection solvents on chromatographic efficiency in HPLC, however has been left rather uninvestigated in the domain of SFC. In this study properties of different injection solvents have been studied and correlated with properties of seven various analytes on three different columns, a C18, a 2-ethylpyridine and a bare-silica column. Aided by calculations of correlation coefficients and principal component analysis (PCA), the physical properties of injection solvents and the interactions between injection solvent, solute and stationary phase were investigated. The findings of this work shows that interactions capable of masking accessible silanol groups on a C18 column are of importance in order to maximize the plate number. While solvents with dipolar and hydrogen bond interaction properties are associated negatively with chromatographic efficiency using polar columns. Properties such as molar density, vapor pressure and boiling point were related to sharper peaks, mostly likely because of solubility issues of the injection solvent into the methanol-modified carbon dioxide. However, no additional solubility due to hydrogen interactions between the injection solvent and the carbon dioxide in SFC was observed. Surface tension and viscosity was not particularly associated with a decrease in plate numbers. By increasing the injection volume a stronger correlation between solubility related properties and plate numbers were obtained. Additional experiments showed that the resistance in solubility became an issue when performing partial-loop injection where additional washing solvent entered the system, thus providing broadened peaks.

  3. Electrochemistry in Near-Critical and Supercritical Fluids. 3. Studies of Br(-), I(-), and Hydroquinone in Aqueous Solutions.

    DTIC Science & Technology

    1986-02-01

    extraction of coal , 5 tar sands, 6 and biomass. 7 Complete oxidation cf most organic pollutants has also been achieved in a mixture of supercritical water...80-8169 136 ELECTROCHEMISTRY IN MERM-CRI TICAL AMD SUPERCRITICAL In1 FLUIDS I STUDIES OF 9.. (U) TEXAS UNIV AT AUSTIN DEPT OF CHENISTRY N M FLARSHEIM... Supercritical Fluids. 3. Studies of B and Hydroquinone in Aqueous Solutions By William M. Flarsheim*, Yu-Min Tsou*, Isacc Trachtenberg*, Keith P. Johnson

  4. Visualization Study of Supercritical Fluid Convection and Heat Transfer in Weightlessness by Interferometry: A Brief Review

    NASA Astrophysics Data System (ADS)

    Deng, Bi-Li; Kanda, Yuki; Chen, Lin; Okajima, Junnosuke; Komiya, Atsuki; Maruyama, Shigenao

    2017-08-01

    Supercritical fluids have become a hot topic in recent years, due to their wide applications in chemical and energy systems. With its sensitive thermal-transport properties in the near-critical region, supercritical/near-critical fluids behaviors, under both microgravity and terrestrial conditions, have become very interesting and challenging topic. This brief review is focused on the visualization experiments of fluid convection and heat transfer related critical phenomena by interferometer. Due to the sensitive property changes of critical fluids, it is very difficult to control and measure the supercritical fluid behaviors. In this review, non-intrusive visualization systems by interferometry are introduced and analyzed for experimental studies of fluids in the near-critical region. For near-critical and supercritical experiments, the temperature/density control and parameter analysis are of critical importance. The analysis of boundary conditions, convection behaviors and energy transfer modes of critical fluids, mainly under weightlessness, are also reviewed with recent opinions toward future development. It is hoped that this review could be helpful for related studies.

  5. Extraction of metals and/or metalloids from acidic media using supercritical fluids and salts

    DOEpatents

    Wai, Chien M.; Smart, Neil G.; Lin, Yuehe

    1998-01-01

    A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a fluid solvent, particularly supercritical carbon dioxide, containing a chelating agent is described. The chelating agent forms chelates that are soluble in the fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent comprises a trialkyl phosphate, a triaryl phosphate, a trialkylphosphine oxide, a triarylphosphine oxide, or mixtures thereof. The method provides an environmentally benign process for removing contaminants from industrial waste. The method is particularly useful for extracting actinides from acidic solutions, and the process can be aided by the addition of nitrate salts. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

  6. Extraction of metals and/or metalloids from acidic media using supercritical fluids and salts

    DOEpatents

    Wai, C.M.; Smart, N.G.; Lin, Y.

    1998-06-23

    A method is described for extracting metalloid and metal species from a solid or liquid material by exposing the material to a fluid solvent, particularly supercritical carbon dioxide, containing a chelating agent. The chelating agent forms chelates that are soluble in the fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent comprises a trialkyl phosphate, a triaryl phosphate, a trialkylphosphine oxide, a triarylphosphine oxide, or mixtures thereof. The method provides an environmentally benign process for removing contaminants from industrial waste. The method is particularly useful for extracting actinides from acidic solutions, and the process can be aided by the addition of nitrate salts. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs.

  7. Decontamination of hazardous substances from solid matrices and liquids using supercritical fluids extraction: a review.

    PubMed

    Sunarso, Jaka; Ismadji, Suryadi

    2009-01-15

    Supercritical fluid has been adopted as an extraction media to remove various kinds of substances from distinct types of solid matrices since three decades ago. Compared to conventional extraction mode, supercritical fluid extraction technology is preferred because of the flexibility in adjusting its dissolving power and inherent elimination of organic solvent which means reducing time and money needed for subsequent purification. Utilization of this method as an environmental remedial technology, however, has become a trend only after its accomplishment in analytical chemistry was acknowledged. This review tries to summarize in a comprehensive manner the multitude aspects involved in hazardous compounds removal from miscellaneous class of environmental matrices. The industrial adsorbent regeneration using supercritical fluid technology is also discussed. Although, this technology has been successfully realized for environmental remediation in laboratory and on pilot-plant scale, its commercialization attempts still lack significant technology improvement in order to reach the economic feasibility.

  8. Nanoscale engineering materials by supercritical fluid and atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Peng, Qing

    With the development of material science and technology, modification of substrates, which have random geometry and high aspect ratio three dimensional (3D) complex structures, with desired functional, reactive and stable coatings becomes important and challenging. The ability to fabricate mono- or multi-layers of functional materials with precisely controlled dimensions, finely tuned composition and molecular structures, attracts significant interests in materials science and is the key to construct such devices and structures at nano- and micro-scale with desired properties. In this study, supercritical carbon dioxide (scCO2) has been studied as an alternative route for modifying substrates due to the unique gas-like (low viscosity, high diffusivity and zero surface tension) and liquid-like properties (high density). (1) The reaction kinetics of metal oxides thin film deposition from pyrolysis of metal organics in scCO2 was studied in detail. This method was demonstrated as a powerful technique to coat oxides, including Al2O3, Ga2O3 and others, into 3D high aspect ratio complex structure of carbon nanotubes (CNTs) forest. (2) The low temperature scCO 2 based hydrogenolysis process was developed as a useful way to functionalize aligned CNTs forest with dense Nickel nanoparticles. On the second part of this work, atomic layer deposition (ALD)/molecular layer deposition (MLD), as a vapor phase, stepwise and self-limiting vacuum based deposition process, was demonstrated as a powerful way to form highly conformal and uniform film onto substrates, even into highly complex 3D complex structures. In this study, (4) Metal oxide ALD is applied onto 3D electrospun polymer microfiber mats template to illustrate an effective and robust strategy to fabricate long and uniform metal oxide microtubes with precisely controllable wall thickness. Designer tubes of various sizes and different materials were demonstrated by using this method. (5) By further extending this technique

  9. CLEANING UP PESTICIDE CONTAMINATED SOILS: COMPARING EFFECTIVENESS OF SUPERCRITICAL FLUID EXTRACTION WITH SOLVENT EXTRACTION AND LOW TEMPERATURE THERMAL DESORPTION

    EPA Science Inventory

    Bench-scale supercritical fluid extraction (SFE) studies were performed on soil samples obtained from a Superfund site that is contaminated with high levels of p,p,-DDT, p,p,-DDD, p,p,-DDE, toxaphene and hexachlorocyclohexane. The effectiveness of supercritical fluid extraction ...

  10. CLEANING UP PESTICIDE CONTAMINATED SOILS: COMPARING EFFECTIVENESS OF SUPERCRITICAL FLUID EXTRACTION WITH SOLVENT EXTRACTION AND LOW TEMPERATURE THERMAL DESORPTION

    EPA Science Inventory

    Bench-scale supercritical fluid extraction (SFE) studies were performed on soil samples obtained from a Superfund site that is contaminated with high levels of p,p,-DDT, p,p,-DDD, p,p,-DDE, toxaphene and hexachlorocyclohexane. The effectiveness of supercritical fluid extraction ...

  11. Understanding physical rock properties and their relation to fluid-rock interactions under supercritical conditions

    NASA Astrophysics Data System (ADS)

    Kummerow, Juliane; Raab, Siegfried; Meyer, Romain

    2017-04-01

    The electrical conductivity of rocks is, in addition to lithological factors (mineralogy, porosity) and physical parameters (temperature, pressure) sensitive to the nature of pore fluids (phase, salinity), and thus may be an indicative measure for fluid-rock interactions. Especially near the critical point, which is at 374.21° C and 22.12 MPa for pure water, the physico-chemical properties of aqueous fluids change dramatically and mass transfer and diffusion-controlled chemical reactivity are enhanced, which in turn leads to the formation of element depletion/ enrichment patterns or cause mineral dissolution. At the same time, the reduction of the dielectric constant of water promotes ion association and consequently mineral precipitation. All this cause changes in the electrical conductivity of geothermal fluids and may have considerable effects on the porosity and hydraulic properties of the rocks with which they are in contact. In order to study the impact of fluid-rock interactions on the physical properties of fluids and rocks in near- and supercritical geological settings in more detail, in the framework of the EU-funded project "IMAGE" (Integrated Methods for Advanced Geothermal Exploration) hydraulic and electrical properties of rock cores from different active and exhumed geothermal areas on Iceland were measured up to supercritical conditions (Tmax = 380° C, pfluid = 23 MPa) during long-term (2-3 weeks) flow-through experiments in an internally heated gas pressure vessel at a maximum confining pressure of 42 MPa. In a second flow-through facility both the intrinsic T-dependent electrical fluid properties as well as the effect of mineral dissolution/ precipitation on the fluid conductivity were measured for increasing temperatures in a range of 24 - 422° C at a constant fluid pressure of 31 MPa. Petro- and fluid physical measurements were supplemented by a number of additional tests, comprising microstructural investigations as well as the chemical

  12. [Supercritical CO2 fluid extraction of Rosmarinus officinalis and capability of extracts eliminate OH radical].

    PubMed

    Zhang, Chong; Li, Jia-Cheng; Zhang, De-La; Feng, Yu-Hong; Zhang, Ya-Nan; Chen, Si-Li

    2008-05-01

    Supercritical CO2 fluid extraction process of antioxidation active components from Rosmarinus officinalis was studied. A new extraction process of components extracted from R. officinalis by supercritical CO2 fluid extraction (SFE-CO2 ) was studied in detail. The capability of that the extract eliminate *OH radical was tested by electron paramagnetic resonance (EPR) technique and spin catch technique. With free radical clearance as index, by range and variance analysis, the optimum extraction process conditions were: keeping pressure at 30 MPa and temperature at 75 degrees C for 1 h, in the same time adding alcohol 0.30 mL x g(-1).

  13. Removal of organic template of mesoporous organosilicate thin films using supercritical carbon dioxide fluids

    NASA Astrophysics Data System (ADS)

    Kondoh, Eiichi; Segawa, Koki; Watanabe, Mitsuhiro; Jin, Lianhua; Zhang, Liping; Baklanov, Mikhail R.

    2017-07-01

    An organic template of periodic mesoporous organosilicate films was removed using supercritical CO2 fluids that are compressive solvents with a nanopenetration capability. The removal efficiency was evaluated by infrared spectroscopy and refractive index measurements. The removal ratio was dependent on treatment pressure and temperature and improved when the fluid density and/or temperature was high. Because a very high process temperature can deteriorate the organosilicate frame structure, the removal at a low temperature and a high pressure is preferable. The films under supercritical CO2 processing were characterized also in situ ellipsometry. It was found that the removal is a fast process and mostly completes during temperature ramping.

  14. Preparation of Dispersed Platinum Nanoparticles on a Carbon Nanostructured Surface Using Supercritical Fluid Chemical Deposition

    PubMed Central

    Hiramatsu, Mineo; Hori, Masaru

    2010-01-01

    We have developed a method of forming platinum (Pt) nanoparticles using a metal organic chemical fluid deposition (MOCFD) process employing a supercritical fluid (SCF), and have demonstrated the synthesis of dispersed Pt nanoparticles on the surfaces of carbon nanowalls (CNWs), two-dimensional carbon nanostructures, and carbon nanotubes (CNTs). By using SCF-MOCFD with supercritical carbon dioxide as a solvent of metal-organic compounds, highly dispersed Pt nanoparticles of 2 nm diameter were deposited on the entire surface of CNWs and CNTs. The SCF-MOCFD process proved to be effective for the synthesis of Pt nanoparticles on the entire surface of intricate carbon nanostructures with narrow interspaces.

  15. CO{sub 2}-based supercritical fluids as environmentally-friendly processing solvents

    SciTech Connect

    Rubin, J.B.; Davenhall, L.B.; Taylor, C.M.V.; Pierce, T.; Tiefert, K.

    1999-03-01

    The production of integrated circuits involves a number of discrete steps that utilize hazardous or regulated solvents. Environmental, safety and health considerations associated with these chemicals have prompted a search for alternative, more environmentally benign, solvent systems. An emerging technology for conventional solvent replacement is the use of supercritical fluids based on carbon dioxide (CO{sub 2}). Supercritical CO{sub 2} (SCCO{sub 2}) is an excellent choice for IC manufacturing processes since it is non-toxic, non-flammable, inexpensive, and is compatible with all substrate and metallizations systems. Also, conditions of temperature and pressure needed to achieve the supercritical state are easily achievable with existing process equipment. The authors first describe the general properties of supercritical fluids, with particular emphasis on their application as alternative solvents. Next, they review some of the work which has been published involving the use of supercritical fluids, and particularly CO{sub 2}, as they may be applied to the various steps of IC manufacture, including wafer cleaning, thin film deposition, etching, photoresist stripping, and waste treatment. Next, they describe the research work conducted at Los Alamos, on behalf of Hewlett-Packard, on the use of SCCO{sub 2} in a specific step of the IC manufacturing process: the stripping of hard-baked photoresist.

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

    SciTech Connect

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

    2006-06-01

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

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

    SciTech Connect

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

    2015-04-07

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

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

    PubMed

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

    2015-04-07

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

  19. 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...

  20. Instabilities encountered during heat transfer to a supercritical fluid

    NASA Technical Reports Server (NTRS)

    Cornelius, A. J.

    1969-01-01

    Investigation was made of the unstable behavior of a heat-transfer loop operating at a supercritical pressure. Natural convection operation of the loop, with observations on acoustic and slow oscillatory behavior, was emphasized during testing. The basic cause of both types of behavior appeared to originate in the heated boundary layer.

  1. Antifungal activities of three supercritical fluid extracted cedar oils

    Treesearch

    Tianchuan Du; Todd F. Shupe; Chung Y. Hse

    2009-01-01

    The antifungal activities of three supercritical CO2 (SCC) extracted cedar oils, Port-Orford-cedar (POC) (Chamaecyparis lawsoniana), Alaska yellow cedar (AYC) (Chamaecyparis nootkatensis), and Eastern red cedar (ERC) (Juniperus virginiana L), were evaluated against two common wood decay fungi, brown-rot fungi (...

  2. Partitioning behaviour of organic compounds between ionic liquids and supercritical fluids.

    PubMed

    Roth, Michal

    2009-03-06

    Applications and prospects of two-phase, tuneable solvent systems composed of ionic liquids (ILs) and supercritical fluids with an emphasis on supercritical carbon dioxide (scCO(2)) are reviewed. The IL-scCO(2) biphasic systems have increasingly been used in diverse fields of chemistry and technology, and some examples of these applications are mentioned here. Rational design of such applications can obviously benefit from pertinent data on phase equilibria including the partition coefficients of the prospective products and reactants between the two phases. Therefore, a reliable technique to measure the limiting partition coefficients would be of value. Here, the pros and cons of supercritical fluid chromatography in this respect are discussed. An overview of methods for predictive thermodynamic modelling of binary (IL-scCO(2)) and ternary (solute-IL-scCO(2)) systems is also included.

  3. Method and apparatus for dissociating metals from metal compounds extracted into supercritical fluids

    DOEpatents

    Wai, Chien M.; Hunt, Fred H.; Smart, Neil G.; Lin, Yuehe

    2000-01-01

    A method for dissociating metal-ligand complexes in a supercritical fluid by treating the metal-ligand complex with heat and/or reducing or oxidizing agents is described. Once the metal-ligand complex is dissociated, the resulting metal and/or metal oxide form fine particles of substantially uniform size. In preferred embodiments, the solvent is supercritical carbon dioxide and the ligand is a .beta.-diketone such as hexafluoroacetylacetone or dibutyldiacetate. In other preferred embodiments, the metals in the metal-ligand complex are copper, silver, gold, tungsten, titanium, tantalum, tin, or mixtures thereof. In preferred embodiments, the reducing agent is hydrogen. The method provides an efficient process for dissociating metal-ligand complexes and produces easily-collected metal particles free from hydrocarbon solvent impurities. The ligand and the supercritical fluid can be regenerated to provide an economic, efficient process.

  4. 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.

  5. Concurrent and supercritical fluid chromatographic analysis of Terpene Lactones and ginkolic acids in Ginko biloba

    USDA-ARS?s Scientific Manuscript database

    Supercritical fluid chromatography was used to resolve and determine ginkgolic acids (GAs) and terpene lactones concurrently in ginkgo plant materials and commercial dietary supplements. Analysis of GAs (C13:0, C15:0, C15:1 and C17:1) was carried out by ESI (-) mass detection. The ESI (-) spectra of...

  6. Synthesis of biodiesel fuel additives from glycerol using green chemistry and supercritical fluids

    USDA-ARS?s Scientific Manuscript database

    For every 3 moles of fatty acid esters produced, 1 mole of glycerol remains, ~11% of the biodiesel volume. One new method of glycerol use could be as a biodiesel fuel additive/extender using eco-friendly heterogeneous catalysts and supercritical fluids (SFs). SFs have advantages such as greater diff...

  7. Processing of poly(hydroxybutyrate-co-hydroxyvalerate)-based bionanocomposite foams using supercritical fluids

    Treesearch

    Alireza Javadi; Yottha Srithep; Craig C. Clemons; L-S. Turng; Shaoqin. Gong

    2012-01-01

    Supercritical fluid (SCF) N2 was used as a physical foaming agent to fabricate microcellular injection-molded poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)–poly(butylene adipate-co-terephthalate) (PBAT)–hyperbranched-polymer (HBP)–nanoclay (NC) bionanocomposites. The effects of incorporating HBP and NC on the morphological, mechanical, and...

  8. 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...

  9. Ultrasound assisted supercritical fluid extraction of oil and coixenolide from adlay seed.

    PubMed

    Hu, Ai-jun; Zhao, Shuna; Liang, Hanhua; Qiu, Tai-qiu; Chen, Guohua

    2007-02-01

    Oil and coixenolide are important components of adlay seed (Coix lachrymal-jobi L. var. Adlay) with many beneficial functions to human health. In this work, a novel extraction technique--ultrasound assisted supercritical fluid extraction (USFE)--was studied. Effects of operating conditions on the extraction, including extraction temperature (T), pressure (P), time (t), CO(2) flow rate (F) and ultrasonic power (I) were investigated. There are optimum temperatures which gives the maximum extraction yields (EYs) for the supercritical fluid extractions with and without ultrasound. The effect of pressure on EYs for is similar to that of pressure on CO(2) density. Based on the yield of extraction, the favorable conditions for supercritical fluid extraction (SFE) were: T at 45 degrees C, P at 25 MPa, t at 4.0 h and F at 3.5L/h. While ultrasound was applied as in USFE, the following parameters were preferred: T at 40 degrees C, P at 20 MPa, t at 3.5h and F at 3.0 L/h, respectively. The results show that supercritical fluid extraction with the assistance of ultrasound could reduce the temperature, pressure, CO(2) flow rate, as well as time used in the process. Compared with SFE, USFE could give a 14% increase in the yield for extracting oil and coixenolide from adlay seed with less severe operating conditions.

  10. DIRECT-DEPOSITION INFRARED SPECTROMETRY WITH GAS AND SUPERCRITICAL FLUID CHROMATOGRAPHY

    EPA Science Inventory

    A direct-deposition Fourier transform infrared (FT-IR) system has been evaluated for applicability to gas chromatography (GC) and supercritical fluid chromatography (SFC) of environmental analytes. A 100-um i.d. fused-silica transfer line was used for GC, and a 50-um transfer lin...

  11. SEPARATION OF T-MAZ ETHOXYLATED SORBITAN FATTY ACID ESTERS BY SUPERCRITICAL FLUID CHROMATOGRAPHY

    EPA Science Inventory

    The application of supercritical fluid chromatography (SFC) to the analysis of T-MAZ ethoxylated sorbitan fatty acid esters is described. FC separation methods utilize a density programming technique and a 50 um I.D. capillary column. his work demonstrates that capillary column S...

  12. 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...

  13. DIRECT-DEPOSITION INFRARED SPECTROMETRY WITH GAS AND SUPERCRITICAL FLUID CHROMATOGRAPHY

    EPA Science Inventory

    A direct-deposition Fourier transform infrared (FT-IR) system has been evaluated for applicability to gas chromatography (GC) and supercritical fluid chromatography (SFC) of environmental analytes. A 100-um i.d. fused-silica transfer line was used for GC, and a 50-um transfer lin...

  14. SEPARATION OF T-MAZ ETHOXYLATED SORBITAN FATTY ACID ESTERS BY SUPERCRITICAL FLUID CHROMATOGRAPHY

    EPA Science Inventory

    The application of supercritical fluid chromatography (SFC) to the analysis of T-MAZ ethoxylated sorbitan fatty acid esters is described. FC separation methods utilize a density programming technique and a 50 um I.D. capillary column. his work demonstrates that capillary column S...

  15. 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 Rs /tR2 than high performance liquid chromatography, which demonstrated that supercritical fluid chromatography had much higher separation efficiency.

  16. Micronutrient and protein-fortified whole grain puffed rice made by supercritical fluid extrusion.

    PubMed

    Paraman, Ilankovan; Wagner, Michael E; Rizvi, Syed S H

    2012-11-07

    Supercritical fluid extrusion (SCFX) was used to produce shelf-stable puffed rice fortified with protein, dietary fiber, and micronutrients. Product ingredients and process parameters were evaluated for end-product nutritional and textural qualities. Supercritical carbon dioxide (SC-CO(2)) served as a viscosity-lowering plasticizer and blowing agent during the process, which has been shown to produce expanded products with good textural qualities at lower temperatures (~100 °C) than conventional steam-based extrusion (130-180 °C). The fortified puffed rice contained 8% dietary fiber, 21.5% protein, and iron, zinc, and vitamins A and C at their recommended daily values in 100 g of product. The SCFX process allowed for the complete retention of all added minerals, 55-58% retention of vitamin A, and 64-76% retention of vitamin C. All essential amino acids including lysine were retained at exceptionally high levels (98.6%), and no losses were observed due to Maillard reaction or oxidation. All of the essential amino acid contents were equal to the reference protein recommended by FAO/WHO. Soy protein fortification improved the total amount of protein in the final rice products and provided a complementary amino acid profile to that of rice; the lysine content improved from 35 to 60 mg/protein, making the end product an excellent source of complete protein. Thus, SC-CO(2)-assisted extrusion is an effective process-based approach to produce cereal grain-based, low-moisture (5-8%) expanded products fortified with protein and any cocktail of micronutrients, without compromising the end-product sensory or nutritional qualities. These products are ideally suited for consumption as breakfast cereals, snack foods, and as part of nutrition bars for school lunch programs. The balanced nutritional profile and use of staple crop byproducts such as broken rice makes these expanded crisps unique to the marketplace.

  17. Multistage structural evolution in simple monatomic supercritical fluids: superstable tetrahedral local order.

    PubMed

    Ryltsev, R E; Chtchelkatchev, N M

    2013-11-01

    The local order units of dense simple liquid are typically three-dimensional (close packed) clusters: hcp, fcc, and icosahedrons. We show that the fluid demonstrates the superstable tetrahedral local order up to temperatures several orders of magnitude higher than the melting temperature and down to critical density. While the solid-like local order (hcp, fcc) disappears in the fluid at much lower temperatures and far above critical density. We conclude that the supercritical fluid shows the temperature (density)-driven two-stage "melting" of the three-dimensional local order. We also find that the structure relaxation times in the supercritical fluid are much larger than ones estimated for weakly interactive gas even far above the melting line.

  18. Ultrasound enhanced process for extracting metal species in supercritical fluids

    DOEpatents

    Wai, Chien M.; Enokida, Youichi

    2006-10-31

    Improved methods for the extraction or dissolution of metals, metalloids or their oxides, especially lanthanides, actinides, uranium or their oxides, into supercritical solvents containing an extractant are disclosed. The disclosed embodiments specifically include enhancing the extraction or dissolution efficiency with ultrasound. The present methods allow the direct, efficient dissolution of UO2 or other uranium oxides without generating any waste stream or by-products.

  19. Supercritical fluid extraction of active components in a drug formulation.

    PubMed

    Mulcahey, L J; Taylor, L T

    1992-05-01

    Sulfamethoxazole and trimethoprim have been extracted from a drug formulation, Septra Infusion, with pure supercritical carbon dioxide. Both direct extraction of the aqueous-based matrix and indirect extraction of the formulation immobilized onto Celite were studied. Exhaustive analytical extraction was achieved when active components were less than 1.0 mg. A number of co-extractants were found, but each was blind to the HPLC/UV assay.

  20. The Development of Improved Capillary Supercritical Fluid Chromatography and Mass Spectrometry

    DTIC Science & Technology

    1990-01-01

    composition about the solute molecule. Investigation of thermochromic shifts in the electronic spectra of 2,4-nitroanisole at constant density and...constant pressure was undertaken. One of the advantages of thermochromic studies in supercritical fluids is the ability to hold the fluid density...local solvent environment about the solute molecule. The thermochromic shifts seen were not as large as previously studied solvatochromic shifts, but

  1. Preheating of fluid in a supercritical Brayton cycle power generation system at cold startup

    DOEpatents

    Wright, Steven A.; Fuller, Robert L.

    2016-07-12

    Various technologies pertaining to causing fluid in a supercritical Brayton cycle power generation system to flow in a desired direction at cold startup of the system are described herein. A sensor is positioned at an inlet of a turbine, wherein the sensor is configured to output sensed temperatures of fluid at the inlet of the turbine. If the sensed temperature surpasses a predefined threshold, at least one operating parameter of the power generation system is altered.

  2. Turbulent mixing of a slightly supercritical van der Waals fluid at low-Mach number

    SciTech Connect

    Battista, F.; Casciola, C. M.; Picano, F.

    2014-05-15

    Supercritical fluids near the critical point are characterized by liquid-like densities and gas-like transport properties. These features are purposely exploited in different contexts ranging from natural products extraction/fractionation to aerospace propulsion. Large part of studies concerns this last context, focusing on the dynamics of supercritical fluids at high Mach number where compressibility and thermodynamics strictly interact. Despite the widespread use also at low Mach number, the turbulent mixing properties of slightly supercritical fluids have still not investigated in detail in this regime. This topic is addressed here by dealing with Direct Numerical Simulations of a coaxial jet of a slightly supercritical van der Waals fluid. Since acoustic effects are irrelevant in the low Mach number conditions found in many industrial applications, the numerical model is based on a suitable low-Mach number expansion of the governing equation. According to experimental observations, the weakly supercritical regime is characterized by the formation of finger-like structures – the so-called ligaments – in the shear layers separating the two streams. The mechanism of ligament formation at vanishing Mach number is extracted from the simulations and a detailed statistical characterization is provided. Ligaments always form whenever a high density contrast occurs, independently of real or perfect gas behaviors. The difference between real and perfect gas conditions is found in the ligament small-scale structure. More intense density gradients and thinner interfaces characterize the near critical fluid in comparison with the smoother behavior of the perfect gas. A phenomenological interpretation is here provided on the basis of the real gas thermodynamics properties.

  3. Turbulent mixing of a slightly supercritical van der Waals fluid at low-Mach number

    NASA Astrophysics Data System (ADS)

    Battista, F.; Picano, F.; Casciola, C. M.

    2014-05-01

    Supercritical fluids near the critical point are characterized by liquid-like densities and gas-like transport properties. These features are purposely exploited in different contexts ranging from natural products extraction/fractionation to aerospace propulsion. Large part of studies concerns this last context, focusing on the dynamics of supercritical fluids at high Mach number where compressibility and thermodynamics strictly interact. Despite the widespread use also at low Mach number, the turbulent mixing properties of slightly supercritical fluids have still not investigated in detail in this regime. This topic is addressed here by dealing with Direct Numerical Simulations of a coaxial jet of a slightly supercritical van der Waals fluid. Since acoustic effects are irrelevant in the low Mach number conditions found in many industrial applications, the numerical model is based on a suitable low-Mach number expansion of the governing equation. According to experimental observations, the weakly supercritical regime is characterized by the formation of finger-like structures - the so-called ligaments - in the shear layers separating the two streams. The mechanism of ligament formation at vanishing Mach number is extracted from the simulations and a detailed statistical characterization is provided. Ligaments always form whenever a high density contrast occurs, independently of real or perfect gas behaviors. The difference between real and perfect gas conditions is found in the ligament small-scale structure. More intense density gradients and thinner interfaces characterize the near critical fluid in comparison with the smoother behavior of the perfect gas. A phenomenological interpretation is here provided on the basis of the real gas thermodynamics properties.

  4. Fischer-Tropsch synthesis in supercritical reaction media

    SciTech Connect

    Subramaniam, B.

    1995-05-01

    The goal of the proposed research is to develop novel reactor operating strategies for the catalytic conversion of syngas to transportation grade fuels and oxygenates using near-critical (nc) fluids as reaction media. This will be achieved through systematic investigations aimed at a better fundamental understanding of the physical and chemical rate processes underlying catalytic syngas conversion in nc reaction media. Syngas conversion to fuels and fuel additives on Fe catalysts (Fischer-Tropsch synthesis) was investigated. Specific objectives are to investigate the effects of various nc media, their flow rates and operating pressure on syngas conversion, reactor temperature profiles, product selectivity and catalyst activity in trickle-bed reactors. Solvents that exhibit gas to liquid-like densities with relatively moderate pressure changes (from 25 to 60 bars) at typical syngas conversion temperatures (in the 220-280{degree}C range) will be chosen as reaction media.

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

    SciTech Connect

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

    2012-07-01

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

  6. [Study on the dynamic model with supercritical CO2 fluid extracting the lipophilic components in Panax notoginseng].

    PubMed

    Duan, Xian-Chun; Wang, Yong-Zhong; Zhang, Jun-Ru; Luo, Huan; Zhang, Heng; Xia, Lun-Zhu

    2011-08-01

    To establish a dynamics model for extracting the lipophilic components in Panax notoginseng with supercritical carbon dioxide (CO2). Based on the theory of counter-flow mass transfer and the molecular mass transfer between the material and the supercritical CO2 fluid under differential mass-conservation equation, a dynamics model was established and computed to compare forecasting result with the experiment process. A dynamics model has been established for supercritical CO2 to extract the lipophilic components in Panax notoginseng, the computed result of this model was consistent with the experiment process basically. The supercritical fluid extract dynamics model established in this research can expound the mechanism in the extract process of which lipophilic components of Panax notoginseng dissolve the mass transfer and is tallied with the actual extract process. This provides certain instruction for the supercritical CO2 fluid extract' s industrialization enlargement.

  7. 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

  8. 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.

  9. Method for separating metal chelates from other materials based on solubilities in supercritical fluids

    DOEpatents

    Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

    2001-01-01

    A method for separating a desired metal or metalloi from impurities using a supercritical extraction process based on solubility differences between the components, as well as the ability to vary the solvent power of the supercritical fluid, is described. The use of adduct-forming agents, such as phosphorous-containing ligands, to separate metal or metalloid chelates in such processes is further disclosed. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones; phosphine oxides, such as trialkylphosphine oxides, triarylphosphine oxides and alkylarylphosphine oxides; phosphinic acids; carboxylic acids; phosphates, such as trialkylphosphates, triarylphosphates and alkylarylphosphates; crown ethers; dithiocarbamates; phosphine sulfides; phosphorothioic acids; thiophosphinic acids; halogenated analogs of these chelating agents; and mixtures of these chelating agents. In especially preferred embodiments, at least one of the chelating agents is fluorinated.

  10. Multidimensional Model of Fluid Flow and Heat Transfer in Generation-IV Supercritical Water Reactors

    SciTech Connect

    Gallaway, Tara; Antal, Steven P.; Podowski, Michael Z.

    2006-07-01

    This paper is concerned with the mechanistic modeling and theoretical/computational analysis of flow and heat transfer in future Generation-IV Supercritical Water Cooled Reactors (SCWR). The issues discussed in the paper include: the development of analytical models of the properties of supercritical water, and the application of full three-dimensional computational modeling framework to simulate fluid flow and heat transfer in SCWRs. Several results of calculations are shown, including the evaluation of water properties (density, specific heat, thermal conductivity, viscosity, and Prandtl number) near the pseudo-critical temperature for various supercritical pressures, and the CFD predictions using the NPHASE computer code. It is demonstrated that the proposed approach is very promising for future mechanistic analyses of SCWR thermal-hydraulics and safety. (authors)

  11. Determination of the column hold-up volume in supercritical fluid chromatography using nitrous-oxide.

    PubMed

    Vajda, Péter; Guiochon, Georges

    2013-09-27

    This study introduces a new tracer that is useful for the determination of the hold-up time or volume of packed columns, particularly of those used in supercritical fluid chromatography. The thermodynamic void volume of three columns packed with different adsorbents were determined using the weight difference method. These void volumes were used as the reference point in the further discussion. The hold-up volumes of these columns were determined under dynamic conditions, using nitrous oxide dissolved in methanol as the hold-up time marker. Changes in the hold-up volumes of these columns were monitored during changes of the volumetric flow rate of pure supercritical carbon dioxide and of dilute mixtures of organic modifier and supercritical carbon dioxide. The results suggest significant methanol enrichment on the adsorbent surface.

  12. Control of optical transport parameters of 'porous medium – supercritical fluid' systems

    SciTech Connect

    Zimnyakov, D A; Ushakova, O V; Yuvchenko, S A; Bagratashvili, V N

    2015-11-30

    The possibility of controlling optical transport parameters (in particular, transport scattering coefficient) of porous systems based on polymer fibres, saturated with carbon dioxide in different phase states (gaseous, liquid and supercritical) has been experimentally studied. An increase in the pressure of the saturating medium leads to a rise of its refractive index and, correspondingly, the diffuse-transmission coefficient of the system due to the decrease in the transport scattering coefficient. It is shown that, in the case of subcritical saturating carbon dioxide, the small-angle diffuse transmission of probed porous layers at pressures close to the saturated vapour pressure is determined by the effect of capillary condensation in pores. The immersion effect in 'porous medium – supercritical fluid' systems, where the fluid pressure is used as a control parameter, is considered. The results of reconstructing the values of transport scattering coefficient of probed layers for different refractive indices of a saturating fluid are presented. (radiation scattering)

  13. Mesoporous silicates prepared using preorganized templates in supercritical fluids.

    PubMed

    Pai, Rajaram A; Humayun, Raashina; Schulberg, Michelle T; Sengupta, Archita; Sun, Jia-Ning; Watkins, James J

    2004-01-23

    Well-ordered mesoporous silicate films were prepared by infusion and selective condensation of silicon alkoxides within microphase-separated block copolymer templates dilated with supercritical carbon dioxide. Confinement of metal oxide deposition to specific subdomains of the preorganized template yields high-fidelity, three-dimensional replication of the copolymer morphology, enabling the preparation of structures with multiscale order in a process that closely resembles biomineralization. Ordered mesoporous silicate films were synthesized with dielectric constants as low as 1.8 and excellent mechanical properties. The films survive the chemical-mechanical polishing step required for device manufacturing.

  14. Mesoporous Silicates Prepared Using Preorganized Templates in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Pai, Rajaram A.; Humayun, Raashina; Schulberg, Michelle T.; Sengupta, Archita; Sun, Jia-Ning; Watkins, James J.

    2004-01-01

    Well-ordered mesoporous silicate films were prepared by infusion and selective condensation of silicon alkoxides within microphase-separated block copolymer templates dilated with supercritical carbon dioxide. Confinement of metal oxide deposition to specific subdomains of the preorganized template yields high-fidelity, three-dimensional replication of the copolymer morphology, enabling the preparation of structures with multiscale order in a process that closely resembles biomineralization. Ordered mesoporous silicate films were synthesized with dielectric constants as low as 1.8 and excellent mechanical properties. The films survive the chemical-mechanical polishing step required for device manufacturing.

  15. Antioxidant effects of supercritical fluid garlic extracts in canned artichokes.

    PubMed

    Bravi, E; Marconi, O; Sileoni, V; Rollo, M R; Perretti, G

    2016-10-01

    The effects of adding supercritical carbon dioxide extracts of garlic (at two different concentrations of allicin) on select chemical indices in extra-virgin olive oil used to canned artichokes were studied. Tests were performed after processing and over a storage period of 1 year. A sensorial test was also conducted on the canned artichokes to establish the impact on flavor (in particular perceptions of rancidity and garlic flavor). Acidity, peroxide levels and p-anisidine values were measured as quality analytical parameters. Radical scavenging activity was also evaluated using the DPPH assay. The samples containing supercritical garlic extracts were compared with several other formulations, including control sample (prepared by mixing artichokes with powdered chili pepper and fresh garlic), artichokes with only garlic or only chili pepper, and artichokes treated with the synthetic antioxidant BHT. The results suggested that the allicin extract may be superior, or at least comparable, with BHT in preserving canned artichokes as demonstrated by its positive effects on oxidative stability and sensory profile.

  16. Growth and Morphology of Supercritical Fluids, a Fluid Physics Experiment Conducted on Mir, Complete

    NASA Technical Reports Server (NTRS)

    Wilkinson, R. Allen

    2001-01-01

    The Growth and Morphology of Supercritical Fluids (GMSF) is an international experiment facilitated by the NASA Glenn Research Center and under the guidance of U.S. principal investor Professor Hegseth of the University of New Orleans and three French coinvestigators: Daniel Beysens, Yves Garrabos, and Carole Chabot. The GMSF experiments were concluded in early 1999 on the Russian space station Mir. The experiments spanned the three science themes of near-critical phase separation rates, interface dynamics in near-critical boiling, and measurement of the spectrum of density fluctuation length scales very close to the critical point. The fluids used were pure CO2 or SF6. Three of the five thermostats used could adjust the sample volume with the scheduled crew time. Such a volume adjustment enabled variable sample densities around the critical density as well as pressure steps (as distinct from the usual temperature steps) applied to the sample. The French-built ALICE II facility was used for these experiments. It allows tightly thermostated (left photograph) samples (right photograph) to be controlled and viewed/measured. Its diagnostics include interferometry, shadowgraph, high-speed pressure measurements, and microscopy. Data were logged on DAT tapes, and PCMCIA cards and were returned to Earth only after the mission was over. The ground-breaking near critical boiling experiment has yielded the most results with a paper published in Physical Review Letters (ref. 1). The boiling work also received press in Science Magazine (ref. 2). This work showed that, in very compressible near-critical two-phase pure fluids, a vapor bubble was induced to temporarily overheat during a rapid heating of the sample wall. The temperature rise in the vapor was 23-percent higher than the rise in the driving container wall. The effect is due to adiabatic compression of the vapor bubble by the rapid expansion of fluid near the boundary during heatup. Thermal diffusivity is low near the

  17. Fluid-loop reaction system

    NASA Technical Reports Server (NTRS)

    Lurie, Boris J. (Inventor); Schier, J. Alan (Inventor); Iskenderian, Theodore C. (Inventor)

    1991-01-01

    An improved fluid actuating system for imparting motion to a body such as a spacecraft is disclosed. The fluid actuating system consists of a fluid mass that may be controllably accelerated through at least one fluid path whereby an opposite acceleration is experienced by the spacecraft. For full control of the spacecraft's orientation, the system would include a plurality of fluid paths. The fluid paths may be circular or irregular, and the fluid paths may be located on the interior or exterior of the spacecraft.

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

    SciTech Connect

    Lin, B.; Akgerman, A.

    1999-12-01

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

  19. Growth of rectangular hollow tube single crystals with rutile-type structure in supercritical fluids

    NASA Astrophysics Data System (ADS)

    Niwa, Ken; Tokunaga, Tomoharu; Hasegawa, Masashi

    2013-06-01

    Super critical fluid is known as a suitable solvent in the dissolution and extraction process, due to its extreme high solubility and reactivity. On the other hand, further experimental approaches using supercritical fluid would offer new insights, especially in the field of novel material synthesis and crystal growth. We here report on the successful growth of single crystals with the rutile-type structure (MO2; M = Ti, Si, Ge and Sn) in the supercritical fluids (water or oxygen) by using laser heated diamond-anvil cell at above 5 GPa. The resultant product showed the rectangular hollow tube with several tens of microns in length and the wall thickness of less than 500 nm. TEM analyses demonstrated that this rectangular hollow tube single crystal is surrounded by the (110) face and grown along the [001] direction. The preferential growth of (110) face is consistent with the lowest surface energy of (110) in the rutile-type structure. In addition, the rapid cooling rate of LHDAC and the high-solubility of oxides into the supercritical fluids also play an important role for the formation of the rectangular hollow tube. The details of the experiments will be discussed in the presentation.

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

    SciTech Connect

    Carmichael, Justin R; Rother, Gernot; Browning, Jim; Ankner, John Francis; Banuelos, Jose Leo; Anovitz, Lawrence {Larry} M; Wesolowski, David J; Cole, David

    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 be used with the cells, depending on the required pressure and momentum transfer range. The fluid volume in the sample cell is very small at about 0.1 ml, which minimizes scattering background and stored energy. The cell design and pressure setup for measurements with supercritical fluids are described. NR data are shown for silicon/silicon oxide and quartz wafers measured against air and subsequently within the high-pressure cell to demonstrate the neutron characteristics of the high-pressure cell. Neutron reflectivity data for supercritical CO2 in contact with quartz and Si/SiO2 wafers are also shown.

  1. Solvent density inhomogeneities and solvation free energies in supercritical diatomic fluids: a density functional approach.

    PubMed

    Husowitz, B; Talanquer, V

    2007-02-07

    Density functional theory is used to explore the solvation properties of a spherical solute immersed in a supercritical diatomic fluid. The solute is modeled as a hard core Yukawa particle surrounded by a diatomic Lennard-Jones fluid represented by two fused tangent spheres using an interaction site approximation. The authors' approach is particularly suitable for thoroughly exploring the effect of different interaction parameters, such as solute-solvent interaction strength and range, solvent-solvent long-range interactions, and particle size, on the local solvent structure and the solvation free energy under supercritical conditions. Their results indicate that the behavior of the local coordination number in homonuclear diatomic fluids follows trends similar to those reported in previous studies for monatomic fluids. The local density augmentation is particularly sensitive to changes in solute size and is affected to a lesser degree by variations in the solute-solvent interaction strength and range. The associated solvation free energies exhibit a nonmonotonous behavior as a function of density for systems with weak solute-solvent interactions. The authors' results suggest that solute-solvent interaction anisotropies have a major influence on the nature and extent of local solvent density inhomogeneities and on the value of the solvation free energies in supercritical solutions of heteronuclear molecules.

  2. Significant substitution effects in dipolar and non-dipolar supercritical fluids.

    PubMed

    Kajiya, Daisuke; Saitow, Ken-ichi

    2011-06-21

    Vibrational Raman spectra of C=C stretching modes of ethylene derivates (cis-C(2)H(2)Cl(2), cis-stilbene, and trans-stilbene) were measured in supercritical fluids along an isotherm as functions of their densities. The substitution effect of the Raman shift is so significant that a difference among three solutes can be 20 times and is observed similarly in dipolar (CHF(3)) and non-dipolar (CO(2)) fluids. In particular, the shifts of trans-stilbene were enormously large among all systems for studies of vibrational spectroscopies of supercritical fluids and were equivalent to those of typical hydrogen-bonded fluids. Such large shifts arising from the significant attractive energy between solute and solvent molecules were attributed to a site-selective solvation around a phenyl group, which was driven by a dispersion force in the absence of steric hindrance. We found that the absence of steric hindrance causes the significant local density augmentation. To the best of our knowledge, Raman experiments and their theoretical analysis are the first ones quantifying how the difference of steric hindrance produces solvation structures in solution as well as supercritical solutions. © 2011 American Institute of Physics

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

    PubMed

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

    2012-04-01

    A new high-pressure cell design for use in neutron reflectometry (NR) for pressures up to 50 MPa and a temperature range of 300-473 K is described. The cell design guides the neutron beam through the working crystal without passing through additional windows or the bulk fluid, which provides for a high neutron transmission, low scattering background, and low beam distortion. The o-ring seal is suitable for a wide range of subcritical and supercritical fluids and ensures high chemical and pressure stability. Wafers with a diameter of 5.08 cm (2 in.) and 5 mm or 10 mm thickness can be used with the cells, depending on the required pressure and momentum transfer range. The fluid volume in the sample cell is very small at about 0.1 ml, which minimizes scattering background and stored energy. The cell design and pressure setup for measurements with supercritical fluids are described. NR data are shown for silicon/silicon oxide and quartz wafers measured against air and subsequently within the high-pressure cell to demonstrate the neutron characteristics of the high-pressure cell. Neutron reflectivity data for supercritical CO(2) in contact with quartz and Si/SiO(2) wafers are also shown. © 2012 American Institute of Physics

  4. A colorimetric reaction to quantify fluid mixing

    NASA Astrophysics Data System (ADS)

    Oates, Peter M.; Harvey, Charles F.

    2006-11-01

    We found the colorimetric reaction of Tiron (1,2-dihydroxybenzene-3,5-disulfonic acid) and molybdate suitable for optical quantification of chemical reaction during fluid-fluid mixing in laboratory chambers. This reaction consists of two colorless reagents that mix to rapidly form colored, stable, soluble products. These products can be digitally imaged and quantified using light absorbance to study fluid-fluid mixing. Here we provide a model and equilibrium constants for the relevant complexation reactions. We also provide methods for relating light absorbance to product concentrations. Practical implementation issues of this reaction are discussed and an example of imaged absorbances for fluid-fluid mixing in heterogeneous porous media is given.

  5. A supercritical fluid-based coating technology. 2: solubility considerations.

    PubMed

    Ribeiro Dos Santos, I; Thies, C; Richard, J; Le Meurlay, D; Gajan, V; VandeVelde, V; Benoit, J-P

    2003-01-01

    Solubility measurements of candidate coating materials have been performed in supercritical (SC) CO(2) so as to select appropriate coating materials for implementation of a solvent-free coating process previously described. Solubility of lipidic compounds such as waxes (paraffin, beeswax, Carnauba wax), pure triglycerides (tricaprin, trimyristin, tripalmitin, tristearin) and mixture of glycerides and fatty acid esters (Gelucire) in SC CO(2) were evaluated in a static mode under different temperature and pressure conditions, ranging from 13-52 degrees C and from 50-220 bar, whether the CO(2)was in its liquid or SC state. It was shown that the compounds which are mixtures of various components give rise to a selective extraction of the lower melting point components, as evidenced from thermal analysis of soluble and insoluble fractions of the coating materials.

  6. Liquefaction of Typha latifolia by supercritical fluid extraction.

    PubMed

    Aysu, Tevfik; Turhan, Mehmet; Küçük, Mehmet Maşuk

    2012-03-01

    Milled Typha latifolia stalk mill was converted to liquid products by using organic solvents (methanol, ethanol, acetone and 2-butanol) with catalysts (10% NaOH or Na(2)CO(3)) and without catalyst in an autoclave at temperatures of 518, 538 and 558 K. The products were extracted by liquid-liquid extraction (benzene and diethyl ether). The percentage yields from supercritical methanol, ethanol, 2-butanol and acetone conversions were 55.0, 58.5, 62.7 and 70.5 at 538 K, respectively. In the catalytic run with NaOH, the highest conversion was obtained by using ethanol as a solvent at the same temperature. Conversion yields were analyzed by GC-MS. The aim of the present study was to obtain an alternative for petroleum derived fuels or chemical raw materials. Copyright © 2011 Elsevier Ltd. All rights reserved.

  7. Membrane Separations Using Reverse Micelles in Nearcritical and Supercritical Fluid Solvents

    SciTech Connect

    Yonker, Clement R.; Fulton, John L.; Phelps, Max R.; Bowman, Lawrence E.

    2003-04-01

    The use of reverse micelles coupled with ultrafiltration membranes for the separation of macromolecules dissolved in the cores of the reverse micelles using nearcritical and supercritical fluid solvents is described. This methodology allows one to address the separation of a wide range of polar molecules greatly extending the type of molecules that can be separated using only pure supercritical fluids. The solutes to be separated are initially dissolved in the reverse micellar solution and introduce into the pressure vessel containing the membrane. The surfactant and water core are passed through the membrane while the macromolecule selectivity is based on size and molecular weight. The ability for continuous recycle in an extraction system is discussed.

  8. Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, January 1, 1994--March 31, 1994

    SciTech Connect

    Akgerman, A.; Bukur, D.B.

    1994-06-01

    We have successfully completed our first Fischer-Tropsch synthesis test with propane as the supercritical fluid. The catalyst activity and hydrocarbon product distribution under the SFT conditions were similar to those obtained during the normal Fischer-Tropsch synthesis, however, the use of supercritical fluid resulted in higher selectivity of the primary products. The use of a new trap with larger inside surface area, improved the collection of liquid products and thus enabling us to achieve better atomic and overall mass balance closures. This has also improved results from on-line GC analysis. However, further improvement are needed to achieve more stable and reproducible gas phase analysis, including the capability of the on-line analysis of the feed gas (mixture of hydrogen, carbon monoxide and propane).

  9. Isolation of oxidative degradation products of atorvastatin with supercritical fluid chromatography.

    PubMed

    Klobčar, Slavko; Prosen, Helena

    2015-12-01

    The isolation of four oxidative degradation products of atorvastatin using preparative high-performance liquid chromatography applying at least two chromatographic steps is known from the literature. In this paper it is shown that the same four impurities could be isolated from similarly prepared mixtures in only one step using supercritical fluid chromatography. The methods for separation were developed and optimized. The preparation of the mixtures was altered in such a way as to enhance the concentration of desired impurities. Appropriate solvents were applied for collection of separated impurities in order to prevent degradation. The structures of the isolated impurities were confirmed and their purity determined. The preparative supercritical fluid chromatography has proven to be superior to preparative HPLC regarding achieved purity of standards applying fewer chromatographic as well as isolation steps.

  10. Supercritical fluid extraction of pesticides from a table-ready food composite of plant origin (gazpacho).

    PubMed

    Aguilera, Ana; Brotons, María; Rodríguez, Mariano; Valverde, Antonio

    2003-09-10

    Supercritical fluid carbon dioxide extraction (SFE) has been evaluated for the extraction of 17 organohalogen and organophosphate pesticides in gazpacho (a table-ready food composite containing crude vegetables, white bread, vegetable oil, water, and other minor components) using anhydrous magnesium sulfate as drying agent. The effects of different parameters, such as fat content in gazpacho composites, magnesium sulfate/gazpacho ratio, supercritical fluid volume, pressure, temperature, and static modifier additions, on SFE recoveries from spiked gazpacho samples have been studied. Analyses were performed by gas chromatography (GC) with flame photometric (FPD), electron capture (ECD), and mass spectrometry (MSD) detectors. In most experiments, recoveries obtained for the nonpolar organohalogen pesticides were lower than those obtained for the most polar organophosphate pesticides, but overall pesticide recoveries determined by using the optimal SFE conditions indicate that SFE could be used to determine pesticide residue levels in gazpacho.

  11. A Novel Supercritical Fluid-Assisted Fabrication Technique for Producing Transparent Nanocomposites

    DTIC Science & Technology

    2013-10-03

    Supercritical Fluid Assisted Process Lih-Sheng Turng and Srikanth Pilla University of Wisconsin - Madison Suite 6401 21 N Park St Madison, WI 53715...Pilla Wisconsin Institute for Discovery University of Wisconsin–Madison 330 N. Orchard Street Madison, WI 53715 ARO-STIR Program Final Progress... compostable under simulated conditions in a composting facility. Experiments Material  PLA: 8052D from Nature Works  PPC: QPAC-40 from Empower

  12. Rapid analysis of polyolefin antioxidants and light stabilisers by supercritical fluid chromatography.

    PubMed

    Kithinji, J P; Bartle, K D; Raynor, M W; Clifford, A A

    1990-02-01

    Nineteen commercial antioxidants and light stabilisers, with a wide range of relative molecular masses and boiling-points, present in polyolefins were analysed by packed column supercritical fluid chromatography on four different phases with CO2 or 10% MeOH-CO2 as the mobile phase and with UV detection. The technique is shown to yield short analysis times and sufficient resolution for a number of additives present in a given polyolefin.

  13. Extending the range of supercritical fluid chromatography by use of water-rich modifiers.

    PubMed

    Liu, Jinchu; Regalado, Erik L; Mergelsberg, Ingrid; Welch, Christopher J

    2013-08-14

    In this study we investigate the recently reported use of water-containing modifiers for separation and purification of hydrophilic compounds by supercritical fluid chromatography. Improved peak shape is obtained for a variety of glycosides and otherwise hydrophilic compounds when 5% water is added to the methanol co-solvent used in SFC separations, and examples of the use of this approach in preparative SFC purifications are presented.

  14. Monodisperse microbeads of hypercrosslinked polystyrene for liquid and supercritical fluid chromatography

    NASA Astrophysics Data System (ADS)

    Tsyurupa, M. P.; Blinnikova, Z. K.; Il'in, M. M.; Davankov, V. A.; Parenago, O. O.; Pokrovskii, O. I.; Usovich, O. I.

    2015-11-01

    Monodisperse styrene-divinylbenzene (1 wt %) copolymer microbeads are obtained via the elaborate method of high-productivity precipitation polymerization. The crosslinking of this copolymer with chloromethyl methyl ether in the presence of Friedel-Crafts catalyst yields porous hypercrosslinked polymers with degrees of crosslinking that range from 200 to 500%. Microbead sorbents are shown to be suited for selective stationary phases for high-performance liquid chromatography and supercritical fluid chromatography.

  15. Phase and chemical equilibria in the transesterification reaction of vegetable oils with supercritical lower alcohols

    NASA Astrophysics Data System (ADS)

    Anikeev, V. I.; Stepanov, D. A.; Ermakova, A.

    2011-08-01

    Calculations of thermodynamic data are performed for fatty acid triglycerides, free fatty acids, and fatty acid methyl esters, participants of the transesterification reaction of vegetable oils that occurs in methanol. Using the obtained thermodynamic parameters, the phase diagrams for the reaction mixture are constructed, and the chemical equilibria of the esterification reaction of free fatty acids and the transesterification reaction of fatty acid triglycerides attained upon treatment with supercritical methanol are determined. Relying on our analysis of the obtained equilibria for the esterification reaction of fatty acids and the transesterification reaction of triglycerides attained upon treatment with lower alcohols, we select the optimum conditions for performing the reaction in practice.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    NASA Technical Reports Server (NTRS)

    Heinmiller, P. J.

    1971-01-01

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

  18. Solvent Supercritical Fluid Technologies to Extract Bioactive Compounds from Natural Sources: A Review.

    PubMed

    Khaw, Kooi-Yeong; Parat, Marie-Odile; Shaw, Paul Nicholas; Falconer, James Robert

    2017-07-14

    Supercritical fluid technologies offer a propitious method for drug discovery from natural sources. Such methods require relatively short processing times, produce extracts with little or no organic co-solvent, and are able to extract bioactive molecules whilst minimising degradation. Supercritical fluid extraction (SFE) provides a range of benefits, as well as offering routes to overcome some of the limitations that exist with the conventional methods of extraction. Unfortunately, SFE-based methods are not without their own shortcomings; two major ones being: (1) the high establishment cost; and (2) the selective solvent nature of CO₂, i.e., that CO₂ only dissolves small non-polar molecules, although this can be viewed as a positive outcome provided bioactive molecules are extracted during solvent-based SFE. This review provides an update of SFE methods for natural products and outlines the main operating parameters for extract recovery. Selected processing considerations are presented regarding supercritical fluids and the development and application of ultrasonic-assisted SFE methods, as well as providing some of the key aspects of SFE scalability.

  19. 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

  20. 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.

  1. Effects of Hexane in Supercritical Fluid Chromatography for the Separation of Enantiomers.

    PubMed

    Wu, Haihong; Yu, Stanley; Zeng, Lu

    2016-03-01

    Supercritical fluid chromatography (SFC), operated in conventional mode, is normally recognized as normal phase chromatography, and uses a solvent combination of supercritical CO2 and alcohols to separate compounds. Hexane, a commonly used solvent in normal phase liquid chromatography (NP-LC), is rarely used in SFC and, in some cases, is added to the organic modifiers to increase liquid content in order to achieve better efficiency in preparative SFC for poorly retained compounds. Although hexane is believed to have similar solvent strength to that of supercritical CO2, its effects on the enantioseparation in SFC is largely unknown. To understand the chromatographic effects of an apolar solvent, such as hexane in SFC, we compared the chromatographic behaviors of 35 chiral compounds using a parallel SFC method under traditional SFC mode of only “pure” alcohol-CO2 to that of hexane-assisted SFC (HA-SFC), which uses mixtures of alcohol and hexane (as cosolvents) and CO2. We observed that, in some cases, hexane behaves just like supercritical CO2, where replacement of a portion of CO2 with hexane does not significantly change retention times or resolution of the peaks. In many cases, however, addition of hexane in mobile phases does affect chromatographic behavior of one or both enantiomers. Such effects might provide opportunities for separation of some enantiomers.

  2. Leavened dough processing by supercritical fluid extrusion (SCFX).

    PubMed

    Hicsasmaz, Zeynep; Dogan, Esref; Chu, Cindy; Rizvi, Syed S H

    2003-10-08

    Yeast-leavened dough processing is semicontinuous due to the requirement for fermentation at constant temperature and humidity. Also, new regulations on the emission of alcohols are becoming burdensome on the baking industry. Extrusion processing of dough with supercritical carbon dioxide (SC-CO(2)) is envisioned to alleviate emission problems and to decrease production time by eliminating fermentation. A bread dough formulation with 50% (w/w) moisture was leavened by injecting 1.5% (w/w) SC-CO(2) in a twin-screw extruder at 37 degrees C. Specific mechanical energy input was 260 kJ/kg. The operating apparent shear rate range was 60-260 s(-1). SCFX-leavened dough density (420-430 kg/m(3)) was in good agreement with values reported for similar doughs. The flow behavior index, obtained by an on-line slit rheometer, was 0.49 for the nonleavened control and 0.63 for the SCFX-leavened dough. Apparent viscosity of the SCFX-leavened dough varied from 37 to 23 Pa-s. This new continuous process offers attractive possibilities for industrial applications if further developed.

  3. Spectroscopic Measurements of Radio Frequency Plasmas in Supercritical Fluids

    SciTech Connect

    Maehara, Tsunehiro; Iwamae, Atsushi; Kawashima, Ayato

    2010-10-29

    Spectroscopic measurements of radio frequency (rf) plasma were performed under high pressure CO{sub 2} conditions (5 and 7 MPa) and supercritical (sc)CO{sub 2} conditions (8-20 MPa). The temperatures evaluated from C{sub 2} Swan bands increased from 3600 K to 4600 K with increasing pressure. The broadening and shifting of the O I line profile ({approx}777 nm) of rf plasma was observed under scCO{sub 2} conditions. The width of the line profile increased with increasing pressure. The reason for the broadening and shifting is still unclear because the present theory used to explain them is not valid for such high pressure conditions. Further, the broadening of the Ar I line profile ({approx}811.5 nm) in rf plasmas was observed under atmospheric Ar (0.1 MPa), high pressure Ar conditions (1-4 MPa), and scAr condition (5 MPa); the observation of the O I line profile in CO{sub 2} plasmas is difficult in this pressure range owing to its weak intensity therein. Similar to the case of the O I line in CO{sub 2} plasmas, the reason for the broadening of the Ar I line profile at 5 MPa is unclear.

  4. Optimization of supercritical phase and combined supercritical/subcritical conversion of lignocellulose for hexose production by using a flow reaction system.

    PubMed

    Zhao, Yan; Lu, Wen-Jing; Wu, Hua-Yong; Liu, Jin-Wen; Wang, Hong-Tao

    2012-12-01

    A flow reaction system was utilized to investigate lignocellulose conversion using combined supercritical/subcritical conditions for hexose production. Initially, investigation of cellulose hydrolysis in supercritical water and optimization of reaction parameters were done. Oligosaccharide yields reached over 30% at cellulose concentrations of 3-5 gL(-1) and reaction times of 6-10s at 375 °C, and 2.5-4 gL(-1) and 8-10s at 380 °C. Temperatures above 380 °C were not appropriate for the supercritical phase in the combined process. Subsequently, conversion of lignocellulosic materials under combined supercritical/subcritical conditions was studied. Around 30% hexose was produced from corn stalks under the optimal parameters for supercritical (380 °C, 23-24 MPa, 9-10s) and subcritical (240 °C, 8-9 MPa, 45-50s) phases. Flow systems utilizing the combined supercritical/subcritical technology present a promising method for lignocellulosic conversion. The results of this study provide an important guide for the operational optimization and practical application of the proposed system.

  5. Time evolution of density fluctuation in the supercritical region. 2. Comparison of hydrogen- and non-hydrogen-bonded fluids.

    PubMed

    Kajiya, Daisuke; Nishikawa, Keiko; Saitow, Ken-ichi

    2005-08-25

    The time evolution of the density fluctuation of molecules is investigated by dynamic light scattering in six neat fluids in supercritical states. This study is the first to compare the dynamics of density inhomogeneity between hydrogen- and non-hydrogen-bonded fluids. Supercritical methanol and ethanol are used as hydrogen-bonded fluids, whereas four non-hydrogen-bonded fluids were used: CHF(3), C(2)H(4), CO(2), and Xe. We measure the time correlation function of the density fluctuation of each fluid at the same reduced temperatures and densities and investigate the relationship between the dynamic and static density inhomogeneities of those supercritical fluids. In all cases, the profile of the time correlation function of the density fluctuation is characterized by a single-exponential function, whose decay is responsible for the dynamics characterized by hydrodynamic conditions. We obtain correlation times from the time correlation function and discuss dynamic and static inhomogeneity using the Kawasaki theory and the Landau-Placzek theory. While the correlation times in the six fluids show noncoincidence, those values agree well with each other except for the supercritical alcohols when scaled to a dimensionless parameter. Although the principle of corresponding state is observed in the non-hydrogen-bonded fluids, both the supercritical methanol and ethanol deviate from that principle. This deviation is attributed to the presence of hydrogen bonding among alcohol molecules at high temperature and low density. The average cluster size of each fluid is estimated under the same thermodynamic conditions, and it is shown that the clusters of supercritical alcohols are on average 1.5-1.7 times larger than those of the four non-hydrogen-bonded fluids. Moreover, the thermal diffusivity of each neat fluid is obtained over wide ranges of density and temperature.

  6. Supercritical synthesis of biodiesel.

    PubMed

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

    2012-07-23

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

  7. The continuous acid-catalyzed dehydration of alcohols in supercritical fluids: A new approach to the cleaner synthesis of acetals, ketals, and ethers with high selectivity

    SciTech Connect

    Gray, W.K.; Smail, F.R.; Hitzler, M.G.; Ross, S.K.; Poliakoff, M.

    1999-11-24

    This report describes a new a continuous method for forming ethers, acetals and ketals using solid acid catalysts, DELOXAN ASP or AMBERLYST 15, and supercritical fluid solvents. In the case of ether formation, the authors observe a high selectivity for linear alkyl ethers with little rearrangement to give branches ethers. Such rearrangement is common in conventional synthesis. The approach is effective for a range of n-alcohols up to n-octanol and also for the secondary alcohol 2-propanol. In the reaction of phenol with an alkylating agent, the continuous reaction can be tuned to give preferential O- or C-alkylation with up to 49% O-alkylation with supercritical propene. The authors also investigate the synthesis of a range of cyclic ethers and show an improved method for the synthesis of THF from 1,4-butandiol under very mild conditions.

  8. Orthogonal array design for the optimization of supercritical fluid extraction of baicalin from roots of Scutellaria baicalensis Georgi.

    PubMed

    Chang, Yiling; Liu, Ben; Shen, Bo

    2007-07-01

    Supercritical fluid was used to extract baicalin from the roots of Scutellaria baicalensis Georgi. An orthogonal array design (OAD), OA(9)(3(4)), was employed as a chemometric method for the optimization of the supercritical fluid extraction of baicalin from the herbal medicine. Four parameters, namely, modifiers, temperature and pressure of supercritical fluid, and the dynamic extraction time, were studied and optimized by a three-level OAD in which the interactions between the parameters were neglected. Determinations of the extracts were performed by high-performance liquid chromatography. The effects of parameters were studied using analysis of variance. The results showed that selection of the modifier was the main factor in attaining higher yields of baicalin. While the other three factors had some effect on the extraction of the compound, the effect was much less than that of the modifiers. 1,2-Propanediol-modified supercritical fluid was more effective than 95% ethanol-modified supercritical carbon dioxide or methanol-modified supercritical carbon dioxide for the extraction of baicalin from the solid matrix. Finally, experimental conditions were proposed which can provide the highest extraction yield with respect to the considered factors.

  9. Fischer-Tropsch synthesis in supercritical reaction media. Progress report, July 10, 1992--September 30, 1992

    SciTech Connect

    Subramaniam, B.

    1992-10-01

    The goal of this research is to thoroughly investigate the feasibility of using supercritical fluid (SCF) solvent medium for carrying out Fischer-Tropsch (FT) synthesis. Research will address the systematic experimental investigations of FT synthesis over supported Fe and Co catalysts in a CSTR and in a fixed-bed reactor at typical synthesis temperatures (240-260{degrees}C). The SCF medium to be employed is n-Hexane (P{sub c} = 29.7 bar; {Tc} = 233.7{degrees}C), while n-Hexadecane will be employed as the liquid reaction medium. Overall conversion, product distribution and catalyst deactivation will be measured in each case for various feed H{sub 2}/CO ratios ranging from 0.5 to 2. Product analyses will be carried out using GC/TCD, GC/FID and GC/MS systems. The fresh and used catalysts will be characterized with respect to active metal dispersion, surface area and pore size distribution.

  10. 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.

  11. Initial results for supercritical cycle experiments using pure and mixed-hydrocarbon working fluids

    SciTech Connect

    Bliem, C.J.; Mines, G.L.

    1984-01-01

    The Heat Cycle Research Program, which is being conducted for the Department of Energy, has as its objective the development of the technology for effecting improved utilization of moderate temperature geothermal resources. Testing at the Heat Cycle Research Facility (HCRF) located at the DOE Geothermal Test Facility (GTF), East Mesa, California, is presently being conducted to meet this objective. Current testing involves a supercritical vaporization and countercurrent in-tube condensing system. The paper presents a brief description of the test facility and a discussion of the test program. Preliminary results on the performance of the supercritical heaters, countercurrent in-tube condenser, and turbine are given for both pure and mixed-hydrocarbon working fluids.

  12. Processing High Level Waste: Spectroscopic Characterization of Redox Reactions in Supercritical Water

    SciTech Connect

    Arrington, Jr., Charles A.

    2000-06-01

    We are engaged in a collaborative research effort with Los Alamos staff scientists Steven Buelow and Jeanne Robinson, staff members in group CST-6. The work proposed by these LANL staff scientists is directed towards the destruction of complexants and oxidation of chromium and technetium by hydrothermal processing in near critical or supercritical aqueous solutions. Our own work has been focused on a careful kinetic study of oxidation reactions of hydrogen peroxide with chromium hydroxide. This reaction occurs readily at ambient temperatures.

  13. [Fluid dynamics of supercritical helium within internally cooled cabled superconductors

    SciTech Connect

    Van Sciver, S.W.

    1995-06-01

    The Applied Superconductivity Center of the University of Wisconsin-Madison proposes to conduct research on low temperature helium fluid dynamics as it applies to the cooling of internally cooled cabled superconductors (ICCS). Such conductors are used in fusion reactor designs including most of the coils in ITER. The proposed work is primarily experimental involving measurements of transient and steady state pressure drop in a variety of conductor configurations. Both model and prototype conductors for actual magnet designs will be investigated. The primary goal will be to measure and model the friction factor for these complex geometries. In addition, an effort will be made to study transient processes such as heat transfer and fluid expulsion associated with quench conditions.

  14. Supercritical fluid chromatography/supersonic jet spectroscopy. Progress report, November 1, 1983-January 31, 1984. [Supersonic jet spectroscopy

    SciTech Connect

    Lee, M.L.; Goates, S.R.

    1984-01-01

    Modifications were made in the designs for the supercritical fluid extraction/fractionation unit and the vacuum chamber for supersonic jet spectroscopy. The construction of the extraction/fractionation unit is nearly complete and the construction of the vaccum system is presently underway. An interface has been constructed for supercritical fluid chromatography - mass spectrometry based on direct fluid injection with provision for circulating a heated liquid for precise temperature control. Initial experiments indicate effective transfer of the chromatographic effluent, and preservation of chromatographic efficiency. 1 reference, 4 figures.

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

    SciTech Connect

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

    2012-07-01

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

  16. 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.

  17. Extraction of Plutonium From Spiked INEEL Soil Samples Using the Ligand-Assisted Supercritical Fluid Extraction (LA-SFE) Technique

    SciTech Connect

    Fox, R.V.; Mincher, B.J.; Holmes, R.G.G.

    1999-08-01

    In order to investigate the effectiveness of ligand-assisted supercritical fluid extraction for the removal of transuranic contaminations from soils an Idaho National Engineering and Environmental Laboratory (INEEL) silty-clay soil sample was obtained from near the Radioactive Waste Management Complex area and subjected to three different chemical preparations before being spiked with plutonium. The spiked INEEL soil samples were subjected to a sequential aqueous extraction procedure to determine radionuclide portioning in each sample. Results from those extractions demonstrate that plutonium consistently partitioned into the residual fraction across all three INEEL soil preparations whereas americium partitioned 73% into the iron/manganese fraction for soil preparation A, with the balance partitioning into the residual fraction. Plutonium and americium were extracted from the INEEL soil samples using a ligand-assisted supercritical fluid extraction technique. Initial supercritical fluid extraction runs produced plutonium extraction technique. Initial supercritical fluid extraction runs produced plutonium extraction efficiencies ranging from 14% to 19%. After a second round wherein the initial extraction parameters were changed, the plutonium extraction efficiencies increased to 60% and as high as 80% with the americium level in the post-extracted soil samples dropping near to the detection limits. The third round of experiments are currently underway. These results demonstrate that the ligand-assisted supercritical fluid extraction technique can effectively extract plutonium from the spiked INEEL soil preparations.

  18. Fluid flow, mineral reactions, and metasomatism

    SciTech Connect

    Ferry, J.M.; Dipple, G.M. )

    1991-03-01

    A general model that relates fluid flow along a temnperature gradient to chemical reaction in rocks can be used to quantitatively interpret petrologic and geochemical data on metasomatism from ancient flow systems in terms of flow direction and time-integrated fluid flux. The model is applied to regional metamorphism, quartz veins, and a metasomatized ductile fault zone.

  19. Supercritical Water Process for the Chemical Recycling of Waste Plastics

    NASA Astrophysics Data System (ADS)

    Goto, Motonobu

    2010-11-01

    The development of chemical recycling of waste plastics by decomposition reactions in sub- and supercritical water is reviewed. Decomposition reactions proceed rapidly and selectively using supercritical fluids compared to conventional processes. Condensation polymerization plastics such as PET, nylon, and polyurethane, are relatively easily depolymerized to their monomers in supercritical water. The monomer components are recovered in high yield. Addition polymerization plastics such as phenol resin, epoxy resin, and polyethylene, are also decomposed to monomer components with or without catalysts. Recycling process of fiber reinforced plastics has been studied. Pilot scale or commercial scale plants have been developed and are operating with sub- and supercritical fluids.

  20. The Iceland Deep Drilling Project (IDDP): (4) A Quartz Fluid Inclusion Tool for Sampling Supercritical Geothermal Fluids Downhole

    NASA Astrophysics Data System (ADS)

    Reed, M. H.; Grist, H.; Fridriksson, T.; Danielsen, P.; Senkovich, D.; Johnston, A.; Elders, W. A.; Fridleifsson, G. O.

    2009-12-01

    Chemical analyses of in situ samples of supercritical geothermal fluids would provide a uniquely good measure of fluid composition at depth relative to compositions reconstructed from analyses of gas and liquid sampled at wellheads. Fluids sampled at the wellhead are commonly a mixture from multiple aquifers and, in many circumstances, they lack components such as sulfate, sulfide, Ca, Cu, Zn, and Fe that precipitated in scale minerals where the fluids boiled or cooled during their ascent. To circumvent the above problems and the failings of downhole mechanical samplers at temperatures exceeding 300°C and to obtain total fluid samples at supercritical conditions in the IDDP wells, we plan to trap fluids in fluid inclusions formed in fractured quartz that we suspend in a geothermal well on a wireline. In a series of hydrothermal laboratory experiments at 450°C and 600 bar and spanning 6 hr to 5 days in length, thermal shock fractures in natural and synthetic quartz crystals heal, forming ragged fluid inclusions in one day and many well formed inclusions in three days. Amorphous silica is added to the experimental charge, without which, fractures heal little and only 1-2 micron inclusions form. Microthermometry measurements on the inclusions produced in experiments return the run temperature within 20°C at the experimental pressure, indicating that inclusions formed and sealed at the run conditions. The fluid inclusion tool (FIT) consists of a perforated stainless steel pipe containing multiple stainless steel mesh canisters with non-mesh ends to minimize vertical fluid flow. The canisters contain 10mm-scale chunks of fractured quartz surrounded by ground quartz glass. The perforated pipe will be fixed within a one-meter outer perforated stainless steel housing that is suspended on a stainless steel slick line. The FIT is weighed by one or more 10kg lead sinker bars. The entire assembly is lowered into the well from a lubricator fitted on the wellhead, thus

  1. The Effects of Supercritical Fluids on High Performance Polymers

    DTIC Science & Technology

    1989-02-01

    testing was conduted on an Instron Tensile Tester using a 0-100 lb cell fitted with Kallaway Clamps. Tests were run an 10 i samples of yarn drawn at a...degraded. We concluded that in these runs the teperature was too high and the primary reaction was thermal degradation of the polymer. When methanol...temperature of methanol is sufficiently high that thermal degradation processes cxmpete with amide alcoholysis. Similar results were obtained with nylon 6

  2. Growth and Morphology of Phase Separating Supercritical Fluids

    NASA Technical Reports Server (NTRS)

    Hegseth, John; Beysens, Daniel; Perrot, Francoise; Nikolayev, Vadim; Garrabos, Yves

    1996-01-01

    The scientific objective is to study the relation between the morphology and the growth kinetics of domains during phase separation. We know from previous experiments performed near the critical point of pure fluids and binary liquids that there are two simple growth laws at late times. The 'fast' growth appears when the volumes of the phases are nearly equal and the droplet pattern is interconnected. In this case the size of the droplets grows linearly in time. The 'slow' growth appears when the pattern of droplets embedded in the majority phase is disconnected. In this case the size of the droplets increases in proportion to time to the power 1/3. The volume fraction of the minority phase is a good candidate to determine this change of behavior. All previous attempts to vary the volume fraction in a single experimental cell have failed because of the extreme experimental difficulties.

  3. Stripping of photoresist on silicon wafer by CO(2) supercritical fluid.

    PubMed

    Chen, Jian-Lian; Wang, Yeoung-Sheng; Kuo, Hsin-I; Shu, Dun-Ying

    2006-09-15

    Supercritical CO(2)-based fluid is not only being considered as environmentally benign medium for photoresist (PR) removal in electronic device manufacture, but also capable of challenging feature dimensions. Despite many attractive properties, clear supercritical CO(2) has little solvating power for PR. Here, two acetate modifiers were selective to add in the CO(2) and evaluated individual contribution to the overall stripping rate by factorial experiment design, which included four other factors with four level ranges for each one and concluded the best 90% extraction efficiency would be obtained under the optimized parameters: 2.5min static time, 35min dynamic time, 1.25ml ethylacetate spiked, 125 degrees C oven temperature and 480atm CO(2) pressure. As analyzing the variances of these contributors to this system, it disclosed that dynamics controlled the stripping mechanism before near 35min purging but thermodynamics took over after then; and that increasing pressure was more competent for removing PR than increasing temperature. All supercritical extracts were from two commercial PR coated on two substrates and analyzed by UV absorption spectrometry. Removing PR coated on silicon oxide layer was easier than that on Al-Cu alloy one.

  4. Supercritical fluid extraction and characterization of lipids from algae Scenedesmus obliquus.

    PubMed

    Choi, K J; Nakhost, Z; Krukonis, V J; Karel, M

    1987-01-01

    Supercritical carbon dioxide (SC-CO2) extractions (with and without ethanol as an entrainer) were carried out to remove lipids and pigments from protein concentrate of green algae (Scenedesmus obliquus) cultivated under controlled conditions. The content and fatty acid composition of algal lipids using column, thin-layer (TLC) and gas-liquid chromatography (GLC) were determined. Absorption spectra of extracted fractions showed the predominance of chlorophyll A (lambda max at 410 nm). Single step supercritical carbon dioxide (SC-CO2) extraction resulted mostly in removal of neutral lipids and a part of glycolipids, but phospholipids were not extracted. Addition of ethanol to SC-CO2 increased the amount of glycolipids and phospholipids in the extract. TLC pattern of algal lipids showed that the main part of neutral lipids consisted of diglycerides, triglycerides, hydrocarbons, free sterols, and sterol esters. The glycolipids were mostly monogalactosyl diglyceride, digalactosyl diglyceride, esterified sterol glycoside, and sterol glycoside. In phospholipids, phosphatidyl choline, phosphatidyl glycerol, and phosphatidyl ethanolamine were the main compounds. Fatty acid composition patterns indicated the main fatty acids to be 16:0, 16:1, 16:2, 16:3, 16:4, 18:1, 18:2, and 18:3(a). Relatively high recovery of polyunsaturated fatty acids and essential fatty acids in supercritical fluid extracted algal lipids and proteins isolates were observed.

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

    PubMed

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

    2011-12-01

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

  6. Comparison of supercritical fluid and Soxhlet extractions for the quantification of hydrocarbons from Euphorbia macroclada.

    PubMed

    Ozcan, Adnan; Ozcan, Asiye Safa

    2004-10-08

    This study compares conventional Soxhlet extraction and analytical scale supercritical fluid extraction (SFE) for their yields in extracting of hydrocarbons from arid-land plant Euphorbia macroclada. The plant material was firstly sequentially extracted with supercritical carbon dioxide, modified with 10% methanol (v/v) in the optimum conditions that is a pressure of 400atm and a temperature of 50 degrees C and then it was sonicated in methylene chloride for an additional 4h. E. macroclada was secondly extracted by using a Soxhlet apparatus at 30 degrees C for 8h in methylene chloride. The validated SFE was then compared to the extraction yield of E. macroclada with a Soxhlet extraction by using the Student's t-test at the 95% confidence level. All of extracts were fractionated with silica-gel in a glass column to get better hydrocarbon yields. Thus, the highest hydrocarbons yield from E. macroclada was achieved with SFE (5.8%) when it compared with Soxhlet extractions (1.1%). Gas chromatography (GC) analysis was performed to determine the quantitative hydrocarbons from plant material. The greatest quantitative hydrocarbon recovery from GC was obtained by supercritical carbon dioxide extract (0.6mgg(-1)).

  7. Enhanced coal liquefaction by hydropyrolysis in supercritical fluids. Quarterly report, April-June 1984

    SciTech Connect

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

    1984-01-01

    Investigation of dibenzyl ether (DBE) thermolysis in supercritical water has continued with a study of the influence of water density on DBE consumption and product yields at the reaction temperature of 374/sup 0/C. The degree to which DBE pyrolysis is affected by water density can be clearly demonstrated by considering these data for a specific reaction time of 20 minutes. As the reduced density is increased from 0.2 to 1.3, the fraction of DBE remaining after 20 minutes decreases from approximately 0.90 to less than 0.10. Further work has also been done on the pyrolysis of benzyl phenyl amine (BPA). Pyrolysis of BPA in subcritical water at 340/sup 0/C gave a product spectrum similar to that obtained for pyrolysis in supercritical water at 386/sup 0/C. However, the yield of aniline decreased slighly with reduced temperature and the yield of toluene decreased substantially with reduced temperature. The product spectrum of BPA pyrolysis in a mixture of water and tetralin at 386/sup 0/C was comparable to that found in previous experiments. Major products were aniline and toluene with lesser amounts of benzyl alcohol. The yield of toluene was unaffected by the addition of tetralin, while the aniline yield and overall BPA conversion decreased from values obtained by pyrolysis in supercritical water. The effect of the addition of tetralin on benzyl alcohol yield could not be determined from the present experimental results. Investigation of the phase equilibria at elevated temperatures and pressures for model coal-derived compounds in supercritical methanol has continued.

  8. Preparative chromatography with supercritical fluids. Comparison of simulated moving bed and batch processes.

    PubMed

    Peper, Stephanie; Johannsen, Monika; Brunner, Gerd

    2007-12-28

    Preparative chromatography is a key technology for the separation of fine chemicals in production scale. Most of the published studies are carried out using liquid solvents as mobile phase. However, the used organic solvents can often be replaced by supercritical fluids. A reduction or renouncement of organic solvents does not only correspond to the trend of the so-called green chemistry--a sustainable, environmentally friendly production of chemical products. But a changeover to chromatography with supercritical fluids can also be reasonable under economic criteria. In this contribution a comparison between the Batch-supercritical fluid chromatography (Batch-SFC) process and the simulated moving bed (SMB)-SFC process is presented. Because of the minor importance of solvent consumption and solvent recovery in SFC, the separation systems were optimized primarily in terms of their specific productivity. For three of the four investigated model systems, the specific productivity of the SMB process is significantly higher than the productivity of the Batch process. Due to the fact, that the process with the higher specific productivity is not inevitably the more economical process, supplementary the costs of the process were considered. Therefore the comparison of the two processes was done from an economic point of view considering the minimum product price that has to be realized to fulfill the defined economic aim. It was found that although the optimized specific productivities of the SMB process were significantly higher than the productivities of the Batch process, the Batch process is the more profitable process for the investigated production rate range between 0.4 and 5t/a.

  9. An accurate equation of state for the exponential-6 fluid applied to dense supercritical nitrogen

    NASA Astrophysics Data System (ADS)

    Fried, Laurence E.; Howard, W. Michael

    1998-11-01

    The exponential-6 potential model is widely used in fluid equation of state studies. We have developed an accurate and efficient complete equation of state for the exponential-6 fluid based on HMSA integral equation theory and Monte Carlo calculations. Our equation of state has average fractional error of 0.2% in pV/NkBT and 0.3% in the excess energy Uex/NkBT. This is a substantial improvement in accuracy over perturbation methods, which are typically used in treatments of dense fluid equations of state. We have applied our equation of state to the problem of dense supercritical N2. We find that we are able to accurately reproduce a wide range of material properties with our model, over a range 0.01⩽P⩽100 GPa and 298⩽T⩽15 000 K.

  10. Isomorphic classical molecular dynamics model for an excess electronin a supercritical fluid

    SciTech Connect

    Miller III, Thomas F.

    2008-08-04

    Ring polymer molecular dynamics (RPMD) is used to directly simulate the dynamics of an excess electron in a supercritical fluid over a broad range of densities. The accuracy of the RPMD model is tested against numerically exact path integral statistics through the use of analytical continuation techniques. At low fluid densities, the RPMD model substantially underestimates the contribution of delocalized states to the dynamics of the excess electron. However, with increasing solvent density, the RPMD model improves, nearly satisfying analytical continuation constraints at densities approaching those of typical liquids. In the high density regime, quantum dispersion substantially decreases the self-diffusion of the solvated electron. In this regime where the dynamics of the electron is strongly coupled to the dynamics of the atoms in the fluid, trajectories that can reveal diffusive motion of the electron are long in comparison to {beta}{h_bar}.

  11. Experimental evidence of symmetry-breaking supercritical transition in pipe flow of shear-thinning fluids

    NASA Astrophysics Data System (ADS)

    Wen, Chaofan; Poole, Robert J.; Willis, Ashley P.; Dennis, David J. C.

    2017-03-01

    Experimental results reveal that the asymmetric flow of shear-thinning fluid through a cylindrical pipe, which was previously associated with the laminar-turbulent transition process, appears to have the characteristics of a nonhysteretic, supercritical instability of the laminar base state. Contrary to what was previously believed, classical transition is found to be responsible for returning symmetry to the flow. An absence of evidence of the instability in simulations (either linear or nonlinear) suggests that an element of physics is lacking in the commonly used rheological model for inelastic shear-thinning fluids. These unexpected discoveries raise new questions regarding the stability of these practically important fluids and how they can be successfully modeled.

  12. pardInvestigation of the Direct Hydrogenation of Aluminum to Alane in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Jensen, Craig; McGrady, Sean; Ayabe, Reyna; Reddy, Ben

    2007-03-01

    Alane, AlH3 has many of the properties that are requisite for materials to be considered viable for onboard hydrogen storage applications. Most notibly, it contains 10.1 wt% hydrogen and undergoes dehydrogenation at appreciable rates at temperatures below 100^oC. However, the very low, >= 6 kJ/mol, enthalpy of dehydrogenation of AlH3 prohibits subsequent re-hydrogenation through standard gas-solid techniques except at very high pressures or very low temperatures. The extremely low solubility of gaseous H2 in conventional organic solvents also vitiates a solution-based approach. Re-hydrogenation of Al using a supercritical fluid potentially offers a workable approach since the fluid can act as a solvent, at the same time remaining completely miscible with permanent gases like hydrogen. Recently, it has been found that mixtures of NaH and Al can be hydrogenated to sodium alanate, NaAlH4 under modest pressures and temperatures in supercritical fluids. We have now extended these studies to the hydrogenation of Al to AlH3. The results of these studies and experimental details will be reported.

  13. The separation of lanthanides and actinides in supercritical fluid carbon dioxide

    DOE PAGES

    Mincher, Bruce J.; Wai, Chien M.; Fox, Robert V.; ...

    2015-10-28

    Supercritical fluid carbon dioxide presents an attractive alternative to conventional solvents for recovery of the actinides and lanthanides. Carbon dioxide is a good solvent for fluorine and phosphate-containing ligands, including the traditional tributylphosphate ligand used in process-scale uranium separations. Actinide and lanthanide oxides may even be directly dissolved in carbon dioxide containing the complexes formed between these ligands and mineral acids, obviating the need for large volumes of acids for leaching and dissolution, and the corresponding organic liquid–liquid solvent extraction solutions. As a result, examples of the application of this novel technology for actinide and lanthanide separations are presented.

  14. 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

  15. [Separation of enantiomers by supercritical fluid chromatography on polysaccharide derivative-based chiral stationary phases].

    PubMed

    Li, Dongyan; Wu, Xi; Hao, Fangli; Yang, Yang; Chen, Xiaoming

    2016-01-01

    Eleven kinds of chiral compounds have been well separated within 10 min on polysaccharide derivative-based chiral stationary phases named Chiralpak IA, IB, IC, ID, IE and IF by supercritical fluid chromatography (SFC). The chiral recognition of these chiral compounds has demonstrated good complementary enantioselectivities of the six chiral columns, which were proved to be useful for chiral SFC. Both the elution time and enantioselectivies could be significantly affected by the modifier types and their concentrations, such as methanol, ethanol and isopropanol, which should be optimized during the experiments. In addition, the solvent versatility of the immobilized chiral stationary phase on the optimization of the chiral separation was helpful.

  16. Advances in supercritical fluid spray application of low-pollution coatings

    SciTech Connect

    Nielsen, K.A.; Dickson, D.J.; Derderian, E.J.; Glancy, C.W.; Goad, J.D.

    1991-12-31

    The volatile organic compound (VOC) content of coating formulations, which causes ozone formation in the environment, has now been reduced up to 80% by using supercritical carbon dioxide to replace volatile organic solvents in conventional coating formulations. Toxic solvents classified as hazardous air pollutants by the Clean Air Act can be totally eliminated. The concept can also be applied to high-solids coatings (1) to further reduce VOC emissions and (2) to improve coating performance by using higher molecular weight polymers. Commercial fluid delivery equipment and spray guns are now available. The technology is being demonstrated on industrial spray lines.

  17. [The extraction technology of epigoitri from isatidis radix by supercritical CO2 fluid].

    PubMed

    Nian, Si-Hui; Liu, Chun-Yun; Liu, Li-Min; Yang, Li-Fen

    2013-07-01

    To study the extraction technology of epigoitri from Isatidis Radix by supercritical CO2 fluid. The effects of pressure, temperature, time, concentration and dosage of alcohol were studied by single factor analysis and orthogonal test. The optimized conditions were as follows: The pressure was 20 MPs, the temperature was 50 degrees C, the time was 2 h, concentration of alcohol was 100%, dosage was 80 mL. The content of epigoitri in the extract could reach 38.63% under the above conditions. This method is simple, rapid and it is suitable for the extraction of epigoitri from Isatidis Radix.

  18. Molecular-scale remnants of the liquid-gas transition in supercritical polar fluids.

    PubMed

    Sokhan, V P; Jones, A; Cipcigan, F S; Crain, J; Martyna, G J

    2015-09-11

    An electronically coarse-grained model for water reveals a persistent vestige of the liquid-gas transition deep into the supercritical region. A crossover in the density dependence of the molecular dipole arises from the onset of nonpercolating hydrogen bonds. The crossover points coincide with the Widom line in the scaling region but extend farther, tracking the heat capacity maxima, offering evidence for liquidlike and gaslike state points in a "one-phase" fluid. The effect is present even in dipole-limit models, suggesting that it is common for all molecular liquids exhibiting dipole enhancement in the liquid phase.

  19. Enantioseparation of methamphetamine by supercritical fluid chromatography with cellulose-based packed column.

    PubMed

    Segawa, Hiroki; Iwata, Yuko T; Yamamuro, Tadashi; Kuwayama, Kenji; Tsujikawa, Kenji; Kanamori, Tatsuyuki; Inoue, Hiroyuki

    2017-02-04

    The enantiomers of methamphetamine were differentiated by supercritical fluid chromatography (SFC) with an enantioselective cellulose-based packed column. The optimization of the chromatographic conditions was achieved by changing column temperature, co-solvent proportion, additive concentration, flow rate and back pressure. In particular, the additive concentration crucially changed the resolution between the enantiomers. After determining the optimized conditions, the enantiomers of methamphetamine were successfully separated. The analytical precision, accuracy and limit of detection were checked by using the authentic standard and seized real samples. We believe that chiral SFC is a promising method for enantioseparation of forensic samples.

  20. Processing of polyphenolic composites with supercritical fluid anti-solvent technology

    NASA Astrophysics Data System (ADS)

    Kurniawansyah, Firman; Mammucari, Raffaella; Foster, Neil R.

    2017-05-01

    Polyphenols have been developed, primarily exploiting their robust antioxidant properties, for medical and food applications. In spite of their advantages, polyphenolic compounds have drawbacks from their natural characteristics of being poorly soluble in aqueous solutions, thermo-labile and low oral bioavailaibility. In this article, strategy of processing with supercritical fluid (SCF) anti-solvent to improve the shortcomings is overviewed. Information obtained from the existing studies commonly confirms SCF technology applicability to produce composites of polyphenols with various morphology, size distributions and crystallinity. The application of SCF technology also enables to develop polyphenolic composites for alternative drug delivery such as in the pulmonary administrations.

  1. Molecular-Scale Remnants of the Liquid-Gas Transition in Supercritical Polar Fluids

    NASA Astrophysics Data System (ADS)

    Sokhan, V. P.; Jones, A.; Cipcigan, F. S.; Crain, J.; Martyna, G. J.

    2015-09-01

    An electronically coarse-grained model for water reveals a persistent vestige of the liquid-gas transition deep into the supercritical region. A crossover in the density dependence of the molecular dipole arises from the onset of nonpercolating hydrogen bonds. The crossover points coincide with the Widom line in the scaling region but extend farther, tracking the heat capacity maxima, offering evidence for liquidlike and gaslike state points in a "one-phase" fluid. The effect is present even in dipole-limit models, suggesting that it is common for all molecular liquids exhibiting dipole enhancement in the liquid phase.

  2. Cleanliness of common air sampling sorbents for application to phenolic compounds measurement using supercritical fluid extraction

    SciTech Connect

    Bowyer, J.R.; Pleil, J.D.

    1994-12-31

    The trace-level measurement of phenolic compounds in the ambient air is complicated by the acidic and polar nature of the compounds especially during recovery from the sampling medium. Recently, supercritical fluid extraction (SFE) has been proposed as an alternative extraction method to Soxhlet extraction or thermal desorption to achieve more efficient recoveries. For such methodology to become practical, the candidate sorbents must first be tested for stability and cleanliness under SFE conditions. This paper describes exploratory research results of background contamination tests and cleanup properties of some common air sampling sorbent media with respect to future application to phenolic compounds monitoring.

  3. Cleanliness of common air sampling sorbents for application to phenolic compounds measurement using supercritical fluid extraction

    SciTech Connect

    Bowyer, J.R.; Pleil, J.D.

    1994-01-01

    The trace-level measurement of phenolic compounds in the ambient air is complicated by the acidic and polar nature of the compounds especially during recovery from the sampling medium. Recently, supercritical fluid extraction (SFE) has been proposed as an alternative extraction method to Soxhlet extraction or thermal desorption to achieve more efficient recoveries. For such methodology to become practical, the candidate sorbents must first be tested for stability and cleanliness under SFE conditions. The paper describes exploratory research results of background contamination tests and cleanup properties of some common air sampling sorbent media with respect to future application to phenolic compounds monitoring.

  4. [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.

  5. MR measurement of critical phase transition dynamics and supercritical fluid dynamics in capillary and porous media flow.

    PubMed

    Rassi, Erik M; Codd, Sarah L; Seymour, Joseph D

    2012-01-01

    Supercritical fluids (SCF) are useful solvents in green chemistry and oil recovery and are of great current interest in the context of carbon sequestration. Magnetic resonance techniques were applied to study near critical and supercritical dynamics for pump driven flow through a capillary and a packed bed porous media. Velocity maps and displacement propagators measure the dynamics of C(2)F(6) at pressures below, at, and above the critical pressure and at temperatures below and above the critical temperature. Displacement propagators were measured at various displacement observation times to quantify the time evolution of dynamics. In capillary flow, the critical phase transition fluid C(2)F(6) showed increased compressibility compared to the near critical gas and supercritical fluid. These flows exhibit large variations in buoyancy arising from large changes in density due to very small changes in temperature.

  6. 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

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

    PubMed

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

    2007-02-01

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

  8. Electron attachment to oxygen in supercritical hydrocarbon fluids

    NASA Astrophysics Data System (ADS)

    Nishikawa, Masaru; Holroyd, R. A.

    1983-10-01

    The rate of attachment of electrons to oxygen was studied in methane, ethane, and propane gas above the critical temperatures up to pressures of ˜200 atm. For all three gases, the rate increases with density and levels off above N=3×1021 molecules/cm3. For ethane, there is little or no effect of temperature on the rate between 25 and 75 °C and the rate is independent of electric field (E) up to E/N=1.2×10-18 V cm2, but increases at higher values of E/N. To explain the results, it is suggested that the energetics of the attachment reaction change with density; i.e., the energy level of the electron in the media (V0) and the polarization energy (P-) of O2- change with N. The rate of attachment increases with the energy term ET=V0-P-+Ek, where Ek is the electron kinetic energy, similar to the way the attachment rate increases with electron kinetic energy in the dilute gas.

  9. Characterization of five chemistries and three particle sizes of stationary phases used in supercritical fluid chromatography.

    PubMed

    Khater, S; West, C; Lesellier, E

    2013-12-06

    Sub-2-microns particles employed as supporting phases are known to favor column efficiency. Recently a set of columns based on sub-2-microns particles for use with supercritical fluid mobile phases have been introduced by Waters. Five different stationary phase chemistries are available: BEH silica, BEHEthyl-pyridine, X Select CSH Fluorophenyl, HSS C18 SB and BEH Shield RP18. This paper describes the characterization of 15 stationary phases, the five different chemistries, and three particle sizes, 1.7 (or 1.8), 3.5 and 5 microns, with the same carbon dioxide–methanol mobile phase and a set of more than a hundred compounds. The interactions established in the 15 different chromatographic systems used in supercritical fluid chromatography (SFC) are assessed with linear solvation energy relationships (LSERs).The results show the good complementarity of the five column chemistries, and their comparative location inside a classification map containing today around 70 different commercial phases. Among the five different chemistries, the HSS C18 SB phase displays a rather unusual behavior in regards of classical C18 phases, as it displays significant hydrogen–bonding interactions. Besides, it appears, as expected, that the BEH Ethyl–pyridine phase has weak interactions with basic compounds. The effect of particle size was studied because smaller particles induce increased inlet and internal pressure. For compressible fluids,this pressure change modifies the fluid density, i.e. the apparent void volume and the eluting strength.These changes could modify the retention and the selectivity of compounds in the case of method trans-fer, by using different particle sizes, from 5 down to 1.7 m. A hierarchical cluster analysis shows that stationary phase clusters were based on the phase chemistry rather than on the particle size, meaning that method transfer from 5 to 1.7 microns can be achieved in the subcritical domain i.e. by using a weakly compressible fluid.

  10. Innovative instrument design and applications in supercritical fluid chromatography and extraction

    SciTech Connect

    Oudsema, J.W.

    1992-01-01

    A novel sample introduction system was developed for supercritical fluid chromatography. The solventless injector utilizes a gas purge for solvent elimination and is capable of handling large sample volumes. Successful operation depends on the difference in volatility between the solvent and the analyte along with effective refocusing mechanisms at the head of the column. Reduced analysis times are achieved by in-line derivatization to permit the separation of polar analytes and elimination of volatile reagents and by products. The construction of a SFC restrictor from a 2 mm metal disc was described. The design is compact, robust and will readily interface with existing detectors. Preliminary results indicate that variable flow control can be achieved by temperature programming. The Knox equation was useful in illustrating the limitations of the solventless injector during isochloric conditions and proved that small particle (<10[mu]m) columns packed by the supercritical fluid displacement method are identical to those packed by the high pressure slurry packing method developed for HPLC. Supercritical CO[sub 2] and microbore columns are compatible with GC style detectors (FID). The use of formamide as a modifier improves the chromatographic properties for compounds containing nitrogen atoms and is compatible with the FID. SFE/SFC with formic acid modified CO[sub 2], polymer encapsulated stationary phases and the FID represent a considerable advance in the analysis of organotin compounds. The method is capable of extracting and separating a diverse group of industrially important organotin compounds. Triorganotins were determined in marine paint, potatoes, almonds and cation exchange resin. Diorganotin compounds were determined in PVC and cation exchange resin. The solventless injector allowed on line collection from the SFE cell and direct introduction to the analytical column.

  11. Glucose and fructose decomposition in subcritical and supercritical water: Detailed reaction pathway, mechanisms, and kinetics

    SciTech Connect

    Kabyemela, B.M.; Adschiri, T.; Malaluan, R.M.; Arai, K.

    1999-08-01

    The authors are developing a new catalyst-free process of cellulose decomposition in supercritical water. In their initial study on the cellulose decomposition in supercritical water, the main products of cellulose decomposition were found to be oligomers of glucose (cellobiose, cellotriose, etc.) and glucose at short residence times (400 C, 25 MPa, 0.05 s). The kinetics of glucose at these conditions can be useful in understanding the reaction pathways of cellulose. Experiments were performed on the products of glucose decomposition at short residence times to elucidate the reaction pathways and evaluate kinetics of glucose and fructose decomposition in sub- and supercritical water. The conditions were a temperature of 300--400 C and pressure of 25--40 MPa for extremely short residence times between 0.02 and 2 s. The products of glucose decomposition were fructose, a product of isomerization, 1,6-anhydroglucose, a product of dehydration, and erythrose and glyceraldehyde, products of C-C bond cleavage. Fructose underwent reactions similar to glucose except that it did not form 1,6-anhydroglucose and isomerization to glucose is negligible. The mechanism for the products formed from C-C bond cleavage could be explained by reverse aldol condensation and the double-bond rule of the respective enediols formed during the Lobry de Bruyn Alberda van Ekenstein transformation. The differential equations resulting from the proposed pathways were fit to experimental results to obtain the kinetic rate constants.

  12. Chemical kinetics and transport processes in supercritical fluid extraction of coal. Final report, August 10, 1990--December 30, 1992

    SciTech Connect

    McCoy, B.J.; Smith, J.M.; Wang, M.; Zhang, C.J.

    1993-02-01

    The overall objective of this project was to study the supercritical fluid extraction of hydrocarbons from coal. Beyond the practical concern of deriving products from coal, the research has provided insights into the structure, properties, and reactivities of coal. Information on engineering fundamentals of coal thermolysis and extraction, including physical and chemical processes, is presented in this final report. To accomplish the goals of the project we developed continuous-flow experiments for fixed-bed samples of coal that allow two types of analysis of the extract: continuous spectrophotometric absorbance measurements of the lumped concentration of extract, and chromatographic determinations of molecular-weight distributions as a function of time. Thermolysis of coal yields a complex mixture of many extract products whose molecular-weight distribution (MWD) varies with time for continuous-flow, semibatch experiments. The flow reactor with a differential, fixed bed of coal particles contacted by supercritical t-butanol was employed to provide dynamic MWD data by means of HPLC gel permeation chromatography of the extract. The experimental results, time-dependent MWDs of extract molecules, were interpreted by a novel mathematical model based on continuous-mixture kinetics for thermal cleavage of chemical bonds in the coal network. The parameters for the MWDs of extractable groups in the coal and the rate constants for one- and two-fragment reaction are determined from the experimental data. The significant effect of temperature on the kinetics of the extraction was explained in terms of one- and two-fragment reactions in the coal.

  13. Collective excitations in supercritical fluids: analytical and molecular dynamics study of "positive" and "negative" dispersion.

    PubMed

    Bryk, Taras; Mryglod, Ihor; Scopigno, Tullio; Ruocco, Giancarlo; Gorelli, Federico; Santoro, Mario

    2010-07-14

    The approach of generalized collective modes is applied to the study of dispersion curves of collective excitations along isothermal lines of supercritical pure Lennard-Jones fluid. An effect of structural relaxation and other nonhydrodynamic relaxation processes on the dispersion law is discussed. A simple analytical expression for the dispersion law in the long-wavelength region of acoustic excitations is obtained within a three-variable viscoelastic model of generalized hydrodynamics. It is shown that the deviation from the linear dependence in the long-wavelength region can be either "positive" or "negative" depending on the ratio between the high-frequency (elastic) and isothermal speed of sound. An effect of thermal fluctuations on positive and negative dispersion is estimated from the analytical solution of a five-variable thermoviscoelastic model that generalizes the results of the viscoelastic treatment. Numerical results are reported for a Lennard-Jones supercritical fluid along two isothermal lines T(*)=1.71,4.78 with different densities and discussed along the theoretical expressions derived.

  14. A Versatile Precursor System for Supercritical Fluid Electrodeposition of Main-Group Materials.

    PubMed

    Bartlett, Philip N; Burt, Jennifer; Cook, David A; Cummings, Charles Y; George, Michael W; Hector, Andrew L; Hasan, Mahboba M; Ke, Jie; Levason, William; Pugh, David; Reid, Gillian; Richardson, Peter W; Smith, David C; Spencer, Joe; Suleiman, Norhidayah; Zhang, Wenjian

    2016-01-04

    For the first time, a versatile electrolyte bath is described that can be used to electrodeposit a wide range of p-block elements from supercritical difluoromethane (scCH2 F2 ). The bath comprises the tetrabutylammonium chlorometallate complex of the element in an electrolyte of 50×10(-3)  mol dm(-3) tetrabutylammonium chloride at 17.2 MPa and 358 K. Through the use of anionic ([GaCl4 ](-) , [InCl4 ](-) , [GeCl3 ](-) , [SnCl3 ](-) , [SbCl4 ](-) , and [BiCl4 ](-) ) and dianionic ([SeCl6 ](2-) and [TeCl6 ](2-) ) chlorometallate salts, the deposition of elemental Ga, In, Ge, Sn, Sb, Bi, Se, and Te is demonstrated. In all cases, with the exception of gallium, which is a liquid under the deposition conditions, the resulting deposits are characterised by SEM, energy-dispersive X-ray analysis, XRD and Raman spectroscopy. An advantage of this electrolyte system is that the reagents are all crystalline solids, reasonably easy to handle and not highly water or oxygen sensitive. The results presented herein significantly broaden the range of materials accessible by electrodeposition from supercritical fluid and open up the future possibility of utilising the full scope of these unique fluids to electrodeposit functional binary or ternary alloys and compounds of these elements. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Supercritical fluid process for removal of polychlorodibenzodioxin and dibenzofuran from fly ash

    SciTech Connect

    Gabarra, P.; Cogollo, A.; Recasens, F.; Fernandez-Escobar, I.; Abad, E.; Bayona, J.M.

    1999-05-01

    A process is proposed for the decontamination of fly ash from an urban solid-waste incineration facility (USWI), where the target contaminants are polychlorodibenzodioxins (PCDDs) and dibenzofurans (PCDFs), a class of highly toxic tricyclopolychlorinated organics. In general, the ash waste requires inertization and disposal into a controlled landfill. Here, the authors propose an inertization process based on the reduction of the PCDDs and PCDFs content before dumping. Inertization is brought about by extraction with a solvent consisting of supercritical carbon dioxide modified with a co-solvent (10% toluene). The plant would run in semibatch mode, with continuous flow of fluid through a packed bed of fly ash. Then, carbon dioxide and the co-solvent would be separated and recycled. Favorable extraction conditions were found in the laboratory at 300 bar and 60 C. Under these conditions, the removal efficiency of native PCDDs and PCDFs is around 50% referred to the extraction of the same sample using the EPA method 1613 (Soxhlet extraction with toluene). A technoeconomic appraisal of a treatment facility is presented for a medium sized incineration plant (50,000 ton urban waste yearly) producing 1,500 ton of fly ash/y. The ash production would be inertized in a specially designed supercritical fluid (SCF) extraction unit, located on-site at the incineration facility.

  16. Comparison of liquid and supercritical fluid chromatography mobile phases for enantioselective separations on polysaccharide stationary phases.

    PubMed

    Khater, Syame; Lozac'h, Marie-Anne; Adam, Isabelle; Francotte, Eric; West, Caroline

    2016-10-07

    Analysis and production of enantiomerically pure compounds is a major topic of interest when active pharmaceutical ingredients are concerned. Enantioselective chromatography has become a favourite both at the analytical and preparative scales. High-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC) are dominating the scene and are often seen as complementary techniques. Nowadays, for economic and ecologic reasons, SFC may be preferred over normal-phase HPLC (NPLC) as it allows significant reductions in solvent consumption. However, the transfer of NPLC methods to SFC is not always straightforward. In this study, we compare the retention of achiral molecules and separation of enantiomers under supercritical fluid (carbon dioxide with ethanol or isopropanol) and liquid normal-phase (heptane with ethanol or isopropanol) elution modes with polysaccharide stationary phases in order to explore the differences between the retention and enantioseparation properties between the two modes. Chemometric methods (namely quantitative structure-retention relationships and discriminant analysis) are employed to compare the results obtained on a large set of analytes (171 achiral probes and 97 racemates) and gain some understanding on the retention and separation mechanisms. The results indicate that, contrary to popular belief, carbon dioxide - solvent SFC mobile phases are often weaker eluents than liquid mobile phases. It appears that SFC and NPLC elution modes provide different retention mechanisms. While some enantioseparations are unaffected, facilitating the transfer between the two elution modes, other enantioseparations may be drastically different due to different types and strength of interactions contributing to enantioselectivity.

  17. Coating properties of a novel water stationary phase in capillary supercritical fluid chromatography.

    PubMed

    Murakami, Jillian N; Thurbide, Kevin B

    2015-05-01

    The coating properties of a novel water stationary phase used in capillary supercritical fluid chromatography were investigated. The findings confirm that increasing the length or internal diameter of the type 316 stainless-steel column used provides a linear increase in the volume of stationary phase present. Under normal operating conditions, results indicate that about 4.9 ± 0.5 μL/m of water phase is deposited uniformly inside of a typical 250 μm internal diameter 316 stainless-steel column, which translates to an area coverage of about 6.3 ± 0.5 nL/mm(2) regardless of dimension. Efforts to increase the stationary phase volume present showed that etching the stainless-steel capillary wall using hydrofluoric acid was very effective for this. For instance, after five etching cycles, this volume doubled inside of both the type 304 and the type 316 stainless-steel columns examined. This in turn doubled analyte retention, while maintaining good peak shape and column efficiency. Overall, 316 stainless-steel columns were more resistant to etching than 304 stainless-steel columns. Results indicate that this approach could be useful to employ as a means of controlling the volume of water stationary phase that can be established inside of the stainless-steel columns used with this supercritical fluid chromatography technique.

  18. Supercritical fluid-mediated alumination of mesoporous silica and its beneficial effect on hydrothermal stability.

    PubMed

    O'Neil, Adam S; Mokaya, Robert; Poliakoff, Martyn

    2002-09-11

    We have investigated the use of supercritical fluids (SCFs) as carriers/solvents during the postsynthesis alumination of mesoporous silica. SCFs were found to be ideally suited for transport of Al into mesoporous silica and to lead to Al-grafted aluminosilicate materials that exhibit exceptional hydrothermal (steam) stability even for highly aluminated materials. The improvements in steam stability arising from the use of SCFs as grafting media (as compared to aqueous or organic solvents) are remarkable, especially for Al-grafted MCM-41 materials with high (Si/Al < or = 10) Al contents. It is proposed that under supercritical fluid conditions Al is sorbed on the surface of the pore walls of the host Si-MCM-41 with little penetration into the pore wall region, that is, the low solvating power of SCFs ensures the deposition of Al onto rather than into the silica framework. This is because the host silica framework cannot undergo any significant hydrolysis (to allow penetration of Al into the pore wall region) during the SCF-mediated alumination. Removal of the Al (i.e., dealumination) which occurs during steaming is therefore less detrimental to the structural integrity of SCF-grafted Al-MCM-41 materials since any dealumination that occurs will not involve removal of Al from deep within the pore walls.

  19. Determination of N-nitrosamines in latex by sequential supercritical fluid extraction and derivatization.

    PubMed

    Reche, F; Garrigós, M C; Marín, M L; Jiménez, A

    2002-11-08

    A new method to determine N-nitrosamines in latex products has been developed by combination of supercritical fluids and chemical derivatization. A new design for a liquid trap has been introduced. A factorial fractional design was used in order to evaluate the influence of the different factors affecting the process. Factors such as pressure, temperature, static and dynamic time, restrictor temperature and volume of an hydrobromic acid-acetic anhydride mixture (1:10, v/v) were included in the design. CO2 was used as the extraction fluid. Gas chromatography with nitrogen and phosphorus sensitive detection was employed to achieve good sensitivity attending to the molecular structure of these compounds (N-nitrosamines and their corresponding secondary amines). The obtained results have shown to be useful to increase selectivity and reduce sample handling.

  20. A study of power cycles using supercritical carbon dioxide as the working fluid

    NASA Astrophysics Data System (ADS)

    Schroder, Andrew Urban

    A real fluid heat engine power cycle analysis code has been developed for analyzing the zero dimensional performance of a general recuperated, recompression, precompression supercritical carbon dioxide power cycle with reheat and a unique shaft configuration. With the proposed shaft configuration, several smaller compressor-turbine pairs could be placed inside of a pressure vessel in order to avoid high speed, high pressure rotating seals. The small compressor-turbine pairs would share some resemblance with a turbocharger assembly. Variation in fluid properties within the heat exchangers is taken into account by discretizing zero dimensional heat exchangers. The cycle analysis code allows for multiple reheat stages, as well as an option for the main compressor to be powered by a dedicated turbine or an electrical motor. Variation in performance with respect to design heat exchanger pressure drops and minimum temperature differences, precompressor pressure ratio, main compressor pressure ratio, recompression mass fraction, main compressor inlet pressure, and low temperature recuperator mass fraction have been explored throughout a range of each design parameter. Turbomachinery isentropic efficiencies are implemented and the sensitivity of the cycle performance and the optimal design parameters is explored. Sensitivity of the cycle performance and optimal design parameters is studied with respect to the minimum heat rejection temperature and the maximum heat addition temperature. A hybrid stochastic and gradient based optimization technique has been used to optimize critical design parameters for maximum engine thermal efficiency. A parallel design exploration mode was also developed in order to rapidly conduct the parameter sweeps in this design space exploration. A cycle thermal efficiency of 49.6% is predicted with a 320K [47°C] minimum temperature and 923K [650°C] maximum temperature. The real fluid heat engine power cycle analysis code was expanded to study a

  1. Parameters optimization of supercritical fluid-CO2 extracts of frankincense using response surface methodology and its pharmacodynamics effects.

    PubMed

    Zhou, Jing; Ma, Xing-miao; Qiu, Bi-Han; Chen, Jun-xia; Bian, Lin; Pan, Lin-mei

    2013-01-01

    The volatile oil parts of frankincense (Boswellia carterii Birdw.) were extracted with supercritical carbon dioxide under constant pressure (15, 20, or 25 MPa) and fixed temperature (40, 50, or 60°C), given time (60, 90, or 120 min) aiming at the acquisition of enriched fractions containing octyl acetate, compounds of pharmaceutical interest. A mathematical model was created by Box-Behnken design, a popular template for response surface methodology, for the extraction process. The response value was characterized by synthetical score, which comprised yields accounting for 20% and content of octyl acetate for 80%. The content of octyl acetate was determined by GC. The supercritical fluid extraction showed higher selectivity than conventional steam distillation. Supercritical fluid-CO(2) for extracting frankincense under optimum condition was of great validity, which was also successfully verified by the pharmacological experiments. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. ORGANIC REACTIONS IN SUPERCRITICAL POLAR FLUIDS. (R825513C004)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  3. ORGANIC REACTIONS IN SUPERCRITICAL POLAR FLUIDS. (R825513C004)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  4. Processing of High Level Waste: Spectroscopic Characterization of Redox Reactions in Supercritical Water - Final Report

    SciTech Connect

    Arrington Jr., C. A.

    2000-11-15

    Current efforts are focused on the oxidative dissolution of chromium compounds found in Hanford tank waste sludge. Samples of chromium oxides and hydroxides with varying degrees of hydration are being characterized using Raman, FTIR, and XPS spectroscopic techniques. Kinetics of oxidation reactions at subcritical and supercritical temperatures are being followed by Raman spectroscopy using a high temperature stainless steel cell with diamond windows. In these reactions both hydrogen peroxide and nitrate anions are used as the oxidizing species with Cr(III) compounds and organic compounds as reducing agents.

  5. Pybox monolithic miniflow reactors for continuous asymmetric cyclopropanation reaction under conventional and supercritical conditions.

    PubMed

    Burguete, M I; Cornejo, A; García-Verdugo, E; Gil, María J; Luis, S V; Mayoral, J A; Martínez-Merino, V; Sokolova, M

    2007-06-08

    Supported catalysts having pybox chiral moieties were prepared as macroporous monolithic miniflow systems. These catalysts are based on styrene-divinylbenzene polymeric backbones having different compositions and pybox chiral moieties. Their corresponding ruthenium complexes were tested for the continuous flow cyclopropanation reaction between styrene and ethyldiazoacetate (EDA) under conventional conditions and in supercritical carbon dioxide (scCO2). Ru-Pybox monolithic miniflow reactors not only provided a highly efficient and robust heterogeneous chiral catalyst but also allowed us to develop more environmental reaction conditions without sacrificing the global efficiency of the process.

  6. Supercritical fluid extraction of the pesticides carbosulfan and imidacloprid from process dust waste.

    PubMed

    Eskilsson, C S; Mathiasson, L

    2000-11-01

    Large amounts of contaminated process dust remain from the procedure of pesticide treatments applied to seed pellets. A pilot study in analytical-scale supercritical fluid extraction (SFE) was performed to determine the possibility of using supercritical carbon dioxide for the extraction of the nonpolar insecticide carbosulfan and the more polar insecticide imidacloprid present in contaminated dust waste, at concentrations of up to 20% (w/w). The effects of various experimental conditions, such as temperature, flow rate, and addition of modifier, on the recovery of the analytes were evaluated by extracting the pesticides both from spiked support material and from real dust samples. It was found that carbosulfan could easily be extracted from the dust waste within 30 min at 138 bar and 40 degrees C with a recovery of 98.9% (RSD = 2.3%, n = 10), compared to values obtained with a validated liquid extraction method. A sufficient removal of the more polar substance imidacloprid required the addition of a modifier, and the results showed a strong dependence of the extraction efficiency on the choice of modifier. Extractions at 276 bar and 80 degrees C with a solvent consisting of supercritical carbon dioxide modified with methanol (5%) gave a recovery of 97.0% (RSD = 3.6%, n = 10) using a 40 min extraction time. The results indicate that it seems to be possible to use process-scale SFE for the decontamination of pesticides from dust waste. The conditions outlined also permit analytical determinations of the two insecticides based on a combination of SFE and liquid chromatography.

  7. Topics in Chemical Instrumentation: An Introduction to Supercritical Fluid Chromatography--Part 2. Applications and Future Trends.

    ERIC Educational Resources Information Center

    Palmieri, Margo D.

    1989-01-01

    Discussed are selected application and future trends in supercritical fluid chromatography (SFC). The greatest application for SFC involves those analytes that are difficult to separate using GC or LC methods. Optimum conditions for SFC are examined. Provided are several example chromatograms. (MVL)

  8. Topics in Chemical Instrumentation: An Introduction to Supercritical Fluid Chromatography--Part 2. Applications and Future Trends.

    ERIC Educational Resources Information Center

    Palmieri, Margo D.

    1989-01-01

    Discussed are selected application and future trends in supercritical fluid chromatography (SFC). The greatest application for SFC involves those analytes that are difficult to separate using GC or LC methods. Optimum conditions for SFC are examined. Provided are several example chromatograms. (MVL)

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

    USDA-ARS?s Scientific Manuscript database

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

  10. An oscillation free shock-capturing method for compressible van der Waals supercritical fluid flows

    NASA Astrophysics Data System (ADS)

    Pantano, C.; Saurel, R.; Schmitt, T.

    2017-04-01

    Numerical solutions of the Euler equations using real gas equations of state (EOS) often exhibit serious inaccuracies. The focus here is the van der Waals EOS and its variants (often used in supercritical fluid computations). The problems are not related to a lack of convexity of the EOS since the EOS are considered in their domain of convexity at any mesh point and at any time. The difficulties appear as soon as a density discontinuity is present with the rest of the fluid in mechanical equilibrium and typically result in spurious pressure and velocity oscillations. This is reminiscent of well-known pressure oscillations occurring with ideal gas mixtures when a mass fraction discontinuity is present, which can be interpreted as a discontinuity in the EOS parameters. We are concerned with pressure oscillations that appear just for a single fluid each time a density discontinuity is present. The combination of density in a nonlinear fashion in the EOS with diffusion by the numerical method results in violation of mechanical equilibrium conditions which are not easy to eliminate, even under grid refinement. A cure to this problem is developed in the present paper for the van der Waals EOS based on previous ideas. A special extra field and its corresponding evolution equation is added to the flow model. This new field separates the evolution of the nonlinear part of the density in the EOS and produce oscillation free solutions. The extra equation being nonconservative the behavior of two established numerical schemes on shocks computation is studied and compared to exact reference solutions that are available in the present context. The analysis shows that shock conditions of the nonconservative equation have important consequence on the results. Last, multidimensional computations of a supercritical gas jet is performed to illustrate the benefits of the present method, compared to conventional flow solvers.

  11. Hydrothermal synthesis of BaTiO 3 nanoparticles using a supercritical continuous flow reaction system

    NASA Astrophysics Data System (ADS)

    Hayashi, Hiromichi; Noguchi, Takio; Islam, Nazrul M.; Hakuta, Yukiya; Imai, Yusuke; Ueno, Nobuhiko

    2010-06-01

    Highly crystalline BaTiO 3 nanoparticle was synthesized rapidly by hydrothermal reaction in supercritical water using a continuous flow reactor. The reactants of TiO 2 sol (or TiCl 4)/Ba(NO 3) 2 mixed solution and KOH solution were used as starting materials and that was heated quickly up to 400 °C under the pressure of 30 MPa for 8 ms as reaction time. The XRD results revealed that the crystal phase of the obtained particles was cubic BaTiO 3, indicating that the hydrothermal reaction in supercritical water was successfully proceeded under present reaction conditions. Primarily particle size of the BaTiO 3 nanoparticle was determined by means of BET surface area, as small as less than 10 nm with decreasing the reaction pH. In contrast, dispersed particle size in solution measured by DLS (dynamic light scattering) technique decreased from 260 to 90 nm with increasing the reactants concentration. Aggregation of BaTiO 3 nanoparticles might be depressed in the presence of coexisting nitrate anions.

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

    SciTech Connect

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

    2013-09-01

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

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

    PubMed

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

    2010-01-14

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

  14. Supercritical Hadley circulation within a layer of fluid saturated porous medium: Bifurcation to traveling wave

    SciTech Connect

    Manole, D.M.; Lage, J.L.; Antohe, B.V.

    1995-12-31

    Hadley circulation induced by horizontal and vertical temperature gradients imposed on a fluid saturated porous medium layer is simulated numerically. The flow is assumed to be longitudinal, that is the secondary flow is composed of cells with axes transverse to the direction of the Hadley circulation. Critical (bifurcation) states predicted theoretically via linear stability analysis are verified by the numerical results giving confidence on the accuracy of the method. Several values of horizontal Rayleigh number, Ra{sub h}, and vertical Rayleigh number, Ra{sub v}, are studied. Results indicate that beyond a threshold horizontal Rayleigh number value the flow and temperature fields evolve from subcritical Hadley circulation to a supercritical time periodic flow. The secondary flow emerges in the form of a traveling wave aligned with the main (Hadley) flow direction. This traveling wave is characterized, at supercritical low vertical Rayleigh numbers, by the continuous drifting of two horizontal layers of flow cells that move in opposite directions. As the vertical Rayleigh number increases, the traveling wave becomes characterized by a unique layer of cells drifting in the direction opposite to the applied horizontal temperature gradient. Numerical animation unravels the main features of the transport process. This simplified model is of fundamental and practical importance, for instance, to the study of geothermal activities, underground transport of pollutants, paper processing, crystal growth, building insulation, and gas reservoirs.

  15. Assay of tolnaftate and related impurities by isocratic supercritical fluid chromatography.

    PubMed

    Patil, S T; Bhoir, I C; Bhagwat, A M; Sundaresan, M

    2000-05-01

    Tolnaftate, an antifungal drug (TF) and related impurities arising from synthesis, viz., N-methyl-m-toluidine (NMmT) and beta-naphthol-1-chlorothio carbamate (beta-NCTC) can be determined by supercritical fluid chromatography. Even though it was possible to elute TF completely with neat SCF CO2, the peaks of the impurities were found to merge. The chromatographic figures of merit of the three analytes such as retention time (tR), capacity factor (k), selectivity factor (alpha), no. of theoretical plates (N), were optimized. The three compounds can be resolved in 5 min on a Hypersil (250 x 4.0 mm) 5 mu, C18 column with supercritical carbon dioxide, modified with 1.96% methanol as the mobile phase at 9.81 MPa and at 40 degrees C. Detection was carried out at 220 nm. The data as evaluated by the linear regression least squares fit method gave linearity ranges from 0.2 to 10.0 microg/mL for TF and NMmT and 0.3 to 10.0 microg/mL for beta-NCTC with correlation coefficients > 0.99. The method was successfully employed to estimate levels of 0.01% for NMmT and 0.02% for beta-NCTC with respect to TF.

  16. Supercritical fluid extraction: Preparing a superior mesophase precursor for carbon fibers. Final report

    SciTech Connect

    Thies, M.C.

    1994-08-01

    Supercritical fluid (SCF) extraction is being investigated for the production of mesophase pitch, the liquid-crystalline precursor for the manufacture of high-performance carbon fibers. The mesophase pitch is produced by fractionation of an isotropic petroleum pitch with supercritical toluene in a region of liquid-liquid equilibrium that exists at pressures above 40 bar. Dramatic improvements in the reliability of the apparatus have recently been made, and mesophase pitch can now be produced on a routine basis. An experimental program was conducted to explore the effects of temperature, solvent-to-pitch (S/P) ratio, and solvent solubility parameter on the properties of the mesophase pitch produced. Temperatures of 320 and 360 deg C, solubility parameters of 3.7 and 5.0 (cal/cc)(1/2), and S/P ratios of 2.5 and 3.5 were chosen to conform to a two-level, augmented factorial experiment. A linear model correlated the data to a high degree of certainty. Results indicate that the authors can adjust SCF operating conditions and tailor-make a mesophase pitch for a given end use. They have discovered a semitheoretical method for predicting a priori the softening point and yield of mesophase pitch for a given set of SCF operating conditions. The SCF extraction process can be represented on a pseudoternary phase diagram, and good estimates of product yields and softening points can be made from a limited experimental data measured at other conditions.

  17. Removal of polycyclic aromatic hydrocarbons from soil: a comparison between bioremoval and supercritical fluids extraction.

    PubMed

    Amezcua-Allieri, M A; Ávila-Chávez, M A; Trejo, A; Meléndez-Estrada, J

    2012-03-01

    Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic substances which are resistant to environmental degradation due to their highly hydrophobic nature. Soils contaminated with PAHs pose potential risks to human and ecological health, therefore concern over their adverse effects have resulted in extensive studies on their removal from contaminated soils. The main purpose of this study was to compare experimental results of PAHs removal, from a natural certified soil polluted with PAHs, by biological methods (using bioaugmentation and biostimulation in a solid-state culture) with those from supercritical fluid extraction (SFE), using supercritical ethane as solvent. The comparison of results between the two methods showed that maximal removal of naphthalene, acenaphthene, fluorene, and chrysene was performed using bioremediation; however, for the rest of the PAHs considered (fluoranthene, pyrene, and benz(a)anthracene) SFE resulted more efficient. Although bioremediation achieved higher removal ratios for certain hydrocarbons and takes advantage of the increased rate of natural biological processes, it takes longer time (i.e. 36 d vs. half an hour) than SFE and it is best for 2-3 PAHs rings.

  18. Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene.

    PubMed

    Hoijemberg, Pablo A; Zerbs, Jochen; Japas, M Laura; Chesta, Carlos A; Schroeder, Jörg; Aramendía, Pedro F

    2009-05-07

    We studied the photolysis of (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene in supercritical CO(2) and Xe, as well as in compressed Kr. The compound has good solubility in the mentioned fluids, allowing the photolysis measurements to be performed in CO(2) at 1.4 K above T(c) and at pressures as low as 70 bar. We monitored relative cage effect after nanosecond laser pulses by measuring the absorbance at 320 nm (DeltaA(t-->0)) corresponding to the total amount of out-of-cage 1-biphenyl-4-yl-1-methyl-ethyl radical (BME.) produced after nitrogen loss of the diazene. In supercritical CO(2) and Xe, isothermal values of DeltaA(t-->0) showed an increase-decrease behavior with increasing pressure at constant temperature, a typical feature of the transition from the solvent energy transfer to the friction controlled regimes. The comparison of the behavior of DeltaA(t-->0) in CO(2) at reduced temperatures between 1.004 and 1.027, in Xe, and in Kr points to an absence of enhanced cage effect near the critical point. Compatibility with spectroscopic data is analyzed.

  19. Growth factors delivery from hybrid PCL-starch scaffolds processed using supercritical fluid technology.

    PubMed

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

    2016-05-20

    Synthetic polymeric scaffolds to be used as surrogates of autologous bone grafts should not only have suitable physicochemical and mechanical properties, but also contain bioactive agents such as growth factors (GFs) to facilitate the tissue growth. For this purpose, cost-effective and autologous GFs sources are preferred to avoid some post-surgery complications after implantation, like immunogenicity or disease transmission, and the scaffolds should be processed using methods able to preserve GFs activity. In this work, poly(ɛ-caprolactone) (PCL) scaffolds incorporating GFs were processed using a green foaming process based on supercritical fluid technology. Preparation rich in growth factors (PRGF), a natural and highly available cocktail of GFs obtained from platelet rich plasma (PRP), was used as GF source. PCL:starch:PRGF (85:10:5 weight ratio) porous solid scaffolds were obtained by a supercritical CO2-assisted foaming process at 100 bar and 37 °C with no need of post-processing steps. Bioactivity of GFs after processing and scaffold cytocompatibility were confirmed using mesenchymal stem cells. The performance of starch as GF control release component was shown to be dependent on starch pre-gelification conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Modeling the supercritical fluid extraction of essential oils from plant materials.

    PubMed

    Sovová, H

    2012-08-10

    Different types of mathematical models were applied in the last decade to simulate kinetics of supercritical fluid extraction (SFE) of essential oils from aromatic plants. Compared to the extraction of fatty oils, modeling of extraction of essential oils is more complicated due to their potential fractionation, co-extraction of less soluble compounds, and stronger effect of flow pattern on extraction yield, which is connected with solute adsorption on plant matrix. Fitting the SFE models to experimental extraction curves alone usually does not enable reliable selection among the models. Major progress was made when detailed models for the extraction from glandular structures of plants were developed. As the type of glands is characteristic for plant families, the choice of models for SFE of essential oils is substantially facilitated. As the extracts from aromatic plants contain also cuticular waxes and other less soluble substances, and essential oils themselves are mixtures of substances of different solubility in supercritical carbon dioxide, modeling of extraction of mixtures and their fractionation in time deserves more attention. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Supercritical fluid extraction of 2,4,6-trichloroanisole from cork stoppers.

    PubMed

    Taylor, M K; Young, T M; Butzke, C E; Ebeler, S E

    2000-06-01

    2,4,6-Trichloroanisole (TCA) is the compound most often associated with cork taint in wines and has been shown to have a very low sensory threshold ( approximately 5 ng/L in wine). A supercritical fluid extraction (SFE) method for TCA in bark cork stoppers was developed with quantification via gas chromatography-mass spectrometry with selected ion monitoring. Supercritical carbon dioxide functioned as the extracting solvent, and temperature and pressure were optimized for the extraction. The method was validated using the stable isotope (2)H(5)-TCA as the internal standard. Recovery of TCA from spiked corks was found to be within 1-4% of the theoretical concentration with a coefficient of variation ranging from 2.6 to 9.7%. TCA levels in corks pulled from wines described as tainted by experienced judges ranged from 0.13 to 2.11 microg/g of cork. The SFE procedure offers a rapid, quantitative, nearly solvent-free, and automated method for the extraction of TCA from complex solid matrices such as cork.

  2. Supercritical Fluid Technology: An Emphasis on Drug Delivery and Related Biomedical Applications.

    PubMed

    Kankala, Ranjith Kumar; Zhang, Yu Shrike; Wang, Shi-Bin; Lee, Chia-Hung; Chen, Ai-Zheng

    2017-08-01

    During the past few decades, supercritical fluid (SCF) has emerged as an effective alternative for many traditional pharmaceutical manufacturing processes. Operating active pharmaceutical ingredients (APIs) alone or in combination with various biodegradable polymeric carriers in high-pressure conditions provides enhanced features with respect to their physical properties such as bioavailability enhancement, is of relevance to the application of SCF in the pharmaceutical industry. Herein, recent advances in drug delivery systems manufactured using the SCF technology are reviewed. We provide a brief description of the history, principle, and various preparation methods involved in the SCF technology. Next, we aim to give a brief overview, which provides an emphasis and discussion of recent reports using supercritical carbon dioxide (SC-CO2 ) for fabrication of polymeric carriers, for applications in areas related to drug delivery, tissue engineering, bio-imaging, and other biomedical applications. We finally summarize with perspectives. © 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Determination of Crude Fat in Food Products by Supercritical Fluid Extraction and Gravimetric Analysis

    NASA Astrophysics Data System (ADS)

    Snow, Nicholas H.; Dunn, Maureen; Patel, Sohita

    1997-09-01

    The use of supercritical fluid extraction (SFE), a recently developed analytical extraction method, in the undergraduate instrumental analysis laboratory is demonstrated. Specifically, the extraction and gravimetric analysis of the fats from a common commercial confection was performed by several groups of undergraduates, and the extraction recoveries were evaluated. The percentage of fat by weight in the candy bar sample was determined to be 21 +/- 2 %, a value found to be in agreement with the product labeling. Under the extraction conditions used, complete extraction required 400-700 mL of supercritical carbon dioxide, applied to a 1.0 g sample of candy in several extraction steps. Data relating extraction recovery to the volume of carbon dioxide used for extraction is shown. SFE is shown to be a versatile addition to the undergraduate instrumental analysis laboratory, requiring a minimum of training and supervision. Finally, SFE can be extended to myriad physical and analytical measurements in the undergraduate laboratories. Examples derived from the current analytical literature are proposed.

  4. Lignin depolymerisation in supercritical carbon dioxide/acetone/water fluid for the production of aromatic chemicals.

    PubMed

    Gosselink, Richard J A; Teunissen, Wouter; van Dam, Jan E G; de Jong, Ed; Gellerstedt, Göran; Scott, Elinor L; Sanders, Johan P M

    2012-02-01

    Valorisation of lignin plays a key role in further development of lignocellulosic biorefinery processes the production of biofuels and bio-based materials. In the present study, organosolv hardwood and wheat straw lignins were converted in a supercritical fluid consisting of carbon dioxide/acetone/water (300-370°C, 100bar) to a phenolic oil consisting of oligomeric fragments and monomeric aromatic compounds with a total yield of 10-12% based on lignin. These yields are similar to the state-of-the-art technologies such as base-catalysed thermal processes applied for lignin depolymerisation. Addition of formic acid increases the yield of monomeric aromatic species by stabilizing aromatic radicals. Supercritical depolymerisation of wheat straw and hardwood lignin yielded monomeric compounds in different compositions with a maximum yield of 2.0% for syringic acid and 3.6% for syringol, respectively. The results of the present study showed that under the applied conditions competition occurred between lignin depolymerisation and recondensation of fragments.

  5. Fast separation of triterpenoid saponins using supercritical fluid chromatography coupled with single quadrupole mass spectrometry.

    PubMed

    Huang, Yang; Zhang, Tingting; Zhou, Haibo; Feng, Ying; Fan, Chunlin; Chen, Weijia; Crommen, Jacques; Jiang, Zhengjin

    2016-03-20

    Triterpenoid saponins (TSs) are the most important components of some traditional Chinese medicines (TCMs) and have exhibited valuable pharmacological properties. In this study, a rapid and efficient method was developed for the separation of kudinosides, stauntosides and ginsenosides using supercritical fluid chromatography coupled with single quadrupole mass spectrometry (SFC-MS). The separation conditions for the selected TSs were carefully optimized after the initial screening of eight stationary phases. The best compromise for all compounds in terms of chromatographic performance and MS sensitivity was obtained when water (5-10%) and formic acid (0.05%) were added to the supercritical carbon dioxide/MeOH mobile phase. Beside the composition of the mobile phase, the nature of the make-up solvent for interfacing SFC with MS was also evaluated. Compared to reversed phase liquid chromatography, the SFC approach showed higher resolution and shorter running time. The developed SFC-MS methods were successfully applied to the separation and identification of TSs present in Ilex latifolia Thunb., Panax quinquefolius L. and Panax ginseng C.A. Meyer. These results suggest that this SFC-MS approach could be employed as a useful tool for the quality assessment of natural products containing TSs as active components.

  6. Analysis of anthraquinones in rhubarb (Rheum palmatum and Rheum officinale) by supercritical fluid chromatography.

    PubMed

    Aichner, Dorothea; Ganzera, Markus

    2015-11-01

    The first report on the separation of five anthraquinones (chrysophanol, physcion, emodin, aloeemodin, and rhein) from rhubarb by supercritical fluid chromatography indicates that this technique is an interesting analytical alternative not just for non-polar substances. Within less than five minutes the compounds could be baseline resolved, using a mobile phase comprising supercritical carbon dioxide and methanol with 0.05% diethylamine. The optimum stationary phase showed to be an Acquity UPC(2) HSS C18 SB 1.8 µm column, operated at a flow rate of 2 ml/min and a temperature of 30 °C. Method validation confirmed that the developed procedure is selective, linear (R(2)≥0.999), accurate (recovery rates: 95.4% to 103.1%), and precise (intra-day≤6.9%, inter-day≤4.7%); the limit of detection was below 0.5 ng on-column. The analysis of plant extracts was feasible with acceptable repeatability (σrel≤3.8%), and it determined 0.3 to 0.7% of free aglyca in the native samples. After hydrolysis according to the European Pharmacopoeia, a rise in the total content up to 2.1% was observed, with rhein being the most dominant derivative in nearly all specimens.

  7. Shale gas and non-aqueous fracturing fluids: Opportunities and challenges for supercritical CO₂

    SciTech Connect

    Middleton, Richard S.; Carey, James William; Currier, Robert P.; Hyman, Jeffrey De'Haven; Kang, Qinjun; Karra, Satish; Jiménez-Martínez, Joaquín; Porter, Mark L.; Viswanathan, Hari S.

    2015-06-01

    Hydraulic fracturing of shale formations in the United States has led to a domestic energy boom. Currently, water is the only fracturing fluid regularly used in commercial shale oil and gas production. Industry and researchers are interested in non-aqueous working fluids due to their potential to increase production, reduce water requirements, and to minimize environmental impacts. Using a combination of new experimental and modeling data at multiple scales, we analyze the benefits and drawbacks of using CO₂ as a working fluid for shale gas production. We theorize and outline potential advantages of CO₂ including enhanced fracturing and fracture propagation, reduction of flow-blocking mechanisms, increased desorption of methane adsorbed in organic-rich parts of the shale, and a reduction or elimination of the deep re-injection of flow-back water that has been linked to induced seismicity and other environmental concerns. We also examine likely disadvantages including costs and safety issues associated with handling large volumes of supercritical CO₂. The advantages could have a significant impact over time leading to substantially increased gas production. In addition, if CO₂ proves to be an effective fracturing fluid, then shale gas formations could become a major utilization option for carbon sequestration.

  8. Shale gas and non-aqueous fracturing fluids: Opportunities and challenges for supercritical CO₂

    DOE PAGES

    Middleton, Richard S.; Carey, James William; Currier, Robert P.; ...

    2015-06-01

    Hydraulic fracturing of shale formations in the United States has led to a domestic energy boom. Currently, water is the only fracturing fluid regularly used in commercial shale oil and gas production. Industry and researchers are interested in non-aqueous working fluids due to their potential to increase production, reduce water requirements, and to minimize environmental impacts. Using a combination of new experimental and modeling data at multiple scales, we analyze the benefits and drawbacks of using CO₂ as a working fluid for shale gas production. We theorize and outline potential advantages of CO₂ including enhanced fracturing and fracture propagation, reductionmore » of flow-blocking mechanisms, increased desorption of methane adsorbed in organic-rich parts of the shale, and a reduction or elimination of the deep re-injection of flow-back water that has been linked to induced seismicity and other environmental concerns. We also examine likely disadvantages including costs and safety issues associated with handling large volumes of supercritical CO₂. The advantages could have a significant impact over time leading to substantially increased gas production. In addition, if CO₂ proves to be an effective fracturing fluid, then shale gas formations could become a major utilization option for carbon sequestration.« less

  9. Fluid transport in reaction induced fractures

    NASA Astrophysics Data System (ADS)

    Ulven, Ole Ivar; Sun, WaiChing; Malthe-Sørenssen, Anders

    2015-04-01

    The process of fracture formation due to a volume increasing chemical reaction has been studied in a variety of different settings, e.g. weathering of dolerites by Røyne et al. te{royne}, serpentinization and carbonation of peridotite by Rudge et al. te{rudge} and replacement reactions in silica-poor igneous rocks by Jamtveit et al. te{jamtveit}. It is generally assumed that fracture formation will increase the net permeability of the rock, and thus increase the reactant transport rate and subsequently the total rate of material conversion, as summarised by Kelemen et al. te{kelemen}. Ulven et al. te{ulven_1} have shown that for fluid-mediated processes the ratio between chemical reaction rate and fluid transport rate in bulk rock controls the fracture pattern formed, and Ulven et al. te{ulven_2} have shown that instantaneous fluid transport in fractures lead to a significant increase in the total rate of the volume expanding process. However, instantaneous fluid transport in fractures is clearly an overestimate, and achievable fluid transport rates in fractures have apparently not been studied in any detail. Fractures cutting through an entire domain might experience relatively fast advective reactant transport, whereas dead-end fractures will be limited to diffusion of reactants in the fluid, internal fluid mixing in the fracture or capillary flow into newly formed fractures. Understanding the feedback process between fracture formation and permeability changes is essential in assessing industrial scale CO2 sequestration in ultramafic rock, but little is seemingly known about how large the permeability change will be in reaction-induced fracturing. In this work, we study the feedback between fracture formation during volume expansion and fluid transport in different fracture settings. We combine a discrete element model (DEM) describing a volume expanding process and the related fracture formation with different models that describe the fluid transport in the

  10. [Study on chemical constituents of the essential oil from Myristica fragrans Houtt. by supercritical fluid extraction and steam distillation].

    PubMed

    Qiu, Qin; Zhang, Guoying; Sun, Xiaomin; Liu, Xinxin

    2004-11-01

    Essential oils were extracted from Myristica fragrans Houtt. by supercritical fluid extraction (SFE) and steam distillation (SD). Their components were analyzed by gas chromatography-mass spectrometry and compared. 48 compounds were identified for the essential oil extracted by supercritical carbon dioxide, and its main components have been found to be myristic acid, myristicin, terpinen-4-ol, alpha-pinene and safrole. 38 compounds were identified for the essential oil obtained by SD, and its main components have been found to be beta-pinene, terpinen-4-ol, alpha-pinene, gamma-terpinene and beta-phellandrene.

  11. Supercritical water oxidation of Quinazoline: Effects of conversion parameters and reaction mechanism.

    PubMed

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

    2016-09-01

    The supercritical water oxidation reaction of quinazoline and a set of related reaction products were investigated in batch reactors by varying the temperature (T, 400-600 °C), time (t, 0-400 s), water density (ρ, 70.79-166.28  kg m(-3)) and oxidation coefficient (OC, 0-4.0). The TOC removal efficiency (CRE) increased significantly as the OC increased, whereas this effect was very limited at high OC (>2.0). Lack of oxygen resulted in low CRE and TN removal efficiency (NRE), also cause coke-formation, and giving high yield of NH3 and nitrogenous organic intermediates. Prolonging reaction time did not provide an appreciable improvement on CRE but remarkably increased NRE at temperature higher than 500 °C. Pyrimidines and pyridines as the nitrogenous intermediates were largely found in GC-MS spectrum. Polymerization among benzene, phenyl radical and benzyl radical played important roles in the formation of PAHs, such as naphthalene, biphenyl, phenanthrene. These collective results showed how the yield of intermediate products responded to changes in the process variables, which permitted the development of a potential reaction network for supercritical water oxidation of quinazoline.

  12. Electrochemistry in Near-Critical and Supercritical Fluids. 6. The Electrochemistry of Ferrocene and Phenazine in Acetonitrile between 25C and 300C.

    DTIC Science & Technology

    1987-07-01

    electrochemical studies in near-critical CO2 with water. We describe here electrochemistry in the organic supercritical fluid acetonitrile (MeCN), where the...RESEARCH 1 FlE COP Contract NO0014- 84-K-0428 Task No. NR 051-693 TECHNICAL REPORT No. 8 (Electrochemistry in Near-Critical and Supercritical Fluids. 6. The...is suggested. FF V.. I r.M I- .- Electrochemistry in Near-Critical and Supercritical Fluids. 6. The Electrochemistry of Ferrocene and Phenazine in

  13. [Optimize the extraction process with supercritical CO2 fluid from lotus leaves by the uniform design and analysis on the chemical constituents by GC-MS].

    PubMed

    Yin, Hui-jing; Qian, Yi-fan; Pu, Cun-hai

    2007-04-01

    To study the optimum parameters of the supercritical CO, fluid extraction of lotus leaves and chemical constituents of extractive matters. Supercritical CO2 fluid extraction condition was selected by uniform design. The extraction pressure, extraction temperature, extraction time were three factors in the experiment. GC-MS was applied for analyzing the extraction. The optimum condition were obtained: the extraction pressure was 26 Mpa, the extraction temperature was 40 degrees C, the extracion time was 90 minutes. The major constituent was 1H-Pyrrole-2-carboxaldehyde, 1-ethyl-in extractive matters. Uniform design can optimize the CO2 Supercritical Fluid Extraction process quickly and accuratly with satisfactory results.

  14. Supercritical fluid chromatography in the routine stability control of antipruritic preparations.

    PubMed

    Anton, K; Bach, M; Geiser, A

    1991-08-16

    A recently developed system for supercritical fluid chromatography (SFC), based on independent flow and pressure control and suitable for packed and capillary columns, was tested on a routine level for the reliable, accurate and precise determination of active pharmaceutical substances in stability control. Only packed columns were used for this analysis. The chromatographic figures of merit and the validation data of the active substance alone and in two different dosage forms (accuracy, 98.8-99.2%; precision, 0.6%; linearity of response, 0.998-0.999) are comparable with the former liquid chromatographic methods. Economical (reduction of analysis time, fewer experimental steps and less sample pre-separation) and ecological (carbon dioxide of organic solvents) advantages make SFC an attractive alternative to liquid chromatography in the determination of crotamiton.

  15. Cost-Effective Solar Thermal Energy Storage: Thermal Energy Storage With Supercritical Fluids

    SciTech Connect

    2011-02-01

    Broad Funding Opportunity Announcement Project: UCLA and JPL are creating cost-effective storage systems for solar thermal energy using new materials and designs. A major drawback to the widespread use of solar thermal energy is its inability to cost-effectively supply electric power at night. State-of-the-art energy storage for solar thermal power plants uses molten salt to help store thermal energy. Molten salt systems can be expensive and complex, which is not attractive from a long-term investment standpoint. UCLA and JPL are developing a supercritical fluid-based thermal energy storage system, which would be much less expensive than molten-salt-based systems. The team’s design also uses a smaller, modular, single-tank design that is more reliable and scalable for large-scale storage applications.

  16. Evaluation of flash supercritical fluid chromatography and alternate sample loading techniques for pharmaceutical medicinal chemistry purifications.

    PubMed

    Miller, Larry; Mahoney, Max

    2012-08-10

    Flash chromatography is the preferred approach for small molecule purification in pharmaceutical discovery. This paper will discuss the potential for flash supercritical fluid chromatography (SFC) as an alternative technology for these purifications. It was shown that the high sample loadings seen with flash LC could also be achieved using flash SFC. The dry load injection technique greatly increases the amount of sample that can be applied to a flash SFC column while still achieving separation. Flash SFC has much lower solvent usage and higher purification productivities relative to flash LC. Product concentrations post purification were higher for flash SFC vs. flash LC, reducing the time required to isolate dry product. There still exist a number of technical details to be worked out with flash SFC, mainly around the equipment and column/cartridge technology.

  17. Elucidation of the absolute configuration of rhizopine by chiral supercritical fluid chromatography and vibrational circular dichroism.

    PubMed

    Krief, Alain; Dunkle, Melissa; Bahar, Masoud; Bultinck, Patrick; Herrebout, Wouter; Sandra, Pat

    2015-07-01

    The absolute configuration of rhizopine, an opine-like natural product present in nitrogen-fixing nodules of alfalfa infected by rhizobia, is elucidated using a combination of state-of-the-art analytical and semi-preparative supercritical fluid chromatography and vibrational circular dichroism spectroscopy. A synthetic peracetylated racemate was fractionated into its enantiomers and subjected to absolute configuration analysis revealing that natural rhizopine exists as a single enantiomer. The stereochemistry of non-derivatized natural rhizopine corresponds to (1R,2S,3R,4R,5S,6R)-4-amino-6-methoxycyclohexane-1,2,3,5-tetraol. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. [Extraction of praeruptorin A from Radix Peucedani by supercritical fluid extraction-CO2].

    PubMed

    Liu, Ai-dong; Hou, Wei; Chen, Xue-song; Qiu, Zhi-dong

    2008-12-01

    To extract praeruptorin A from Radix Peucedani by supercritical fluid extraction (SFE)-CO2. After preliminary experiment, three main factors were acquired that could influence the result of SFE-CO2, including the time, pressure and temperature of the extraction. The optimal extraction process was carried out on orthogonal design, and SFE-CO2 was compared with the traditional methods. In the extraction of the praeruptorin A, the best extraction conditions were 60 degrees C, 20 MPa, and duration for three hours. As cosolvent alcohol was added, the amount of extraction of the praeruptorin A increased, and the amount of SFE-CO2 extraction was higher than those of decoction and heating reflux. The SFE-CO2 in extracting praeruptorin A from Radix Peucedani is feasible and reliable.

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

    PubMed

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

    2016-05-10

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

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

    PubMed

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

    1990-11-01

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

  1. Differentiation of ring-substituted regioisomers of amphetamine and methamphetamine by supercritical fluid chromatography.

    PubMed

    Segawa, Hiroki; T Iwata, Yuko; Yamamuro, Tadashi; Kuwayama, Kenji; Tsujikawa, Kenji; Kanamori, Tatsuyuki; Inoue, Hiroyuki

    2017-03-01

    Chromatographic differentiation of the ring-substituted regioisomers of amphetamine (AMP) and methamphetamine (MA) was performed by supercritical fluid chromatography (SFC). The behaviour of the retention against the changes of column temperature and co-solvent proportion was studied. The obtained information facilitated the optimization of the each regioisomer. As a result, 2-, 3-, and 4-ring-substituted analogues of AMP and MA with methyl, methoxy, fluoro, chloro, and bromo groups were separated, generally within 6 min. In addition, we found that the separation pattern of the examined regioisomers was classified into two, which depended on the electron donating/withdrawing effect of the substituent. Our results indicate that SFC could be used in forensic drug analysis for fast, reliable identification of structurally similar drugs of abuse. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  2. Experimental evidence of a helical, supercritical instability in pipe flow of shear thinning fluids

    NASA Astrophysics Data System (ADS)

    Picaut, L.; Ronsin, O.; Caroli, C.; Baumberger, T.

    2017-08-01

    We study experimentally the flow stability of entangled polymer solutions extruded through glass capillaries. We show that the pipe flow becomes linearly unstable beyond a critical value (Wic≃5 ) of the Weissenberg number, via a supercritical bifurcation which results in a helical distortion of the extrudate. We find that the amplitude of the undulation vanishes as the aspect ratio L /R of the capillary tends to zero, and saturates for large L /R , indicating that the instability affects the whole pipe flow, rather than the contraction or exit regions. These results, when compared to previous theoretical and experimental works, lead us to argue that the nature of the instability is controlled by the level of shear thinning of the fluids. In addition, we provide strong hints that the nonlinear development of the instabiilty is mitigated, in our system, by the gradual emergence of gross wall slip.

  3. Improving sensitivity in chiral supercritical fluid chromatography for analysis of active pharmaceutical ingredients.

    PubMed

    Helmy, Roy; Biba, Mirlinda; Zang, Jia; Mao, Bing; Fogelman, Kimber; Vlachos, Vaso; Hosek, Paul; Welch, Christopher J

    2007-11-01

    Despite its status as the preferred method for routine enantiopurity analysis in pharmaceutical research, supercritical fluid chromatography (SFC) has historically been unsuited for the accurate and precise measurements required for release testing of active pharmaceutical ingredients (APIs) under current good manufacturing processes (cGMPs). Insufficient signal to noise, as compared to HPLC, has heretofore been the major limitation of the chiral SFC approach. We herein describe an investigation into the fundamental limitations and sources of noise in the SFC approach, identifying thermal, electronic, and mechanical sources of noise within the flow cell as key parameters contributing to reduced sensitivity. A variety of instrument modifications are explored, ultimately leading to the development of a new and improved flow cell and other instrument modifications that allow suitable sensitivity and accuracy to carry out GMP release testing for enantiopurity analysis using SFC.

  4. Optimization of supercritical fluid extraction of saikosaponins from Bupleurum falcatum with orthogonal array design.

    PubMed

    Sun, Yinshi; Wei, Li; Wang, Jianhua; Bi, Jianjie; Liu, Zhengbo; Wang, Ying; Guo, Zude

    2010-04-01

    Supercritical fluid extraction (SFE) was used to extract saikosaponins a, c and d from the root of Bupleurum falcatum. An orthogonal array design L(9)(3)(4) was employed as a chemometric method for the optimization of the SFE conditions. The effects of four factors including pressure (30-40 MPa), temperature (40-50 degrees C), ethanol concentration (60-100%) and time (2.5-3.5 h) on the yields of saikosaponins were investigated by a preparative SFE system in the SFE mode. Under the optimized conditions, namely 35 MPa of pressure, 45 degrees C of temperature, 80% of ethanol concentration and 3.0 h of time, the yields of saikosaponin c, saikosaponin a, saikosaponin d, total saikosaponins and SFE extract were 0.16, 0.12, 0.96, 1.24 and 16.48 mg/g, respectively. Determinations of the saikosaponins were performed by HPLC.

  5. Supercritical fluid extraction of N-nitrosamines in hams processed in elastic rubber nettings.

    PubMed

    Pensabene, J W; Fiddler, W; Maxwell, R J; Lightfield, A R; Hampson, J W

    1995-01-01

    A method for analysing N-nitrosamines in hams processed in elastic rubber nettings by supercritical fluid extraction (SFE) is described. The study was carried out with the prototype of a commercial extractor with a silica gel adsorption cartridge integrally attached to the variable restrictor. The SFE method was compared with a solid-phase extraction procedure currently used for ham analysis. Both methods used the same gas chromatographic-chemiluminescence detection conditions. No significant difference (p < 0.05) was found between results obtained with the 2 methods. Repeatability standard deviation of the SFE method was 1.7 ppb, with a coefficient of variation (CV) of 2.7%, compared with 2.2 ppb, with a CV of 3.5%, for solid-phase extraction. SFE permits minimal use of solvent and more rapid analysis of nitrosamines.

  6. [Investigation on extraction conditions of tebufenozide residue from cabbage using supercritical fluid extraction].

    PubMed

    Yang, Lirong; Zhang, Xing; Chen, Anliang; Li, Guangze

    2004-05-01

    An extraction method of tebufenozide using supercritical fluid extraction (SFE) and high performance liquid chromatography (HPLC) was developed. The selected conditions were 48.3 MPa (7000 psi), 60 degrees C, 20 min of static time, dynamic extraction with 10 mL of CO2, 0.04 mL/g of methanol as static modifier, and 5 mL of acetone as collecting solvent. Under these conditions, the recovery of tebufenozide extracted by SFE was 100.75%. The extract was analyzed directly by HPLC with a photodiode array detector. The chromatographic conditions were: UV detection wavelength, 245 nm; column, a C18 column; mobile phase, acetonitrile-water (55:45, v/v); flow rate, 1.0 mL/min; injection volume, 5 microL.

  7. Comparison of supercritical fluid and Soxhlet extractions for the isolation of nitro compounds from soils.

    PubMed

    Bajerová, Petra; Eisner, Ales; Jezová, Vera; Adam, Martin; Ventura, Karel

    2008-05-01

    Supercritical fluid extraction (SFE) with CO(2), a clean and rapid alternative to conventional Soxhlet extraction, was investigated for the extraction of nitro compounds from soil samples. Quantitative extraction by SFE was accomplished at a pressure of 25 MPa and an extraction temperature of 60 degrees C, for 30 min in dynamic mode and using acetonitrile as modifier, and the results were comparable with those obtained by acetonitrile Soxhlet extraction (3 h) for all soil samples. Extracts from these two procedures were analyzed by gas chromatography coupled with mass spectrometry. Quantitative reproducibility for SFE extracts was acceptable (RSD 2-10%), and the quantity of solvent was reduced from 160 mL for Soxhlet extraction to 5 mL in the case of SFE.

  8. Design of controlled release systems for THEDES-Therapeutic deep eutectic solvents, using supercritical fluid technology.

    PubMed

    Aroso, Ivo M; Craveiro, Rita; Rocha, Ângelo; Dionísio, Madalena; Barreiros, Susana; Reis, Rui L; Paiva, Alexandre; Duarte, Ana Rita C

    2015-08-15

    Deep eutectic solvents (DES) can be formed by bioactive compounds or pharmaceutical ingredients. A therapeutic DES (THEDES) based on ibuprofen, a non-steroidal anti-inflammatory drug (NSAID), and menthol was synthesized and its thermal behavior was analyzed by differential scanning calorimetry (DSC). A controlled drug delivery system was developed by impregnating a starch:poly-ϵ-caprolactone polymeric blend (SPCL 30:70) with the menthol:ibuprofen THEDES in different ratios (10 and 20 wt%), after supercritical fluid sintering at 20 MPa and 50 °C. The morphological characterization of SPCL matrices impregnated with THEDES was performed by scanning electron microscopy (SEM) and micro-computed tomography (micro-CT). Drug release studies were carried out in a phosphate buffered saline. The results obtained provide important clues for the development of carriers for the sustainable delivery of bioactive compounds. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Supercritical fluid extraction of polyhalogenated pollutants from aquaculture and marine environmental samples: a review.

    PubMed

    García-Rodríguez, Diego; Carro-Díaz, Antonia María; Lorenzo-Ferreira, Rosa Antonia

    2008-05-01

    This article focuses on the state-of-the-art in sample preparation using supercritical fluid extraction (SFE), to monitor the content of polyhalogenated pollutants in aquaculture and marine environmental samples. Marine sediments and biological applications, including several types of samples matrices (fish, shellfish, seaweed and fish feed) and analyte groups (polychlorinated biphenyls (PCBs), polybrominated biphenyls (PBBs), polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxin (PCDD)/Fs and organochlorinated pesticide (OCPs)) are discussed with respect to SFE use and optimisation of conditions. We also discuss the great analytical potential of SFE, the integration of the extraction and clean-up steps for rapid sample processing justifying its use for routine work. The most recent SFE applications to the determination of these pollutants in marine environmental (biota and sediment) samples, published in the last 15 years, are reviewed.

  10. Supercritical fluid chromatography for GMP analysis in support of pharmaceutical development and manufacturing activities.

    PubMed

    Hicks, Michael B; Regalado, Erik L; Tan, Feng; Gong, Xiaoyi; Welch, Christopher J

    2016-01-05

    Supercritical fluid chromatography (SFC) has long been a preferred method for enantiopurity analysis in support of pharmaceutical discovery and development, but implementation of the technique in regulated GMP laboratories has been somewhat slow, owing to limitations in instrument sensitivity, reproducibility, accuracy and robustness. In recent years, commercialization of next generation analytical SFC instrumentation has addressed previous shortcomings, making the technique better suited for GMP analysis. In this study we investigate the use of modern SFC for enantiopurity analysis of several pharmaceutical intermediates and compare the results with the conventional HPLC approaches historically used for analysis in a GMP setting. The findings clearly illustrate that modern SFC now exhibits improved precision, reproducibility, accuracy and robustness; also providing superior resolution and peak capacity compared to HPLC. Based on these findings, the use of modern chiral SFC is recommended for GMP studies of stereochemistry in pharmaceutical development and manufacturing.

  11. Free-standing arrays of isolated TiO2 nanotubes through supercritical fluid drying.

    PubMed

    Deneault, James R; Xiao, Xiaoyin; Kang, Tae-Sik; Wang, Joanna S; Wai, Chien M; Brown, Gail J; Durstock, Michael F

    2012-01-16

    A common complication in fabricating arrays of TiO(2) nanotubes is that they agglomerate into tightly packed bundles during the inevitable solvent evaporation step. This problem is particularly acute for template-fabricated TiO(2) nanotubes, as the geometric tunability of this technique enables relatively large inter-pore spacings or, from another perspective, more space for lateral displacement. Our work showed that agglomeration results from the surface tension forces that are present as the ambient solvent is evaporated from the nanotube film. Herein, we report a processing and fabrication approach that utilizes supercritical fluid drying (CO(2)) to prepare arrays of template-fabricated TiO(2) nanotubes that are free-standing and spatially isolated. This approach could be beneficial to many emerging technologies, such as solid-state dye-sensitized solar cells and vertically-oriented carbon nanotube electrodes.

  12. Drying Using Supercritical Fluid Technology as a Potential Method for Preparation of Chitosan Aerogel Microparticles.

    PubMed

    Obaidat, Rana M; Tashtoush, Bassam M; Bayan, Mohammad F; Al Bustami, Rana T; Alnaief, Mohammad

    2015-12-01

    Supercritical fluid technology offers several advantages in preparation of microparticles. These include uniformity in particle size, morphology, and drug distribution without degradation of the product. One of the recent advantages is preparation of porous aerogel carrier with proper aerodynamic properties. In this study, we aimed to prepare chitosan aerogel microparticles using supercritical fluid (SCF) technology and compare that with microparticles produced by freeze drying (FD). Loading the prepared carriers with a model drug (salbutamol) was also performed. Comparisons of the particle properties and physicochemical characterizations were undertaken by evaluating particle size, density, specific surface area, and porosity. In vitro drug release studies were also investigated. The effect of many variables, such as molecular weight of chitosan oligomers, concentrations of chitosan, and concentrations of tripolyphosphate on the release, were also investigated. Chitosan aerogels were efficiently produced by SCF technology with an average particle size of 10 μm with a tapped density values around 0.12 g/mL, specific surface area (73-103) m(2)/g, and porosity (0.20-0.29) cc/g. Whereas, microparticles produced by FD method were characterized as cryogels with larger particle size (64 microns) with clear cracking at the surface. Sustained release profile was achieved for all prepared microparticles of salbutamol produced by the aforementioned methods as compared with pure drug. The results also demonstrates that chitosan molecular weight, polymer concentration, and tripolyphosphate concentration affected the release profile of salbutamol from the prepared microparticles. In conclusion, SCF technology was able to produce chitosan aerogel microparticles loaded with salbutamol that could be suitable for pulmonary drug delivery system.

  13. Supercritical fluid extraction of lipids from linseed with on-line evaporative light scattering detection.

    PubMed

    Abrahamsson, Victor; Rodriguez-Meizoso, Irene; Turner, Charlotta

    2015-01-01

    Supercritical fluid extraction (SFE) is a green alternative method of extraction for neutral lipids in seeds compared to conventional methods utilizing organic solvents. In this work, a novel method where SFE is hyphenated with an evaporative light scattering detector is presented. The method was subsequently applied to determine lipid content in crushed linseed. The new method enables rapid quantification of extracted lipids as well as be ability to continuously monitor the extraction rate in real-time, thus being able to determine the time point of completed extraction. Both the detector and the method was validated. The results show that any of several tested oils can be used to calibrate the detection method for the determination of lipids extraction from linseed. The overall method repeatability and intermediate precision was 2.6% relative standard deviations. The extracted amount was significantly less than that obtained using the standard method of Soxhlet with petroleum ether, 26.0±0.4% (95% CI, n=9) compared to 32.3±1.3% (95% CI, n=3) of extracted amounts. It was found that channeling effects were present, and by either performing sequential repeated extractions with decompression in-between or by using a relatively large vessel a more complete extraction could be obtained. Interestingly, a substantially higher extracted amount (approximately 50%) was obtained compared to both a single extraction by SFE and the Soxhlet method. Therefore, it is recommended that an additional extraction including a rapid decompression in-between should be included in the validation of a method using supercritical fluid extraction, in order to either rule out channeling effects or to acquire a full recovery.

  14. 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

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

    PubMed

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

    2016-05-27

    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.

  16. Continuous reactions in supercritical carbon dioxide: problems, solutions and possible ways forward.

    PubMed

    Han, Xue; Poliakoff, Martyn

    2012-02-21

    This Tutorial Review focuses on supercritical carbon dioxide (scCO(2)), and discusses some of the problems that have frustrated its wide use on an industrial scale. It gives some recent examples where strategies have been developed to reduce the energy requirements, including sequential reactions and gas-expanded liquids. It then describes a number of cases where scCO(2) offers real chemical advantages over more conventional solvents, for example by controlled phase separation, tunable selectivity, oxidation and on-line analysis and self-optimisation. Overall, this review indicates where scCO(2) could deliver value in the future.

  17. Gas dynamics of heat-release-induced waves in supercritical fluids: revisiting the Piston Effect

    NASA Astrophysics Data System (ADS)

    Migliorino, Mario Tindaro; Scalo, Carlo

    2016-11-01

    We investigate a gasdynamic approach to the modeling of heat-release-induced compression waves in supercritical fluids. We rely on highly resolved one-dimensional fully compressible Navier-Stokes simulations of CO2 at pseudo-boiling conditions in a closed duct inspired by the experiments of Miura et al.. Near-critical fluids exhibit anomalous variations of thermodynamic variables taken into account by adopting the Peng-Robinson equation of state and Chung's Method. An idealized heat source is applied, away from the boundaries, resulting in the generation of compression waves followed by contact discontinuities bounding a region of hot expanding fluid. For higher heat-release rates such compressions are coalescent with distinct shock-like features (i.e. non-isentropicity and propagation Mach numbers measurably greater than unity) and a non-uniform post-shock state, not present in ideal gas simulations, caused by the highly nonlinear equation of state. Thermoacoustic effects are limited to: (1) a one-way/one-time thermal-to-acoustic energy conversion, and (2) cumulative non-isentropic bulk heating due to the resonating compression waves, resulting in what is commonly referred to as the Piston Effect.

  18. An oscillation free shock-capturing method for compressible van der Waals supercritical fluid flows

    DOE PAGES

    Pantano, C.; Saurel, R.; Schmitt, T.

    2017-02-01

    Numerical solutions of the Euler equations using real gas equations of state (EOS) often exhibit serious inaccuracies. The focus here is the van der Waals EOS and its variants (often used in supercritical fluid computations). The problems are not related to a lack of convexity of the EOS since the EOS are considered in their domain of convexity at any mesh point and at any time. The difficulties appear as soon as a density discontinuity is present with the rest of the fluid in mechanical equilibrium and typically result in spurious pressure and velocity oscillations. This is reminiscent of well-knownmore » pressure oscillations occurring with ideal gas mixtures when a mass fraction discontinuity is present, which can be interpreted as a discontinuity in the EOS parameters. We are concerned with pressure oscillations that appear just for a single fluid each time a density discontinuity is present. As a result, the combination of density in a nonlinear fashion in the EOS with diffusion by the numerical method results in violation of mechanical equilibrium conditions which are not easy to eliminate, even under grid refinement.« less

  19. Supercritical carbon dioxide interpolymer complexes improve survival of B. longum Bb-46 in simulated gastrointestinal fluids.

    PubMed

    Thantsha, Mapitsi S; Cloete, Thomas E; Moolman, Francis S; Labuschagne, Philip W

    2009-01-31

    Gastric acidity is the main factor affecting viability of probiotics in the gastrointestinal tract (GIT). This study investigated the survival in simulated gastrointestinal fluids of Bifidobacterium longum Bb-46 encapsulated in interpolymer complexes formed in supercritical carbon dioxide (scCO(2)). Bacteria were exposed sequentially to simulated gastric fluid (SGF, pH 2) for 2 h and simulated intestinal fluid (SIF, pH 6.8) for 6 or 24 h. Total encapsulated bacteria were determined by suspending 1 g of product in SIF for 6 h at 37 degrees C prior to plating out. Plates were incubated anaerobically at 37 degrees C for 72 h. The interpolymer complex displayed pH-responsive release properties, with little to no release in SGF and substantial release in SIF. There was a limited reduction in viable counts at the end of exposure period due to encapsulation. Protection efficiency of the interpolymer complex was improved by addition of glyceryl monostearate (GMS). Gelatine capsules delayed release of bacteria from the interpolymer complex thus minimizing time of exposure to the detrimental conditions. Use of poly(caprolactone) (PCL), ethylene oxide-propylene oxide triblock copolymer (PEO-PPO-PEO) decreased the protection efficiency of the matrix. Interpolymer complex encapsulation showed potential for protection of probiotics and therefore for application in food and pharmaceuticals.

  20. Supercritical-fluid carbon dioxide (SCCO{sub 2}) cleaning of nuclear weapon components

    SciTech Connect

    Taylor, C.M.V.; Sivils, L.D.; Rubin, J.B.

    1998-05-01

    Supercritical fluid carbon dioxide (SCCO{sub 2}) has been evaluated as a cleaning solvent for the cleaning of plutonium (Pu) metal parts. The results of the evaluation show that SCCO{sub 2} is an effective alternative to halogenated solvents that are conventionally used for removing organic and inorganic contaminants from the surface of these parts. The cleaning process was demonstrated at the laboratory scale for steel and uranium substrates and has been found to be compatible with Pu. The efficacy of this cleaning method is found to be dependent on process conditions of pressure, temperature, fluid-flow rate, as well as cleaning time. Process parameters of P > 2,500 psi, T > 40 C, and moderate fluid flow rates, produced good cleaning results in less than 10 minutes using a simple flow-through process configuration. Within the parameter range studied, cleaning efficiency generally improved with increasing process pressure and flow rate. SCCO{sub 2} cleaning is suitable for a variety of component cleaning tasks and is adaptable to precision cleaning requirements. The SCCO{sub 2} cleaning process is currently being developed for deployment for weapons production at LANL.

  1. Comprehensive two-dimensional GC of supercritical fluid and pressurized liquid extracts of tobaccos.

    PubMed

    Vial, Jérôme; Thiébaut, Didier; Sassiat, Patrick; Beldean-Galea, Mihail Simion; Gomez Ramos, Maria José; Cognon, Guillaume; Mallipattu, Sreedhar; Teillet, Beatrice; Bouzige, Marianne

    2010-04-01

    The developments of an analytical strategy based on rapid extraction techniques coupled to comprehensive bi-dimensional gas chromatography (GCxGC) for the characterization of the volatile fraction of tobaccos are presented. The high-peak capacity of GCxGC allows considering global extraction techniques that do not focus on restricted chemical families of products. Thus, potential of pressurized fluid extraction and supercritical fluid extraction (SFE) to provide informative extracts is evaluated and compared. As expected, both techniques enable rapid extraction of compounds of interest. However, because of the easy removal of the extracting fluid, SFE provides more concentrated extracts, allowing a GCxGC direct injection without any concentration step. Moreover, the use of pure carbon dioxide with tuneable extraction power favors the extraction of the compounds of interest while reducing the extraction of interfering heavy compounds. GCxGC conditions, especially concerning the set of columns used, are selected thanks to the comparison of separations obtained on model compounds. The developed methodology is applied not only to compare the three main types of tobaccos but also to discriminate between different tobaccos of the same type.

  2. Numerical Simulations Studies of the Convective Instability Onset in a Supercritical Fluid

    NASA Technical Reports Server (NTRS)

    Furukawa, A.; Meyer, H.; Onuki, A.

    2004-01-01

    Numerical simulation studies are reported for the convection of a supercritical fluid, He-3, in a Rayleigh-Benard cell. The calculations provide the temporal profile DeltaT(t) of the temperature drop across the fluid layer. In a previous article, systematic delays in the onset of the convective instability in simulations relative to experiments were reported, as seen from the DeltaT(t) profiles. They were attributed to the smallness of the noise which is needed to start the instability. Therefore i) homogeneous temperature noise and ii) spatial lateral periodic temperature variations in the top plate were programmed into the simulations, and DeltaT(t) compared with that of an experiment with the same fluid parameters. An effective speed-up in the instability onset was obtained, with the best results obtained through the spatial temperature variations with a period of 2L, close to the wavelength of a pair of convections rolls. For a small amplitude of 0.5 micro-K, this perturbation gave a semiquantitative agreement with experimental observations. Results for various noise amplitudes are presented and discussed in relation to predictions by El Khouri and Carl es.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  4. Numerical Modeling of a Thermal-Hydraulic Loop and Test Section Design for Heat Transfer Studies in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    McGuire, Daniel

    A numerical tool for the simulation of the thermal dynamics of pipe networks with heat transfer has been developed with the novel capability of modeling supercritical fluids. The tool was developed to support the design and deployment of two thermal-hydraulic loops at Carleton University for the purpose of heat transfer studies in supercritical and near-critical fluids. First, the system was characterized based on its defining features; the characteristic length of the flow path is orders of magnitude larger than the other characteristic lengths that define the system's geometry; the behaviour of the working fluid in the supercritical thermodynamic state. An analysis of the transient thermal behaviour of the model's domains is then performed to determine the accuracy and range of validity of the modeling approach for simulating the transient thermal behaviour of a thermal-hydraulic loop. Preliminary designs of three test section geometries, for the purpose of heat transfer studies, are presented in support of the overall design of the Carleton supercritical thermal-hydraulic loops. A 7-rod-bundle, annular and tubular geometries are developed with support from the new numerical tool. Materials capable of meeting the experimental requirements while operating in supercritical water are determined. The necessary geometries to satisfy the experimental goals are then developed based on the material characteristics and predicted heat transfer behaviour from previous simulation results. An initial safety analysis is performed on the test section designs, where they are evaluated against the ASME Boiler, Pressure Vessel, and Pressure Piping Code standard, required for safe operation and certification.

  5. MEASUREMENT OF PYRETHROID RESIDUES IN ENVIRONMENTAL AND FOOD SAMPLES BY ENHANCED SOLVENT EXTRACTION/SUPERCRITICAL FLUID EXTRACTION COUPLED WITH GAS CHROMATOGRAPHY-TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    The abstract summarizes pyrethorid methods development research. It provides a summary of sample preparation and analytical techniques such as supercritical fluid extraction, enhance solvent extraction, gas chromatography and tandem mass spectrometry.

  6. MEASUREMENT OF PYRETHROID RESIDUES IN ENVIRONMENTAL AND FOOD SAMPLES BY ENHANCED SOLVENT EXTRACTION/SUPERCRITICAL FLUID EXTRACTION COUPLED WITH GAS CHROMATOGRAPHY-TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    The abstract summarizes pyrethorid methods development research. It provides a summary of sample preparation and analytical techniques such as supercritical fluid extraction, enhance solvent extraction, gas chromatography and tandem mass spectrometry.

  7. Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation

    PubMed Central

    Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

    2015-01-01

    Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions. PMID:26574523

  8. Enantiomeric separation and quantification of citalopram in serum by ultra-high performance supercritical fluid chromatography-tandem mass spectrometry.

    PubMed

    Hegstad, Solfrid; Havnen, Hilde; Helland, Arne; Falch, Berit Margrethe Hasle; Spigset, Olav

    2017-09-01

    A method for enantiomeric separation and quantification of R/S-citalopram in serum was developed and validated using ultra-high performance supercritical fluid chromatography-tandem mass spectrometry (UHPSFC-MS/MS). Sample preparation prior to UHPSFC-MS/MS analysis consisted of protein precipitation with acidic acetonitrile and filtration through a phospholipid removal plate. The UHPSFC-MS/MS method used an UPC(2) Trefoil CEL2 column with a mobile phase consisting of CO2 and methanol/acetonitrile (70:30, v/v) with 10mM ammonium acetate. The injection volume was 1μL and run time was 4min. MS/MS detection was performed with positive electrospray ionization and two multiple reaction monitoring transitions (m/z 325.1>262.0 and m/z 325.1>109.0). The calibration range was 5-500nM for each analyte. The between-assay relative standard deviations were in the range of 3.4-4.5%. Recovery was 81-91% and matrix effects ranged from 96 to 101% (corrected with internal standard). After development and initial testing, the method has been successfully implemented in routine use in our laboratory for both separation and quantification of R/S-citalopram in more than 250 serum samples for therapeutic drug monitoring. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation.

    PubMed

    Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

    2015-12-28

    Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions.

  10. Probing the vapor-liquid phase behaviors of near-critical and supercritical fluids using a shear mode piezoelectric sensor.

    PubMed

    Oag, Robert M; King, Peter J; Mellor, Christopher J; George, Michael W; Ke, Jie; Poliakoff, Martyn

    2003-02-01

    With the rapidly expanding industrial and research applications of near-critical and supercritical technology there is a pressing need for a simple and inexpensive sensor that may be used to determine the phase coexistence regions of fluid mixtures and to establish whether a fluid system is below, at, or above, a critical point. Mechanically vibrating AT-cut quartz plates may be used to determine the product of the fluid density and viscosity of a fluid in which it is immersed, through measurement of the impedance minimum of the electrical equivalent circuit or of the corresponding frequency. The density-viscosity product changes abruptly between fluid phases and rapidly along the isotherm corresponding to the critical temperature, enabling such a plate to act as a sensor of these fluid features. We consider the limitations and linearity of such a sensor and its behavior when a liquid-gas meniscus crosses its surface. We demonstrate for the first time the effective use of an AT-cut quartz sensor in mapping the phase behavior of fluids, using measurements made on carbon dioxide and ethane for calibration and then investigating an ethane-carbon dioxide mixture. The advantages of this experimental approach are that (i) piezoelectric sensors are available for operation up to 1,000 degrees C and at extremely high pressures and (ii) the measurement of the density-viscosity product of supercritical fluids is inherently simpler than traditional techniques for determining phase behavior.

  11. High performance carbon fibers from mesophases produced by supercritical fluid extraction

    NASA Astrophysics Data System (ADS)

    Dauche, Franck Michel

    The purpose of this research is to investigate the potential of supercritical fluid extraction for the production of an improved precursor for the manufacture of high thermal conductivity carbon fibers. Mesophase pitch fractions were produced by the continuous fractionation of an isotropic petroleum-based pitch with supercritical toluene in a region of liquid-liquid equilibrium. A statistical experimental design was used to investigate a region of extraction operating conditions from which the fractions were expected to exhibit superior spinnability. Chemical and physical characterizations were performed on the fractions, and the results were used to explore the effect of the extraction conditions on the mesophase properties. DRIFT data were shown to be particularly useful for characterizing the chemical composition of the mesophase fractions produced, and GPC was successfully used to determine their molecular weight distribution. Two thermodynamic models based on the SAFT equation together with (1) the concepts of continuous thermodynamics (2) molecular weight information on the oligomeric nature of the feed pitch were used to correlate the measured results. By using three adjustable parameters, solvent compositions and molecular weight distributions in each phase were calculated. Although the oligomeric model is able to qualitatively represent trends observed in the data, it cannot as yet be used to quantitatively predict phase compositions. Based on the characterizations of the supercritically extracted mesophases produced, selected fractions were melt-spun into round- and ribbon-shaped fibers using a laboratory-scale melt-spinning apparatus. It was found that a relatively narrow window of mesophase properties and compositions allowed fiber making without off-gassing. For a given spinnable mesophase, wide angle X-ray diffraction was used on as-spun fibers produced over a wide range of spinning temperatures to evaluate their potential to yield, after proper heat

  12. Molecular dynamics study of the density and temperature dependence of bridge functions in normal and supercritical Lennard-Jones fluids.

    PubMed

    Kunor, Tapas R; Taraphder, Srabani

    2005-09-01

    A systematic study of the density and temperature dependence of bridge functions has been carried out using molecular dynamics simulation studies in one-component Lennard-Jones fluids. In deriving the liquid structure, approximate closures are generally used in integral equation theories of liquids to obtain static density correlations. In the present work, we have directly compared the simulated bridge function to two such commonly used closures, viz., hybrid mean spherical approximation (HMSA) [J. Chem. Phys. 84, 2336 (1986)] and Duh-Henderson [J. Chem. Phys. 104, 6742 (1996)] closures with thermodynamic parameters varying from the normal liquid to the supercritical fluid phase far from and near the critical point. In the normal liquid region, both closures show a qualitative agreement with the simulated bridge function, although the extent of correlation at distances sigma < r < or = 2.5sigma is generally underestimated. A similar behavior is obtained in supercritical fluids far from the critical point where critical fluctuations are no longer important. In contrast, significant deviations are observed in the bridge functions in supercritical fluids near the critical point even at densities as small as 25% or 50% of the critical density. Such behavior appears to have resulted from competing contributions to the bridge function from decreasing indirect correlations and small yet significant cavity correlations persistent even at very low densities.

  13. Determination of coumarins in the roots of Angelica dahurica by supercritical fluid chromatography.

    PubMed

    Pfeifer, Isabella; Murauer, Adele; Ganzera, Markus

    2016-09-10

    The fact that supercritical fluid chromatography (SFC) offers many desirable features is known for a long time. Yet, the number of applications on natural products is still limited, because robust and user-friendly instrumentation became available just a few years ago. As coumarins hardly have been studied by this technique we developed the first SFC assay for their determination in crude plant material. After method optimization eight standard compounds, including simple coumarins, linear and angular furanocoumarins, could be baseline separated in 6min using an Acquity UPC(2) CSH Fluoro-Phenyl 1.7μm column with supercritical CO2, methanol and diethylamine as mobile phase. Method validation confirmed that the assay is linear (R(2)≥0.9995), precise (intra-day variation≤5.8%; inter-day variation≤4.4%) and accurate (recovery rates from 96.5 to 104.2%). Detection limits determined at 300nm were below 2ng on-column, and the method showed to be well suited for the analysis of coumarins in Angelica dahurica roots. It was observed that qualitative as well as quantitative composition vary significantly. In all samples Imperatorin (0.09-0.28%) was the major coumarin, followed either by Isoimperatorin or Oxypeucedanin; the total coumarin content ranged from 0.16 to 0.77%. The results were in good agreement to published data, so that because of its speed and green nature SFC is definitely an interesting alternative for the analysis of this important class of natural products. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Fractionation of petroleum pitch by supercritical fluid extraction: Experimental phase behavior and thermodynamic modeling

    SciTech Connect

    Hutchenson, K.W.

    1990-01-01

    Petroleum pitch is being considered as a raw material for the economical production of high-performance carbon fibers and composites. This dissertation presents part of ongoing research that is investigating a supercritical fluid extraction process for producing a mesophase precursor pitch for carbon fibers. The process can be used to separate the parent pitch into several fractions having narrow molecular weight distributions. A continuous-flow apparatus for measuring vapor-liquid and liquid-liquid phase equilibria is described that is capable of operation at pressures to 350 bar and temperatures to 675 K. A key feature of the apparatus is a nonvisual interface detection technique for operation with opaque phases. Phase equilibrium measurements are presented for mixtures of toluene with phenanthrene and with two petroleum pitches: Ashland A-240 pitch and a proprietary heat-soaked pitch obtained from Conoco. These measurements and analytical results for extracted fractions demonstrate that supercritical extraction can be used to separate pitch into fractions by molecular weight. High extraction yields and significant mesophase formation are observed in a region of liquid-liquid phase equilibrium, indicating this region is likely to be of practical interest for fractionating petroleum pitch. Initial efforts toward the development of a thermodynamic model of the phase equilibria for these systems are also presented. The model uses generalized correlations for equation-of-state constants in terms of average molecular structure parameters and does reasonably well in fitting VLE data for the pitch/toluene system. The model should be useful for guiding future phase equilibrium measurements.

  15. Supercritical methanol for polyethylene terephthalate depolymerization: Observation using simulator

    SciTech Connect

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

    2007-07-01

    To apply PET depolymerization in supercritical methanol to commercial recycling, the benefits of supercritical methanol usage in PET depolymerization was investigated from the viewpoint of the reaction rate and energy demands. PET was depolymerized in a batch reactor at 573 K in supercritical methanol under 14.7 MPa and in vapor methanol under 0.98 MPa in our previous work. The main products of both reactions were the PET monomers of dimethyl terephthalate (DMT) and ethylene glycol (EG). The rate of PET depolymerization in supercritical methanol was faster than that of PET depolymerization in vapor methanol. This indicates supercritical fluid is beneficial in reducing reaction time without the use of a catalyst. We depicted the simple process flow of PET depolymerization in supercritical methanol and in vapor methanol, and by simulation evaluated the total heat demand of each process. In this simulation, bis-hydroxyethyl terephthalate (BHET) was used as a model component of PET. The total heat demand of PET depolymerization in supercritical methanol was 2.35 x 10{sup 6} kJ/kmol Produced-DMT. That of PET depolymerization in vapor methanol was 2.84 x 10{sup 6} kJ/kmol Produced-DMT. The smaller total heat demand of PET depolymerization in supercritical methanol clearly reveals the advantage of using supercritical fluid in terms of energy savings.

  16. 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.

  17. Coal liquefaction process streams characterization and evaluation. Characterization of coal-derived materials by field desorption mass spectrometry, two-dimensional nuclear magnetic resonance, supercritical fluid extraction, and supercritical fluid chromatography/mass spectrometry

    SciTech Connect

    Campbell, J.A.; Linehan, J.C.; Robins, W.H.

    1992-07-01

    Under contract from the DOE , and in association with CONSOL Inc., Battelle, Pacific Northwest Laboratory (PNL) evaluated four principal and several complementary techniques for the analysis of non-distillable direct coal liquefaction materials in support of process development. Field desorption mass spectrometry (FDMS) and nuclear magnetic resonance (NMR) spectroscopic methods were examined for potential usefulness as techniques to elucidate the chemical structure of residual (nondistillable) direct coal liquefaction derived materials. Supercritical fluid extraction (SFE) and supercritical fluid chromatography/mass spectrometry (SFC/MS) were evaluated for effectiveness in compound-class separation and identification of residual materials. Liquid chromatography (including microcolumn) separation techniques, gas chromatography/mass spectrometry (GC/MS), mass spectrometry/mass spectrometry (MS/MS), and GC/Fourier transform infrared (FTIR) spectroscopy methods were applied to supercritical fluid extracts. The full report authored by the PNL researchers is presented here. The following assessment briefly highlights the major findings of the project, and evaluates the potential of the methods for application to coal liquefaction materials. These results will be incorporated by CONSOL into a general overview of the application of novel analytical techniques to coal-derived materials at the conclusion of CONSOL`s contract.

  18. Thermodynamic and Structural Properties of C-bearing Supercritical Aqueous Fluids

    NASA Astrophysics Data System (ADS)

    Seclaman, A. C.; Cohen, R. E.

    2016-12-01

    Aqueous fluids are important agents of mass transport in the Earth's crust and upper mantle. Their role in the deep mantle is poorly understood due to a lack of thermodynamic data at relevant pressures (P) and temperatures (T). Speciation of volatiles also plays a key role in understanding the reactivity of fluids, and the formation of complex anionic C species in supercritical fluids has been linked to the precipitation of diamond during fluid-rock interaction.1 Models have predicted equilibria between all oxidation states of C in aqueous fluids above 3 GPa.2 First principles approaches can help expand the PT range of models, and give an atomic-level understanding of fluid behavior. We are using first principles molecular dynamics to study the H-C-O system up to pressures of 40 GPa and 2500K, spanning a wide range of C concentrations. Since van der Waals (vdW) interactions play important roles in water and organic complexes we take into account vdW by using the non-local vdW-DF2 functional.3 From this data, we obtained the PVTX equation of state and investigated the dependence of pressure, temperature, and concentration on the C speciation. Water dissociation and the PT stability field of aqueous cations and anions were also investigated. The results of this work contribute to a better understanding of the C mantle cycle. Our work can help significantly expand the data sets employed by models4,5 used in the study of complex rock-fluid interactions. This work is supported by the ERC Advanced grant ToMCaT. 1. Sverjensky, D. A. & Huang, F. Nat. Commun. 53, 1689-1699 (2015). 2. Sverjensky, D. a., Stagno, V. & Huang, F. Nat. Geosci. 7, 909-913 (2014). 3. Lee, K., Murray, É. D., Kong, L., Lundqvist, B. I. & Langreth, D. C. Phys. Rev. B - Condens. Matter Mater. Phys. 82, 3-6 (2010). 4. Sverjensky, D. A., Harrison, B. & Azzolini, D. Geochim. Cosmochim. Acta 129, 125-145 (2014). 5. Ghiorso, M. S. & Gualda, G. A. R. Contrib. to Mineral. Petrol. 169, 1-30 (2015).

  19. [Study on uniform-design for optimizing supercritical-CO2 fluid extraction technique of tanshinones in radix salviae].

    PubMed

    Luo, Xiao-Jian; Liu, Yong; Li, Yi; He, Yan

    2006-12-01

    To explore the optimal supercritical-CO2 fluid extraction technique of extracting tanshinones in Radix salviae. The contents of tanshinones were determined by HPLC. Choosing the overall contents of 3 tanshinones as inspecting marker and uniform-design as method, the experimentation was carried out to study the main factors that influence the result of extraction. Among all the 5 inspected factors, the amount of entrainer was most notable. The optimal technique of extraction was: extraction pressure at 30 MPa; extraction temperature at 40 degrees C; separation pressure of separating kettle I at 6 MPa; separation temperature of separating kettle I at 50 degrees C; the amount of entrainer at 10%. Adopting supercritical-CO2 fluid extraction method to extract the tanshinones in Radix salviae was feasible. The contents of tanshinones in the extract were high and the manipulation was simple, convenient and time saving.

  20. Optimization of parameters for the supercritical fluid extraction in the determination of N-nitrosamines in rubbers.

    PubMed

    Rech, F; Garrigós, M C; Marín, M L; Cantó, A; Jiménez, A

    2002-07-19

    The study of the possibilities of supercritical fluid extraction (SFE) with N-nitrosamines in rubbers has been carried out. Home-made materials fortified with several N-nitrosamines were prepared in order to optimize the SFE parameters. A Plackett-Burman design was employed to evaluate the influence of those parameters to be controlled in SFE, such as pressure, temperature, static and dynamic time, restrictor temperature and volume of modifier while CO2 was used as the extraction fluid. An extra central composite design for the main factors (according to the previously obtained results) was also developed in order to refine the best supercritical conditions for the extraction of N-nitrosamines from rubbers. Gas chromatography with a nitrogen and phosphorus sensitive detector was used to achieve sensitivity and limits of detection for the concentrations expected in plastic materials. The proposed analytical method has shown to be useful in the determination of N-nitrosamines even for complex matrices.

  1. The resolved layer of a collisionless, high beta, supercritical, quasi-perpendicular shock wave. II - Dissipative fluid electrodynamics

    NASA Technical Reports Server (NTRS)

    Scudder, J. D.; Aggson, T. L.; Mangeney, A.; Lacombe, C.; Harvey, C. C.

    1986-01-01

    Using the results of Scudder et al. (1986) on the bow shock wave observed by ISEE satellites, a quantitative description is presented of the electrodynamics of ion and electron fluids, and phase-standing wave interaction which manifests itself as a supercritical MHD shock. The cross-shock electrical profile was determined in both the normal incidence frame and in the deHoffman-Teller frame by two different methods, and the results were compared with dc electric field measurements.

  2. The resolved layer of a collisionless, high beta, supercritical, quasi-perpendicular shock wave. II - Dissipative fluid electrodynamics

    NASA Technical Reports Server (NTRS)

    Scudder, J. D.; Aggson, T. L.; Mangeney, A.; Lacombe, C.; Harvey, C. C.

    1986-01-01

    Using the results of Scudder et al. (1986) on the bow shock wave observed by ISEE satellites, a quantitative description is presented of the electrodynamics of ion and electron fluids, and phase-standing wave interaction which manifests itself as a supercritical MHD shock. The cross-shock electrical profile was determined in both the normal incidence frame and in the deHoffman-Teller frame by two different methods, and the results were compared with dc electric field measurements.

  3. Supercritical fluid of particles with a Yukawa potential: A new approximation for the direct correlation function and the Widom line

    NASA Astrophysics Data System (ADS)

    Tareyeva, E. E.; Ryzhov, V. N.

    2016-12-01

    We propose an approximation of a direct correlation function corresponding to the linearization with respect to - βϕ( r) of a generalized mean spherical approximation for a hard-core multi-Yukawa system of particles. We use the results to study the behavior of maximums of thermodynamic response functions in the supercritical region of a fluid with a two-term Yukawa potential imitating the Lennard-Jones potential.

  4. Development and evaluation of supercritical fluid chromatography/mass spectrometry for polar and high-molecular-weight coal components: Technical progress report for the period October 1, 1985 - September 30, 1986

    SciTech Connect

    Chess, E.K.; Kalinoski, H.T.; Wright, B.W.; Smith, R.D.

    1987-02-01

    Technical progress toward the programmatic goals of developing and evaluating SFC/MS for the analysis of higher-molecular-weight compounds was made in the following areas: Studies have been conducted to characterize the requirements for and to facilitate the transfer of thermal energy to the capillary flow restrictor region. Such studies have resulted in a new interface probe design which allows better transport of higher molecular weight, less volatile compounds decreasing the mass discrimination at the supercritical fluid chromatograph mass spectrometer interface region. Calibration of the magnetic sector mass spectrometer to 1400 daltons has been developed. A digital syringe pump controller, interfaced to an Apple IIe computer allows much finer and more reproducible control of the pressure (density) of the supercritical fluid mobile phase. Nonpolar supercritical fluid mobile phases have been modified by the addition of small amounts of polar fluids to create fluids with higher solvating powers than, but with similar operating parameters. An in-depth knowledge of the fluid behavior is required for successful utilization of these modified fluids. Polar-modified fluids have been used with three types of supercritical fluid introduction to the mass spectrometer: direct fluid injection, supercritical fluid chromatography, and supercritical fluid extraction. Capillary columns evaluated for stability indicated that our present methods for preparing columns are sufficient, for many of the stationary phase and supercritical fluid combinations tested, to create columns that can be used successfully with supercritical fluid chromatography. 9 refs., 11 figs.

  5. 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

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

    PubMed Central

    Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta

    2016-01-01

    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. PMID:27452148

  7. Simultaneous analysis of antioxidants and preservatives in cosmetics by supercritical fluid extraction combined with liquid chromatography-mass spectrometry.

    PubMed

    Lee, Maw-Rong; Lin, Chueh-Yu; Li, Zu-Guang; Tsai, Tzu-Feng

    2006-07-07

    This study evaluated supercritical fluid extraction (SFE) combined with liquid chromatography-mass spectrometry (LC-MS) to determine trace preservatives and antioxidants including methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), alpha-tocopherol (alpha-t) and alpha-tocopherol acetate (alpha-ta) in cosmetic products. A supercritical fluid extraction procedure was used to isolate four paraben preservatives and four antioxidants from the cosmetic matrix before quantitative analysis. The optimum extraction condition was performed with static extraction for 5 min, then dynamic extraction for 20 min by using carbon dioxide supercritical fluid at 14,000 kPa and 65 degrees C. Methanol was used as collection solvent and the sea sand was chosen as a filling material. The analytes were separated on a C18 reversed-phase column using methanol-water as mobile phase and quantified by measuring its mass spectrometry. The linearity range is from 10 to 20,000 ng/g with RSD values below 18%. Detection limits are achieved at the level of 4.7-142 ng/g. It was successfully applied to the determination of paraben preservatives and antioxidants in cosmetics without tedious pretreatment.

  8. 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.

  9. Enantioselective simultaneous analysis of selected pharmaceuticals in environmental samples by ultrahigh performance supercritical fluid based chromatography tandem mass spectrometry.

    PubMed

    Camacho-Muñoz, Dolores; Kasprzyk-Hordern, Barbara; Thomas, Kevin V

    2016-08-31

    In order to assess the true impact of each single enantiomer of pharmacologically active compounds (PACs) in the environment, highly efficient, fast and sensitive analytical methods are needed. For the first time this paper focuses on the use of ultrahigh performance supercritical fluid based chromatography coupled to a triple quadrupole mass spectrometer to develop multi-residue enantioselective methods for chiral PACs in environmental matrices. This technique exploits the advantages of supercritical fluid chromatography, ultrahigh performance liquid chromatography and mass spectrometry. Two coated modified 2.5 μm-polysaccharide-based chiral stationary phases were investigated: an amylose tris-3,5-dimethylphenylcarbamate column and a cellulose tris-3-chloro-4-methylphenylcarbamate column. The effect of different chromatographic variables on chiral recognition is highlighted. This novel approach resulted in the baseline resolution of 13 enantiomers PACs (aminorex, carprofen, chloramphenicol, 3-N-dechloroethylifosfamide, flurbiprofen, 2-hydroxyibuprofen, ifosfamide, imazalil, naproxen, ofloxacin, omeprazole, praziquantel and tetramisole) and partial resolution of 2 enantiomers PACs (ibuprofen and indoprofen) under fast-gradient conditions (<10 min analysis time). The overall performance of the methods was satisfactory. The applicability of the methods was tested on influent and effluent wastewater samples. To the best of our knowledge, this is the first feasibility study on the simultaneous separation of chemically diverse chiral PACs in environmental matrices using ultrahigh performance supercritical fluid based chromatography coupled with tandem mass spectrometry.

  10. 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.

  11. 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

  12. Fabrication of Mesoporous Silicate Films by Three Dimensional Replication of Block Copolymer Templates in Supercritical Fluids

    NASA Astrophysics Data System (ADS)

    Pai, Rajaram; Watkins, James

    2003-03-01

    The optimization of electrical and mechanical properties of mesoporous silicate and organosilicate thin films requires strict control over porosity, pore structure, matrix composition and ultimately, as device dimensions recede, the ability to control long range order and patterning at the device level. Here we discuss a new approach to mesoporous silicates that involves the infusion and selective condensation of metal oxide precursors within one phase domain of highly ordered, preformed block copolymer templates using supercritical carbon dioxide as the reaction medium. The template is then removed to produce the mesoporous oxide. To date we have replicated ordered spherical and cylindrical morphologies to yield silica, organosilicate and mixed silica/organosilicate mesostructures in films over 1 micron thick while maintaining all the structural details of the sacrificial copolymer template. The elimination of excess alcohol from the reaction media enables rapid and high degrees of network condensation. After post-processing, these films exhibit dielectric constants as low as 1.8. Moreover, separation of the template formation and infusion steps is enabling as structure on both the local and device levels can be achieved wholly in the polymer template prior to infusion of the inorganic phase.

  13. Electrocatalytic Reactivity for Oxygen Reduction of Palladium-Modified Carbon Nanotubes Synthesized in Supercritical Fluid

    SciTech Connect

    Lin, Yuehe; Cui, Xiaoli; Ye, Xiangrong

    2005-02-02

    The electrocatalytic reactivity of palladium-modified carbon nanotubes (Pd-CNTs) for the oxygen reduction reaction (ORR) was investigated at the glassy carbon electrode surface in 1 M H2SO4 saturated by oxygen. Carbon nanotubes modified by palladium nanoparticles were synthesized in supercritical carbon dioxide and characterized by transmission electron micrograph. The electrocatalytic activity of the CNTs film and Pd–CNTs film toward oxygen reduction was studied using cyclic voltammetry and linear sweep voltammetry methods. The molecular oxygen reduction at the Pd-CNTs electrode started at a more positive potential than that at the CNTs electrode. A possible reaction mechanism was proposed in which the ORR may proceed through two-step two-electron processes for the Pd-CNTs modified electrode. Experimental results revealed that Pd-CNTs possess a remarkable activity and high stability for oxygen reduction in acid medium, which implies the potential applications of the Pd–CNTs for constructing electrodes of fuel cells.

  14. Supercritical water oxidation of quinazoline: Reaction kinetics and modeling.

    PubMed

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

    2017-03-01

    This paper presents a first quantitative kinetic model for supercritical water oxidation (SCWO) of quinazoline that describes the formation and interconversion of intermediates and final products at 673-873 K. The set of 11 reaction pathways for phenol, pyrimidine, naphthalene, NH3, etc, involved in the simplified reaction network proved sufficient for fitting the experimental results satisfactorily. We validated the model prediction ability on CO2 yields at initial quinazoline loading not used in the parameter estimation. Reaction rate analysis and sensitivity analysis indicate that nearly all reactions reach their thermodynamic equilibrium within 300 s. The pyrimidine yielding from quinazoline is the dominant ring-opening pathway and provides a significant contribution to CO2 formation. Low sensitivity of NH3 decomposition rate to concentration confirms its refractory nature in SCWO. Nitrogen content in liquid products decreases whereas that in gaseous phase increases as reaction time prolonged. The nitrogen predicted by the model in gaseous phase combined with the experimental nitrogen in liquid products gives an accurate nitrogen balance of conversion process.

  15. A transferable coarse-grained potential to study the structure of confined, supercritical Lennard-Jones fluids.

    PubMed

    Sanghi, T; Aluru, N R

    2010-01-28

    In this paper, we develop a transferable coarse-grained interatomic potential to study the structure of simple (spherical and nonpolar) Lennard-Jones (LJ) fluids confined at supercritical temperatures. The potential is used in empirical potential based quasicontinuum theory, [A. V. Raghunathan et al., J. Chem. Phys. 127, 174701 (2007)] to study the structure of three simple LJ fluids (oxygen, methane, and argon) confined in slitlike geometries. The results obtained using the coarse-grained interatomic potential are found to be in good agreement with those predicted by equilibrium molecular dynamics simulations.

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

    PubMed

    Sun, Yongda

    2014-01-01

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

  17. Determination of PCBs and total lipids in edible fish and crab tissue using supercritical fluid extraction

    SciTech Connect

    Gavlor, M.; Hale, R.; Smith, C.; Thames, J.; Mothershead, R.

    1995-12-31

    An offline supercritical fluid extraction (SFE) method has been developed to determine PCB congeners and total tissue lipid content in edible fish and crab tissues collected from several river systems in Virginia. The method is rapid and safe, requiring only 40 minutes per sample and uses nonorganic solvents for total lipid extraction and only 1.5 mL isooctane for PCB extraction. The SFE approach compares favorably with soxhlet extraction, ASE and column elution. Over 800 fish and crab tissue samples were analyzed successfully, thus demonstrating the robustness of the method. Total lipid values obtained using SFE showed considerable spatial and interspecies variability ranging from 1.8% in blue crab (Callinectes sapidus) to 36.4% in striped bass (Morone saxatilis). Total PCB concentrations also varied greatly by site and species. These ranged from below the quantitation limit (1.0 {micro}1 g/kg) to 9,910 {micro}g/kg on a dry weight basis using GCELCD. Dominant PCB congeners detected were in good agreement with those reported by other researchers. Mean total PCB concentrations did not correlate well with total tissue lipid content.

  18. Numerical modeling of the elution peak profiles of retained solutes in supercritical fluid chromatography

    SciTech Connect

    Kaczmarski, Krzysztof; Guiochon, Georges A

    2011-01-01

    In supercritical fluid chromatography (SFC), the significant expansion of the mobile phase along the column causes the formation of axial and radial gradients of temperature. Due to these gradients, the mobile phase density, its viscosity, its velocity, its diffusion coefficients, etc. are not constant throughout the column. This results in a nonuniform flow velocity distribution, itself causing a loss of column efficiency in certain cases, even at low flow rates, as they do in HPLC. At high flow rates, an important deformation of the elution profiles of the sample components may occur. The model previously used to account satisfactorily for the retention of an unsorbed solute in SFC is applied to the modeling of the elution peak profiles of retained compounds. The numerical solution of the combined heat and mass balance equations provides the temperature and the pressure profiles inside the column and values of the retention time and the band profiles of retained compounds that are in excellent agreement with independent experimental data for large value of mobile phase reduced density. At low reduced densities, the band profiles can strongly depend on the column axial distribution of porosity.

  19. Quantification of seed oil from species with varying oil content using supercritical fluid extraction.

    PubMed

    Seal, Charlotte E; Kranner, Ilse; Pritchard, Hugh W

    2008-01-01

    The quantity and composition of seed oil affects seed viability and storability and hence the value of a species as a resource for nutrition and plant conservation. Supercritical fluid extraction with carbon dioxide (SFE-CO2) offers a rapid, environmentally friendly alternative to traditional solvent extraction. To develop a method using SFE-CO2 to quantify the seed oil content in a broad range of species with high to low oil contents. Seed oil was extracted using SFE-CO2 from four crop species representing high, medium and low oil content: Helianthus annuus, Asteraceae, with ca. 55% oil; Brassica napus, Brassicaceae, with ca. 50% oil; Glycine max, Fabaceae, with ca. 20% oil; and Pisum sativum, Fabaceae, with ca. 2% oil. Extraction pressures of 5000, 6000 and 7500 psi and temperatures of 40, 60 and 80 degrees C were examined and a second step using 15% ethanol as a modifier included. Oil yields were compared with that achieved from Smalley Butt extraction. The optimised SFE-CO2 method was validated on six species from taxonomically distant families and with varying oil contents: Swietenia humilis (Meliaceae), Stenocereus thurberi (Cactaceae), Sinapis alba (Brassicaceae), Robinia pseudoacacia (Fabaceae), Poa pratensis (Poaceae) and Trachycarpus fortunei (Arecaceae). The two-step extraction at 6000 psi and 80 degrees C produced oil yields equivalent to or higher than Smalley Butt extraction for all species, including challenging species from the Brassicaceae family. SFE-CO2 enables the rapid analysis of seed oils across a broad range of seed oil contents.

  20. Sum of ranking differences to rank stationary phases used in packed column supercritical fluid chromatography.

    PubMed

    West, Caroline; Khalikova, Maria A; Lesellier, Eric; Héberger, Károly

    2015-08-28

    The identification of a suitable stationary phase in supercritical fluid chromatography (SFC) is a major source of difficulty for those with little experience in this technique. Several protocols have been suggested for column classification in high-performance liquid chromatography (HPLC), gas chromatography (GC), and SFC. However, none of the proposed classification schemes received general acceptance. A fair way to compare columns was proposed with the sum of ranking differences (SRD). In this project, we used the retention data obtained for 86 test compounds with varied polarity and structure, analyzed on 71 different stationary phases encompassing the full range in polarity of commercial packed columns currently available to the SFC chromatographer, with a single set of mobile phase and operating conditions (carbon dioxide-methanol mobile phase, 25°C, 150bar outlet pressure, 3ml/min). First, a reference column was selected and the 70 remaining columns were ranked based on this reference column and the retention data obtained on the 86 analytes. As these analytes previously served for the calculation of linear solvation energy relationships (LSER) on the 71 columns, SRD ranks were compared to LSER methodology. Finally, an external comparison based on the analysis of 10 other analytes (UV filters) related the observed selectivity to SRD ranking. Comparison of elution orders of the UV filters to the SRD rankings is highly supportive of the adequacy of SRD methodology to select similar and dissimilar columns.