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Sample records for supercritical solutions ress

  1. Preparation and Characterization of Micronized Artemisinin via a Rapid Expansion of Supercritical Solutions (RESS Method

    Directory of Open Access Journals (Sweden)

    Xiaonan Zhang

    2012-04-01

    Full Text Available The particle sizes of pharmaceutical substances are important for their bioavailability. Bioavailability can be improved by reducing the particle size of the drug. In this study, artemisinin was micronized by the rapid expansion of supercritical solutions (RESS. The particle size of the unprocessed white needle-like artemisinin particles was 30 to 1200 µm. The optimum micronization conditions are determined as follows: extraction temperature of 62 °C, extraction pressure of 25 MPa, precipitation temperature 45 °C and nozzle diameter of 1000 μm. Under the optimum conditions, micronized artemisinin with a (mean particle size MPS of 550 nm is obtained. By analysis of variance (ANOVA, extraction temperature and pressure have significant effects on the MPS of the micronized artemisinin. The particle size of micronized artemisinin decreased with increasing extraction temperature and pressure. Moreover, the SEM, LC-MS, FTIR, DSC and XRD allowed the comparison between the crystalline initial state and the micronization particles obtained after the RESS process. The results showed that RESS process has not induced degradation of artemisinin and that processed artemisinin particles have lower crystallinity and melting point. The bulk density of artemisinin was determined before and after RESS process and the obtained results showed that it passes from an initial density of 0.554 to 0.128 g·cm−3 after the processing. The decrease in bulk density of the micronized powder can increase the liquidity of drug particles when they are applied for medicinal preparations. These results suggest micronized powder of artemisinin can be of great potential in drug delivery systems.

  2. Micronization of Griseofulvin by Ress in Supercritical CO2 with Cosolvent Acetone

    Institute of Scientific and Technical Information of China (English)

    胡国勤; 陈鸿雁; 蔡建国; 邓修

    2003-01-01

    Griseofulvin (GF) is an antifungal drug whose pharmaceutical activity can be improved by reducing particle size. In this study the rapid expansion of supercritical solution (RESS) was employed to micronize GF.Carbon dioxide with cosolvent acetone was chosen as a supercritical mixed solvent. The solubility of GF in super-critical CO2 with cosolvent acetone was measured using a dynamic apparatus at pressures between 12 and 32 MPa,temperatures at 313, 323 and 333 K and cosolvent concentration at 1.5, 3.0, 4.5 and 6.0% (by mole). The effect of pre-expansion pressure, extraction temperature, spraying distance, nozzle size and concentration of cosolvent on the precipitated particles was investigated. The results show that the mean particle size of griseofulvin precipitated by RESS was less than 1.2μm. An increase in pre-expansion pressure, extraction temperature, spraying distance and concentration of cosolvent resulted in a decrease in particle size under the operating condition studied. With the decrease of nozzle diameter the particle size reduces. The crystallinity and melting point of the original material and the processed particle by RESS were tested by X-ray diffraction (XRD) and differential scanning calorimetry (DSC).No evident modification in the crystal habit was found under the experimental conditions tested. The morphology of particles precipitated was analyzed bY scanning electron microscopy (SEM).

  3. Crystal doping aided by rapid expansion of supercritical solutions.

    Science.gov (United States)

    Vemavarapu, Chandra; Mollan, Matthew J; Needham, Thomas E

    2002-01-01

    The purpose of this study was to test the utility of rapid expansion of supercritical solution (RESS) based cocrystallizations in inducing polymorph conversion and crystal disruption of chlorpropamide (CPD). CPD crystals were recrystallized by the RESS process utilizing supercritical carbon dioxide as the solvent. The supercritical region investigated for solute extraction ranged from 45 to 100 degrees C and 2000 to 8000 psi. While pure solute recrystallization formed stage I of these studies, stage II involved recrystallization of CPD in the presence of urea (model impurity). The composition, morphology, and crystallinity of the particles thus produced were characterized utilizing techniques such as microscopy, thermal analysis, x-ray powder diffractometry, and high-performance liquid chromatography. Also, comparative evaluation between RESS and evaporative crystallization from liquid solvents was performed. RESS recrystallizations of commercially available CPD (form A) resulted in polymorph conversion to metastable forms C and V, depending on the temperature and pressure of the recrystallizing solvent. Cocrystallization studies revealed the formation of eutectic mixtures and solid solutions of CPD + urea. Formation of the solid solutions resulted in the crystal disruption of CPD and subsequent amorphous conversion at urea levels higher than 40% wt/wt. Consistent with these results were the reductions in melting point (up to 9 degrees C) and in the DeltaH(f) values of CPD (up to 50%). Scanning electron microscopy revealed a particle size reduction of up to an order of magnitude upon RESS processing. Unlike RESS, recrystallizations from liquid organic solvents lacked the ability to affect polymorphic conversions. Also, the incorporation of urea into the lattice of CPD was found to be inadequate. In providing the ability to control both the particle and crystal morphologies of active pharmaceutical ingredients, RESS proved potentially advantageous to crystal

  4. RESS essentials

    CERN Document Server

    Krenz-Kurowska, Joanna

    2013-01-01

    This is a step-by-step, practical guide which will introduce you to RESS and its key features.This book is aimed primarily at web developers interested in writing applications that leverage both client- and server-side code to optimise content for various devices.

  5. THE TEMPERATURE AND TURBULENCE CHARACTERISTICS IN RESS PROCESS

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    IntroductionSupercritical fluid has high diffusivity like gas,strong solubility like liquid, low viscosity and surfacetension, and strong penetrability. Therefore, it hasspecial advantages in eXtraction, separation, reaction,coating and ultrafine panicle preparation etc. Solutecan be quickly separated from solvent, which is agreen process of chemical engineering.In the Rapid Expansion of Supercritical fluidSolution (RESS), an ultra-high supersaturating ratio inthe solution occurs instantaneously, forming ul...

  6. Processing of polyolefin blends in supercritical propane solution

    Science.gov (United States)

    Han, Suh Joon

    New polymer blending methods are developed and studied by processing polyolefins in supercritical propane in this research. Polypropylene and ethylene copolymers were dissolved in supercritical propane, and processed via various paths and reactions, i.e., RESS (rapid expansion of supercritical solution), ICSS (isobaric crystallization from supercritical solution), and thermoplastic vulcanizate (TPV) formation. Each process resulted in a unique morphology of polyolefin blends. The effect of polyolefin microstructure on the solution behavior in supercritical propane was investigated, and the relationship between the morphology of the polyolefin blends and processing paths in supercritical propane solutions was established. To understand the thermodynamic properties of polyolefins in bulk and solutions, the solubility parameter was estimated by measurement of the internal pressure from the experimental P-V-T data for polyolefins in the melt state. As the short chain branch content in the ethylene copolymers increased, the internal pressure decreased. The cloud-point pressures of binary polymer solutions in propane decreased as the extent of short chain branching increased in the ethylene copolymers. At the same degree of branching, the cloud-point pressure decreased slightly with increasing branch length. The cloud-point pressures of a ternary polymer solution in the pressure-temperature phase diagrams were higher than those of binary polymer solutions at the same composition (indicating poorer solubility). Microfibers and microparticles (10 ˜ 50 mum diameter) were precipitated from the RESS process while microcellular foams were obtained from the ICSS process. The phase domains of the ethylene-butene (EB) copolymer in the polypropylene from the RESS process were smaller for highly branched EB copolymer. The surface morphology of ethylene copolymers in the microcelluar foams was also changed by increasing the branch content from microparticles to a viscous layer. New

  7. Metal Nanoparticles Preparation In Supercritical Carbon Dioxide Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Harry W. Rollins

    2004-04-01

    The novel optical, electronic, and/or magnetic properties of metal and semiconductor nanoparticles have resulted in extensive research on new methods for their preparation. An ideal preparation method would allow the particle size, size distribution, crystallinity, and particle shape to be easily controlled, and would be applicable to a wide variety of material systems. Numerous preparation methods have been reported, each with its inherent advantages and disadvantages; however, an ideal method has yet to emerge. The most widely applied methods for nanoparticle preparation include the sonochemical reduction of organometallic reagents,(1&2) the solvothermal method of Alivisatos,(3) reactions in microemulsions,(4-6) the polyol method (reduction by alcohols),(7-9) and the use of polymer and solgel materials as hosts.(10-13) In addition to these methods, there are a variety of methods that take advantage of the unique properties of a supercritical fluid.(14&15) Through simple variations of temperature and pressure, the properties of a supercritical fluid can be continuously tuned from gas-like to liquid-like without undergoing a phase change. Nanoparticle preparation methods that utilize supercritical fluids are briefly reviewed below using the following categories: Rapid Expansion of Supercritical Solutions (RESS), Reactive Supercritical Fluid Processing, and Supercritical Fluid Microemulsions. Because of its easily accessible critical temperature and pressure and environmentally benign nature, carbon dioxide is the most widely used supercritical solvent. Supercritical CO2 is unfortunately a poor solvent for many polar or ionic species, which has impeded its use in the preparation of metal and semiconductor nanoparticles. We have developed a reactive supercritical fluid processing method using supercritical carbon dioxide for the preparation of metal and metal sulfide particles and used it to prepare narrowly distributed nanoparticles of silver (Ag) and silver sulfide

  8. [Preparation of microparticles of SCF-CO2 extraction of Salvia miltiorrhiza by RESS].

    Science.gov (United States)

    He, Shuai; Lei, Zheng-Jie; Huang, Dong-Yi; Zhang, Zhong-Yi

    2008-09-01

    Application of rapid expansion of supercritical solution (RESS) in preparing micropaticles of SCF-CO2 extraction of Salvia miltiorrhiza. The mixture which was composed of beta-cyclodextrin and SCF-CO2 extraction of S. miltiorrhiza with proportion 8:1 by weight, was granulated by RESS. The characteristics of the resululting particles were studied by scanning electron microscopy (SEM) and the assay of salviol IIA in particles which was determinated by HPLC. The resulting particles were jacinth and photomicrograph produced by SEM showed that the morphology were silkiness and rugosity globular, the size distribution between 2 and 80 microm, and the contents of salviol IIA was 0.54%. The RESS method is applicable for preparing microparticles of SCF-CO2 extraction of S. miltiorrhiza and low operating temperature, simple processing, and no environmental pollution, and no residual solvent.

  9. Environmentally benign formation of polymeric microspheres by rapid expansion of supercritical carbon dioxide solution with a nonsolvent.

    Science.gov (United States)

    Matsuyama, K; Mishima, K; Umemoto, H; Yamaguchi, S

    2001-10-15

    A novel method is reported for forming polymer microparticles, which reduce atmospheric emissions of environmentally harmful volatile organic compounds such as toluene and xylene used as paint solvent in paint industry. The polymer microparticles have formed through rapid expansion from supercritical solution with a nonsolvent (RESS-N). Solubilization of poly(styrene)-b-(poly(methyl methacrylate)-co-poly (glycidyl methacrylate)) copolymer(PS-b-(PMMA-co-PGMA), MW = 5000, PS/PMMA/PGMA = 2/5/3), poly(ethylene glycol) (PEG, M. W = 4000), bisphenol A type epoxy resin (EP, MW = 3000), poly(methyl methacrylate) (PMMA; MW = 15000, 75000, 120000), and poly(oxyalkylene) alkylphenyl ether (MW = 4000) in carbon dioxide (CO2) was achieved with the use of small alcohols as cosolvents. The solubility of the PS-b-(PMMA-co-PGMA) is extremely low in either CO2 or ethanol but becomes 20 wt % in a mixture of the two. Because ethanol is a nonsolvent for the polymer, it can be used as a cosolvent in rapid expansion from supercritical solution to produce 1-3 microm particles that do not agglomerate. Obtained polymer particles by RESS-N were applied as powder coatings. The resulting coatings have a smooth and coherent film. The particle size distribution of microspheres was controlled by changing the polymer concentration, preexpansion pressure, temperature, and injection distance. The feed compositions were more effective than the other factors in controlling the particle size. The polymeric microparticles formed by RESS-N method can be utilized to make the thin coating film without anytoxic organic solvents and/or surfactants.

  10. Materials processing using supercritical fluids

    Directory of Open Access Journals (Sweden)

    Orlović Aleksandar M.

    2005-01-01

    Full Text Available One of the most interesting areas of supercritical fluids applications is the processing of novel materials. These new materials are designed to meet specific requirements and to make possible new applications in Pharmaceuticals design, heterogeneous catalysis, micro- and nano-particles with unique structures, special insulating materials, super capacitors and other special technical materials. Two distinct possibilities to apply supercritical fluids in processing of materials: synthesis of materials in supercritical fluid environment and/or further processing of already obtained materials with the help of supercritical fluids. By adjusting synthesis parameters the properties of supercritical fluids can be significantly altered which further results in the materials with different structures. Unique materials can be also obtained by conducting synthesis in quite specific environments like reversed micelles. This paper is mainly devoted to processing of previously synthesized materials which are further processed using supercritical fluids. Several new methods have been developed to produce micro- and nano-particles with the use of supercritical fluids. The following methods: rapid expansion of supercritical solutions (RESS supercritical anti-solvent (SAS, materials synthesis under supercritical conditions and encapsulation and coating using supercritical fluids were recently developed.

  11. Solid crystallization by rapid expansion of supercritical ternary mixtures

    Science.gov (United States)

    Domingo, C.; Wubbolts, F. E.; Rodríguez-Clemente, R.; van Rosmalen, G. M.

    1999-03-01

    The objective of the present work was to examine the effect of a solid entrainer in the RESS-process. A RESS-equipment with two extraction columns running in series was used to perform the experiments. Salicylic acid or phenanthrene was used as a solute and benzoic acid as a cosolute. The presence of the cosolute modifies solid crystal size distribution, since it alters solute solubility in the supercritical phase. Homogeneous solid mixtures are obtained after expansion. Alternatively, if the aim is to precipitate a pure compound, solid-solid separation could be aided by selective adsorption into an adsorbent.

  12. Crystallization of micro particles of sulindac using rapid expansion of supercritical solution

    Science.gov (United States)

    Zeinolabedini Hezave, Ali; Esmaeilzadeh, Feridun

    2010-11-01

    In pharmaceutical industry, many drugs exhibit poor solubility in biological fluid. Solubility of drugs affects on the rate of dissolution and bioavailability in biological fluids. The bioavailability of drugs can be enhanced by decreasing the drug particle size. In this study, sulindac was micronized via rapid expansion of supercritical solution (RESS) where CO2 was used as a solvent. The experiments were conducted to investigate the effect of the extraction pressure and temperature (140-230 bar and 40-60 °C), collection distance (1-10 cm), effective nozzle diameter (450-1700 μm) and nozzle length (2-15 mm) on the size and morphology of the sulindac particles. The size and morphology of the precipitated particles were monitored by scanning electron microscopy (SEM). The particle size of intact sulindac particles was about 33.03 μm, while the average particle size of the micronized sulindac particles was between 0.76 and 8.02 μm based on different experimental conditions. Additionally, the different morphology of the micronized particles was observed like needle, rectangular, quasi spherical and irregular form while the morphology of the intact particles of sulindac was rectangular and irregular.

  13. Nanotechnology and supercritical fluids | Hamidreza | Journal of ...

    African Journals Online (AJOL)

    Several techniques have been proposed to produce nanomaterials using ... of the supercritical based techniques applied to the production of nanoparticles materials. Keywords: Supercritical fluids; Nanoparticles; SCF technology; RESS; SAS.

  14. Modeling supercritical fluid extraction process involving solute-solid interaction

    Energy Technology Data Exchange (ETDEWEB)

    Goto, M.; Roy, B. Kodama, A.; Hirose, T. [Kumamoto Univ., Kumamoto (Japan)

    1998-04-01

    Extraction or leaching of solute from natural solid material is a mass transfer process involving dissolution or release of solutes from a solid matrix. Interaction between the solute and solid matrix often influences the supercritical fluid extraction process. A model accounting for the solute-solid interaction as well as mass transfer is developed. The BET equation is used to incorporate the interaction and the solubility of solutes into the local equilibrium in the model. Experimental data for the supercritical extraction of essential oil and cuticular wax from peppermint leaves are successfully analyzed by the model. The effects of parameters on the extraction behavior are demonstrated to illustrate the concept of the model. 18 refs., 5 figs., 1 tab.

  15. 超临界流体技术制各类胡萝卜素纳米颗粒%Carotenoids particle formation by supercritical fluid technologies

    Institute of Scientific and Technical Information of China (English)

    全灿; Johan Carlfors; Charlotta Turner

    2009-01-01

    Based on the solubility in supercritical CO2, two strategies in which CO2 plays different roles are used to make quercetine and astaxanthin particles by supercritical fluid technologies. The experimental results showed that micronized quercetine particles with mean particle size of 1.0-1.5 um can be made via solution enhanced dis-persion by supercritical fluids (SEDS) process, in which CO2 worked as turbulent anti-solvent; while for astaxan-thin, micronized particles with mean particle size of 0.3-0.8 um were also made successfully by rapid expansion supercritical solution (RESS) process.

  16. Spontaneous Ignition of Hydrothermal Flames in Supercritical Ethanol Water Solutions

    Science.gov (United States)

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

    2017-01-01

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

  17. Positive Singular Solutions for Quasilinear Elliptic Equations With Supercritical Growth

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    @@ In this paper we study the existence of positive singular solutions of the following problems div(|(△)u|p-2(△)u)+f(u)=0 in Ω\{0}(1) limx→0u(x)=∞.(2) Where 1supercritical condition as u→∞ , that is f satisfies that following conditions:

  18. Formation of energetic materials using supercritical fluids

    Energy Technology Data Exchange (ETDEWEB)

    Teipel, U.; Kroeber, H.; Krause, H.H. [Fraunhofer-Institut fuer Chemische Technologie (ICT), Pfinztal (Germany)

    2001-10-01

    A new field of applications of compressed gases is the formation of solid particles with well-defined properties, e.g. the particle size, the particle size distribution, the particle shape, the specific surface area and free of solvent inclusions. It is possible to process moderately solids like energetic materials which are difficult to comminute due to their sensitivity to mechanical or thermal stress. The characteristics of compressed gases allow to vary the morphology of solid particles in a wide range. A pilot plant is presented, which has been built to prepare fine particles by the rapid expansion of supercritical solutions (RESS process) and precipitation by a compressed fluid antisolvent (PCA process). In this contribution the micronization of different energetic materials by the RESS and PCA processes will be under investigation. (orig.)

  19. Fixed Bed Adsorption of Drugs on Silica Aerogel from Supercritical Carbon Dioxide Solutions

    OpenAIRE

    Giuseppe Caputo

    2013-01-01

    Supercritical adsorption coupled with the high adsorption capacity of silica aerogel allows the preparation of a new kind of delivery systems of poor water soluble drugs. In order to overcome drawbacks of conventional techniques where the use of liquid solvents can cause the fracture of aerogel porous structure, in this work a new adsorption process of drugs from a supercritical mixture is proposed. Adsorption takes place from a fluid solution of the drug in supercritical CO2 and ethanol as c...

  20. Birch Bark Dry Extract by Supercritical Fluid Technology: Extract Characterisation and Use for Stabilisation of Semisolid Systems

    Directory of Open Access Journals (Sweden)

    Markus Armbruster

    2017-03-01

    Full Text Available Triterpene compounds like betulin, betulinic acid, erythrodiol, oleanolic acid and lupeol are known for many pharmacological effects. All these substances are found in the outer bark of birch. Apart from its pharmacological effects, birch bark extract can be used to stabilise semisolid systems. Normally, birch bark extract is produced for this purpose by extraction with organic solvents. Employing supercritical fluid technology, our aim was to develop a birch bark dry extract suitable for stabilisation of lipophilic gels with improved properties while avoiding the use of toxic solvents. With supercritical carbon dioxide, three different particle formation methods from supercritical solutions have been tested. First, particle deposition was performed from a supercritical solution in an expansion chamber. Second, the Rapid Expansion of Supercritical Solutions (RESS method was used for particle generation. Third, a modified RESS-procedure, forming the particles directly into the thereby gelated liquid, was developed. All three methods gave yields from 1% to 5.8%, depending on the techniques employed. The triterpene composition of the three extracts was comparable: all three gave more stable oleogels compared to the use of an extract obtained by organic solvent extraction. Characterizing the rheological behaviour of these gels, a faster gelling effect was seen together with a lower concentration of the extract required for the gel formation with the supercritical fluid (SCF-extracts. This confirms the superiority of the supercritical fluid produced extracts with regard to the oleogel forming properties.

  1. Fluctuational parameters based on the Bhatia-Thornton theory for supercritical solutions: Application to a supercritical aqueous solution of n-pentane

    Science.gov (United States)

    Shibuta, Satoshi; Imamura, Hiroshi; Nishikawa, Keiko; Morita, Takeshi

    2017-04-01

    To study the structural fluctuation of supercritical solutions, we introduced three fluctuational parameters, a scattering factor, a density factor and a volume factor, which were based on the Bhatia-Thornton theory. In the present study, the density dependence of the structural inhomogeneity in a supercritical aqueous solution of n-pentane was discussed using the scattering factor and the density factor obtained from small-angle X-ray scattering and the fluid density measurements, respectively. Although both these factors have their maxima at the same density position in the case of neat supercritical fluids, a significant difference between the two factors is observed in the binary solution. The large difference occurs by the contribution of the concentration fluctuation in the system. Based on the difference between the factors, it is suggested that a phase separation of the system exists in the higher-fluid-density region.

  2. Existence of high-energy solutions for supercritical fractional Schrodinger equations in R^N

    Directory of Open Access Journals (Sweden)

    Lu Gan

    2016-12-01

    Full Text Available In this article, we study supercritical fractional Schr\\"odinger equations. Applying the finite-dimensional reduction method and the penalization method, we obtain the high-energy solutions for this equation.

  3. Biodegradable particle formation for drug and gene delivery using supercritical fluid and dense gas.

    Science.gov (United States)

    Mishima, Kenji

    2008-02-14

    Recent developments in biodegradable particle formation using supercritical fluids and dense gases have been reviewed with an emphasis on studies of micronizing and encapsulating poorly-soluble pharmaceuticals and gene. General review articles published in previous years have then been provided. A brief description of the operating principles of some types of particle formation processes is given. These include the rapid expansion of supercritical solutions (RESS), the particles from gas-saturated solution (PGSS) processes, the gas antisolvent process (GAS), and the supercritical antisolvent process (SAS). The papers have been reviewed under two groups, one involving the production of particles from pure biodegradable substances, and the other involving coating, capsule, and impregnation that contain active components, especially those that relate to pharmaceuticals. This review is a comprehensive review specifically focused on the formation of biodegradable particles for drug and gene delivery system using supercritical fluid and dense gas.

  4. Singular solutions of the L^2-supercritical biharmonic Nonlinear Schrodinger equation

    CERN Document Server

    Baruch, Guy

    2010-01-01

    We use asymptotic analysis and numerical simulations to study peak-type singular solutions of the supercritical biharmonic NLS. These solutions have a quartic-root blowup rate, and collapse with a quasi self-similar universal profile, which is a zero-Hamiltonian solution of a fourth-order nonlinear eigenvalue problem.

  5. Preparation of nanoparticles of Magnolia bark extract by rapid expansion from supercritical solution into aqueous solutions.

    Science.gov (United States)

    He, Shuai; Zhou, Benjie; Zhang, Shouyao; Lei, Zhengjie; Zhang, Zhongyi

    2011-01-01

    A rapid expansion from supercritical solution into aqueous solution (RESSAS) technology was presented for the micronization of Chinese medicinal material. Magnolia bark extract (MBE) obtained by supercritical carbon dioxide (scCO₂) extraction technology was chosen as the experimental material. RESSAS process produced 303.0 nm nanoparticles (size distribution, 243.6-320.5 nm), which was significantly smaller than the 55.3 µm particles (size distribution, 8.3-102.4 µm) prepared by conventional mechanical milling. The effect of process parameters, including extraction temperature (30 °C, 40 °C, 50 °C), extraction pressure (200, 250, 300 bar) and nozzle size (50, 100, 200 µm), on the size distribution of nanoparticles was investigated. The characteristics of nanoparticles and materials were also studied by scanning electron microscopy (SEM) and laser light scattering (LLS). This study demonstrates that RESSAS is applicable for preparing nanoparticles of MBE at low operating temperature; the process is simple without any residual solvent.

  6. Improvement of dissolution property of poorly water-soluble drug by supercritical freeze granulation.

    Science.gov (United States)

    Sonoda, Ryoichi; Hara, Yuko; Iwasaki, Tomohiro; Watano, Satoru

    2009-10-01

    The dissolution property of the poorly water-soluble drug, flurbiprofen (FP) was improved by a novel supercritical freeze granulation using supercritical carbon dioxide. Supercritical freeze granulation was defined as a production method of the granulated substances by using the dry ice to generate intentionally for the rapid atomization of the supercritical carbon dioxide to the atmospheric pressure. This process utilized a rapid expansion of supercritical solutions (RESS) process with the mixture of the drug and lactose. In the supercritical freeze granulation, needle-like FP fine particles were obtained which adhered to the surface of lactose particles, which did not dissolve in supercritical carbon dioxide. The number of FP particles that adhered to the surface of particles decreased with an increase in the ratio of lactose added, leading to markedly improve the dissolution rate. This improvement was caused not only by the increase in the specific surface area but also the improvement of the dispersibility of FP in water. It is thus concluded that the supercritical freeze granulation is a useful technique to improve the dissolution property of the poorly water-soluble flurbiprofen.

  7. Fixed Bed Adsorption of Drugs on Silica Aerogel from Supercritical Carbon Dioxide Solutions

    Directory of Open Access Journals (Sweden)

    Giuseppe Caputo

    2013-01-01

    Full Text Available Supercritical adsorption coupled with the high adsorption capacity of silica aerogel allows the preparation of a new kind of delivery systems of poor water soluble drugs. In order to overcome drawbacks of conventional techniques where the use of liquid solvents can cause the fracture of aerogel porous structure, in this work a new adsorption process of drugs from a supercritical mixture is proposed. Adsorption takes place from a fluid solution of the drug in supercritical CO2 and ethanol as cosolvent. A fixed bed adsorption plant has been developed to allow fast mixing of fluid phase and effective contact in the adsorption column. The use of ethanol as cosolvent allows to overcome the limitation of supercritical adsorption due to low solubility of many drugs in supercritical CO2. Adsorption isotherms were measured for one-model substance, nimesulide, at 40°C, and breakthrough curve was experimentally obtained. The drug loading of the drug into silica aerogel was up to 9 wt%. The drug composite was characterized using scanning electron microscopy, and release kinetics of the adsorbed drug were also evaluated by in vitro dissolution tests. The dissolution of nimesulide from loaded aerogel is much faster than dissolution of crystalline nimesulide. Around 80% of nimesulide dissolves from the aerogel within 6 minutes, whereas dissolving 80% of the crystalline drug takes about 90 min.

  8. Supercritical supersaturations and ultrafast cooling of the growth solution in liquid-phase epitaxy of semiconductors

    Science.gov (United States)

    Abramov, A. V.; Deryagin, N. G.; Tret'yakov, D. N.

    1996-04-01

    A method for accomplishing ultrafast cooling is proposed which makes possible supercritical supersaturations of the growth solution in liquid-phase epitaxy. Growth boat designs providing cooling rates as high as 0268-1242/11/4/025/img1 are considered. The temperatures of contact, 0268-1242/11/4/025/img2, of a GaAs substrate with a Ga-based solution and of a Si substrate with a Sn-based growth solution, calculated for various substrate 0268-1242/11/4/025/img3 and solution temperatures 0268-1242/11/4/025/img4, are in good agreement with experimental values. The maximum attainable supercooling is markedly increased to as high as 0268-1242/11/4/025/img5 for the Ga - As system, when the growth solution is subjected to ultrafast cooling. The prospects of using the method for fabricating heterostructures with a large lattice mismatch are discussed.

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

    Science.gov (United States)

    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

  10. Blow-up solutions for L 2 supercritical gKdV equations with exactly k blow-up points

    Science.gov (United States)

    Lan, Yang

    2017-08-01

    In this paper we consider the slightly L 2-supercritical gKdV equations \\partialt u+(uxx+u\\vert u\\vert p-1)_x=0 , with the nonlinearity 5 and 0L 2-supercritical gKdV equations. Such solutions can be viewed as solutions with a single blow-up point. In this paper we will prove the existence of solutions with multiple blow-up points, and give a description of the formation of the singularity near the blow-up time.

  11. Continuous supercritical synthesis and dielectric behaviour of the whole BST solid solution

    Energy Technology Data Exchange (ETDEWEB)

    Reveron, H; Elissalde, C; Aymonier, C; Bousquet, C; Maglione, M; Cansell, F [Institut de Chimie de la Matiere Condensee de Bordeaux (ICMCB), CNRS-UPR 9048, Bordeaux I University, 87, avenue du Dr Schweitzer, 33608 PESSAC Cedex (France)

    2006-07-28

    In this study we show that pure and well crystallized nanoparticles of Ba{sub x}Sr{sub 1-x}TiO{sub 3} (BST) can be synthesized over the entire range of composition through the hydrolysis and further crystallization of alkoxide precursors under supercritical conditions. To our knowledge, this is the first time that the whole ferroelectric solid solution has been produced in a continuous way, using the same experimental conditions. The composition of the powder can be easily controlled by adjusting the feed solution composition. The powders consist of soft-aggregated monocrystalline nanoparticles with an average particle size ranging from {approx}20 to 40 nm. Ferroelectric ceramics with accurately adjustable Curie temperature (100-390 K) can thus be obtained by sintering.

  12. Thermodynamics and kinetics of ion speciation in supercritical aqueous solutions: A molecular based study

    Energy Technology Data Exchange (ETDEWEB)

    Chialvo, A.A.; Cummings, P.T. [Tennessee Univ., Knoxville, TN (United States). Dept. of Chemical Engineering]|[Oak Ridge National Lab., TN (United States); Simonson, J.M.; Mesmer, R.E. [Oak Ridge National Lab., TN (United States)

    1997-05-01

    Molecular simulation of infinitely dilute NaCl aqueous solutions are performed to study the Na{sup +}/Cl{sup -} ion pairing in a polarizable and a nonpolarizable solvent at supercritical conditions. The Simple Point Charge, Pettitt-Rossky, and Fumi-Tosi models for the water-water, ion-water, and ion-ion interactions are used in determining the degree of dissociation, its temperature and density dependence, and the kinetics of the interconversion between ion-pair configurations in a nonpolarizable medium. To assess the effect of the solvent polarizability on the stability of the ion-pair configurations, we replace the Simple Point Charge by the Polarizable Point Charge water model and determine the anion-cation potential of mean force at T{sub r}=1.20 and {rho}{sub r}=1.5.

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

    Directory of Open Access Journals (Sweden)

    Zhao Z

    2015-04-01

    Full Text Available Zheng Zhao,1,3 Maobin Xie,2 Yi Li,2 Aizheng Chen,4 Gang Li,5 Jing Zhang,2 Huawen Hu,2 Xinyu Wang,1,3 Shipu Li1,31State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, People’s Republic of China; 2Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hong Kong; 3Biomedical Materials and Engineering Research Center of Hubei Province, Wuhan University of Technology, Wuhan, People’s Republic of China; 4College of Chemical Engineering, Huaqiao University, Xiamen, People’s Republic of China; 5National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou, People’s Republic of ChinaAbstract: In order to enhance the bioavailability of poorly water-soluble curcumin, solution-enhanced dispersion by supercritical carbon dioxide (CO2 (SEDS was employed to prepare curcumin nanoparticles for the first time. A 24 full factorial experiment was designed to determine optimal processing parameters and their influence on the size of the curcumin nanoparticles. Particle size was demonstrated to increase with increased temperature or flow rate of the solution, or with decreased precipitation pressure, under processing conditions with different parameters considered. The single effect of the concentration of the solution on particle size was not significant. Curcumin nanoparticles with a spherical shape and the smallest mean particle size of 325 nm were obtained when the following optimal processing conditions were adopted: P =20 MPa, T =35°C, flow rate of solution =0.5 mL.min-1, concentration of solution =0.5%. Fourier transform infrared (FTIR spectroscopy measurement revealed that the chemical composition of curcumin basically remained unchanged. Nevertheless, X-ray powder diffraction (XRPD and thermal analysis indicated that the crystalline state of the original curcumin decreased after the SEDS process. The

  14. Preliminary Study on Supercritical Fluid Extraction of Ce(Ⅳ) in Solution

    Institute of Scientific and Technical Information of China (English)

    SONG; Zhi-jun; LIANG; Xiao-hu; DING; You-qian

    2013-01-01

    Supercritical fluid extraction(SFE)has many advantages,such as rapid mass transfer and high solubility.Metal samples can be extracted using supercritical fluid with a small amount of complexant.So in comparison to conventional solvent extraction process,SFE minimizes the amount of secondary waste and the pollution to environment.In order to study the extraction of Pu using supercritical CO2,the

  15. A closer study of methanol adsorption and its impact on solute retentions in supercritical fluid chromatography.

    Science.gov (United States)

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

    2016-04-15

    Surface excess adsorption isotherms of methanol on a diol silica adsorbent were measured in supercritical fluid chromatography (SFC) using a mixture of methanol and carbon dioxide as mobile phase. The tracer pulse method was used with deuterium labeled methanol as solute and the tracer peaks were detected using APCI-MS over the whole composition range from neat carbon dioxide to neat methanol. The results indicate that a monolayer (4Å) of methanol is formed on the stationary phase. Moreover, the importance of using the set or the actual methanol fractions and volumetric flows in SFC was investigated by measuring the mass flow respective pressure and by calculations of the actual volume fraction of methanol. The result revealed a significant difference between the value set and the actually delivered volumetric methanol flow rate, especially at low modifier fractions. If relying only on the set methanol fraction in the calculations, the methanol layer thickness should in this system be highly overestimated. Finally, retention times for a set of solutes were measured and related to the findings summarized above concerning methanol adsorption. A strongly non-linear relationship between the logarithms of the retention factors and the modifier fraction in the mobile phase was revealed, prior to the established monolayer. At modifier fractions above that required for establishment of the methanol monolayer, this relationship turns linear which explains why the solute retention factors are less sensitive to changes in modifier content in this region.

  16. Regularity of weak solutions of elliptic and parabolic equations with some critical or supercritical potentials

    Science.gov (United States)

    Li, Zijin; Zhang, Qi S.

    2017-07-01

    We prove H\\"older continuity of weak solutions of the uniformly elliptic and parabolic equations %$\\Delta u-\\frac{A}{|x|^{2+\\beta}}u=0,\\,\\,(\\beta\\geq 0)$, and variable second order term coefficients case $%% \\begin{equation}\\label{01} \\partial_{i} (a_{ij}(x) \\partial_{j}u(x)) - \\frac{A}{|x|^{2+\\beta}} u(x) =0\\quad (A>0,\\quad\\beta\\geq 0), \\end{equation} \\begin{equation}\\label{02} \\partial_{i} (a_{ij}(x,t) \\partial_{j}u(x,t)) - \\frac{A}{|x|^{2+\\beta}} u(x,t)-\\partial_{t}u(x,t) =0\\quad (A>0,\\quad\\beta\\geq 0), \\end{equation} with critical or supercritical 0-order term coefficients which are beyond De Giorgi-Nash-Moser's Theory. We also prove, in some special cases, weak solutions are even differentiable. Previously P. Baras and J. A. Goldstein \\cite{Baras1984} treated the case when $A0$, $\\beta=0$ and $(a_{ij})=I$, P. D. Milman and Y. A. Semenov \\cite{Milman2003}\\cite{Milman2004} obtain bounds for the heat kernel.

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

    Science.gov (United States)

    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.

  18. On the solubility of gallium nitride in supercritical ammonia-sodium solutions

    Science.gov (United States)

    Griffiths, Steven; Pimputkar, Siddha; Speck, James S.; Nakamura, Shuji

    2016-12-01

    Due to the disparity between observed gallium nitride (GaN) growth under conditions for which literature reports normal solubility, GaN solubility in supercritical NH3-Na containing solutions was re-evaluated. Isothermal gravimetric experiments on polycrystalline GaN were performed in the temperature range (T =415-650 °C) for which retrograde growth of GaN routinely occurs (P ≈ 200 MPa, molar NH3:Na fill ratio =20:1). Two previously-unreported error contributions to the gravimetric determination of GaN solubility were identified: Ga-alloying of exposed Ni-containing components, and the presence of a dense, Ga-absorbing Na-rich, second phase under these conditions. Due to the inability to measure Ga-alloying of the exposed autoclave wall for each experiment, considerable scatter was introduced in the refined GaN solubility curve. No clear dependence of GaN solubility on temperature was resolvable, while most solubility values were determined to be within a band of 0.03-0.10 mol% GaN, normalized by fill NH3.

  19. ReSS: Resource Selection Service for National and Campus Grid Infrastructure

    Science.gov (United States)

    Mhashilkar, Parag; Garzoglio, Gabriele; Levshina, Tanya; Timm, Steve

    2010-04-01

    The Open Science Grid (OSG) offers access to around hundred Compute elements (CE) and storage elements (SE) via standard Grid interfaces. The Resource Selection Service (ReSS) is a push-based workload management system that is integrated with the OSG information systems and resources. ReSS integrates standard Grid tools such as Condor, as a brokering service and the gLite CEMon, for gathering and publishing resource information in GLUE Schema format. ReSS is used in OSG by Virtual Organizations (VO) such as Dark Energy Survey (DES), DZero and Engagement VO. ReSS is also used as a Resource Selection Service for Campus Grids, such as FermiGrid. VOs use ReSS to automate the resource selection in their workload management system to run jobs over the grid. In the past year, the system has been enhanced to enable publication and selection of storage resources and of any special software or software libraries (like MPI libraries) installed at computing resources. In this paper, we discuss the Resource Selection Service, its typical usage on the two scales of a National Cyber Infrastructure Grid, such as OSG, and of a campus Grid, such as FermiGrid.

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

    Science.gov (United States)

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

    2016-01-08

    Biomass-derived ethyl lactate is a green solvent with a growing market as the replacement for petroleum-derived toxic organic solvents. Here we report, for the first time, the production of ethyl lactate directly from cellulose with the mesoporous Zr-SBA-15 silicate catalyst in a supercritical mixture of ethanol and water. The relatively strong Lewis and weak Brønsted acid sites on the catalyst, as well as the surface hydrophobicity, were beneficial to the reaction and led to synergy during consecutive reactions, such as depolymerization, retro-aldol condensation, and esterification. Under the optimum reaction conditions, ∼33 % yield of ethyl lactate was produced from cellulose with the Zr-SBA-15 catalyst at 260 °C in supercritical 95:5 (w/w) ethanol/water.

  1. Have we observed the skin vibration of realistic strange stars (ReSS) ?

    CERN Document Server

    Sinha, M N; Dey, M; Ray, S; Bhowmick, S; Sinha, Monika; Dey, Jishnu; Dey, Mira; Ray, Subharthi; Bhowmick, Siddhartha

    2003-01-01

    Skin vibration of ReSS and consequent resonance absorption can account for the absorption lines in the spectrum of X-ray emission from many compact stellar objects and in particular, the stars J1210$-$5226 and RXJ1856$-$3754. Observations of the X-ray spectrum of these stars is difficult to explain, if they are neutron stars.

  2. Continuous reactions in supercritical carbon dioxide: problems, solutions and possible ways forward.

    Science.gov (United States)

    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.

  3. Coating of magnesium powder by rapid expansion of supercritical solution method

    Institute of Scientific and Technical Information of China (English)

    ZHANG Shu-hai

    2006-01-01

    In order to solve the reserve stability problem of pyrotechnic explosives containing magnesium powder,a coating method named rapid expansion of supercritical fluid is studied. Continuous coating film of paraffin can be formed on the surface of magnesium powder when paraffin content is about 1.5%. Humidity resistance property of the coated magnesium is promoted obviously. The flame sensitivity of the coated magnesium is 4.8% lower than that of the original magnesium powder after mixed with oxidant. The burning velocity of the coated magnesium is 4.7% lower than that of the contrastive sample. This method may be used to enhance the reserve stability problem of pyrotechnic explosives and the safety of magnesium powder modifying process.

  4. Supercritical water

    CERN Document Server

    Marcus, Yizhak

    2012-01-01

    Discover the many new and emerging applications of supercritical water as a green solvent Drawing from thousands of original research articles, this book reviews and summarizes what is currently known about the properties and uses of supercritical water. In particular, it focuses on new and emerging applications of supercritical water as a green solvent, including the catalytic conversion of biomass into fuels and the oxidation of hazardous materials. Supercritical Water begins with an introduction that defines supercritical fluids in general. It then defines supercritical wa

  5. Nitrate conversion and supercritical fluid extraction of UO{sub 2}-CeO{sub 2} solid solution prepared by an electrolytic reduction-coprecipitation method

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, L.Y. [Tsinghua Univ., Beijing (China). Inst. of Nuclear and New Energy Technology; China Institute of Atomic Energy, Beijing (China); Duan, W.H.; Wen, M.F.; Xu, J.M.; Zhu, Y.J. [Tsinghua Univ., Beijing (China). Inst. of Nuclear and New Energy Technology

    2014-04-01

    A low-waste technology for the reprocessing of spent nuclear fuel (SNF) has been developed recently, which involves the conversion of actinide and lanthanide oxides with liquid N{sub 2}O{sub 4} into their nitrates followed by supercritical fluid extraction of the nitrates. The possibility of the reprocessing of SNF from high-temperature gas-cooled reactors (HTGRs) with nitrate conversion and supercritical fluid extraction is a current area of research in China. Here, a UO{sub 2}-CeO{sub 2} solid solution was prepared as a surrogate for a UO{sub 2}-PuO{sub 2} solid solution, and the recovery of U and Ce from the UO{sub 2}-CeO{sub 2} solid solution with liquid N{sub 2}O{sub 4} and supercritical CO{sub 2} containing tri-n-butyl phosphate (TBP) was investigated. The UO{sub 2}-CeO{sub 2} solid solution prepared by electrolytic reduction-coprecipitation method had square plate microstructures. The solid solution after heat treatment was completely converted into nitrates with liquid N{sub 2}O{sub 4}. The XRD pattern of the nitrates was similar to that of UO{sub 2}(NO{sub 3}){sub 2} . 3H{sub 2}O. After 120 min of online extraction at 25 MPa and 50 , 99.98% of the U and 98.74% of the Ce were recovered from the nitrates with supercritical CO{sub 2} containing TBP. The results suggest a promising potential technology for the reprocessing of SNF from HTGRs. (orig.)

  6. Method for growth of crystals by pressure reduction of supercritical or subcritical solution

    Science.gov (United States)

    Shlichta, P. J. (Inventor)

    1985-01-01

    Crystals of high morphological quality are grown by dissolution of a substance to be grown into the crystal in a suitable solvent under high pressure, and by subsequent slow, time-controlled reduction of the pressure of the resulting solution. During the reduction of the pressure interchange of heat between the solution and the environment is minimized by performing the pressure reduction either under isothermal or adiabatic conditions.

  7. A Single-phase of Supercritical CO2/Polystyrene Solution in Foam Extrusion

    Institute of Scientific and Technical Information of China (English)

    WU Xiaodan; CENG Haohua; CAI Yiebin; PENG Yucheng

    2008-01-01

    The high quality single-phase solution of CO2/Polystyrene was achieved,by analyzing the influential factors for polymer microcellular foaming extrusion.The curve of pressure distribution along the barrel was determined.The axial position of gas-injecting port on the barrel was chosen form the results of stable foaming,and the number of gas-injecting ports in the circumference of the barrel was determined from the CO2 solubility in polymer.The effect of the screw rotation speed on CO2 solubility was studied,and the effects of pressure difference between the gas and the polymer melt on gas-injecting process and on the foaming stability were investigated.The influence of the gas temperature before injection on the single-phase of CO2/Polystyrene solution also was studied.

  8. Effect of Molecular Size of Solutes on Their Partial Molar Volumes in Supercritical n-Pentane

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The densities of n-pentane, methane-n-pentane, propane-n-pentane, n-heptane-n-pentane, and n-decane-n-pentane binary mixtures were determined at 476.5K in the pressure range from 2 to 5 MPa. The partial molar volumes of the solutes in n-pentane were calculated using the density data. It was found that the partial molar volumes of methane and propane are positive , while those of n-heptane and n-decane are negative.

  9. Complete Fiber/Copper Cable Solution for Long-Term Temperature and Pressure Measurement in Supercritical Reservoirs and EGS Wells

    Energy Technology Data Exchange (ETDEWEB)

    Pastouret, Alan [Draka Cableteq USA, Inc., North Dighton, MA (United States); Gooijer, Frans [Draka Cableteq USA, Inc., North Dighton, MA (United States); Overton, Bob [Draka Cableteq USA, Inc., North Dighton, MA (United States); Jonker, Jan [Draka Cableteq USA, Inc., North Dighton, MA (United States); Curley, Jim [Draka Cableteq USA, Inc., North Dighton, MA (United States); Constantine, Walter [Draka Cableteq USA, Inc., North Dighton, MA (United States); Waterman, Kendall Miller [Draka Cableteq USA, Inc., North Dighton, MA (United States)

    2015-11-13

    High Temperature insulated wire and optical fiber cable is a key enabling technology for the Geothermal Technologies Program (GTP). Without insulated electrical wires and optical fiber, downhole temperature and pressure sensors, flow meters and gauges cannot communicate with the surface. Unfortunately, there are currently no insulated electrical wire or fiber cable constructions capable of surviving for extended periods of deployment in a geothermal well (240-325°C) or supercritical (374°C) reservoir. This has severely hindered engineered reservoir creation, management and utilization, as hot zones and cool water intrusions cannot be understood over time. The lack of a insulated electrical wire and fiber cable solution is a fundamental limitation to the viability of this energy source. The High Temperature Downhole Tools target specification is development of tools and sensors for logging and monitoring wellbore conditions at depths of up to 10,000 meters and temperatures up to 374oC. It well recognized in the industry that no current electronic or fiber cable can be successfully deployed in a well and function successfully for more a few days at temperatures over 240oC. The goal of this project was to raise this performance level significantly. Prysmian Group’s objective in this project was to develop a complete, multi-purpose cable solution for long-term deployment in geothermal wells/reservoirs that can be used with the widest variety of sensors. In particular, the overall project objective was to produce a manufacturable cable design that can perform without serious degradation: • At temperatures up to 374°C; • At pressures up to 220 bar; • In a hydrogen-rich environment; and • For the life of the well (> 5 years). This cable incorporates: • Specialty optical fibers, with specific glass chemistry and high temperature and pressure protective coatings for data communication and distributed temperature and pressure sensing, and • High

  10. Precipitation polymerization of hydrophobically modified polyelectrolyte poly(AA-co-ODA) in supercritical carbon dioxide and solution rheology properties

    Science.gov (United States)

    Zhang, Huaiping; Li, Wei; Cao, Qing; Chen, Mingcai

    2014-05-01

    Hydrophobically modified (HM) polyelectrolytes were prepared by using precipitation polymerization of acrylic acid (AA) and octadecyl acrylate (ODA) in various molar ratios in supercritical carbon dioxide. The product was obtained in the form of a white powder and the micrographs show aggregates of primary particles properties.

  11. Preparation of Poly-(Methyl vinyl ether-co-maleic Anhydride Nanoparticles by Solution-Enhanced Dispersion by Supercritical CO2

    Directory of Open Access Journals (Sweden)

    Yong-Qiang Kang

    2012-10-01

    Full Text Available The supercritical CO2-based technologies have been widely used in the formation of drug and/or polymer particles for biomedical applications. In this study, nanoparticles of poly-(methyl vinyl ether-co-maleic anhydride (PVM/MA were successfully fabricated by a process of solution-enhanced dispersion by supercritical CO2 (SEDS. A 23 factorial experiment was designed to investigate and identify the significance of the processing parameters (concentration, flow and solvent/nonsolvent for the surface morphology, particle size, and particle size distribution of the products. The effect of the concentration of PVM/MA was found to be dominant in the results regarding particle size. Decreasing the initial solution concentration of PVM/MA decreased the particle size significantly. After optimization, the resulting PVM/MA nanoparticles exhibited a good spherical shape, a smooth surface, and a narrow particle size distribution. Fourier transform infrared spectroscopy (FTIR spectra demonstrated that the chemical composition of PVM/MA was not altered during the SEDS process and that the SEDS process was therefore a typical physical process. The absolute value of zeta potential of the obtained PVM/MA nanoparticles was larger than 40 mV, indicating the samples’ stability in aqueous suspension. Analysis of thermogravimetry-differential scanning calorimetry (TG-DSC revealed that the effect of the SEDS process on the thermostability of PVM/MA was negligible. The results of gas chromatography (GC analysis confirmed that the SEDS process could efficiently remove the organic residue.

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

    Science.gov (United States)

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

    2013-12-01

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

  13. One-pot synthesis of ZnS/polymer composites in supercritical CO2-ethanol solution and their applications in degradation of dyes.

    Science.gov (United States)

    Xie, Yun; Zhang, Chengliang; Miao, Shiding; Liu, Zhimin; Ding, Kunlun; Miao, Zhenjiang; An, Guimin; Yang, Zhenzhong

    2008-02-01

    A facile method to decorate the polymeric hollow spheres with ZnS nanoparticles has been presented. In this method, the precursors, Zn(Ac)(2)H(2)O and CH(3)CSNH(2), were first adsorbed by the polymer substrate in supercritical CO(2)-ethanol solution at 35 degrees C. Followed by heating the mixture at 100 degrees C for 2 h, ZnS/polymer composites were obtained. The as-produced ZnS/polymer composites were characterized by means of IR spectra, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy. It was demonstrated that crystalline ZnS nanoparticles with size of 3-5 nm were uniformly decorated on the polymer spheres under suitable conditions. The resultant ZnS/polymer composites exhibited high efficiency for degrading eosin B, methyl orange and methylene blue under UV light irradiation.

  14. Engineering solutions related to the furnace arrangement of a boiler designed for operating at supercritical steam conditions

    Science.gov (United States)

    Shtegman, A. V.; Ryzhii, I. A.; Sosin, D. V.; Kotler, V. R.

    2014-04-01

    When developing a coal-fired power unit designed for operating at supercritical steam conditions (SSCs), it is necessary not only to achieve high economic performance and the high reliability of a new power unit, but also to tackle many problems related to the efficient combustion of the solid fuel without exceeding the future standards for limitations on emissions of harmful substances into the atmosphere. The technological methods of suppression of nitrogen oxides capable of providing the permissible NO x emissions are discussed. The results of calculations are given that demonstrate the feasibility of achieving the purpose in view by means of installation of new low-NO x burners and staged injection of the fuel even on combustion of the Ekibastuz black coal high in ash content.

  15. Continuous-flow Heck synthesis of 4-methoxybiphenyl and methyl 4-methoxycinnamate in supercritical carbon dioxide expanded solvent solutions

    Directory of Open Access Journals (Sweden)

    Phei Li Lau

    2013-12-01

    Full Text Available The palladium metal catalysed Heck reaction of 4-iodoanisole with styrene or methyl acrylate has been studied in a continuous plug flow reactor (PFR using supercritical carbon dioxide (scCO2 as the solvent, with THF and methanol as modifiers. The catalyst was 2% palladium on silica and the base was diisopropylethylamine due to its solubility in the reaction solvent. No phosphine co-catalysts were used so the work-up procedure was simplified and the green credentials of the reaction were enhanced. The reactions were studied as a function of temperature, pressure and flow rate and in the case of the reaction with styrene compared against a standard, stirred autoclave reaction. Conversion was determined and, in the case of the reaction with styrene, the isomeric product distribution was monitored by GC. In the case of the reaction with methyl acrylate the reactor was scaled from a 1.0 mm to 3.9 mm internal diameter and the conversion and turnover frequency determined. The results show that the Heck reaction can be effectively performed in scCO2 under continuous flow conditions with a palladium metal, phosphine-free catalyst, but care must be taken when selecting the reaction temperature in order to ensure the appropriate isomer distribution is achieved. Higher reaction temperatures were found to enhance formation of the branched terminal alkene isomer as opposed to the linear trans-isomer.

  16. Gas-saturated solution process to obtain microcomposite particles of alpha lipoic acid/hydrogenated colza oil in supercritical carbon dioxide.

    Science.gov (United States)

    Mishima, Kenji; Honjo, Masatoshi; Sharmin, Tanjina; Ito, Shota; Kawakami, Ryo; Kato, Takafumi; Misumi, Makoto; Suetsugu, Tadashi; Orii, Hideaki; Kawano, Hiroyuki; Irie, Keiichi; Sano, Kazunori; Mishima, Kenichi; Harada, Takunori; Ouchi, Mikio

    2016-09-01

    Alpha lipoic acid (ALA), an active substance in anti-aging products and dietary supplements, need to be masked with an edible polymer to obscure its unpleasant taste. However, the high viscosity of the ALA molecules prevents them from forming microcomposites with masking materials even in supercritical carbon dioxide (scCO2). Therefore, the purpose of this study was to investigate and develop a novel production method for microcomposite particles for ALA in hydrogenated colza oil (HCO). Microcomposite particles of ALA/HCO were prepared by using a novel gas-saturated solution (PGSS) process in which the solid-dispersion method is used along with stepwise temperature control (PGSS-STC). Its high viscosity prevents the formation of microcomposites in the conventional PGSS process even under strong agitation. Here, we disperse the solid particles of ALA and HCO in scCO2 at low temperatures and change the temperature stepwise in order to mix the melted ALA and HCO in scCO2. As a result, a homogeneous dispersion of the droplets of ALA in melted HCO saturated with CO2 is obtained at high temperatures. After the rapid expansion of the saturated solution through a nozzle, microcomposite particles of ALA/HCO several micrometers in diameter are obtained.

  17. Determination of solvation kinetics in supercritical fluids

    Energy Technology Data Exchange (ETDEWEB)

    Bright, F.V.

    1993-01-01

    Objective was to study solvation processes in pure and entrainer-modified supercritical fluids. Specific topics were: Kinetics for solvation in supercritical media, influence on entrainers on solvation, reversibility of solvation, effects of solvation on intramolecular solute-solute interaction kinetics, and impact of fluid density on these processes. Time-resolved fluorescence spectroscopy was used as the main analytical tool. A summary is given of the 2.5 years' research.

  18. Charting the landscape of supercritical string theory.

    Science.gov (United States)

    Hellerman, Simeon; Swanson, Ian

    2007-10-26

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

  19. Structural evolution of aqueous NaCl solutions dissolved in supercritical carbon dioxide under isobaric heating by mid and near infrared spectroscopy.

    Science.gov (United States)

    Oparin, R; Tassaing, T; Danten, Y; Besnard, M

    2005-03-01

    The local order in aqueous NaCl solutions diluted in supercritical carbon dioxide at constant pressure as a function of NaCl concentration and temperature has been investigated using near and mid infrared absorption spectroscopy. The near IR results have allowed us to estimate the water concentration in CO(2) rich phase, whereas the state of water aggregation in CO(2) phase was investigated using mid IR spectroscopy. The analysis of the band shape variations of the OD stretching mode of HOD led us to conclude that below 100 degrees C, water molecules dissolved in CO(2) exist only under their monomeric form, whatever the salt concentration is, whereas hydrogen-bonded species, namely, dimers start to appear at higher temperatures. Larger aggregates have a negligible concentration in the range of temperature-pressure investigated. Using near and mid infrared data, we have calculated the concentrations of water species in the CO(2) phase. Upon heating, it was found that the concentration of dimers considerably increases at the expense of the monomers and only dimers are detected in carbon dioxide at highest temperatures. Changing the salt concentration affects significantly the concentration of monomers and decreases strongly the dimers population as the solution becomes progressively saturated in salt. In the saturated solution, at 340 degrees C, the dimer concentration is at least two times smaller than in the binary water-CO(2) mixture. These findings are in qualitative agreement with existing thermodynamics data showing that addition of NaCl to the binary H(2)O-CO(2) system shifts the range of partial miscibility of water and CO(2) towards higher pressure and temperature.

  20. INTEGRATED SUPERCRITICAL FLUID EXTRACTION AND BIOPROCESSING

    Directory of Open Access Journals (Sweden)

    Owen Catchpole

    2012-01-01

    Full Text Available Supercritical fluids are increasingly being used and promoted at a laboratory and pilot scale to produce high value, natural bioactives from biologically based raw materials. Supercritical CO2 is overwhelmingly the solvent of choice for these operations, but is largely limited to the processing of dry raw materials and the extraction of low polarity, low molecular weight compounds. The use of co-solvents and the use of alternative ‘near-critical’ extraction fluids such as dimethyl ether show potential to mitigate these limitations. Commercialisation of new supercritical extraction processes has arguably been limited because the supercritical extraction process has been developed in isolation of other processing steps necessary to achieve a successful product. This study reviews recent developments in integrated processing that incorporate the use of supercritical fluids for bioseparations and in particular process schemes that produce high value natural bioactives. Integrated processes include prior operation (fermentation, extraction, enzyme pre-treatment, physical fractionation or size reduction followed by supercritical extraction or fractionation and processes in which operations are carried out in situ in supercritical fluids (supercritical chromatography, enzymatic conversion, precipitation and coating of solutes. The use of co-solvents and alternative extraction solvents in these processes is discussed. Prospects for future developments are also discussed.

  1. Supercritical fluid thermodynamics for coal processing

    Energy Technology Data Exchange (ETDEWEB)

    van Swol, F. (Illinois Univ., Urbana, IL (United States). Dept. of Chemical Engineering); Eckert, C.A. (Georgia Inst. of Tech., Atlanta, GA (United States). 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)

  2. Industrial applications and current trends in supercritical fluid technologies

    OpenAIRE

    Gamse Thomas

    2005-01-01

    Supercritical fluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercritical fluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop...

  3. Solubility and Phase Behavior of CL20 in Supercritical Fluids

    Science.gov (United States)

    2006-09-01

    supercritical state. The fugacity of the solute in the supercritical fluid can be evaluated using a cubic equation of state such as the Redlich - Kwong ...pro- gram was validated using available literature data for the solubility of naphthalene and of biphenyl in supercritical CO2. The applicability of...promising process using environmentally benign compressed gases as either solvents or anti-solvents is being investi- gated for applications in

  4. Generic supercritical water technology; Generic technology to shite no chorinkaisui riyo gijutsu

    Energy Technology Data Exchange (ETDEWEB)

    Arai, K.; Ajiri, M.; Inomata, H.; Smith, R.; Hakuta, Y. [Tohoku University, Sendai (Japan). Faculty of Engineering; Yokoyama, C. [Tohoku University, Sendai (Japan). The Institute forChemical Reaction Science; Chin, L. [New Energy and Industrial Technology Development Organization, Tokyo, (Japan)

    1997-02-01

    This paper describes the measurement and analysis for clarifying solution structure of supercritical water and exhibition mechanism of solvent functions. It also describes the development of new processes using supercritical water as reaction solvent. The PVT measurements were conducted in the supercritical region using pure water and NaCl aqueous solution, to confirm the reduction of molar volume of the electrolyte solution. The hydration structure was examined in the supercritical aqueous solution by the molecular dynamic simulation. As a result, presence of hydrogen bond structure, where the contribution of two branching hydrogen bond can not be ignored, was suggested under the supercritical condition. Characteristics of supercritical aqueous solutions are analyzed through in-situ Raman and scattered X-ray spectral measurements. Moreover, this paper introduces developments of some processes in the supercritical water, such as decomposition of wasted polymers, recovery of chemical materials, reforming of heavy hydrocarbons by contact hydrogenation, and synthesis of fine powders of metal oxide by reaction crystallization.

  5. 超临界直流炉主蒸汽温度控制积分饱和问题解决方法%Solution of Integral Saturationon Steam Temperature Control in Supercritical Monotubeboiler

    Institute of Scientific and Technical Information of China (English)

    蒋明达

    2015-01-01

    The paper introduces the cause and its effect and puts forward a solution to the problem of integral saturation in main steam temperature control system in Luohe Power Plant of Datang Power's #6 supercritical monotube boiler.%本文分析了超临界直流炉主蒸汽温度控制积分饱和问题产生原因及影响,对大唐洛河发电厂#6超临界直流锅炉主蒸汽温控制系统出现的积分饱和问题提出了解决方案.

  6. Dependence of Reaction Rate Constants on Density in Supercritical Fluids

    Institute of Scientific and Technical Information of China (English)

    WANGTao; SHENZhongyao

    2002-01-01

    A new method,which correlates rate constants of chemical reactions and density or pressure in supercritical fluids,was developed.Based on the transition state theory and thermodynamic principles, the rate constant can be reasonably correlated with the density of the supercritical fluid,and a correlation equation was obtained. Coupled with the equation of state (EOS) of a supercritical solvent,the effect of pressure on reaction rate constant could be represented.Two typical systems were used to test this method.The result indicates that this method is suitable for dilute supercritical fluid solutions.

  7. Supercritical fluid technology

    Energy Technology Data Exchange (ETDEWEB)

    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.)

  8. 超临界流体快速膨胀法分散碳纳米管%Dispersion of carbon nanotubes in a polymer by the rapid expansion of a supercritical suspension

    Institute of Scientific and Technical Information of China (English)

    赵健; 刘振生; 胡文彬

    2014-01-01

    We report a scalable and volatile organic compound-free process for the production of well-dispersed carbon nanotubes ( CNTs) in a polymer by the rapid expansion of a supercritical suspension ( RESS) , in which CNTs had been suspended in super-critical carbon dioxide, and CO2 and CNTs released from the suspension were rapidly vented through a nozzle. Reagglomeration of the CNTs after RESS can be prevented by premixing them with dimethyl isophthalate or poly( methyl methacrylate) , which can be dissolved in supercritical carbon dioxide, or by embedding the nozzle in molten poly( methyl methacrylate) .%利用超临界状态下CO2的快速膨胀( RESS)来分散碳纳米管,为可放大化且无挥发性有机化合物的新方法。将碳纳米管在超临界CO2悬浮液中经由微细喷嘴快速膨胀使其均匀分散。电子显微镜( SEM)表征证实RESS可有效地实现碳纳米管的分散。同时,为了解决再团聚难题,提出利用小分子包覆法和将碳纳米管嵌入高分子基体法来防止其再团聚,均起到良好的效果。

  9. Supercritical Water Mixture (SCWM) Experiment

    Science.gov (United States)

    Hicks, Michael C.; Hegde, Uday G.

    2012-01-01

    The subject presentation, entitled, Supercritical Water Mixture (SCWM) Experiment, was presented at the International Space Station (ISS) Increment 33/34 Science Symposium. This presentation provides an overview of an international collaboration between NASA and CNES to study the behavior of a dilute aqueous solution of Na2SO4 (5% w) at near-critical conditions. The Supercritical Water Mixture (SCWM) investigation, serves as important precursor work for subsequent Supercritical Water Oxidation (SCWO) experiments. The SCWM investigation will be performed in DECLICs High Temperature Insert (HTI) for the purpose of studying critical fluid phenomena at high temperatures and pressures. The HTI includes a completely sealed and integrated test cell (i.e., Sample Cell Unit SCU) that will contain approximately 0.3 ml of the aqueous test solution. During the sequence of tests, scheduled to be performed in FY13, temperatures and pressures will be elevated to critical conditions (i.e., Tc = 374C and Pc = 22 MPa) in order to observe salt precipitation, precipitate agglomeration and precipitate transport in the presence of a temperature gradient without the influences of gravitational forces. This presentation provides an overview of the motivation for this work, a description of the DECLIC HTI hardware, the proposed test sequences, and a brief discussion of the scientific research objectives.

  10. Charting the landscape of supercritical string theory

    CERN Document Server

    Hellerman, Simeon

    2007-01-01

    Special solutions of string theory in supercritical dimensions can interpolate in time between theories with different numbers of spacetime dimensions (via dimension quenching) and different amounts of worldsheet supersymmetry (via c-duality). These solutions connect supercritical string theories to the more familiar string duality web in ten dimensions, and provide a precise link between supersymmetric and purely bosonic string theories. Dimension quenching and c-duality appear to be natural concepts in string theory, giving rise to large networks of interconnected theories. We describe some of these networks in detail and discuss general consistency constraints on the types of transitions that arise in this framework.

  11. Supercritical fluid extraction

    Science.gov (United States)

    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.

  12. Etchant solutions for the removal of Cu(0) in a supercritical CO2-based "dry" chemical mechanical planarization process for device fabrication.

    Science.gov (United States)

    Bessel, Carol A; Denison, Ginger M; DeSimone, Joseph M; DeYoung, James; Gross, Stephen; Schauer, Cynthia K; Visintin, Pamela M

    2003-04-30

    The microelectronics industry is focused on increasing chip complexity, improving the density of electron carriers, and decreasing the dimensions of the interconnects into the sub-0.25 mum regime while maintaining high aspect ratios. Water-based chemical mechanical planarization or polishing (CMP) faces several technical and environmental challenges. Condensed CO2 has significant potential for replacing current CMP solvents as a "dry" etching medium because of its unique properties. In working toward a condensed CO2-based CMP process, we have successfully investigated the oxidation and chelation of solid copper metal in liquid and supercritical CO2 using ethyl peroxydicarbonate and a beta-diketone chelating agent.

  13. Determination of solvation kinetics in supercritical fluids. Summary report

    Energy Technology Data Exchange (ETDEWEB)

    Bright, F.V.

    1993-01-01

    Objective was to study solvation processes in pure and entrainer-modified supercritical fluids. Specific topics were: Kinetics for solvation in supercritical media, influence on entrainers on solvation, reversibility of solvation, effects of solvation on intramolecular solute-solute interaction kinetics, and impact of fluid density on these processes. Time-resolved fluorescence spectroscopy was used as the main analytical tool. A summary is given of the 2.5 years` research.

  14. Supercritical separation process for complex organic mixtures

    Science.gov (United States)

    Chum, Helena L.; Filardo, Giuseppe

    1990-01-01

    A process is disclosed for separating low molecular weight components from complex aqueous organic mixtures. The process includes preparing a separation solution of supercritical carbon dioxide with an effective amount of an entrainer to modify the solvation power of the supercritical carbon dioxide and extract preselected low molecular weight components. The separation solution is maintained at a temperature of at least about 70.degree. C. and a pressure of at least about 1,500 psi. The separation solution is then contacted with the organic mixtures while maintaining the temperature and pressure as above until the mixtures and solution reach equilibrium to extract the preselected low molecular weight components from the organic mixtures. Finally, the entrainer/extracted components portion of the equilibrium mixture is isolated from the separation solution.

  15. Electrochemistry in supercritical fluids

    Science.gov (United States)

    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

  16. Electrochemistry in supercritical fluids.

    Science.gov (United States)

    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.

  17. Supercritical Airfoil Coordinates

    Data.gov (United States)

    National Aeronautics and Space Administration — Rectangular Supercritical Wing (Ricketts) - design and measured locations are provided in an Excel file RSW_airfoil_coordinates_ricketts.xls . One sheet is with Non...

  18. 超临界二氧化碳萃取分离塑料溶液中多溴联苯醚的研究%Study on removal of polybrominated diphenyl ethers from plastic solution by supercritical carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    彭绍洪; 梁莎; 赵向阳; 余梅

    2012-01-01

    A new recycling process with supercritical CO2 extraction of PBDEs from waste HIPS plastic is developed in this study. The influences of the temperature, pressure and volume of supercritical CO2 and decabromodiphenyl ether concentraction on the extraction process are investigated. The measures for reducing the amount of decabromodiphenyl ether in the recycled HIPS are proposed. The experimental results show that, after the most of decabromodiphenyl ether particles is separated by centrifuge at speed of 10 000 r/min and at 30℃ , the recycled HIPS with lower than 0. 1% (dry) of the total amount of decabromodiphenyl ether can be obtained by further removing decabromodiphenyl ether under the following conditions:65℃ of temperature,20 MPa of the pressure and 2- 1 volume ratio of supercritical CO2 to HIPS solution. The removal rate of PBDEs is over 97%.%建立了利用超临界CO2从阻燃高抗冲聚苯乙烯塑料溶液中萃取分离多溴联苯醚的新工艺,研究了超临界CO2的温度、压力、体积及十溴联苯醚浓度等因素对超临界萃取分离过程的影响规律,提出了从阻燃塑料中分离十溴联苯醚的措施.实验结果表明,采用离心分离除去塑料溶液中大部分十溴联苯醚颗粒后,再在65℃、20 MPa超临界条件下,使用2倍于塑料溶液体积的超临界CO2进行萃取,所得的再生塑料的多溴联苯醚总含量低于0.1%(干基),多溴联苯醚的脱除率超过97%.

  19. A finite-dimensional reduction method for slightly supercritical elliptic problems

    Directory of Open Access Journals (Sweden)

    Riccardo Molle

    2004-01-01

    Full Text Available We describe a finite-dimensional reduction method to find solutions for a class of slightly supercritical elliptic problems. A suitable truncation argument allows us to work in the usual Sobolev space even in the presence of supercritical nonlinearities: we modify the supercritical term in such a way to have subcritical approximating problems; for these problems, the finite-dimensional reduction can be obtained applying the methods already developed in the subcritical case; finally, we show that, if the truncation is realized at a sufficiently large level, then the solutions of the approximating problems, given by these methods, also solve the supercritical problems when the parameter is small enough.

  20. Supercritical fluid reverse micelle separation

    Science.gov (United States)

    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.

  1. Supercritical fluid reverse micelle separation

    Science.gov (United States)

    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.

  2. German Resource Efficiency Programme (ProgRess). Programme for the sustainable utilization and protection of natural ressources. Decision of the Federal Cabinet from February 29, 2012; Deutsches Ressourceneffizienzprogramm (ProgRess). Programm zur nachhaltigen Nutzung und zum Schutz der natuerlichen Ressourcen. Beschluss des Bundeskabinetts vom 29.2.2012

    Energy Technology Data Exchange (ETDEWEB)

    Kaiser, Reinhard; Miehe, Anne; Schwenk, Birgit (comps.)

    2012-05-14

    The Federal Cabinet adopted the German Resource Efficiency Programme (ProgRess) today. The goal of the Programme is to continuously increase raw material productivity in German industry through market incentives, research and innovation and advice, and thus to promote a further decoupling of our growth from resource consumption. ProgRess is the first comprehensive programme by the German government to address the sustainable use of raw materials. At the core of ProgRess are new strategic approaches, activities and examples geared towards increasing resource efficiency. The Programme covers the entire value chain. It is about securing a sustainable raw material supply, raising resource efficiency in production, steering consumption towards resource efficiency, enhancing resource-efficient closed cycle management and using overarching instruments. The Programme seeks to support voluntary measures and initiatives in industry and society. Examples include strengthening efficiency advice for small and medium-sized enterprises, supporting environmental management systems, integrating resource aspects into technical standardisation processes, placing greater emphasis on resource-efficient products and services in public procurement, strengthening voluntary product labelling and certification systems, enhancing closed cycle management and facilitating the transfer of technologies and knowledge to developing and emerging economies.

  3. Drug delivery goes supercritical

    Directory of Open Access Journals (Sweden)

    Patrick J. Ginty

    2005-08-01

    Full Text Available In the field of drug delivery, the ability to control the size, morphology, and release of drug particles is fundamental to good targeting, but is often hampered by harsh processing conditions or inadequate methods; likewise for the processing of polymeric controlled-release systems. However, the use of supercritical fluids such as supercritical CO2 (scCO2 has provided a ‘clean’ and effective alternative to traditional methods of drug and polymer processing. In particular, scCO2 has a number of unique properties that make it possible to process both bioactive molecules and amorphous polymers without using toxic organic solvents or elevated temperatures. Here, we review the positive impact that supercritical fluids have had on the micronization, encapsulation, and impregnation of molecules of interest to both the pharmaceutical and biotechnology industries.

  4. Supercritical fluid technology for energy and environmental applications

    CERN Document Server

    Anikeev, Vladimir

    2014-01-01

    Supercritical Fluid Technology for Energy and Environmental Applications covers the fundamental principles involved in the preparation and characterization of supercritical fluids (SCFs) used in the energy production and other environmental applications. Energy production from diversified resources - including renewable materials - using clean processes can be accomplished using technologies like SCFs. This book is focused on critical issues scientists and engineers face in applying SCFs to energy production and environmental protection, the innovative solutions they have found, and the challenges they need to overcome. The book also covers the basics of sub- and supercritical fluids, like the thermodynamics of phase and chemical equilibria, mathematical modeling, and process calculations. A supercritical fluid is any substance at a temperature and pressure above its critical point where distinct liquid and gas phases do not exist. At this state the compound demonstrates unique properties, which can be "fine...

  5. Supercritical Synthesis of Biodiesel

    Directory of Open Access Journals (Sweden)

    Michel Vaultier

    2012-07-01

    Full Text Available 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.

  6. Supercritical CO2 Extraction of Ethanol

    OpenAIRE

    GÜVENÇ, A.; MEHMETOĞLU, Ü.; ÇALIMLI, A.

    1999-01-01

    Extraction of ethanol was studied from both synthetic ethanol solution and fermentation broth using supercritical CO2 in an extraction apparatus in ranges of 313 to 333 K and 80 to 160 atmospheres, for varying extraction times. The experimental system consists mainly of four parts: a CO2 storage system, a high-pressure liquid pump, an extractor and a product collection unit. Samples were analyzed by gas chromatography. Effects of temperature, pressure, extraction time, initial ethan...

  7. Structural Transition in Supercritical Fluids

    Directory of Open Access Journals (Sweden)

    Boris I. Sedunov

    2011-01-01

    Full Text Available The extension of the saturation curve ( on the PT diagram in the supercritical region for a number of monocomponent supercritical fluids by peak values for different thermophysical properties, such as heat capacities and and compressibility has been studied. These peaks signal about some sort of fluid structural transition in the supercritical region. Different methods give similar but progressively diverging curves st( for this transition. The zone of temperatures and pressures near these curves can be named as the zone of the fluid structural transition. The outstanding properties of supercritical fluids in this zone help to understand the physical sense of the fluid structural transition.

  8. Surfactant/Supercritical Fluid Cleaning of Contaminated Substrates

    Science.gov (United States)

    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.

  9. Supercritical solvent coal extraction

    Science.gov (United States)

    Compton, L. E. (Inventor)

    1984-01-01

    Yields of soluble organic extract are increased up to about 50% by the supercritical extraction of particulate coal at a temperature below the polymerization temperature for coal extract fragments (450 C.) and a pressure from 500 psig to 5,000 psig by the conjoint use of a solvent mixture containing a low volatility, high critical temperature coal dissolution catalyst such as phenanthrene and a high volatility, low critical temperature solvent such as toluene.

  10. Extraction of metals using supercritical fluid and chelate forming legand

    Science.gov (United States)

    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.

  11. Extraction of metals using supercritical fluid and chelate forming ligand

    Science.gov (United States)

    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.

  12. Thermodynamic behaviour of supercritical matter.

    Science.gov (United States)

    Bolmatov, Dima; Brazhkin, V V; Trachenko, K

    2013-01-01

    Since their discovery in 1822, supercritical fluids have been of enduring interest and have started to be deployed in many important applications. Theoretical understanding of the supercritical state is lacking and is seen to limit further industrial deployment. Here we study thermodynamic properties of the supercritical state and discover that specific heat shows a crossover between two different regimes, an unexpected result in view of currently perceived homogeneity of supercritical state in terms of physical properties. We subsequently formulate a theory of system thermodynamics above the crossover, and find good agreement between calculated and experimental specific heat with no free-fitting parameters. In this theory, energy and heat capacity are governed by the minimal length of the longitudinal mode in the system only, and do not explicitly depend on system-specific structure and interactions. We derive a power law and analyse supercritical scaling exponents in the system above the Frenkel line.

  13. Precipitation of fluticasone propionate microparticles using supercritical antisolvent

    Directory of Open Access Journals (Sweden)

    A Vatanara

    2009-03-01

    Full Text Available ABSTRACT Background: The ability of supercritical fluids (SCFs, such as carbon dioxide, to dissolve and expand or extract organic solvents and as result lower their solvation power, makes it possible the use of SCFs for the precipitation of solids from organic solutions. The process could be the injection of a solution of the substrate in an organic solvent into a vessel which is swept by a supercritical fluid. The aim of this study was to ascertain the feasibility of supercritical processing to prepare different particulate forms of fluticasone propionate (FP, and to evaluate the influence of different liquid solvents and precipitation temperatures on the morphology, size and crystal habit of particles. Method: The solution of FP in organic solvents, was precipitated by supercritical carbon dioxide (SCCO2 at two pressure and temperature levels. Effects of process parameters on the physicochemical characteristics of harvested microparticles were evaluated. Results: Particle formation was observed only at the lower selected pressure, whilst at the higher pressure, no precipitation of particles was occurred due to dissolution of FP in supercritical antisolvent. The micrographs of the produced particles showed different morphologies for FP obtained from different conditions. The results of thermal analysis of the resulted particles showed that changes in the processing conditions didn't influence thermal behavior of the precipitated particles. Evaluation of the effect of temperature on the size distribution of particles showed that increase in the temperature from 40 oC to 50 oC, resulted in reduction of the mean particle size from about 30 µm to about 12 μm. ‍Conclusion: From the results of this study it may be concluded that, processing of FP by supercritical antisolvent could be an approach for production of diverse forms of the drug and drastic changes in the physical characteristics of microparticles could be achieved by changing the

  14. Industrial applications and current trends in supercritical fluid technologies

    Directory of Open Access Journals (Sweden)

    Gamse Thomas

    2005-01-01

    Full Text Available Supercritical fluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercritical fluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop extraction or removal of pesticides from rice, activity in supercritical extraction producing total extract from the raw material or different fractions by using the fractionated separation of beverages (rum, cognac, whisky, wine, beer cider, of citrus oils and of lipids (fish oils, tall oil were also discussed. The main interest is still for the extraction of natural raw materials producing food ingredients, nutraceuticals and phytopharmaceuticals but also cleaning purposes were tested such as the decontamination of soils the removal of residual solvents from pharmaceutical products, the extraction of flame retardants from electronic waste or precision degreasing and cleaning of mechanical and electronic parts. An increasing interest obviously exists for impregnation purposes based on supercritical fluids behaviour, as well as for the dying of fibres and textiles. The production of fine particles in the micron and submicron range, mainly for pharmaceutical products is another important application of supercritical fluids. Completely new products can be produced which is not possible under normal conditions. Supercritical fluid technology has always had to compete with the widespread opinion that these processes are very expensive due to very high investment costs in comparison with classical low-pressure equipment. Thus the opinion is that these processes should be restricted to high-added value products. A cost estimation for different plant sizes and

  15. On the cluster composition of supercritical water combining molecular modeling and vibrational spectroscopic data.

    Science.gov (United States)

    Tassaing, T; Garrain, P A; Bégué, D; Baraille, I

    2010-07-21

    The present study is aimed at a detailed analysis of supercritical water structure based on the combination of experimental vibrational spectra as well as molecular modeling calculations of isolated water clusters. We propose an equilibrium cluster composition model where supercritical water is considered as an ideal mixture of small water clusters (n=1-3) at the chemical equilibrium and the vibrational spectra are expected to result from the superposition of the spectra of the individual clusters, Thus, it was possible to extract from the decomposition of the midinfrared spectra the evolution of the partition of clusters in supercritical water as a function of density. The cluster composition predicted by this model was found to be quantitatively consistent with the near infrared and Raman spectra of supercritical water analyzed using the same procedure. We emphasize that such methodology could be applied to determine the portion of cluster in water in a wider thermodynamic range as well as in more complex aqueous supercritical solutions.

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

    Science.gov (United States)

    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.

  17. Application of Neutron Radiography to Flow Visualization in Supercritical Water

    Science.gov (United States)

    Takenaka, N.; Sugimoto, K.; Takami, S.; Sugioka, K.; Tsukada, T.; Adschiri, T.; Saito, Y.

    Supercritical water is used in various chemical reaction processes including hydrothermal synthesis of metal oxide nano-particles, oxidation, chemical conversion of biomass and plastics. Density of the super critical water is much less than that of the sub-critical water. By using neutron radiography, Peterson et al. have studied salt precipitation processes in supercritical water and the flow pattern in a reverse-flow vessel for salt precipitation, and Balasko et al. have revealed the behaviour of supercritical water in a container. The nano-particles were made by mixing the super critical flow and the sub critical water solution. In the present study, neutron radiography was applied to the flow visualization of the super and sub critical water mixture in a T-junction made of stainless steel pipes for high pressure and temperature conditions to investigate their mixing process. Still images by a CCD camera were obtained by using the neutron radiography system at B4 port in KUR.

  18. Molecular Dynamics Investigation of Benzene in Supercritical Water

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Microscopic structure and diffusion properties of benzene in ambient water (298 K, 0.1 MPa) and super critical water (673-773 K, 25-35 MPa) are investigated by molecular dynamics simulation with site-site models. It is found that at the ambient condition, the water molecules surrounding a benzene molecule form a hydrogen bond network. The hydrogen bond interaction between supercritical water molecules decreases dramatically under supercritical conditions. The diffusion coefficients of both the solute molecule and solvent molecule at supercritical conditions increase by 30-180 times than those at the ambient condition. With the temperature approaching the critical temperature, the change of diffusion coefficient with pressure becomes pronounced.

  19. Corrosion in supercritical fluids

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

  1. ENGINEERING BULLETIN: SUPERCRITICAL WATER OXIDATION

    Science.gov (United States)

    This engineering bulletin presents a description and status of supercritical water oxidation technology, a summary of recent performance tests, and the current applicability of this emerging technology. This information is provided to assist remedial project managers, contractors...

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

    Energy Technology Data Exchange (ETDEWEB)

    van Swol, F. [Illinois Univ., Urbana, IL (United States). Dept. of Chemical Engineering; Eckert, C.A. [Georgia Inst. of Tech., Atlanta, GA (United States). School of Chemical Engineering

    1988-09-15

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

  3. Particle Formation and Deposition from Supercritical Solutions.

    Science.gov (United States)

    1986-12-12

    interaction parameters were derived to permit interpolation using the Peng-Robinson *modification of the Redlich - Kwong equation of state (10), which...ORGANIZATION (If applicable ) Office of Naval Research N00014-83-C-0439 3c. A DDRESS (City, State , and ZIP Code) 10 SOURCE OF FUNDING NUMBERS 800 N. Quincy...N00014-83-C-0439 6a. NAME OF PERFORMING ORGANIZATION 6b OFFICE SYMBOL 7a NAME OF -MONITORING ORGANIZATION Critical Fluid Systems, Inc. (If applicable

  4. Supercritical Water Oxidation Data Acquisition Testing

    Energy Technology Data Exchange (ETDEWEB)

    K. M. Garcia

    1996-08-01

    Supercritical Water Oxidation (SCWO) is a high pressure oxidation process that blends air, water, and organic waste material in an oxidizer in which where the temperature and pressure in the oxidizer are maintained above the critical point of water. Supercritical water mixed with hydrocarbons, which would be insoluble at subcritical conditions, forms a homogeneous phase which possesses properties associated with both a gas and a liquid. Hydrocarbons in contact with oxygen and SCW are readily oxidized. These properties of SCW make it an attractive means for the destruction of waste streams containing organic materials. SCWO technology holds great promise for treating mixed wastes in an environmentally safe and efficient manner. In the spring of 1994 the U.S. Department of Energy (DOE) initiated a Supercritical Water Oxidation Data Acquisition Testing (SCWODAT) program. The SCWODAT program provided further information and operational data on the effectiveness of treating both simulated mixed waste and typical Navy hazardous waste using the SCWO technology. The program concentrated on the acquisition of data through pilot plant testing. The Phase I DOE testing used a simulated waste stream that contained a complex machine cutting oil and metals, that acted as surrogates for radionuclides. The Phase II Navy testing included pilot testing using hazardous waste materials to demonstrate the effectiveness of the SCWO technology. The SCWODAT program demonstrated that the SCWO process oxidized the simulated waste stream containing complex machine cutting oil, selected by DOE as representative of one of the most difficult of the organic waste streams for which SCWO had been applied. The simulated waste stream with surrogate metals in solution was oxidized, with a high destruction efficiency, on the order of 99.97%, in both the neutralized and unneutralized modes of operation.

  5. Supercritical Antisolvent Precipitation of Microparticles of Quercetin

    Institute of Scientific and Technical Information of China (English)

    刘学武; 李志义; 韩冰; 苑塔亮

    2005-01-01

    Supercritical antisolvent (SAS) process is a recently developed technology to produce micro- and nanoparticles. This paper presents a continuous apparatus to conduct experiment of SAS process. With the apparatus,the effects of pressure, temperature and flow ratio of CO2 to the solution on the shape and size of particles are studied for the quercetin-ethanol-CO2 system. Spherical quercetin microparticles with diameters ranging form i μm to 6μm can be obtained while ethanol is used as organic solvent. The most effective fact on the shape and size of particles is pressure, the next is temperature and the last is the flow ratio of CO2 to solution.

  6. Dynamic transition in supercritical iron.

    Science.gov (United States)

    Fomin, Yu D; Ryzhov, V N; Tsiok, E N; Brazhkin, V V; Trachenko, K

    2014-11-26

    Recent advance in understanding the supercritical state posits the existence of a new line above the critical point separating two physically distinct states of matter: rigid liquid and non-rigid gas-like fluid. The location of this line, the Frenkel line, remains unknown for important real systems. Here, we map the Frenkel line on the phase diagram of supercritical iron using molecular dynamics simulations. On the basis of our data, we propose a general recipe to locate the Frenkel line for any system, the recipe that importantly does not involve system-specific detailed calculations and relies on the knowledge of the melting line only. We further discuss the relationship between the Frenkel line and the metal-insulator transition in supercritical liquid metals. Our results enable predicting the state of supercritical iron in several conditions of interest. In particular, we predict that liquid iron in the Jupiter core is in the "rigid liquid" state and is highly conducting. We finally analyse the evolution of iron conductivity in the core of smaller planets such as Earth and Venus as well as exoplanets: as planets cool off, the supercritical core undergoes the transition to the rigid-liquid conducting state at the Frenkel line.

  7. Supercritical water oxidation: application to reduce industrial wastes. Oxidacion en agua supercritica (OASC): aplicacion a la eliminacion de residuos industriales

    Energy Technology Data Exchange (ETDEWEB)

    Cocero, M.J.; Gonzalez, R.; Fernandez-Polanco, F.

    1994-01-01

    The incineration of wastes presents many problems with environmental laws. A solution could be the Supercritic oxidation water. (SOW). This method is clean, without air pollution. The article analyzes process, depressurization, energetical approvement, and applications for wastes. (Author) 18 refs.

  8. Supercritical Fluid Extraction: Present Status and Prospects

    Energy Technology Data Exchange (ETDEWEB)

    King, J. W.

    2002-07-01

    Supercritical extraction (SFE), using primarily environmentally-benign carbon dioxide (CO{sub 2}) as the extraction agent, is reviewed with respect to its present status and future use. SFE was developed for analytical application in the mid 1980's in response to the desire to reduce the use of organic solvents in the laboratory environment and is becoming a standard method for the preparation and analysis of lipid-containing sample matrices. Currently, analytical SFE is predominately practiced in the off-line mode, using both sequential and parallel extraction modes. Depending on the instrumental configuration, the preparation of up to 24 samples can be accomplished on one instrument on a daily basis. Several other benefits can be achieved using SFE, such as the processing of thermally-sensitive analytes and rapid analyte extraction kinetics relative to extraction with liquid solvents. Examples are provided not only of the analytical SFE of oils and fats, but of volatile solutes from an array of sample types. Finally, the relevance of analytical SFE to processing with supercritical fluids (SFs) is documented using examples from our own research involving a combinatorial approach to optimising processing conditions. (Author) 70 refs.

  9. Supercritical extraction of oleaginous: parametric sensitivity analysis

    Directory of Open Access Journals (Sweden)

    Santos M.M.

    2000-01-01

    Full Text Available The economy has become universal and competitive, thus the industries of vegetable oil extraction must advance in the sense of minimising production costs and, at the same time, generating products that obey more rigorous patterns of quality, including solutions that do not damage the environment. The conventional oilseed processing uses hexane as solvent. However, this solvent is toxic and highly flammable. Thus the search of substitutes for hexane in oleaginous extraction process has increased in the last years. The supercritical carbon dioxide is a potential substitute for hexane, but it is necessary more detailed studies to understand the phenomena taking place in such process. Thus, in this work a diffusive model for semi-continuous (batch for the solids and continuous for the solvent isothermal and isobaric extraction process using supercritical carbon dioxide is presented and submitted to a parametric sensitivity analysis by means of a factorial design in two levels. The model parameters were disturbed and their main effects analysed, so that it is possible to propose strategies for high performance operation.

  10. Preparing silica aerogel monoliths via a rapid supercritical extraction method.

    Science.gov (United States)

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

    2014-02-28

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

  11. Supercritical Fluid Reactions for Coal Processing

    Energy Technology Data Exchange (ETDEWEB)

    Charles A. Eckert

    1997-11-01

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

  12. Eventual Regularity of the Two-Dimensional Boussinesq Equations with Supercritical Dissipation

    Science.gov (United States)

    Jiu, Quansen; Wu, Jiahong; Yang, Wanrong

    2015-02-01

    This paper studies solutions of the two-dimensional incompressible Boussinesq equations with fractional dissipation. The spatial domain is a periodic box. The Boussinesq equations concerned here govern the coupled evolution of the fluid velocity and the temperature and have applications in fluid mechanics and geophysics. When the dissipation is in the supercritical regime (the sum of the fractional powers of the Laplacians in the velocity and the temperature equations is less than 1), the classical solutions of the Boussinesq equations are not known to be global in time. Leray-Hopf type weak solutions do exist. This paper proves that such weak solutions become eventually regular (smooth after some time ) when the fractional Laplacian powers are in a suitable supercritical range. This eventual regularity is established by exploiting the regularity of a combined quantity of the vorticity and the temperature as well as the eventual regularity of a generalized supercritical surface quasi-geostrophic equation.

  13. Etching of glass microchips with supercritical water.

    Science.gov (United States)

    Karásek, Pavel; Grym, Jakub; Roth, Michal; Planeta, Josef; Foret, František

    2015-01-07

    A novel method of etching channels in glass microchips with the most tunable solvent, water, was tested as an alternative to common hydrogen fluoride-containing etchants. The etching properties of water strongly depend on temperature and pressure, especially in the vicinity of the water critical point. The chips were etched at the subcritical, supercritical and critical temperature of water, and the resulting channel shape, width, depth and surface morphology were studied by scanning electron microscopy and 3D laser profilometry. Channels etched with the hot water were compared with the chips etched with standard hydrogen fluoride-containing solution. Depending on the water pressure and temperature, the silicate dissolved from the glass could be re-deposited on the channel surface. This interesting phenomenon is described together with the conditions necessary for its utilization. The results illustrate the versatility of pure water as a glass etching and surface morphing agent.

  14. Removing Solids From Supercritical Water

    Science.gov (United States)

    Hong, Glenn T.

    1992-01-01

    Apparatus removes precipitated inorganic salts and other solids in water-recycling process. Designed for use with oxidation in supercritical water which treats wastes and yields nearly pure water. Heating coils and insulation around vessel keep it hot. Locking bracket seals vessel but allows it to be easily opened for replacement of filled canisters.

  15. Supercritical multicomponent solvent coal extraction

    Science.gov (United States)

    Corcoran, W. H.; Fong, W. S.; Pichaichanarong, P.; Chan, P. C. F.; Lawson, D. D. (Inventor)

    1983-01-01

    The yield of organic extract from the supercritical extraction of coal with larger diameter organic solvents such as toluene is increased by use of a minor amount of from 0.1 to 10% by weight of a second solvent such as methanol having a molecular diameter significantly smaller than the average pore diameter of the coal.

  16. Universal scaling behavior of supercritical matter

    CERN Document Server

    Bolmatov, Dima; Trachenko, K

    2013-01-01

    Properties of supercritical fluids have been of enduring interest since the critical phenomena were discovered by Cagniard de la Tour in 1822, stimulating fundamental theoretical work and development of experimental techniques. Here, we study the thermodynamic properties of the supercritical state, and discover that specific heat shows a crossover between two different dynamic regimes of the low-temperature rigid liquid and high-temperature non-rigid supercritical fluid. We formulate a theory of heat capacity above the crossover, and find good agreement between calculated and experimental data for rare-gas supercritical liquids (Ne, Ar, Kr and Xe) with no free fitting parameters. We derive the relationship between scaling exponents of heat capacity and viscosity in the supercritical region, and show that these exponents exhibit universality. The universality is explained by the universal temperature behavior of the maximal length of the longitudinal phonons that can exist in the supercritical system and that ...

  17. The ultrasonic-enhanced factor of mass-transfer coefficient in the supercritical carbon dioxide extraction

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Based on several hypotheses about the process of supercritical carbon dioxide extraction, the onflow around the solute granule is figured out by the Navier-Stocks equation. In combination with the Higbie’s solute infiltration model, the link be-tween the mass-transfer coefficient and the velocity of flow is found. The mass-transfer coefficient with the ultrasonical effect is compared with that without the ultrasonical effect, and then a new parameter named the ultrasonic-enhanced fac-tor of mass-transfer coefficient is brought forward, which describes the mathe-matical model of the supercritical carbon dioxide extraction process enhanced by ultrasonic. The model gives out the relationships among the ultrasonical power, the ultrasonical frequency, the radius of solute granule and the ultrasonic-enhanced factor of mass-transfer coefficient. The results calculated by this model fit well with the experimental data, including the extraction of Coix Lacryma-jobi Seed Oil (CLSO) and Coix Lacryma-jobi Seed Ester (CLSE) from coix seeds and the extrac-tion of Eicosapentaenoic Acid (EPA) and Docosahexaenoic Acid (DHA) from the alga by means of the ultrasonic-enhanced supercritical carbon dioxide extraction (USFE) and the supercritical carbon dioxide extraction (SFE) respectively. This proves the rationality of the ultrasonic-enhanced factor model. The model provides a theoretical basis for the application of ultrasonic-enhanced supercritical fluid extraction technique.

  18. Remediation of Contaminated Soils By Supercritical Carbon Dioxide Extraction

    Science.gov (United States)

    Ferri, A.; Zanetti, M. C.; Banchero, M.; Fiore, S.; Manna, L.

    The contaminants that can be found in soils are many, inorganic, like heavy metals, as well as organic. Among the organic contaminants, oil and coal refineries are responsi- ble for several cases of soil contamination with PAHs (Polycyclic Aromatic Hydrocar- bons). Polynuclear aromatic hydrocarbons (PAHs) have toxic, carcinogenic and mu- tagenic effects. Limits have been set on the concentration of most contaminants, and growing concern is focusing on soil contamination issues. USA regulations set the maximum acceptable level of contamination by PAHs equal to 40 ppm at residential sites and 270 ppm at industrial sites. Stricter values are usually adopted in European Countries. Supercritical carbon dioxide extraction is a possible alternative technology to remove volatile organic compounds from contaminated soils. Supercritical fluid extraction (SFE) offers many advantages over conventional solvent extraction. Super- critical fluids combine gaseous properties as a high diffusion coefficient, and liquid properties as a high solvent power. The solvent power is strongly pressure-dependent near supercritical conditions: selective extractions are possible without changing the solvent. Solute can be separate from the solvent depressurising the system; therefore, it is possible to recycle the solvent and recover the contaminant. Carbon dioxide is frequently used as supercritical fluid, because it has moderate critical conditions, it is inert and available in pure form. In this work, supercritical fluid extraction technology has been used to remove a polynuclear aromatic hydrocarbon from contaminated soils. The contaminant choice for the experiment has been naphthalene since several data are available in literature. G. A. Montero et al. [1] studied soil remediation with supercrit- ical carbon dioxide extraction technology; these Authors have found that there was a mass-transfer limitation. In the extraction vessel, the mass transfer coefficient in- creases with the

  19. Pulsed discharge plasmas in supercritical carbon dioxide

    OpenAIRE

    Kiyan, Tsuyoshi; Uemura, A.; Tanaka, K.; Zhang, C. H.; Namihira, Takao; Sakugawa, Takashi; Katsuki, Sunao; Akiyama, Hidenori; Roy, B.C.; Sasaki, M.; Goto, M.; キヤン, ツヨシ; ナミヒラ, タカオ; サクガワ, タカシ; カツキ, スナオ

    2005-01-01

    In recent years, several studies about electrical discharge plasma in supercritical carbon dioxide (CO2) have been carried out. One of the unique characteristics of supercritical fluid is a large density fluctuation near the critical point that can result in marked dramatic changes of thermal conductivity. Therefore, the electrical discharge plasma produced in supercritical fluid has unique features and reactions unlike those of normal plasma produced in gas phase. In our experiments, two typ...

  20. Polarization and spectral shift of benzophenone in supercritical water.

    Science.gov (United States)

    Fonseca, T L; Georg, H C; Coutinho, K; Canuto, S

    2009-04-30

    Monte Carlo simulation and quantum mechanics calculations based on the INDO/CIS and TD-DFT methods were utilized to study the solvatochromic shift of benzophenone when changing the environment from normal water to supercritical (P = 340.2 atm and T = 673 K) condition. Solute polarization increases the dipole moment of benzophenone, compared to gas phase, by 88 and 35% in normal and supercritical conditions, giving the in-solvent dipole value of 5.8 and 4.2 D, respectively. The average number of solute-solvent hydrogen bonds was analyzed, and a large decrease of 2.3 in normal water to only 0.8 in the supercritical environment was found. By using these polarized models of benzophenone in the two different conditions of water, we performed MC simulations to generate statistically uncorrelated configurations of the solute surrounded by the solvent molecules and subsequent quantum mechanics calculations on these configurations. When changing from normal to supercritical water environment, INDO/CIS calculations explicitly considering all valence electrons of the 235 solvent water molecules resulted in a solvatochromic shift of 1425 cm(-1) for the most intense pi-pi* transition of benzophenone, that is, slightly underestimated in comparison with the experimentally inferred result of 1700 cm(-1). TD-B3LYP/6-311+G(2d,p) calculations on the same configurations but with benzophenone electrostatically embedded in the 320 water molecules resulted in a solvatochromic shift of 1715 cm(-1) for this transition, in very good agreement with the experimental result. When using the unpolarized model of the benzophenone, this calculated solvatochromic shift was only 640 cm(-1). Additional calculations were also made by using BHandHLYP/6-311+G(2d,p) to analyze the effect of the asymptotic decay of the exchange functional. This study indicates that, contrary to the general expectation, there is a sizable solute polarization even in the low-density regime of supercritical condition and

  1. Lipidomics by Supercritical Fluid Chromatography

    Directory of Open Access Journals (Sweden)

    Laurent Laboureur

    2015-06-01

    Full Text Available 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.

  2. Lipidomics by Supercritical Fluid Chromatography

    Science.gov (United States)

    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

  3. Recuperative supercritical carbon dioxide cycle

    Science.gov (United States)

    Sonwane, Chandrashekhar; Sprouse, Kenneth M; Subbaraman, Ganesan; O'Connor, George M; Johnson, Gregory A

    2014-11-18

    A power plant includes a closed loop, supercritical carbon dioxide system (CLS-CO.sub.2 system). The CLS-CO.sub.2 system includes a turbine-generator and a high temperature recuperator (HTR) that is arranged to receive expanded carbon dioxide from the turbine-generator. The HTR includes a plurality of heat exchangers that define respective heat exchange areas. At least two of the heat exchangers have different heat exchange areas.

  4. Supercritical Fuel Pyrolysis

    Science.gov (United States)

    2010-05-30

    200 l (40 µl in the case of n-decane product fractions) of dimethylsulfoxide , a solvent compatible with the solvents used in the reversed-phase HPLC...aliquot of the product/ dimethylsulfoxide solution is injected onto an Agilent Model 1100 high-pressure liquid chromatograph, coupled to a diode- array

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

    Energy Technology Data Exchange (ETDEWEB)

    Henry, Matthew C.; Yonker, Clement R.

    2006-06-15

    In this review we examine the related fields of supercritical fluid chromatography (SFC) and supercritical fluid extraction (SFE). We reviewed the published literature in the period from November 2003 to November 2005. Well over 300 papers were published in this period. This large body of work indicates continuing active growth of the field, but an exhaustive review is beyond the scope of this work. We have chosen to include a sampling of publications that best represent the continuing trends and new ideas in the field. In keeping with past reviews on this subject1, we have broadened our scope to include fluid systems operating at high temperature and pressure, but below the critical point. Various terms have been applied to this state: sub-critical fluid extraction, pressurized liquid extraction, and accelerated solvent extraction. The term accelerated solvent extraction has been used by instrument manufacturers to refer to this process, but we will use the more descriptive term pressurized liquid extraction (PLE) to refer to these systems. Most of the research in the field is of an “evolutionary” rather than “revolutionary” nature. As in the previous review period, applications papers make up a majority of the published work. Pharmaceutical applications continue to be a strong theme. Most of the pharmaceutical work has centered on preparative, rather than analytical, separations. Chiral separations are an exception, as analytical scale separations of chiral compounds are an area of intense interest. Food and natural products represent the next largest body of work. Major themes are the isolation and characterization of high-value added foodstuffs, fragrances, and flavor compounds from novel natural materials or agricultural by-products. The areas of food, natural products, and pharmaceutical separation science converge in the area of so-called nutraceuticals. These are typically high-value products, either sold alone or as part of a fortified food, that

  6. SOLUTIONING

    Directory of Open Access Journals (Sweden)

    Maria de Hoyos Guajardo, Ph.D. Candidate, M.Sc., B.Eng.

    2004-11-01

    Full Text Available The theory that is presented below aims to conceptualise how a group of undergraduate students tackle non-routine mathematical problems during a problem-solving course. The aim of the course is to allow students to experience mathematics as a creative process and to reflect on their own experience. During the course, students are required to produce a written ‘rubric’ of their work, i.e., to document their thoughts as they occur as well as their emotionsduring the process. These ‘rubrics’ were used as the main source of data.Students’ problem-solving processes can be explained as a three-stage process that has been called ‘solutioning’. This process is presented in the six sections below. The first three refer to a common area of concern that can be called‘generating knowledge’. In this way, generating knowledge also includes issues related to ‘key ideas’ and ‘gaining understanding’. The third and the fourth sections refer to ‘generating’ and ‘validating a solution’, respectively. Finally, once solutions are generated and validated, students usually try to improve them further before presenting them as final results. Thus, the last section deals with‘improving a solution’. Although not all students go through all of the stages, it may be said that ‘solutioning’ considers students’ main concerns as they tackle non-routine mathematical problems.

  7. Supercritical water oxidation - Microgravity solids separation

    Science.gov (United States)

    Killilea, William R.; Hong, Glenn T.; Swallow, Kathleen C.; Thomason, Terry B.

    1988-01-01

    This paper discusses the application of supercritical water oxidation (SCWO) waste treatment and water recycling technology to the problem of waste disposal in-long term manned space missions. As inorganic constituents present in the waste are not soluble in supercritical water, they must be removed from the organic-free supercritical fluid reactor effluent. Supercritical water reactor/solids separator designs capable of removing precipitated solids from the process' supercritical fluid in zero- and low- gravity environments are developed and evaluated. Preliminary experiments are then conducted to test the concepts. Feed materials for the experiments are urine, feces, and wipes with the addition of reverse osmosis brine, the rejected portion of processed hygiene water. The solid properties and their influence on the design of several oxidation-reactor/solids-separator configurations under study are presented.

  8. Review of the coal-fired, over-supercritical and ultra-supercritical steam power plants

    Science.gov (United States)

    Tumanovskii, A. G.; Shvarts, A. L.; Somova, E. V.; Verbovetskii, E. Kh.; Avrutskii, G. D.; Ermakova, S. V.; Kalugin, R. N.; Lazarev, M. V.

    2017-02-01

    The article presents a review of developments of modern high-capacity coal-fired over-supercritical (OSC) and ultra-supercritical (USC) steam power plants and their implementation. The basic engineering solutions are reported that ensure the reliability, economic performance, and low atmospheric pollution levels. The net efficiency of the power plants is increased by optimizing the heat balance, improving the primary and auxiliary equipment, and, which is the main thing, by increasing the throttle conditions. As a result of the enhanced efficiency, emissions of hazardous substances into the atmosphere, including carbon dioxide, the "greenhouse" gas, are reduced. To date, the exhaust steam conditions in the world power industry are p 0 ≈ 30 MPa and t 0 = 610/620°C. The efficiency of such power plants reaches 47%. The OSC plants are being operated in Germany, Denmark, Japan, China, and Korea; pilot plants are being developed in Russia. Currently, a project of a power plant for the ultra-supercritical steam conditions p 0 ≈ 35 MPa and t 0 = 700/720°C with efficiency of approximately 50% is being studied in the EU within the framework of the Thermie AD700 program, project AD 700PF. Investigations in this field have also been launched in the United States, Japan, and China. Engineering solutions are also being sought in Russia by the All-Russia Thermal Engineering Research Institute (VTI) and the Moscow Power Engineering Institute. The stated steam parameter level necessitates application of new materials, namely, nickel-base alloys. Taking into consideration high costs of nickel-base alloys and the absence in Russia of technologies for their production and manufacture of products from these materials for steam-turbine power plants, the development of power plants for steam parameters of 32 MPa and 650/650°C should be considered to be the first stage in creating the USC plants as, to achieve the above parameters, no expensive alloys are require. To develop and

  9. One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol

    DEFF Research Database (Denmark)

    Hansen, Thomas Søndergaard; Barta, Katalin; Anastas, Paul T.

    2012-01-01

    Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions...

  10. One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol

    NARCIS (Netherlands)

    Hansen, Thomas S.; Barta, Katalin; Anastas, Paul T.; Ford, Peter C.; Riisager, Anders

    2012-01-01

    Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions. The hydrog

  11. Development of artificial neural network models for supercritical fluid solvency in presence of co-solvents

    Energy Technology Data Exchange (ETDEWEB)

    Shokir, Eissa Mohamed El-Moghawry; El-Midany, Ayman Abdel-Hamid [Cairo University, Giza (Egypt); Al-Homadhi, Emad Souliman; Al-Mahdy, Osama [King Saud University, Riyadh (Saudi Arabia)

    2014-08-15

    This paper presents the application of artificial neural networks (ANN) to develop new models of liquid solvent dissolution of supercritical fluids with solutes in the presence of cosolvents. The neural network model of the liquid solvent dissolution of CO{sub 2} was built as a function of pressure, temperature, and concentrations of the solutes and cosolvents. Different experimental measurements of liquid solvent dissolution of supercritical fluids (CO{sub 2}) with solutes in the presence of cosolvents were collected. The collected data are divided into two parts. The first part was used in building the models, and the second part was used to test and validate the developed models against the Peng- Robinson equation of state. The developed ANN models showed high accuracy, within the studied variables range, in predicting the solubility of the 2-naphthol, anthracene, and aspirin in the supercritical fluid in the presence and absence of co-solvents compared to (EoS). Therefore, the developed ANN models could be considered as a good tool in predicting the solubility of tested solutes in supercritical fluid.

  12. Supercritical CO2-assisted preparation of ibuprofen loaded PEG-PVP complexes

    CSIR Research Space (South Africa)

    Labuschagne, Philip W

    2010-06-01

    Full Text Available Stoichiometric ratios of poly (ethylene glycol) (PEG, Mw = 400) with poly(vinylpyrrolidone) (PVP, Mw = ±3.1 x 104 & Mw = 1.25 x 106 Mw) were prepared from ethanol cast solutions and in supercritical CO2. The complex formation was studied via glass...

  13. Dependence of Reaction Rate Constants on Density in Supercritical Fluids%超临界流体中反应速率常数与密度的相互关系

    Institute of Scientific and Technical Information of China (English)

    王涛; 沈忠耀

    2002-01-01

    A new method, which correlates rate constants of chemical reactions and density or pressure in supercritical fluids, was developed. Based on the transition state theory and thermodynamic principles, the rate constant can be reasonably correlated with the density of the supercritical fluid, and a correlation equation was obtained.Coupled with the equation of state (EOS) of a supercritical solvent, the effect of pressure on reaction rate constant could be represented. Two typical systems were used to test this method. The result indicates that this method is suitable for dilute supercritical fluid solutions.

  14. Adsorption of ethyl acetate onto modified clays and its regeneration with supercritical CO2

    Directory of Open Access Journals (Sweden)

    A. M. Cavalcante

    2005-03-01

    Full Text Available Modified clays were used to remove ethyl acetate from aqueous solutions. These clays were regenerated using supercritical CO2. Structural changes in the montmorillonite clay after treatment with quaternary amines were studied. The surface properties of the modified clay changed from highly hydrophilic to highly organophilic. The clay was regenerated by percolation of a stream of CO2 through the porous montmorillonite matrix. Different pressures and temperatures were employed, resulting in different fluid conditions (gas, liquid, and supercritical. The experimental data was fitted with a simplified model. The best desorption result was found under supercritical conditions. A crossover effect was observed. The capacity of the modified clay as a pollutant attenuator remained almost unchanged after a regeneration cycle.

  15. Application of supercritical fluid to separation techniques; Chorinkai ryutai no bunri gijutsu eno oyo

    Energy Technology Data Exchange (ETDEWEB)

    Minamino, Y.; Aki, T. [Mitsubishi Kakoki Kaisha Ltd., Tokyo (Japan)

    1994-09-05

    The application of supercritical fluid on separation techniques and its problems are reviewed. The application is at a standstill contrary to large expectation for it except component extraction from natural foods such as caffeine removal from coffee. Various problems are thus pointed out to be solved as follows; a study on new applications other than substitutional use for organic solvents, cost reduction, a study on new safe advanced fluids suitable for specific objects other than CO2, and combination with other several separation techniques. The new practical applications of supercritical fluid expected in the near future are as follows; low-cost mass production of antibodies by use of the immunity system of hens, drying of porous bodies intercalated in aqueous solution, removal of residual unreacted monomers and organic solvents from medical polymers, development of supercritical chromatographic equipment possible to separate pure functional food materials, and analytical extraction of functional groups including hetero atoms from harmful substances. 6 refs., 2 figs., 2 tabs.

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

    Science.gov (United States)

    Park, Kwangheon; Lee, Jeongken; Sung, Jinhyun

    2013-04-01

    Supercritical fluids have good penetrating power with a high capacity to dissolve certain solutes in the fluid itself, making it applicable for soil cleaning. Supercritical CO2 along with mixed ligands has been used for cleaning artificially contaminated soil. The extraction of metal from the soil was successful, and the molar ratio of ligands to the extracted metal was as low as 3. Complicated structures with a large surface area of the real soil seemed to cause the lower efficiency. Reduced efficiency was also observed over time after the sample preparation, indicating the possibility of chemisorption of the metal ion onto the soil. The use of supercritical CO2 with dissolved mixed ligands was sufficient to extract metal from the soil. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Pilot-scale laboratory waste treatment by supercritical water oxidation.

    Science.gov (United States)

    Oshima, Yoshito; Hayashi, Rumiko; Yamamoto, Kazuo

    2006-01-01

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

  18. The separation of particulates from supercritical water oxidation processes

    Energy Technology Data Exchange (ETDEWEB)

    Dell`Orco, P.C.; Li, L.; Gloyna, E.F. [Univ. of Texas, Austin (United States)

    1993-01-01

    Small hydrocyclones with batch underflow receivers were assessed for their ability to separate micron-sized particulates from near-critical water solutions. Such particulates are expected from the effluent of a supercritical water oxidation reactor. The separation of micron-sized quartz silica, zirconia, and titania particles was investigated. An empirical expression was developed for the prediction of gross removal efficiencies as a function of a Stokes` number. Particle size distributions provided grade efficiencies for all experiments, and from these data, cut sizes were determined. Gross efficiencies up to 99% were observed for zirconia; cut sizes (d{sub 90} and d{sub 95}) near one micron were measured.

  19. Degradation Characteristics of Wood Using Supercritical Alcohols

    Directory of Open Access Journals (Sweden)

    Jeeban Poudel

    2012-11-01

    Full Text Available In this work, the characteristics of wood degradation using supercritical alcohols have been studied. Supercritical ethanol and supercritical methanol were used as solvents. The kinetics of wood degradation were analyzed using the nonisothermal weight loss technique with heating rates of 3.1, 9.8, and 14.5 °C/min for ethanol and 5.2, 11.3, and 16.3 °C/min for methanol. Three different kinetic analysis methods were implemented to obtain the apparent activation energy and the overall reaction order for wood degradation using supercritical alcohols. These were used to compare with previous data for supercritical methanol. From this work, the activation energies of wood degradation in supercritical ethanol were obtained as 78.0–86.0, 40.1–48.1, and 114 kJ/mol for the different kinetic analysis methods used in this work. The activation energies of wood degradation in supercritical ethanol were obtained as 78.0–86.0, 40.1–48.1, and 114 kJ/mol. This paper also includes the analysis of the liquid products obtained from this work. The characteristic analysis of liquid products on increasing reaction temperature and time has been performed by GC-MS. The liquid products were categorized according to carbon numbers and aromatic/aliphatic components. It was found that higher conversion in supercritical ethanol occurs at a lower temperature than that of supercritical methanol. The product analysis shows that the majority of products fall in the 2 to 15 carbon number range.

  20. Using supercritical fluids to refine hydrocarbons

    Science.gov (United States)

    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.

  1. Spatial and Orientational Structure of the Hydration Shell of Benzene in Sub- and Supercritical Water.

    Science.gov (United States)

    Choudhary, Ashu; Chandra, Amalendu

    2015-07-09

    The spatial and orientational structure of the solvation shell of benzene in sub- and supercritical water are investigated by means of molecular dynamics simulations. The present study reveals different local organization of water molecules at different parts of the solute. The π-hydrogen-bonding between benzene and water along the axial direction is found to exist even at supercritical conditions although to a reduced extent. The coordination number of benzene decreases substantially on increase of temperature and decrease of density. While the π-hydrogen-bonded part in the axial region shows a slight expansion, the hydrophobically solvated part in the equatorial plane shows an opposite behavior as the temperature is increased from normal to the supercritical temperature. Two other distribution functions, namely the radial/angular and spatial orientational functions (SOFs) are calculated to explore the spatially resolved angular preferences of water molecules around the benzene solute. Water molecules located axial to the benzene are found to have strong inward orientation toward the solute, however an opposite behavior is found in the equatorial region. Although at supercritical conditions, the orientational distributions of water molecules are broadened, the preferential orientations in the axial and equatorial regions remain similar to that under ambient condition on average.

  2. Oxy-combustor operable with supercritical fluid

    Energy Technology Data Exchange (ETDEWEB)

    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.

  3. Water in supercritical carbon dioxide dyeing

    Directory of Open Access Journals (Sweden)

    Zheng Lai-Jiu

    2015-01-01

    Full Text Available This paper investigates the effect of water serving as entrainer on the dyeing of wool fabrics in supercritical carbon dioxide. Compared with previous supercritical dyeing methods, addition of water makes the dyeing process more effective under low temperature and low pressure. During dyeing process, dyestuff can be uniformly distributed on fabrics’s surface due to water interaction, as a result coloration is enhanced while color difference is decreased.

  4. Simulations of dissociation constants in low pressure supercritical water

    Science.gov (United States)

    Halstead, S. J.; An, P.; Zhang, S.

    2014-09-01

    This article reports molecular dynamics simulations of the dissociation of hydrochloric acid and sodium hydroxide in water from ambient to supercritical temperatures at a fixed pressure of 250 atm. Corrosion of reaction vessels is known to be a serious problem of supercritical water, and acid/base dissociation can be a significant contributing factor to this. The SPC/e model was used in conjunction with solute models determined from density functional calculations and OPLSAA Lennard-Jones parameters. Radial distribution functions were calculated, and these show a significant increase in solute-solvent ordering upon forming the product ions at all temperatures. For both dissociations, rapidly decreasing entropy of reaction was found to be the controlling thermodynamic factor, and this is thought to arise due to the ions produced from dissociation maintaining a relatively high density and ordered solvation shell compared to the reactants. The change in entropy of reaction reaches a minimum at the critical temperature. The values of pKa and pKb were calculated and both increased with temperature, in qualitative agreement with other work, until a maximum value at 748 K, after which there was a slight decrease.

  5. Recovery of cobalt from spent lithium-ion batteries using supercritical carbon dioxide extraction.

    Science.gov (United States)

    Bertuol, Daniel A; Machado, Caroline M; Silva, Mariana L; Calgaro, Camila O; Dotto, Guilherme L; Tanabe, Eduardo H

    2016-05-01

    Continuing technological development decreases the useful lifetime of electronic equipment, resulting in the generation of waste and the need for new and more efficient recycling processes. The objective of this work is to study the effectiveness of supercritical fluids for the leaching of cobalt contained in lithium-ion batteries (LIBs). For comparative purposes, leaching tests are performed with supercritical CO2 and co-solvents, as well as under conventional conditions. In both cases, sulfuric acid and H2O2 are used as reagents. The solution obtained from the supercritical leaching is processed using electrowinning in order to recover the cobalt. The results show that at atmospheric pressure, cobalt leaching is favored by increasing the amount of H2O2 (from 0 to 8% v/v). The use of supercritical conditions enable extraction of more than 95wt% of the cobalt, with reduction of the reaction time from 60min (the time employed in leaching at atmospheric pressure) to 5min, and a reduction in the concentration of H2O2 required from 8 to 4% (v/v). Electrowinning using a leach solution achieve a current efficiency of 96% and a deposit with cobalt concentration of 99.5wt%.

  6. Supercritical fluid molecular spray film deposition and powder formation

    Science.gov (United States)

    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.

  7. Supercritical Fluid Facilitated Growth of Copper and Aluminum Oxide Nanoparticles

    Science.gov (United States)

    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.

  8. Supercritical Extraction of Lycopene from Tomato Industrial Wastes with Ethane

    OpenAIRE

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

    2012-01-01

    Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO2...

  9. Supercritical Extraction of Lycopene from Tomato Industrial Waste with Ethane

    OpenAIRE

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

    2012-01-01

    Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO2 and a near critical mixture of ethane and p...

  10. Exergoeconomic Evaluation of a Modern Ultra-Supercritical Power Plant

    Directory of Open Access Journals (Sweden)

    Lingnan Wu

    2012-09-01

    Full Text Available In this paper, the exergoeconomic analysis was conducted to an existing ultra-supercritical coal-fired power plant in China to understand the cost-formation process, to evaluate the economic performance of each component and to find possible solutions for more cost-effective designs. The total revenue requirement (TRR and the specific exergy costing (SPECO methods were applied for economic analysis and exergy costing, respectively. Quantitative balances of exergy and exergetic costs as well as necessary auxiliary equations for both individual component and the overall system were established. The results show that the exergoeconomic factors of the furnace and heat exchangers at low temperature levels, including air preheater and low-pressure feedwater preheaters, are rather small; while those of other components are relatively large. Moving more heat absorption into furnace to use the effective radiation heat transfer, increasing the air preheating temperature and adding more low pressure feedwater preheaters can be promising solutions for future design.

  11. Drying of supercritical carbon dioxide with membrane processes

    NARCIS (Netherlands)

    Lohaus, Theresa; Scholz, Marco; Koziara, Beata T.; Benes, N.E.; Wessling, Matthias

    2015-01-01

    In supercritical extraction processes regenerating the supercritical fluid represents the main cost constraint. Membrane technology has potential for cost efficient regeneration of water-loaded supercritical carbon dioxide. In this study we have designed membrane-based processes to dehydrate water-l

  12. Advanced Supercritical Carbon Dioxide Brayton Cycle Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Mark [Univ. of Wisconsin, Madison, WI (United States); Sienicki, James [Argonne National Lab. (ANL), Argonne, IL (United States); Moisseytsev, Anton [Argonne National Lab. (ANL), Argonne, IL (United States); Nellis, Gregory [Univ. of Wisconsin, Madison, WI (United States); Klein, Sanford [Univ. of Wisconsin, Madison, WI (United States)

    2015-10-21

    Fluids operating in the supercritical state have promising characteristics for future high efficiency power cycles. In order to develop power cycles using supercritical fluids, it is necessary to understand the flow characteristics of fluids under both supercritical and two-phase conditions. In this study, a Computational Fluid Dynamic (CFD) methodology was developed for supercritical fluids flowing through complex geometries. A real fluid property module was implemented to provide properties for different supercritical fluids. However, in each simulation case, there is only one species of fluid. As a result, the fluid property module provides properties for either supercritical CO2 (S-CO2) or supercritical water (SCW). The Homogeneous Equilibrium Model (HEM) was employed to model the two-phase flow. HEM assumes two phases have same velocity, pressure, and temperature, making it only applicable for the dilute dispersed two-phase flow situation. Three example geometries, including orifices, labyrinth seals, and valves, were used to validate this methodology with experimental data. For the first geometry, S-CO2 and SCW flowing through orifices were simulated and compared with experimental data. The maximum difference between the mass flow rate predictions and experimental measurements is less than 5%. This is a significant improvement as previous works can only guarantee 10% error. In this research, several efforts were made to help this improvement. First, an accurate real fluid module was used to provide properties. Second, the upstream condition was determined by pressure and density, which determines supercritical states more precise than using pressure and temperature. For the second geometry, the flow through labyrinth seals was studied. After a successful validation, parametric studies were performed to study geometric effects on the leakage rate. Based on these parametric studies, an optimum design strategy for the see

  13. Pharmaceutical applications of supercritical carbon dioxide.

    Science.gov (United States)

    Kaiser, C S; Römpp, H; Schmidt, P C

    2001-12-01

    The appearance of a supercritical state was already observed at the beginning of the 19th century. Nevertheless, the industrial extraction of plant and other natural materials started about twenty years ago with the decaffeination of coffee. Today carbon dioxide is the most common gas for supercritical fluid extraction in food and pharmaceutical industry. Since pure supercritical carbon dioxide is a lipophilic solvent, mixtures with organic solvents, especially alcohols, are used to increase the polarity of the extraction fluid; more polar compounds can be extracted in this way. The main fields of interest are the extraction of vegetable oils from plant material in analytical and preparative scale, the preparation of essential oils for food and cosmetic industry and the isolation of substances of pharmaceutical relevance. Progress in research was made by the precise measurement of phase equilibria data by means of different methods. Apart from extraction, supercritical fluid chromatography was introduced in the field of analytics, as well as micro- and nanoparticle formation using supercritical fluids as solvent or antisolvent. This review presents pharmaceutical relevant literature of the last twenty years with special emphasis on extraction of natural materials.

  14. Characteristics of compressible flow of supercritical kerosene

    Institute of Scientific and Technical Information of China (English)

    Feng-Quan Zhong; Xue-Jun Fan; Jing Wang; Gong Yu; Jian-Guo Li

    2012-01-01

    In this paper,compressible flow of aviation kerosene at supercritical conditions has been studied both numerically and experimentally.The thermophysical properties of supercritical kerosene are calculated using a 10-species surrogate based on the principle of extended corresponding states (ECS).Isentropic acceleration of supercritical kerosene to subsonic and supersonic speeds has been analyzed numerically.It has been found that the isentropic relationships of supercritical kerosene are significantly different from those of ideal gases.A two-stage fuel heating and delivery system is used to heat the kerosene up to a temperature of 820 K and pressure of 5.5 MPa with a maximum mass flow rate of 100 g/s.The characteristics of supercritical kerosene flows in a converging-diverging nozzle (Laval nozzle) have been studied experimentally.The results show that stable supersonic flows of kerosene could be established in the temperature range of 730 K-820 K and the measurements in the wall pressure agree with the numerical calculation.

  15. Microbial Inactivation by Ultrasound Assisted Supercritical Fluids

    Science.gov (United States)

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

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

  16. Analysis of supercritical vapor explosions using thermal detonation wave theory

    Energy Technology Data Exchange (ETDEWEB)

    Shamoun, B.I.; Corradini, M.L. [Univ. of Wisconsin, Madison, WI (United States)

    1995-09-01

    The interaction of certain materials such as Al{sub 2}O{sub 3} with water results in vapor explosions with very high (supercritical) pressures and propagation velocities. A quasi-steady state analysis of supercritical detonation in one-dimensional multiphase flow was applied to analyze experimental data of the KROTOS (26-30) set of experiments conducted at the Joint Research Center at Ispra, Italy. In this work we have applied a new method of solution which allows for partial fragmentation of the fuel in the shock adiabatic thermodynamic model. This method uses known experiment values of the shock pressure and propagation velocity to estimate the initial mixing conditions of the experiment. The fuel and coolant were both considered compressible in this analysis. In KROTOS 26, 28, 29, and 30 the measured values of the shock pressure by the experiment were found to be higher than 25, 50, 100, and 100 Mpa respectively. Using the above data for the wave velocity and our best estimate for the values of the pressure, the predicted minimum values of the fragmented mass of the fuel were found to be 0.026. 0.04, 0.057, and 0.068 kg respectively. The predicted values of the work output corresponding to the above fragmented masses of the fuel were found to be 40, 84, 126, and 150 kJ respectively, with predicted initial void fractions of 112%, 12.5%, 8%, and 6% respectively.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-08-29

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

  18. Driving Interconnected Networks to Supercriticality

    Directory of Open Access Journals (Sweden)

    Filippo Radicchi

    2014-04-01

    Full Text Available Networks in the real world do not exist as isolated entities, but they are often part of more complicated structures composed of many interconnected network layers. Recent studies have shown that such mutual dependence makes real networked systems potentially exposed to atypical structural and dynamical behaviors, and thus there is an urgent necessity to better understand the mechanisms at the basis of these anomalies. Previous research has mainly focused on the emergence of atypical properties in relation to the moments of the intra- and interlayer degree distributions. In this paper, we show that an additional ingredient plays a fundamental role for the possible scenario that an interconnected network can face: the correlation between intra- and interlayer degrees. For sufficiently high amounts of correlation, an interconnected network can be tuned, by varying the moments of the intra- and interlayer degree distributions, in distinct topological and dynamical regimes. When instead the correlation between intra- and interlayer degrees is lower than a critical value, the system enters in a supercritical regime where dynamical and topological phases are no longer distinguishable.

  19. Supercritical fluid extraction of hops

    Directory of Open Access Journals (Sweden)

    ZORAN ZEKOVIC

    2007-01-01

    Full Text Available Five cultivars of hop were extracted by the method of supercritical fluid extraction using carbon dioxide (SFE–CO2 as extractant. The extraction (50 g of hop sample using a CO2 flow rate of 97.725 L/h was done in the two steps: 1. extraction at 150 bar and 40°C for 2.5 h (sample of series A was obtained and, after that, the same sample of hop was extracted in the second step: 2. extraction at 300 bar and 40 °C for 2.5 h (sample of series B was obtained. The Magnum cultivar was chosen for the investigation of the extraction kinetics. For the qualitative and quantitative analysis of the obtained hop extracts, the GC-MS method was used. Two of four themost common compounds of hop aroma (a-humulene and b-caryophyllene were detected in samples of series A. In addition, isomerized a-acids and a high content of b-acids were detected. The a-acids content in the samples of series B was the highest in the extract of the Magnum cultivar (it is a bitter variety of hop. The low contents of a-acids in all the other hop samples resulted in extracts with low a-acids content, i.e., that contents were under the prescribed a-acids content.

  20. Supercritical carbon dioxide hop extraction

    Directory of Open Access Journals (Sweden)

    Pfaf-Šovljanski Ivana I.

    2005-01-01

    Full Text Available The hop of Magnum cultivar was extracted using supercritical carbon dioxide (SFE-as extractant. Extraction was carried out in the two steps: the first one being carried out at 150 bar and 40°C for 2.5 h (Extract A, and the second was the extraction of the same hop sample at 300 bar and 40°C for 2.5 h (Extract B. Extraction kinetics of the system hop-SFE-CO2 was investigated. Two of four most common compounds of hop aroma (α-humulene and β-caryophyllene were detected in Extract A. Isomerised α-acids and β-acids were detected too. a-Acid content in Extract B was high (that means it is a bitter variety of hop. Mathematical modeling using empirical model characteristic time model and simple single sphere model has been performed on Magnum cultivar extraction experimental results. Characteristic time model equations, best fitted experimental results. Empirical model equation, fitted results well, while simple single sphere model equation poorly approximated the results.

  1. Supercritical waste oxidation pump investigation

    Energy Technology Data Exchange (ETDEWEB)

    Thurston, G.; Garcia, K.

    1993-02-01

    This report investigates the pumping techniques and pumping equipment that would be appropriate for a 5,000 gallon per day supercritical water oxidation waste disposal facility. The pumps must boost water, waste, and additives from atmospheric pressure to approximately 27.6 MPa (4,000 psia). The required flow ranges from 10 gpm to less than 0.1 gpm. For the higher flows, many commercial piston pumps are available. These pumps have packing and check-valves that will require periodic maintenance; probably at 2 to 6 month intervals. Several commercial diaphragm pumps were also discovered that could pump the higher flow rates. Diaphragm pumps have the advantage of not requiring dynamic seals. For the lower flows associated with the waste and additive materials, commercial diaphragm pumps. are available. Difficult to pump materials that are sticky, radioactive, or contain solids, could be injected with an accumulator using an inert gas as the driving mechanism. The information presented in this report serves as a spring board for trade studies and the development of equipment specifications.

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

    Science.gov (United States)

    Gallaway, Tara

    2011-12-01

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

  3. Spectroscopy, modeling and computation of metal chelate solubility in supercritical CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    J. F. Brennecke; M. A. Stadtherr

    1999-12-10

    The overall objectives of this project were to gain a fundamental understanding of the solubility and phase behavior of metal chelates in supercritical CO{sub 2}. Extraction with CO{sub 2} is an excellent way to remove organic compounds from soils, sludges and aqueous solutions, and recent research has demonstrated that, together with chelating agents, it is a viable way to remove metals, as well. In this project the authors sought to gain fundamental knowledge that is vital to computing phase behavior, and modeling and designing processes using CO{sub 2} to separate organics and metal compounds from DOE mixed wastes. The overall program was a comprehensive one to measure, model and compute the solubility of metal chelate complexes in supercritical CO{sub 2} and CO{sub 2}/cosolvent mixtures. Through a combination of phase behavior measurements, spectroscopy and the development of a new computational technique, the authors have achieved a completely reliable way to model metal chelate solubility in supercritical CO{sub 2} and CO{sub 2}/co-contaminant mixtures. Thus, they can now design and optimize processes to extract metals from solid matrices using supercritical CO{sub 2}, as an alternative to hazardous organic solvents that create their own environmental problems, even while helping in metals decontamination.

  4. Sensitivity analysis of CFD code FLUENT-12 for supercritical water in vertical bare tubes

    Energy Technology Data Exchange (ETDEWEB)

    Farah, A.; Haines, P.; Harvel, G.; Pioro, I., E-mail: amjad.farah@yahoo.com, E-mail: patrickjhaines@gmail.com, E-mail: glenn.harvel@uoit.ca, E-mail: igor.pioro@uoit.ca [Univ. of Ontario Inst. of Technology, Faculty of Energy Systems and Nuclear Science,Oshawa, Ontario (Canada)

    2012-07-01

    The ability to use FLUENT 12 or other CFD software to accurately model supercritical water flow through various geometries in diabatic conditions is integral to research involving coal-fired power plants as well as Supercritical Water-cooled Reactors (SCWR). The cost and risk associated with constructing supercritical water test loops are far too great to use in a university setting. Previous work has shown that FLUENT 12, specifically realizable k-ε model, can reasonably predict the bulk and wall temperature distributions of externally heated vertical bare tubes for cases with relatively low heat and mass fluxes. However, sizeable errors were observed for other cases, often those which involved large heat fluxes that produce deteriorated heat transfer (DHT) regimes. The goal of this research is to gain a more complete understanding of how FLUENT 12 models supercritical water cases and where errors can be expected to occur. One control case is selected where expected changes in bulk and wall temperatures occur and they match empirical correlations' predictions, and the operating parameters are varied individually to gauge their effect on FLUENT's solution. The model used is the realizable k-ε, and the parameters altered are inlet pressure, mass flux, heat flux, and inlet temperature. (author)

  5. Characterization of Ketoprofen/Methyl-β-Cyclodextrin Complexes Prepared Using Supercritical Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Mauro Banchero

    2013-01-01

    Full Text Available Complexes of methyl-β-cyclodextrin and ketoprofen, a crystalline anti-inflammatory drug with poor water solubility, have been prepared for the first time in the presence of supercritical CO2 at 40°C and 20 MPa. The supercritical treatment allows these pharmaceutical formulations to be prepared without the use of any auxiliary agents or organic solvents. The treated samples were characterized through differential scanning calorimetry, X-ray diffractometry, and the Fourier transform infrared spectroscopy to exclude the presence of crystalline drug and check the formation of the complexes. The increase of the drug dissolution rate was investigated performing in vitro release tests in aqueous solutions. The results showed that the supercritical treatment can be an efficient method to obtain inclusion complexes with enhanced release kinetics. The operating methods of the release tests, that is, the “tablet method” or the “dispersed amount method,” affected both the dissolution rate and its dependence on the drug amount in the samples. On the contrary, the variation of the pH of the dissolution medium did not show any effect on the release rate of the supercritical complexes.

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

    Science.gov (United States)

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

    2015-11-01

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

  7. Spectroscopy, modeling and computation of metal chelate solubility in supercritical CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    J. F. Brennecke; M. A. Stadtherr

    1999-12-10

    The overall objectives of this project were to gain a fundamental understanding of the solubility and phase behavior of metal chelates in supercritical CO{sub 2}. Extraction with CO{sub 2} is an excellent way to remove organic compounds from soils, sludges and aqueous solutions, and recent research has demonstrated that, together with chelating agents, it is a viable way to remove metals, as well. In this project the authors sought to gain fundamental knowledge that is vital to computing phase behavior, and modeling and designing processes using CO{sub 2} to separate organics and metal compounds from DOE mixed wastes. The overall program was a comprehensive one to measure, model and compute the solubility of metal chelate complexes in supercritical CO{sub 2} and CO{sub 2}/cosolvent mixtures. Through a combination of phase behavior measurements, spectroscopy and the development of a new computational technique, the authors have achieved a completely reliable way to model metal chelate solubility in supercritical CO{sub 2} and CO{sub 2}/co-contaminant mixtures. Thus, they can now design and optimize processes to extract metals from solid matrices using supercritical CO{sub 2}, as an alternative to hazardous organic solvents that create their own environmental problems, even while helping in metals decontamination.

  8. Group separation of rare earth substances utilizing supercritical fluid extraction technique

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Ki Pung; Joung, Seung Nam; Kim, Sun Hee; Jeon, Seong Ho; Choi, Eun Hyun [Sogang University, Seoul (Korea)

    1998-04-01

    The solubilities of TBP and DEHPA in supercritical CO{sub 2} were measured at various equilibrium temperatures(i.e., 313.15, 323.15, 333.15K) and pressures(i.e., 10, 15, 20, 25MPa). It is observed that both the solubilities of TBP and DEHPA are increasing wit increasing temperatures and pressures(ant, thus the density). In general TBP showed higher solubility than DEHPA in CO{sub 2}. were carried out for recovering rare earth elements from the aqueous acidic feed waste solutions. We found that the level of Nd extraction with such supercritically mixed solvent tends to decreasing with increasing HNO{sub 3} and tends to uniform with increasing temperature and pressures. Also, extraction of rare earth TPPO, and TOPO in supercritical CO{sub 2}. For example, the SFE of Nd by these supercritical CO{sub 2}-containing organic solvents showed that the case of TBPO was higher than that of any other organic solvent. (author). 46 refs., 36 figs., 12 tabs.

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

    Science.gov (United States)

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

    2016-09-13

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

  10. Hydrodynamics and Mass Transfer Performance in Supercritical Fluid Extraction Columns

    Institute of Scientific and Technical Information of China (English)

    石冰洁; 张泽廷; 等

    2002-01-01

    New models for describing hydrodynamics and mass transfer performance in supercritical fluid extraction columns were proposed.Those models were proved by experimental data,which were obtained in supercritical fluid extraction packed column,spray column and sieve tray column respectively.The inner diameter of those columns areΦ25mm,These experimental systems include supercritical carbon dioxideisopropanol-water and supercritical carbon dioxide-ethanol-water,in which supercritical carbon dioxide was dispersed phase,and another was continuous phase.The extraction processes were operated with continuous countercurrent flow.The predicted values are agreed well with experimental data.

  11. DNS of High Pressure Supercritical Combustion

    Science.gov (United States)

    Chong, Shao Teng; Raman, Venkatramanan

    2016-11-01

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

  12. Supercritical fluid mixing in Diesel Engine Applications

    Science.gov (United States)

    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).

  13. Heat Transfer Phenomena of Supercritical Fluids

    Energy Technology Data Exchange (ETDEWEB)

    Krau, Carmen Isabella; Kuhn, Dietmar; Schulenberg, Thomas [Forschungszentrum Karlsruhe, Institute for Nuclear and Energy Technologies, 76021 Karlsruhe (Germany)

    2008-07-01

    In concepts for supercritical water cooled reactors, the reactor core is cooled and moderated by water at supercritical pressures. The significant temperature dependence of the fluid properties of water requires an exact knowledge of the heat transfer mechanism to avoid fuel pin damages. Near the pseudo-critical point a deterioration of heat transfer might happen. Processes, that take place in this case, are not fully understood and are due to be examined systematically. In this paper a general overview on the properties of supercritical water is given, experimental observations of different authors will be reviewed in order to identify heat transfer phenomena and onset of occurrence. The conceptional design of a test rig to investigate heat transfer in the boundary layer will be discussed. Both, water and carbon dioxide, may serve as operating fluids. The loop, including instrumentation and safety devices, is shown and suitable measuring methods are described. (authors)

  14. Radially Symmetric Solutions of

    Directory of Open Access Journals (Sweden)

    William C. Troy

    2012-01-01

    Full Text Available We investigate solutions of and focus on the regime and . Our advance is to develop a technique to efficiently classify the behavior of solutions on , their maximal positive interval of existence. Our approach is to transform the nonautonomous equation into an autonomous ODE. This reduces the problem to analyzing the phase plane of the autonomous equation. We prove the existence of new families of solutions of the equation and describe their asymptotic behavior. In the subcritical case there is a well-known closed-form singular solution, , such that as and as . Our advance is to prove the existence of a family of solutions of the subcritical case which satisfies for infinitely many values . At the critical value there is a continuum of positive singular solutions, and a continuum of sign changing singular solutions. In the supercritical regime we prove the existence of a family of “super singular” sign changing singular solutions.

  15. Micronization processes by supercritical fluid technologies: a short review on process design (2008-2012 - doi: 10.4025/actascitechnol.v35i4.18819

    Directory of Open Access Journals (Sweden)

    Jose Vladimir de Oliveira

    2013-10-01

    Full Text Available Several micronization processes based on supercritical fluids have been developed. These processes can be classified according to the role of the supercritical fluid in the process: solvent, solute or co-solvent, and anti-solvent. Application of supercritical fluids as alternative to traditional micronization methods and the growing demand of the industrial sector for new technologies motivated this review. In this context, the objective of this work was to present the operating principles of the micronization process by means of supercritical fluids and the effects of the main process variables on particles characteristics. The review continues with an update of current experimental data presented in the literature in the period from 2008 to 2012.   

  16. Adsorption from Experimental Isotherms of Supercritical Gases

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A mathematical method was proposed for the determination of absolute adsorption from experimental isotherms. The method is based on the numerical equality of the absolute and the excess adsorption when either the gas phase density or the amount adsorbed is not quite considerable. The initial part of the experimental isotherms, which represents the absolute adsorption, became linear with some mathematical manipulations. The linear isotherms were reliably formulated. As consequence, either the volume or the density of the supercritical adsorbate could be determined by a non-empirical way. This method was illustrated by the adsorption data of supercritical hydrogen and methane on a superactivated carbon in large ranges of temperature and pressure.

  17. Supercritical fluid extraction: Present status and prospects

    Directory of Open Access Journals (Sweden)

    King, Jerry W.

    2002-03-01

    Full Text Available Supercritical extraction (SFE, using primarily environmentally-benign carbon dioxide (CO2 as the extracting agent, is reviewed with respect to its present status and future use. SFE was developed for analytical application in the mid 1980’s in response to the desire to reduce the use of organic solvents in the laboratory environment and is becoming a standard method for the preparation and analysis of lipid-containing sample matrices. Currently, analytical SFE is predominately practiced in the off-line mode, using both sequential and parallel extraction modes. Depending on the instrumental configuration, the preparation of up to 24 samples can be accomplished on one instrument on a daily basis. Several other benefits can be achieved using SFE, such as the processing of thermally-sensitive analytes and rapid analyte extraction kinetics relative to extraction with liquid solvents. Examples are provided not only of the analytical SFE of oils and fats, but of volatile solutes from an array of sample types. Finally, the relevance of analytical SFE to processing with supercritical fluids (SFs is documented using examples from our own research involving a combinatorial approach to optimising processing conditions.Este artículo revisa el presente y el uso futuro de la extracción con fluidos supercríticos (SFE, principalmente dióxido de carbono (CO2 benigno para el ambiente. La extracción con fluidos supercríticos se desarrolló como aplicación analítica a mediados de los años 80 como respuesta al deseo de reducir el uso de disolventes orgánicos en el ambiente del laboratorio, y se está convirtiendo en un método estándar con respecto a la preparación y análisis de muestras conteniendo lípidos. Actualmente, la analítica de SFE es predominantemente aplicada en modo “off-line”, usando modos de extracción secuenciales y paralelos. Dependiendo de la configuración de la instrumentación, se pueden llegar a preparar diariamente

  18. Efficiency of water removal from water/ethanol mixtures using supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    M. A. Rodrigues

    2006-06-01

    Full Text Available Techniques involving supercritical carbon dioxide have been successfully used for the formation of drug particles with controlled size distributions. However, these processes show some limitations, particularly in processing aqueous solutions. A diagram walking algorithm based on available experimental data was developed to evaluate the effect of ethanol on the efficiency of water removal processes under different process conditions. Ethanol feeding was the key parameter resulting in a tenfold increase in the efficiency of water extraction.

  19. Forsterite Carbonation in Wet Supercritical CO2 and Sodium Citrate

    Science.gov (United States)

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

    2013-12-01

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

  20. Supercritical synthesis and in situ deposition of PbS nanocrystals with oleic acid passivation for quantum dot solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Tavakoli, M.M. [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Simchi, A., E-mail: simchi@sharif.edu [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Institute for Nanoscience and Nanotechnology, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Aashuri, H. [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of)

    2015-04-15

    Colloidal quantum dot solar cells have recently attracted significant attention due to their low-processing cost and surging photovoltaic performance. In this paper, a novel, reproducible, and simple solution-based process based on supercritical fluid toluene is presented for in situ growth and deposition PbS nanocrystals with oleic-acid passivation. A lead precursor containing sulfur was mixed with oleic acid in toluene and processed in a supercritical fluid condition at different temperatures of 140, 270 and 330 °C for 20 min. The quantum dots were deposited on a fluorine-doped tin oxide glass substrate inside the supercritical reactor. Transmission electron microscopy, X-ray diffraction, absorption and dynamic light scattering showed that the nanocrystals processed at the supercritical condition (330 °C) are fully crystalline with a narrow size distribution of ∼3 nm with an absorption wavelength of 915 nm (bandgap of 1.3 eV). Fourier transform infrared spectroscopy indicated that the PbS quantum dots are passivated by oleic acid molecules during the growth. Photovoltaic characteristics of Schottky junction solar cells showed an improvement over devices prepared by spin-coating. - Highlights: • Supercritical fluid processing and in situ deposition of PbS QDs are presented. • The prepared nanocrystals are mono-dispersed with an optical bandgap of 1.3 eV. • Photovoltaic performance of the in situ deposited nanocrystals is reported. • An improved PV performance compared to spin coated Schottky solar cells is shown.

  1. Supercritical water oxidation of polyvinyl alcohol and desizing wastewater: influence of NaOH on the organic decomposition.

    Science.gov (United States)

    Zhang, Jie; Wang, Shuzhong; Guo, Yang; Xu, Donghai; Gong, Yanmeng; Tang, Xingying

    2013-08-01

    Polyvinyl alcohol is a refractory compound widely used in industry. Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition. However, it is difficult to implement complete degradation of organics even though polyvinyl alcohol can readily crack under supercritical water treatment. Sodium hydroxide had a significant catalytic effect during the supercritical water oxidation of polyvinyl alcohol. It appears that the OH- ion participated in the C-C bond cleavage of polyvinyl alcohol molecules, the CO2-capture reaction and the neutralization of intermediate organic acids, promoting the overall reactions moving in the forward direction. Acetaldehyde was a typical intermediate product during reaction. For supercritical water oxidation of desizing wastewater, a high destruction rate (98.25%) based on total organic carbon was achieved. In addition, cases where initial wastewater was alkaline were favorable for supercritical water oxidation treatment, but salt precipitation and blockage issues arising during the process need to be taken into account seriously.

  2. Supercritical water oxidation of polyvinyl alcohol and desizing wastewater:Influence of NaOH on the organic decomposition

    Institute of Scientific and Technical Information of China (English)

    Jie Zhang; Shuzhong Wang; Yang Guo; Donghai Xu; Yanmeng Gong; Xingying Tang

    2013-01-01

    Polyvinyl alcohol is a refractory compound widely used in industry.Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition.However,it is difficult to implement complete degradation of organics even though polyvinyl alcohol can readily crack under supercritical water treatment.Sodium hydroxide had a significant catalytic effect during the supercritical water oxidation of polyvinyl alcohol.It appears that the OH-ion participated in the C-C bond cleavage of polyvinyl alcohol molecules,the CO2-capture reaction and the neutralization of intermediate organic acids,promoting the overall reactions moving in the forward direction.Acetaldehyde was a typical intermediate product during reaction.For supercritical water oxidation of desizing wastewater,a high destruction rate (98.25%) based on total organic carbon was achieved.In addition,cases where initial wastewater was alkaline were favorable for supercritical water oxidation treatment,but salt precipitation and blockage issues arising during the process need to be taken into account seriously.

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

    Directory of Open Access Journals (Sweden)

    Yunzhao Fan

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

  4. The separation of particulates from supercritical water oxidation processes

    Energy Technology Data Exchange (ETDEWEB)

    Dell' Orco, P.C.; Li, L.; Gloyna, E.F.

    1991-01-01

    Small hydrocyclones with batch underflow receivers were assessed for their ability to separate micron-sized particulates from near-critical water solutions. Such particulates are expected from the effluent of a supercritical water oxidation reactor. The separation of micron-sized quartz silica, zirconia, and titania particles was investigated. A model was developed for the prediction of gross removal efficiencies as a function of a Stokes' number. Particle size distributions provided grade efficiencies for all experiments, and from these data, cut sizes were determined. Gross efficiencies up to 99% were observed for zirconia; cut sizes (d{sub 90} and d{sub 95}) near one micron were measured. 19 refs., 5 figs.

  5. Extraction of Genistein from Sophora flavescens with Supercritical Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Han, Chang-Nam; Kang, Choon-Hyoung [Chonnam National University, Gwangju (Korea, Republic of)

    2015-08-15

    This study was directed to finding an optimum extraction condition of genistein from the S. flavescens with supercritical carbon dioxide as a solvent. In this effort, effects of the extraction conditions including pressure, temperature and a co-solvent on the extraction efficiency were investigated. The aqueous ethanol and methanol solutions were used as co-solvents while the tested operating pressure and temperature ranges were from 200 bar to 300 bar and from 308.15 K to 323.15 K, respectively. The concentration of genistein was determined by means of HPLC equipped with a UV detector. From the results, it was observed that an increase in pressure led to the higher extraction efficiency. Further, methanol showed better performance as a co-solvent than ethanol. The DPPH radical scavenging activities were measured to compare antioxidant activities of S. flavescens extracts.

  6. The influence of outflow in supercritical accretion flows

    CERN Document Server

    Zeraatgari, Fatemeh Zahra; Mosallanezhad, Amin

    2016-01-01

    We solve the radiation-hydrodynamic (RHD) equations of supercritical accretion flows in the presence of radiation force and outflow by using self similar solutions. Compare with the pioneer works, in this paper we consider power-law function for mass inflow rate as $ \\dot{M} \\propto r^{s} $. We found that $ s = 1 $ when the radiative cooling term is included in the energy equation. Correspondingly, the effective temperature profile with respect to the radius was obtained as $ T_{\\text{eff}} \\varpropto r^{-1/2} $. In addition, we investigated the influence of the outflow on the dynamics of the accretion flow. We also calculated the continuum spectrum emitted from the disk surface as well as the bolometric luminosity of the accretion flow. Furthermore, our results show that the advection parameter, $ f $, strongly depends on mass inflow rate.

  7. Impact of supercritical adsorption mechanism on research of hydrogen carrier

    Institute of Scientific and Technical Information of China (English)

    SUN Yan; ZHOU Li; SU Wei; ZHOU YaPing

    2007-01-01

    Hydrogen storage receives the worldwide attention due to its importance in sustainable energy and the solution of greenhouse effect. Adsorption provides an efficient way to compress gases and, therefore,has been applied to the development of hydrogen storage technology. However, hydrogen is a supercritical gas at the temperature of engineering interest and follows a different adsorption mechanism compared to the sub-critical gases. The present work shows why only monolayer coverage mechanism functions at above-critical temperatures and what consequences will result in the application study.Although there are pros and cons to this point of view, understanding the adsorption mechanism is, indeed, essential for the research of hydrogen storage method since it claims that any storage material based on adsorption will not satisfy the practical need of on board storage no matter how novel the material is.

  8. Supercritical carbondioxide extraction of cypermethrin in different ...

    African Journals Online (AJOL)

    STORAGESEVER

    2010-04-12

    Apr 12, 2010 ... century coincided with the development of industrial methods of cultivation ... though supercritical CO2 is a good solvent only for the extraction of non-polar to ..... 101-111. Lange's Handbook of Chemistry (1985) . ed. Dean JA ...

  9. Destruction of Energetic Materials in Supercritical Water

    Science.gov (United States)

    2002-06-25

    THERMOCHEMISTRY OF ENERGETIC MATERIALS IN SUPERCRITICAL WATER...fringe spacing is 13.5 µm and the acoustic signal period is 28.3 ns. 138 SECTION VI THERMOCHEMISTRY OF ENERGETIC MATERIALS IN...validation calculation studied the solvation free energies of alkali–chloride ion pairs in liquid water. Such information can teach us about the

  10. Supercritical fluid extraction and processing of foods

    Science.gov (United States)

    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...

  11. Supercritical-Multiple-Solvent Extraction From Coal

    Science.gov (United States)

    Corcoran, W.; Fong, W.; Pichaichanarong, P.; Chan, P.; Lawson, D.

    1983-01-01

    Large and small molecules dissolve different constituents. Experimental apparatus used to test supercritical extraction of hydrogen rich compounds from coal in various organic solvents. In decreasing order of importance, relevant process parameters were found to be temperature, solvent type, pressure, and residence time.

  12. Improved Supercritical-Solvent Extraction of Coal

    Science.gov (United States)

    Compton, L.

    1982-01-01

    Raw coal upgraded by supercritical-solvent extraction system that uses two materials instead of one. System achieved extraction yields of 20 to 49 weight percent. Single-solvent yields are about 25 weight percent. Experimental results show extraction yields may be timedependent. Observed decreases in weight of coal agreed well with increases in ash content of residue.

  13. Diiodination of Alkynes in supercritical Carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    李金恒; 谢叶香; 尹笃林; 江焕峰

    2003-01-01

    A general,green and efficient method for the synthesis of transdiiodoalkenes in CO2(sc) has been developed.Trans-diiodoalkenes were obtained stereospecifically in quantitative yields via diiodination of both electron-rich and electron-deficient alkynes in the presence of KI,Ce(SO4)2 and water in supercritical carbon dioxide [CO2(sc)]at 40℃.

  14. Petrophysical core characterization at supercritical geothermal conditions

    Science.gov (United States)

    Kummerow, Juliane; Raab, Siegfried

    2015-04-01

    There is a growing scientific interest in the exploitation of supercritical geothermal reservoirs to increase the efficiency of geothermal power plants. The utilisation of geothermal energy requires in any case the detailed knowledge of the reservoir. In reservoir engineering, the characterisation of the geothermal system by electrical resistivity tomography (ERT) is a common geophysical exploration and monitoring strategy. For a realistic interpretation of the field measurements it is necessary to know both, the physical properties of the rock and those of the interacting fluid at defined temperature and pressure conditions. While there have been made great effort in determine the physical and chemical properties of water above its critical point (Tcritical = 374.21° C and pcritical = 221.2 bar), the influence of fluid-rock interactions on petrophysical properties in supercritical aqueous systems is nearly unknown. At supercritical conditions the viscosity of the fluid is low, which enhances the mass transfer and diffusion-controlled chemical reactions. This may have considerable effects on the porosity and hydraulic properties of a rock. To investigate high-enthalpy fluid-rock systems, in the framework of the EU-funded project IMAGE we have built a new percolation set-up, which allows for the measurement of electrical resistivity and permeability of rock samples at controlled supercritical conditions of aqueous fluids (pore pressure = 400 bar and a temperature = 400° C). First results will be presented.

  15. Supercritical fluid molecular spray thin films and fine powders

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Durak, Halil, E-mail: halildurak@yyu.edu.tr [Yuzuncu Yıl University, Vocational School of Health Services, 65080, Van (Turkey)

    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.

  18. Supercritical Fluids Processing of Biomass to Chemicals and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Olson, Norman K. [Iowa State Univ., Ames, IA (United States)

    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.”

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

    Science.gov (United States)

    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.

  20. Cluster in Dehydrogenation of Dodecane to Internal Dodecane in Supercritical Phase%超临界相中正十二烷烃脱氢各物种的聚集行为

    Institute of Scientific and Technical Information of China (English)

    魏伟; 常杰; 孙予罕; 钟炳

    2001-01-01

    The pressure dependence of partial molar volumes was calculatedin detail by R-K equation of state for the dehydrogenation of dodecane to internal dodecane.The results showed that clustering between supercritical medium and internal dodecane and hydrogen was much stronger in supercritical phase than in gas phase,and that,clustering between supercritical medium and the reaction products was more remarkable.This provided a quantitative description of the change in cluster size resulted by an increase in solute-solvent attraction force.

  1. Analysis of prompt supercritical process with heat transfer and temperature feedback

    Institute of Scientific and Technical Information of China (English)

    ZHU BO; ZHU Qian; CHEN Zhiyun

    2009-01-01

    The prompt supercritical process of a nuclear reactor with temperature feedback and initial power as well as heat transfer with a big step reactivity (ρ0>β) is analyzed in this paper.Considering the effect of heat transfer on temperature of the reactor,a new model is set up.For any initial power,the variations of output power and reactivity with time are obtained by numerical method.The effects of the big inserted step reactivity and initial power on the prompt supercritical process are analyzed and discussed.It was found that the effect of heat transfer on the output power and reactivity can be neglected under any initial power,and the output power obtained by the adiabatic model is basically in accordance with that by the model of this paper,and the analytical solution can be adopted.The results provide a theoretical base for safety analysis and operation management of a power reactor.

  2. Solubility of Paclitaxel in Mixtures of Dichloromethane and Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    LUO Nin; LU Yingmei; JIANG Yanbin

    2011-01-01

    Phase behavior of paclitaxel in solvent mixtures of dichloromethane and supercritical carbon dioxide was investigated using a supercritical phase monitor.Cloud point pressures were determined as a function of temperature,pressure and paclitaxel content from 313.1 to 343.1K and pressures up to 33.52 MPa.The ternary mixtures exhibit a typical lower critical solution temperature behavior.When paclitaxel content increases,the single-phase region shrinks in size.Three cubic equations of state(Redlich-Kworng,Soave-Redlich-Kwong and Peng-Robinson equation of state) coupled with the van der Waals one-fluid mixing rules were selected to correlate the experimental data.The results indicate that SRK EOS coupled with two binary interaction parameters kij and lij can predict paclitaxel solubility for the best fit of experimental data.

  3. Polymer-filled microcontainers for oral delivery loaded using supercritical impregnation

    DEFF Research Database (Denmark)

    Marizza, Paolo; Keller, Stephan Sylvest; Müllertz, Anette

    2014-01-01

    In the last years a large variety of drug delivery systems have been developed to improve bioavailability of therapeutics in oral administration. An increasing interest has arisen in reservoir-based microdevices designed for active ingredients like water insoluble compounds and fragile biomolecules...... procedures. This work proposes an effective loading technique for a poorly soluble model drug in microcontainers, by combining inkjet printing and supercritical fluid impregnation. Well defined quantities of poly(vinyl pyrrolidone) (PVP) solutions are dispensed into microcontainers by inkjet printing...... with a quasi-no-waste performance. Then ketoprofen is impregnated in the polymer matrix by using supercritical carbon dioxide (scCO2) as loading medium. The amount of polymer is controlled by the volume and the number of droplets of dispensed polymer and drug loading is tuned by varying the impregnation...

  4. Super-Critical Growth of Massive Black Holes from Stellar-Mass Seeds

    CERN Document Server

    Madau, Piero; Dotti, Massimo

    2014-01-01

    We consider super-critical accretion with angular momentum onto stellar-mass black holes as a possible mechanism for growing billion-solar-mass holes from light seeds at early times. We use the radiatively-inefficient "slim disk" solution -- advective, optically thick flows that generalize the standard geometrically thin disk model -- to show how mildly super-Eddington intermittent accretion may significantly ease the problem of assembling the first massive black holes when the Universe was less than 0.8 Gyr old. Because of the low radiative efficiencies of slim disks around non-rotating as well as rapidly rotating holes, the mass e-folding timescale in this regime is nearly independent of the spin parameter. The conditions that may lead to super-critical growth in the early Universe are briefly discussed.

  5. Microwave Effect for Glycosylation Promoted by Solid Super Acid in Supercritical Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Takahiko Maeda

    2009-12-01

    Full Text Available The effects of microwave irradiation (2.45 GHz, 200 W on glycosylation promoted by a solid super acid in supercritical carbon dioxide was investigated with particular attention paid to the structure of the acceptor substrate. Because of the symmetrical structure and high diffusive property of supercritical carbon dioxide, microwave irradiation did not alter the temperature of the reaction solution, but enhanced reaction yield when aliphatic acceptors are employed. Interestingly, the use of a phenolic acceptor under the same reaction conditions did not show these promoting effects due to microwave irradiation. In the case of aliphatic diol acceptors, the yield seemed to be dependent on the symmetrical properties of the acceptors. The results suggest that microwave irradiation do not affect the reactivity of the donor nor promoter independently. We conclude that the effect of acceptor structure on glycosylation yield is due to electric delocalization of hydroxyl group and dielectrically symmetric structure of whole molecule.

  6. Supercritical CO2-based solvents in next generation micro- electronics processing

    Institute of Scientific and Technical Information of China (English)

    ZHANG XiaoGang; Keith P.JOHNSTON

    2007-01-01

    Large amount of chemicals and highly purified-water are needed in microelectronic manufacture. The ability of solutions to penetrate tiny spaces will become significantly more challenging as the feature size of semiconductor devices decreases to nanoscale dimensions and the functional complexity of integrated circuitries (ICs) ever increases. Supercritical fluids (SCFs) possess a unique combination of properties (no surface tension and gas-like viscosity) that can potentially be exploited for application in microelectronics manufacturing and processing in response to needs for material-compatible cleaning systems, small-dimension developing solvents, and low chemical-use processes. Recent microelectronics processes for cleaning and rinsing of patterned porous low-k dielectrics and drying of photoresist in CO2-based solvents are the main focus of this review. Additional topics in supercritical fluid processing include spin coating of photoresists, development with nanoscale dimensions, metal deposition and silylation.

  7. Solvent adsorption in SFC : Adsorption of methanol under supercritical conditions

    OpenAIRE

    Edström, Emelie

    2015-01-01

    Chromatography is a widely used separation technique including many different modes, for example supercritical fluid chromatography (SFC) which uses a supercritical fluid as mobile phase. A supercritical fluid is achieved when a substance is subjected to a temperature and pressure above the critical point and the boundary between the liquid phase and gas phase is erased. The interest for SFC has increased in recent years, mainly for separation of chiral molecules in the pharmaceutical industr...

  8. Supercritical water oxidation of products of human metabolism

    Science.gov (United States)

    Tester, Jefferson W.; Orge A. achelling, Richard K. ADTHOMASSON; Orge A. achelling, Richard K. ADTHOMASSON

    1986-01-01

    Although the efficient destruction of organic material was demonstrated in the supercritical water oxidation process, the reaction kinetics and mechanisms are unknown. The kinetics and mechanisms of carbon monoxide and ammonia oxidation in and reaction with supercritical water were studied experimentally. Experimental oxidation of urine and feces in a microprocessor controlled system was performed. A minaturized supercritical water oxidation process for space applications was design, including preliminary mass and energy balances, power, space and weight requirements.

  9. Separation processes using expulsion from dilute supercritical solutions

    Science.gov (United States)

    Cochran, Jr., Henry D.

    1993-01-01

    A process for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

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

    Science.gov (United States)

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

    2013-06-01

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

  11. Glycerol and bioglycerol conversion in supercritical water for hydrogen production.

    Science.gov (United States)

    Yu-Wu, Q M; Weiss-Hortala, E; Barna, R; Boucard, H; Bulza, S

    2012-01-01

    Catalytic transesterification of vegetable oils leads to biodiesel and an alkaline feed (bioglycerol and organic residues, such as esters, alcohols. . .). The conversion ofbioglycerol into valuable organic molecules represents a sustainable industrial process leading to the valorization of a renewable organic resource. The physicochemical properties in the supercritical domain (T > 374 degrees C, P > 22.1 MPa) transform water into a solvent for organics and a reactant favouring radical reactions. In this context, the conversion ofbioglycerol in supercritical water (SCW) into platform molecules and/or high energetic gases (hydrogen, hydrocarbons) could represent an interesting valorization process. The reported research results concern the conversion of bioglycerol compared to pure glycerol. The experiments have been done in batch autoclaves (5 ml and 500 ml stirred). Solutions of pure (5 or 10 wt%) and crude (3.5 wt%) glycerol have been processed with or without catalyst (K2CO3 1.5 wt%) in the range of 450-600 degrees C. The molecular formula of bioglycerol was determined as C4.3H9.7O1.8Na0.1Si0.08. Glycerol was partially decomposed in the batch systems during the heating (42% before reaching 420 degrees C) and some intermediates (propanediol, ethylene glycol . . .) were quantified, leading to a proposition of a reaction pathway. Acrolein, a valuable platform molecule, was mainly produced in the absence of catalyst. No solid phase was recovered after SCW conversion of pure and bioglycerol in batch reactors. The optimal parameters for gasification were 600 degrees C, 25 MPa for bioglycerol and 525 degrees C, 25 MPa, for pure glycerol. In these operating conditions, 1 kg of pure or bioglycerol leads to 15 and, respectively, 10 mol of hydrogen. Supercritical water gasification of crude glycerol favoured the generation of light hydrocarbons, while pure glycerol promoted H2 production. SCW conversion of glycerol (pure and crude) allows to obtain simultaneously energetic

  12. Drug loading of foldable commercial intraocular lenses using supercritical impregnation.

    Science.gov (United States)

    Bouledjouidja, A; Masmoudi, Y; Sergent, M; Trivedi, V; Meniai, A; Badens, E

    2016-03-16

    The drug delivery through intraocular lenses (IOLs) allows the combination of cataract surgery act and postoperative treatment in a single procedure. In order to prepare such systems, "clean" supercritical CO2 processes are studied for loading commercial IOLs with ophthalmic drugs. Ciprofloxacin (CIP, an antibiotic) and dexamethasone 21-phosphate disodium (DXP, an anti-inflammatory drug) were impregnated into foldable IOLs made from poly-2-hydroxyethyl methacrylate (P-HEMA). A first pre-treatment step was conducted in order to remove absorbed conditioning physiological solution. Supercritical impregnations were then performed by varying the experimental conditions. In order to obtain transparent IOLs and avoid the appearance of undesirable foaming, it was necessary to couple slow pressurization and depressurization phases during supercritical treatments. The impregnation yields were determined through drug release studies. For both drugs, release studies show deep and reproducible impregnation for different diopters. For the system P-HEMA/CIP, a series of impregnations was performed to delimit the experimental range at two pressures (80 and 200 bar) in the presence or absence of ethanol as a co-solvent for two diopters (+5.0 D and +21.0 D). Increase in pressure in the absence of a co-solvent resulted in improved CIP impregnation. The addition of ethanol (5 mol%) produced impregnation yields comparable to those obtained at 200 bar without co-solvent. A response surface methodology based on experimental designs was used to study the influence of operating conditions on impregnation of IOLs (+21.0 D) in the absence of co-solvent. Two input variables with 5 levels each were considered; the pressure (80-200 bar) and the impregnation duration (30-240 min). CIP impregnation yields ranging between 0.92 and 3.83 μg CIP/mg IOL were obtained from these experiments and response surface indicated the pressure as a key factor in the process. The DXP impregnation in P-HEMA was

  13. Solute-matrix and Solute-Solute Interactions during Supercritical Fluid Extraction of Sea Buckthorn Leaves

    OpenAIRE

    Sajfrtová, M. (Marie); Sovová, H. (Helena)

    2012-01-01

    In this work, the SFE was applied to extract selected medicinal substances from sea buckthorn (Hippophae rhamnoides L.) leaves at different conditions (pressure 20-28 MPa, temperature 40-60 °C and ethanol concentration in CO2 0-6.9 wt. %) influencing solvent power of CO2. Interest was focused on the leaf oleoresin (total extract) and its minor components (fat soluble vitamins and carotenoids). The yield of polar component was still steadily increasing at the moment when the extraction is al...

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

    Science.gov (United States)

    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.

  15. Supercritical Water Liquefaction of Coal and Waste Tires

    National Research Council Canada - National Science Library

    Prapan KUCHONTHARA; Yukihiko MATSUMURA

    2001-01-01

      Supercritical water liquefaction of scrap tire rubber and Ishikari coal, separately and in mixtures was investigated to study the possible synergetic effects of coliquefaction between the feedstocks...

  16. Reaction Behavior of Unsaturated Compounds in Sub- and Supercritical Water

    Institute of Scientific and Technical Information of China (English)

    K. Kobiro

    2005-01-01

    @@ 1Introduction Much attention has been paid on the chemistry of sub- and supercritical water, because of their unique prosperities such as low viscosity, low polarity, and high solubility to organic compounds[1]. Recently, the unique sub- and supercritical water is applied as reaction media and reaction catalysts for organic reactions[2,3].We herein disclose the unique reaction of unsaturated compounds in sub- and supercritical water with specific interaction between unsaturated bond(s) and high-density and high-energy water molecule(s) in sub- and supercritical water.

  17. Supercritical CO{sub 2} fluid for chip resistor cleaning

    Energy Technology Data Exchange (ETDEWEB)

    Wang, C.W.; Chang, R.T.; Lin, W.K.; Lin, R.D.; Liang, M.T.; Yang, J.F.; Wang, J.B.

    1999-09-01

    The cleaning ability of supercritical CO{sub 2} was examined on chip resistors. Extraction analyses were made by atomic absorption spectroscopy and the extent of surface cleaning observed by scanning electron microscopy. Experimental results showed that the flow-cleaning process of supercritical CO{sub 2} possessed the advantages of having a superior cleaning ability and permitting a nondrying step. These characteristics strongly suggest that supercritical CO{sub 2} is a superior alternative to the traditional deionized water used in rinsing chip resistors. Moreover, a higher pressure and temperature can benefit the cleaning ability of this novel supercritical CO{sub 2} cleaning technique.

  18. Supercritical boiler material selection using fuzzy analytic network process

    Directory of Open Access Journals (Sweden)

    Saikat Ranjan Maity

    2012-08-01

    Full Text Available The recent development of world is being adversely affected by the scarcity of power and energy. To survive in the next generation, it is thus necessary to explore the non-conventional energy sources and efficiently consume the available sources. For efficient exploitation of the existing energy sources, a great scope lies in the use of Rankin cycle-based thermal power plants. Today, the gross efficiency of Rankin cycle-based thermal power plants is less than 28% which has been increased up to 40% with reheating and regenerative cycles. But, it can be further improved up to 47% by using supercritical power plant technology. Supercritical power plants use supercritical boilers which are able to withstand a very high temperature (650-720˚C and pressure (22.1 MPa while producing superheated steam. The thermal efficiency of a supercritical boiler greatly depends on the material of its different components. The supercritical boiler material should possess high creep rupture strength, high thermal conductivity, low thermal expansion, high specific heat and very high temperature withstandability. This paper considers a list of seven supercritical boiler materials whose performance is evaluated based on seven pivotal criteria. Given the intricacy and difficulty of this supercritical boiler material selection problem having interactions and interdependencies between different criteria, this paper applies fuzzy analytic network process to select the most appropriate material for a supercritical boiler. Rene 41 is the best supercritical boiler material, whereas, Haynes 230 is the worst preferred choice.

  19. Method to remove poisonous chlorine compounds using supercritical carbon dioxide. Chorinkai tansan gas wo mochiita yudoku enso kagobutsu no jokyoho

    Energy Technology Data Exchange (ETDEWEB)

    Ikushima, Y. (Government Industrial Research Institute, Tohoku, Sendai (Japan))

    1989-12-15

    This paper describes a method to extract and remove selectively poisonous chlorine compounds from aqueous solution using supercritical CO2. This method is characterized in that it extracts and separates only chlorine compounds in short time under a moderate condition, and removes it without a need of whatever post-treatment. The supercritical CO2 pressure was 80 kg/cm[sup 2], and the extraction temperature was 40[degree]C. The supercritical CO2 extracted 70% to 80% by weight of trichloroethylene and tetrachloroethylene in 15 to 30 minutes, almost all of 1,2-dichloroethane and 1,1,1-trichloroethane in one hour, and about 70% by weight of benzil chloride after 90 minutes. When the supercritical CO2 extraction was carried out for a dilute chlorine compound at 1000 ppm for three hours, the concentrations of trichloroethylene and tetrachloroethylene in the aqueous solution decreased down to several ppm, with no other substances than chlorine compounds detected in the extracts. This proves that no water has been extracted at all. 5 figs., 1 tab.

  20. Existence of solutions for a nonlinear degenerate elliptic system

    Directory of Open Access Journals (Sweden)

    Nguyen Minh

    2004-07-01

    Full Text Available In this paper, we study the existence of solutions for degenerate elliptic systems. We use the sub-super solution method, and the existence of classical and weak solutions. Some sub-supersolutions are constructed explicitly, when the nonlinearities have critical or supercritical growth.

  1. The pseudocritical regions for supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Imre, A.R., E-mail: imre.attila@energia.mta.hu [HAS Centre for Energy Research, Thermohydraulics Department, P.O. Box 49, H-1525 Budapest (Hungary); University Cologne, Institute for Physical Chemistry, Luxemburger Str. 116, D-50939 Koeln (Germany); Deiters, U.K.; Kraska, T. [University Cologne, Institute for Physical Chemistry, Luxemburger Str. 116, D-50939 Koeln (Germany); Tiselj, I. [Jozef Stefan Institute, Reactor Engineering Division, Jamova 39, 1000 Ljubljana (Slovenia)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Supercritical water behaves anomalously around the Widom lines. Black-Right-Pointing-Pointer We calculated the location of the Widom lines for several thermodynamic functions. Black-Right-Pointing-Pointer Simple quadratic fitting equations are given to describe these lines. - Abstract: Vapour pressure curves and stability lines can be extended beyond the critical points into the supercritical domain by so-called Widom lines, along which some thermodynamic property undergoes a rapid change and liquid-like behaviour turns to vapour-like one. Knowledge about such lines is therefore important for thermohydraulic calculations and design. There are several properties that can be chosen as defining property of a Widom line. In this short note we calculate and compare several kinds of Widom lines for water.

  2. Depolymerization of polyethylene terephthalate in supercritical methanol

    Science.gov (United States)

    Goto, Motonobu; Koyamoto, Hiroshi; Kodama, Akio; Hirose, Tsutomu; Nagaoka, Shoji

    2002-11-01

    The degradation of polyethylene terephthalate (PET) in supercritical methanol was investigated with the aim of developing a process for chemical recycling of waste plastics. A batch reactor was used at temperatures of 573-623 K under an estimated pressure of 20 MPa for a reaction time of 2-120 min. PET was decomposed to its monomers, dimethyl terephthalate and ethylene glycol, by methanolysis in supercritical methanol. The reaction products were analysed using size-exclusion chromatography, gas chromatography-mass spectrometry, and reversed-phase liquid chromatography. The molecular weight distribution of the products was obtained as a function of reaction time. The yields of monomer components of the decomposition products including by-products were measured. Continuous kinetics analysis was performed on the experimental data.

  3. Supercritical Fluid Extraction of Flavonoids from Dandelion

    Directory of Open Access Journals (Sweden)

    Wu Jun

    2014-01-01

    Full Text Available In this study, the total flavonoids from dandelion was extracted by supercritical CO2 and the total flavonoids content in the extract was investigated by the sodium nitrite-aluminum nitrate method with Rutin as a standard product. Single-factor experiments were carried out to map the effects of extraction pressure, temperature, time and entrainer amount on the yield of flavonoids. The orthogonal experiments on the optimum technology parameters demonstrated that the influence of the experimental conditions over the yield from high to low was: (a pressure, (b temperature, (c entrainer amount, (d time. The optimization result showed that under the conditions of 50°C, 35 MPa, 80 min and 4.0 mL/g entrainer amount, the yield of the preparative supercritical fluid extraction was 4.974%.

  4. Stochastic simulation of supercritical fluid extraction processes

    Directory of Open Access Journals (Sweden)

    Mizutani F. T.

    2000-01-01

    Full Text Available Process simulation involves the evaluation of output variables by the specification of input variables and process parameters. However, in a real process, input data and parameters cannot be known without uncertainty. This fact may limit the utilization of simulation results to predict plant behavior. In order to achieve a more realistic analysis, the procedure of stochastic simulation can be conducted. This technique is based on a large set of simulation runs where input variables and parameters are randomly selected according to adequate probability density functions. The objective of this work is to illustrate the application of a stochastic simulation procedure to the process of fractionation of orange essential oil, using supercritical carbon dioxide in a multistage extraction column. Analysis of the proposed example demonstrates the importance of the stochastic simulation to develop more reliable designs and operating conditions for a supercritical fluid extraction process.

  5. Using supercritical fluids to refine hydrocarbons

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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. Dye solubility in supercritical carbon dioxide fluid

    Directory of Open Access Journals (Sweden)

    Yan Jun

    2015-01-01

    Full Text Available Supercritical carbon dioxide fluid is an alternative solvent for the water of the traditional dyeing. The solubility of dyestuff affects greatly the dyeing process. A theoretical model for predicting the dye solubility is proposed and verified experimentally. The paper concludes that the pressure has a greater impact on the dyestuff solubility than temperature, and an optimal dyeing condition is suggested for the highest distribution coefficient of dyestuff.

  8. Computational Modeling of Supercritical and Transcritical Flows

    Science.gov (United States)

    2017-01-09

    reasonably accurate for supercritical and transcritical combustion. 15. SUBJECT TERMS N/A 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF...pr Reduced pressure (p/pc) Tc Critical temperature Tr Reduced temperature (T/Tc) Vm Molar volume Xi Mole fraction of species i Z Compressibility ω...pressure states. A 5.5mm by 0.4064mm domain uses a uniform 256 × 512 Cartesian grid. The code is fifth order accurate in space and a third order

  9. Supercritical fluid extraction of mercury species.

    Science.gov (United States)

    Foy, G P; Pacey, G E

    2003-12-23

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

  10. Advanced Thermal Storage for Central Receivers with Supercritical Coolants

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, Bruce D.

    2010-06-15

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

  11. Use of supercritical carbon dioxide extraction

    Energy Technology Data Exchange (ETDEWEB)

    Taniguchi, Masayuki (Niigata Univ., Faculty of Engineering, Niigata, (Japan))

    1989-09-25

    Supercritical fluid extraction is a novel diffusion and separation technique which exploits simultaneously the increase of vapor pressure and the difference of chemical affinities of fluids near the critical point. A solvent which is used as the supercritical fluid has the following features: the critical point exists in the position of relatively ease of handling, the solvent is applicable to the extraction of a physiological active substance of thermal instability. Carbon dioxide as the solvent is non-flammable, non-corrosive, non-toxic, cheap, and readily available of high purity. The results of studies on the use of supercritical carbon dioxide (SC-CO{sub 2}) as a solvent for natural products in the fermentation and food industries, were collected. SC-CO{sub 2} extraction are used in many fields, examples for the application are as follows: removal of organic solvents from antibiotics; extraction of vegetable oils contained in wheat germ oil, high quality mustard seeds, rice bran and so on; brewing of sake using rice and rice-koji; use as a non-aqueous medium for the synthesis of precursors of the Aspartame; and use in sterilization. 66 refs., 17 figs., 21 tabs.

  12. Determination of binary diffusion coefficients in supercritical carbon dioxide with supercritical fluid chromatography (SFC)

    Energy Technology Data Exchange (ETDEWEB)

    Dahmen, N.; Duelberg, A.; Schneider, G.M. (Bochum Univ. (Germany, F.R.). Lehrstuhl fuer Physikalische Chemie 2)

    1990-03-01

    Binary diffusion coefficient D{sub 12} in supercritical carbon dioxide were determined in a Supercritical Fluid Chromatography (SFC) apparatus by the peak broadening method (PBM). Some cyclic and linear ketones were investigated as a function of pressure between 9.5 and 18 MPa at about 314 K corresponding to densities form 513 to 820 kg m{sup -3}. The resulting D{sub 12} values are of the order of 10{sup -8} m{sup 2} s{sup -1} and lnD{sub 12} decreases about linearly with increasing density {rho} of the CO{sub 2}. (orig.).

  13. Supercritical N = 2 string theory

    CERN Document Server

    Hellerman, Simeon

    2007-01-01

    The N=2 string is examined in dimensions above the critical dimension (D=4) in a linear dilaton background. We demonstrate that string states in this background propagate in a single physical time dimension, as opposed to two such dimensions present when the dilaton gradient vanishes in D=4. We also find exact solutions describing dynamical dimensional reduction and transitions from N=2 string theory to bosonic string theory via closed-string tachyon condensation.

  14. Thermodynamic Optimization of Supercritical CO{sub 2} Brayton Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Rhim, Dong-Ryul; Park, Sung-Ho; Kim, Su-Hyun; Yeom, Choong-Sub [Institute for Advanced Engineering, Yongin (Korea, Republic of)

    2015-05-15

    The supercritical CO{sub 2} Brayton cycle has been studied for nuclear applications, mainly for one of the alternative power conversion systems of the sodium cooled fast reactor, since 1960's. Although the supercritical CO{sub 2} Brayton cycle has not been expected to show higher efficiency at lower turbine inlet temperature over the conventional steam Rankine cycle, the higher density of supercritical CO{sub 2} like a liquid in the supercritical region could reduce turbo-machinery sizes, and the potential problem of sodium-water reaction with the sodium cooled fast reactor might be solved with the use of CO{sub 2} instead of water. The supercritical CO{sub 2} recompression Brayton cycle was proposed for the better thermodynamic efficiency than for the simple supercritical CO{sub 2} Brayton cycle. Thus this paper presents the efficiencies of the supercritical CO{sub 2} recompression Brayton cycle along with several decision variables for the thermodynamic optimization of the supercritical CO{sub 2} recompression Brayton cycle. The analytic results in this study show that the system efficiency reaches its maximum value at a compressor outlet pressure of 200 bars and a recycle fraction of 30 %, and the lower minimum temperature approach at the two heat exchangers shows higher system efficiency as expected.

  15. Introduction to supercritical fluids a spreadsheet-based approach

    CERN Document Server

    Smith, Richard; Peters, Cor

    2013-01-01

    This text provides an introduction to supercritical fluids with easy-to-use Excel spreadsheets suitable for both specialized-discipline (chemistry or chemical engineering student) and mixed-discipline (engineering/economic student) classes. Each chapter contains worked examples, tip boxes and end-of-the-chapter problems and projects. Part I covers web-based chemical information resources, applications and simplified theory presented in a way that allows students of all disciplines to delve into the properties of supercritical fluids and to design energy, extraction and materials formation systems for real-world processes that use supercritical water or supercritical carbon dioxide. Part II takes a practical approach and addresses the thermodynamic framework, equations of state, fluid phase equilibria, heat and mass transfer, chemical equilibria and reaction kinetics of supercritical fluids. Spreadsheets are arranged as Visual Basic for Applications (VBA) functions and macros that are completely (source code) ...

  16. Supercritical Water Mixture (SCWM) Experiment in the High Temperature Insert-Reflight (HTI-R)

    Science.gov (United States)

    Hicks, Michael C.; Hegde, Uday G.; Garrabos, Yves; Lecoutre, Carole; Zappoli, Bernard

    2013-01-01

    Current research on supercritical water processes on board the International Space Station (ISS) focuses on salt precipitation and transport in a test cell designed for supercritical water. This study, known as the Supercritical Water Mixture Experiment (SCWM) serves as a precursor experiment for developing a better understanding of inorganic salt precipitation and transport during supercritical water oxidation (SCWO) processes for the eventual application of this technology for waste management and resource reclamation in microgravity conditions. During typical SCWO reactions any inorganic salts present in the reactant stream will precipitate and begin to coat reactor surfaces and control mechanisms (e.g., valves) often severely impacting the systems performance. The SCWM experiment employs a Sample Cell Unit (SCU) filled with an aqueous solution of Na2SO4 0.5-w at the critical density and uses a refurbished High Temperature Insert, which was used in an earlier ISS experiment designed to study pure water at near-critical conditions. The insert, designated as the HTI-Reflight (HTI-R) will be deployed in the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on the International Space Station (ISS). Objectives of the study include measurement of the shift in critical temperature due to the presence of the inorganic salt, assessment of the predominant mode of precipitation (i.e., heterogeneously on SCU surfaces or homogeneously in the bulk fluid), determination of the salt morphology including size and shapes of particulate clusters, and the determination of the dominant mode of transport of salt particles in the presence of an imposed temperature gradient. Initial results from the ISS experiments will be presented and compared to findings from laboratory experiments on the ground.

  17. Design of an efficient space constrained diffuser for supercritical CO2 turbines

    Science.gov (United States)

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

    2017-03-01

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

  18. Subcritical and supercritical water oxidation of CELSS model wastes

    Science.gov (United States)

    Takahashi, Y.; Wydeven, T.; Koo, C.

    1989-01-01

    A mixture of ammonium hydroxide with acetic acid and a slurry of human feces, urine, and wipes were used as CELSS model wastes to be wet-oxidized at temperatures from 250 to 500 C, i.e. below and above the critical point of water (374 C and 218 kg/sq cm or 21.4 MPa). The effects of oxidation temperature ( 250-500 C) and residence time (0-120 mn) on carbon and nitrogen and on metal corrosion from the reactor material were studied. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 C, above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. A substantial amount of nitrogen remained in solution in the form of ammonia at temperatures ranging from 350 to 450 C suggesting that, around 400 C, organic carbon is completely oxidized and most of the nitrogen is retained in solution. The Hastelloy C-276 alloy reactor corroded during subcritical and supercritical water oxidation.

  19. Molecular Dynamics Simulation of Na(+)-Cl(-) Ion-Pair in Water-Methanol Mixtures under Supercritical and Ambient Conditions.

    Science.gov (United States)

    Keshri, Sonanki; Sarkar, Atanu; Tembe, B L

    2015-12-17

    Constrained molecular dynamics simulations have been performed to investigate the structure and thermodynamics of Na(+)-Cl(-) ion-pair association in water-methanol mixtures under supercritical and ambient conditions in dilute solutions. From the computed potentials of mean force (PMFs) we find that contact ion pairs (CIPs) are more stable than all other associated states of the ion pairs in both ambient and supercritical conditions. Stabilities of CIPs increase with increase in the mole fraction of methanol. In supercritical conditions, major changes in PMFs occur as we go from x(methanol) = 0.00 to x(methanol) = 0.50. The stable solvent shared ion pair (SShIP) which occurs in x(methanol) = 0.00 and 0.25, vanishes when x(methanol) is 0.50 or greater. The stabilities of these ion pairs increase with increasing temperature. Local structures around the ions are studied using the radial distribution functions, density profiles, angular distribution functions, running coordination numbers and excess coordination numbers. Preferential solvation analysis shows that both Na(+) and Cl(-) ions are preferentially solvated by water. From the calculation of enthalpies and entropies, we find that Na(+)-Cl(-) ion-pair association in water-methanol binary mixtures is endothermic and driven by entropy both in ambient as well as under supercritical conditions.

  20. Hot and cold water as a supercritical solvent

    Science.gov (United States)

    Fuentevilla, Daphne Anne

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

  1. Supercritical fluids: Reactions, materials and applications

    Energy Technology Data Exchange (ETDEWEB)

    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).

  2. Reator de membrana enzimático e fluidos supercríticos: associação de processos Enzymatic membrane reactor and supercritical fluids: process association

    Directory of Open Access Journals (Sweden)

    Juliana Maria Leite Nóbrega de Moura

    2007-08-01

    Full Text Available The aim of this work is to present the new applications of membrane technology in fat and oil processing, with emphasis on development and applications of the enzymatic membrane reactor and its association with extraction and purification technology by supercritical fluids (SCF. Combining the extraction by SCFs and the separation by membranes allows the integration of extractions reactions with selective separation by membranes through filtration of the supercritical mixture (SCF + extracted solutes. This association provides important energy savings regarding the SCF recompression costs.

  3. Supercritical fluid thermodynamics from equations of state

    Science.gov (United States)

    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.

  4. Supercritical-pressure light water cooled reactors

    CERN Document Server

    Oka, Yoshiaki

    2014-01-01

    This book focuses on the latest reactor concepts, single pass core and experimental findings in thermal hydraulics, materials, corrosion, and water chemistry. It highlights research on supercritical-pressure light water cooled reactors (SCWRs), one of the Generation IV reactors that are studied around the world. This book includes cladding material development and experimental findings on heat transfer, corrosion and water chemistry. The work presented here will help readers to understand the fundamental elements of reactor design and analysis methods, thermal hydraulics, materials and water

  5. Determination of panaxadiol and panaxatriol in ginseng and its preparations by capillary supercritical fluid chromatography (SFC).

    Science.gov (United States)

    Li, Y H; Li, X L; Hong, L; Liu, J Y; Zhang, M Y

    1992-01-01

    Capillary supercritical fluid chromatographic (SFC) method has been developed for the determination of panaxadiol and panaxatriol in ginseng and its preparations. 0.1 g ginseng or an appropriate amount of its preparations was hydrolysed by 15% H2SO4 in an ethanol:water (1:1 v/v) solution for 4 h followed by 15% NaOH for 0.5 h. The mixture was extracted by cyclohexane. The cyclohexane extracts were purified by a partition column and concentrated by an adsorption column and then analysed by SFC. Methyltestosterone was used as the internal standard.

  6. Near-critical and supercritical water and their applications for biorefineries

    CERN Document Server

    Fang, Zhen

    2014-01-01

    The book provides fundamental chemistry and properties of near-critical water (NCW) and supercritical water (SCW), criteria and challenges/solutions in reactor design for NCW and SCW processes, and up-to-date reviews and practice of a wide range of their applications in bio refineries including: production of hydrochars from biomass, SCW oxidation (SCWO) for waste treatment, SCW gasification (SCWG) of biomass and waste for hydrogen and methane production, hydrothermal liquefaction of biomass, production of chemicals and SCWO of biofuels for energy. It also presents techno-economic analysis of

  7. Supercritical as well as subcritical Hopf bifurcation in nonlinear flutter systems

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The Hopf bifurcations of an airfoil flutter system with a cubic nonlinearity are investigated,with the flow speed as the bifurcation parameter.The center manifold theory and complex normal form method are used to obtain the bifurcation equation.Interestingly,for a certain linear pitching stiffness the Hopf bifurcation is both supercritical and subcritical.It is found,mathematically,this is caused by the fact that one coefficient in the bifurcation equation does not contain the first power of the bifurcation parameter.The solutions of the bifurcation equation are validated by the equivalent linearization method and incremental harmonic balance method.

  8. Rapid Production of Micro- and Nano-particles Using Supercritical Water

    CERN Document Server

    Fang, Zhen

    2010-01-01

    This book shows how to use supercritical water (SCW) to synthesize nano- and micro- oxides, inorganic salts and metal particles and its recent advancement. Also polymer/biomass particles can be produced by using the method of precipitation of solutes from SCW. The particles can be used as catalysts for biomass conversions, materials in ceramics & electronic devices and composite materials. Particles are easily produced continuously in a flow reactor in short and long reaction times. Besides the synthesis process, the book also present studies of the properties of these materials. The size, siz

  9. Effects of supercritical environment on hydrocarbon-fuel injection

    Science.gov (United States)

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

    2017-04-01

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

  10. Performance of supercritical methanol in polyurethane degradation

    Directory of Open Access Journals (Sweden)

    Liu Lu

    2016-01-01

    Full Text Available Polyurethane is a group of block copolymer which is composed of diisocyanate, chain extender, and polyol, including polyurethane foam, polyurethane elastomer, waterborne polyurethane, etc. This research focused on thermoplastic polyurethane elastomer (TPU which is formed with 4,4’-diphenylmethane diisocyanate (MDI, poly(1,4-butanediol-hexanedioic acid diolpolyester(PBA and extended with 1,4-butanediol(BDO.The degradation of TPU was carried out with the help of methanol as the supercritical solvent. The SEM of the reaction residues revealed the process of the depolymerisation. The products were measured by GC-MS and found out to be PBA, BDO and 4,4’-methylene diphenyl carbamate(MDC which is themethylate of MDI.GC-FID, HPLC-UV and GPC were used to further analysis. The experimental results showed that supercritical methanol performed outstandingly in TPU recycling, it needed lower temperature and shorter time than regular methods. At 230°C/70min, over 90% raw materials of TPU could be recovered.

  11. Supercritical fluid chromatography (SFC). Pt. 3. Applications

    Energy Technology Data Exchange (ETDEWEB)

    Leyendecker, D.; Hoefler, F.

    1989-05-01

    During the last few years, Supercritical Fluid Chromatography (SFC) has been emerged from an academic object of research to an important tool for the analytical chemist. Persuasive SFC-applications have been reported analyzing substrates with low volatilities, either due to high molecular weights or to high polarities, thermally or solvatolytically labile molecules, or analytes without chromophores or electroactive groups. Examples are oligomers and polymers up to a molecular weight of 10,000 g/mol, e.g., polysiloxanes, polyethers (nonionic surfactants), polyesters, polystyrenes and other vinyl polymers, polyenes etc. In addition, SFC is applicable to the analysis of several monomers. In the petroleum and coal industries, SFC was employed for the characterization of high boiling hydrocarbon mixtures as well as for group separations of alkanes, olefins, and aromatics. Due to the high solvent strength of supercritical fluids, several pesticides, herbicides, and fungicides can be determined either separately or in combination with polar metabolites. Physiologically active substances often are thermally labile and polar at the same time. SFC has been successfully applied to the analysis of steroids, prostaglandins, cannabinoids and other drugs, flavours, and medicines. It is also well suited for analyzing natural or synthetic mono-, di-, and triglycerides. (orig.).

  12. Toward Better Modeling of Supercritical Turbulent Mixing

    Science.gov (United States)

    Selle, Laurent; Okongo'o, Nora; Bellan, Josette; Harstad, Kenneth

    2008-01-01

    study was done as part of an effort to develop computational models representing turbulent mixing under thermodynamic supercritical (here, high pressure) conditions. The question was whether the large-eddy simulation (LES) approach, developed previously for atmospheric-pressure compressible-perfect-gas and incompressible flows, can be extended to real-gas non-ideal (including supercritical) fluid mixtures. [In LES, the governing equations are approximated such that the flow field is spatially filtered and subgrid-scale (SGS) phenomena are represented by models.] The study included analyses of results from direct numerical simulation (DNS) of several such mixing layers based on the Navier-Stokes, total-energy, and conservation- of-chemical-species governing equations. Comparison of LES and DNS results revealed the need to augment the atmospheric- pressure LES equations with additional SGS momentum and energy terms. These new terms are the direct result of high-density-gradient-magnitude regions found in the DNS and observed experimentally under fully turbulent flow conditions. A model has been derived for the new term in the momentum equation and was found to perform well at small filter size but to deteriorate with increasing filter size. Several alternative models were derived for the new SGS term in the energy equation that would need further investigations to determine if they are too computationally intensive in LES.

  13. Supercritical water oxidation treatment of textile sludge.

    Science.gov (United States)

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

    2016-10-17

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

  14. Supercritical Fluid Extraction of Palm Carotenoids

    Directory of Open Access Journals (Sweden)

    Puah C. Wei

    2005-01-01

    Full Text Available The extraction of carotenoids from crude palm oil was carried out in a dynamic (flow- through supercritical fluid extraction system. The carotenoids obtained were quantified using off-line UV-visible spectrophotometry. The effects of operating pressure and temperature, flow rate of the supercritical carbon dioxide (SC-CO2, sample size of feed used on the solubility of palm carotenoids were investigated. The results showed that the extraction of carotenoids was governed by its solubility in the SC-CO2 and can be enhanced by increasing pressure at a constant temperature or decreasing temperature at a constant pressure. Increasing the flow rate and decreasing the sample size can reduce the extraction time but do not enhance the solubility. Palm carotenoids have very low solubility in SC-CO2 in the range of 1.31 x 10-4 g kg-1 to 1.58 x 10-3 g kg-1 for the conditions investigated in this study. The experimental data obtained were compared with those published by other workers and correlated by a density-based equation as proposed by Chrastil.

  15. Supercritical fluid extraction of Beauvericin from maize.

    Science.gov (United States)

    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.

  16. Desorption of toluene from modified clays using supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    Carneiro D. G. P.

    2004-01-01

    Full Text Available The main objective of this work is to study the regeneration capacity of modified clays using supercritical fluid. These modified clays are used as organic compound adsorvents. The experimental step was done using a packed column with the clay contaminated by toluene. The results obtained showed the influence of the density of the supercritical CO2 and of the organic modifier in the desorption process. These data were modeled with first- and second-order models. Better results were obtained using the second-order model. This study makes possible the scale-up of the desorption process for regeneration of solid matrices using supercritical fluids.

  17. High Density Thermal Energy Storage with Supercritical Fluids

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  19. Method of making supercritical fluid molecular spray films, powder and fibers

    Science.gov (United States)

    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 heated nozzle having 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. In another embodiment, the temperature of the solution and nozzle is elevated above the melting point of the solute, which is preferably a polymer, and the solution is maintained at a pressure such that, during expansion, the solute precipitates out of solution within the nozzle in a liquid state. Alternatively, a secondary solvent mutually soluble with the solute and primary solvent and having a higher critical temperature than that of primary solvent is used in a low concentration (<20%) to maintain the solute in a transient liquid state. The solute is discharged in the form of long, thin fibers. The fibers are collected at sufficient distance from the orifice to allow them to solidify in the low pressure/temperature region.

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

    Science.gov (United States)

    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%).

  1. Nonlinear indirect combustion noise for compact supercritical nozzle flows

    Science.gov (United States)

    Huet, M.

    2016-07-01

    In this paper, indirect combustion noise generated by the acceleration of entropy perturbations through a supercritical nozzle is investigated in the nonlinear regime and in the low-frequency limit (quasi-static hypothesis). This work completes the study of Huet and Giauque (Journal of Fluid Mechanics 733 (2013) 268-301) for nonlinear noise generation in nozzle flows without shock and particularly focuses on shocked flow regimes. It is based on the analytical model of Marble and Candel for compact nozzles (Journal of Sound and Vibration 55 (1977) 225-243), initially developed for excitations in the linear regime and rederived here for nonlinear perturbations. Full nonlinear analytical solutions are provided in the absence of shock as well as second-order analytical expressions when a shock is present in the diffuser. An analytical evaluation of the shock displacement inside the nozzle caused by the forcing is proposed and maximum possible forcings to avoid unchoke and 'over-choke' are discussed. The accuracy of the second-order model and the nonlinear contributions to the generated waves are then addressed. This model is found to be very accurate for the generated entropy wave with negligible nonlinear contributions. Nonlinearities are more visible, but still limited, for the downstream acoustic wave for large inlet Mach numbers. Analytical developments are validated thanks to comparisons with numerical simulations.

  2. Microparticle Formation and Crystallization Rate of HMX with Supercritical CO2 Antisolvent Recrystallization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Microparticle formation and crystallization rate of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) in acetone solution using supercritical carbon dioxide antisolvent (GAS) recrystallization were studied. Scanning electronic microscopy, X-ray diffraction and infrared radiation were used to examine particle size, crystallinity and chemical structure. The results show that β-HMX microparticle in different average size (2-9.5μm) and with narrow size distribution were obtained by controlling the expansibility, expansion speed, initial concentration and temperature during recrystallization of HMX. The formation of nuclei may be a main cause of consumption of solute when the solution is expanded rapidly enough and the equilibrium concentration is lower, in which almost monodisperse microparticle can be obtained.

  3. Microparticle Formation and Crystallization Rate of HMX with Supercritical CO2 Antisolvent Recrystallization

    Institute of Scientific and Technical Information of China (English)

    蔡建国; 周展云; 邓修

    2001-01-01

    Microparticle formation and crystallization rate of 1,3,5,7-tetranitro-l,3,5,7-tetraazacyclooctane (HMX) in acetone solution using supercritical carbon dioxide antisolvent (GAS) recrystallization were studied. Scanning electronic microscopy, X-ray diffraction and infrared radiation were used to examine particle size, crystallinity and chemical structure. The results show that β-HMX microparticle in different average size (2--9.5μm) and with narrow size distribution were obtained by controlling the expansibility, expansion speed, initial concentration and temperature during recrystallization of HMX. The formation of nuclei may be a main cause of consumption of solute when the solution is expanded rapidly enough and the equilibrium concentration is lower, in which almost monodisperse microparticle can be obtained.

  4. Thermodynamic properties of supercritical carbon dioxide: Widom and Frenkel lines

    Science.gov (United States)

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

    2015-02-01

    Supercritical fluids are widely used in a number of important technological applications, yet the theoretical progress in the field has been rather moderate. Fairly recently, a new understanding of the liquidlike and gaslike properties of supercritical fluids has come to the fore, particularly with the advent of the Widom and Frenkel lines that aim to demarcate different physical properties on the phase diagram. Here, we report the results of a computational study of supercritical carbon dioxide, one of the most important fluids in the chemical industry. We study the response functions of CO2 in the supercritical state and calculate the locations of their maxima (Widom lines). We also report the preliminary calculations of the Frenkel line, the line of crossover of microscopic dynamics of particles. Our insights are relevant to physical processes in the atmosphere of Venus and its evolution.

  5. Supercritical Fluid Extraction of Aflatoxin B 1 from Soil

    Science.gov (United States)

    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, ...

  6. Measurement of Orotic Acid in Urine by Supercritical Fluid Chromatography

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    This work presents a simple, rapid and reliable supercritical fluid chromatography (SFC) method for a sensitive measurement of orotic acid in human urine. The samples were diluted with deionized water and analyzed directly without any pretreatment.

  7. Finite connections for supercritical Bernoulli bond percolation in 2D

    CERN Document Server

    Campanino, Massimo; Louidor, Oren

    2009-01-01

    Two vertices are said to be finitely connected if they belong to the same cluster and this cluster is finite. We derive sharp asymptotics for finite connection probabilities for supercritical Bernoulli bond percolation on Z^2.

  8. Simultaneous Graphite Exfoliation and N Doping in Supercritical Ammonia.

    Science.gov (United States)

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

    2016-11-16

    We report the exfoliation of graphite and simultaneous N doping of graphene by two methods: supercritical ammonia treatment and liquid-phase exfoliation with NH4OH. While the supercritical ammonia allowed N doping at a level of 6.4 atom % in 2 h, the liquid-phase exfoliation with NH4OH allowed N doping at a level of 2.7 atom % in 6 h. The N doped graphene obtained via the supercritical ammonia route had few layers (supercritical ammonia as an exfoliation agent and N doping precursor for graphene. Notably, the N doped graphene showed electrocatalytic activity toward oxygen reduction reaction with high durability and good methanol tolerance compared to those of commercial Pt/C catalyst.

  9. Supercritical Fluid Extraction of Aflatoxin B 1 from Soil

    Science.gov (United States)

    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, ...

  10. Physical properties of the benchmark models program supercritical wing

    Science.gov (United States)

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

    1993-01-01

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

  11. Plasticisation and complexation of certain polymers in supercritical CO2

    CSIR Research Space (South Africa)

    Labuschagne, Philip W

    2004-09-01

    Full Text Available A polymer system (polyvinylpyrrolidone + polyvinyl acetate-co-crotonic acid) was successfully identified for use as encapsulation material for sensitive actives using supercritical CO2 as plasticisation medium, having the following properties: 1...

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

    Science.gov (United States)

    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.

  13. Research in Supercritical Fuel Properties and Combustion Modeling

    Science.gov (United States)

    2015-09-18

    any significant impact on the normal hydrocarbon oxidation kinetics . These are ethanol, dimethyl ether( DME ), and methyl formate (C2H5OH, CH3OCH3...research are to develop stimulated scattering as a diagnostic for supercritical fluids, and to evaluate reaction kinetics inputs involving 2-4...measurements for refractive index measurements, and tested our supercritical cell. On the reaction kinetics task, review and evaluation of reactions, rate

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

    Energy Technology Data Exchange (ETDEWEB)

    Akgerman, A.; Bukur, D.B.

    1998-12-31

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

  15. Electrochemistry in Near-Critical and Supercritical Fluids. I. Ammonia.

    Science.gov (United States)

    1984-07-18

    in a supercritical fluid containing an electrolyte. We show j here that electrocheical techniques, such as cyclic voltametry and .’ chronocoulametrY...8217,_- Electrochemistry, supercritical, ammonia S&. ASSTRACT. (CGWIU&UI VOWO *fo of Rea@ d 8~ US F &I-*I 81116 Cyclic voltanmetric and chronocoulometric studies of N...Bard 4 Department of Chemi stry, The University of Texas Austin, TX 78712 (Abstract) Cyclic voittuuntric and chronocoulometric studies of NH3

  16. Independent Research and Design of 600-MW Supercritical CFB Boiler

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    In order to further develop and improve the technologies for large-capacity supercritical CFB boiler, the key technologies for large CFB boiler were systematically studied, based on the development of first domestically-made 210-MW and 330-MW CFB boilers. The scheme of 600-MW supercritical CFB boiler was designed, including the furnace structure, key components, steam-water system and auxiliary systems, which laid a technical foundation for the engineering applications.

  17. Isolation of Organochlorine Pesticide from Ginseng with Supercritical CO2

    Institute of Scientific and Technical Information of China (English)

    李淑芬; 王幼君; 全灿; 田松江

    2005-01-01

    The feasibility of removal of the organochlorine pesticides residues of hexachlorocyclohexane(BHC) from radix ginseng with supercritical CO2 was explored. Some factors, such as extraction pressure, extraction temperature, and kinds of co-solvents were investigated. The experimental results indicate that it is possible to reduce BHC residues in radix ginseng to the level of 0.1 × 10-6 with supercritical CO2 in the presence of suitable amount of co-solvent, such as water.

  18. Extraction of olive oil with supercritical carbon dioxide / Ilana Geerdts

    OpenAIRE

    Geerdts, Ilana

    2005-01-01

    The principal objective of this study was to extract olive oil from the fruit of Olea europaea by means of supercritical carbon dioxide (sc-C02) as an alternative to traditional methods. Extractions were performed on a laboratory scale supercritical fluid extractor of the latest design, featuring three mutually independent flow systems and extremely high flow rates. A number of extraction runs based on a statistical design was performed to establish the conditions (time, pressu...

  19. Production of all trans-beta-carotene by using impinging flow of supercritical carbon dioxide anti-solvent pulverization.

    Science.gov (United States)

    Shen, Yi-Chen; Chng, Lee-Muei; Wang, Yuan-Chuen; Shieh, Chwen-Jen; Lin, Kuo-Li; Hsu, Shih-Lan; Chou, Hong-Nong; Chang, Chieh-Ming J

    2012-12-28

    This work investigated column elution chromatography coupled with supercritical anti-solvent precipitation to produce carotenoid rich microsized particulates from microalgal Dunaliella salina species. The extract contained carotenoids ranging from 61.3 mg/g(salina) to 72.5 mg/g(salina) using ultrasonic stirred ethyl ether or tetrahydrofuran (THF) extraction. When 10 L of ethyl alcohol was employed to elute the THF extract, purity of trans-β-carotene is 823.6 mg/g with a recovery of 86.2%. It was found that the supercritical anti-solvent of THF solution at 160 bar and 318 K produced powdered particulates with a purity of carotenoids above 90%. Subsequently, a central composite response surface design method was used to design supercritical anti-solvent precipitation of carotenoid-rich THF solution. This was accomplished by increasing the pressure from 140 bar to 180 bar and the time from 40 min to 60 min at a feed flow rate of 0.2 mL/min. A CO(2) flow rate of 15 L/min and a temperature of 318 K were also used to determine the effects on purity and recovery of trans-β-carotene. The combined process produced micronized precipitates with a mean particle size ranging from 3.5 μm to 19 μm and the purity of trans-β-carotene attained was 926.8 mg/g with a recovery of 54%.

  20. Hydrogenation of diesel aromatic compounds in supercritical solvent environment

    Directory of Open Access Journals (Sweden)

    E.P. Martins

    2000-09-01

    Full Text Available Reactions under supercritical conditions have been employed in many processes. Furthermore, an increasing number of commercial reactions have been conducted under supercritical or near critical conditions. These reaction conditions offer several advantages when compared to conditions in conventional catalytic processes in liquid-phase, gas-liquid interface, or even some gas-phase reactions. Basically, a supercritical solvent can diminish the reactant’s transport resistance from the bulk region to the catalyst surface due to enhancement of liquid diffusivity values and better solubility than those in different phases. Another advantage is that supercritical solvents permit prompt and easy changes in intermolecular properties in order to modify reaction parameters, such as conversion or selectivity, or even proceed with the separation of reaction products. Diesel fractions from petroleum frequently have larger than desirable quantities of aromatic compounds. Diesel hydrogenation is intended to decrease these quantities, i.e., to increase the quantity of paraffin present in this petroleum fraction. In this work, the hydrogenation of tetralin was studied as a model reaction for the aromatic hydrogenation process. A conventional gas-liquid-solid catalytic process was compared with that of supercritical carbon dioxide substrate under similar conditions. Additionally, an equilibrium conversion diagram was calculated for this reaction in a wide range of temperature and reactant ratios, so as to optimize the operational conditions and improve the results of subsequent experiments. An increase in the rate of reaction at 493 K in supercritical fluid, as compared to that in the conventional process, was observed.

  1. Effects of Gravity on Supercritical Water Oxidation (SCWO) Processes

    Science.gov (United States)

    Hegde, Uday; Hicks, Michael

    2013-01-01

    The effects of gravity on the fluid mechanics of supercritical water jets are being studied at NASA to develop a better understanding of flow behaviors for purposes of advancing supercritical water oxidation (SCWO) technologies for applications in reduced gravity environments. These studies provide guidance for the development of future SCWO experiments in new experimental platforms that will extend the current operational range of the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on board the International Space Station (ISS). The hydrodynamics of supercritical fluid jets is one of the basic unit processes of a SCWO reactor. These hydrodynamics are often complicated by significant changes in the thermo-physical properties that govern flow behavior (e.g., viscosity, thermal conductivity, specific heat, compressibility, etc), particularly when fluids transition from sub-critical to supercritical conditions. Experiments were conducted in a 150 ml reactor cell under constant pressure with water injections at various flow rates. Flow configurations included supercritical jets injected into either sub-critical or supercritical water. Profound gravitational influences were observed, particularly in the transition to turbulence, for the flow conditions under study. These results will be presented and the parameters of the flow that control jet behavior will be examined and discussed.

  2. Hydrogenation of diesel aromatic compounds in supercritical solvent environment

    Energy Technology Data Exchange (ETDEWEB)

    Martins, E.P.; Aranda, D.A.G.; Pessoa, F.L.P. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Escola de Quimica. Dept. de Engenharia Quimica. E-mail: donato@h2o.eq.ufrj.br; pessoa@h2o.eq.ufrj.br; Zotin, J.L. [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas. E-mail: zotin@cenpes.petrobras.com.br

    2000-09-01

    Reactions under supercritical conditions have been employed in many processes. Furthermore, an increasing number of commercial reactions have been conducted under supercritical or near critical conditions. These reaction conditions offer several advantages when compared to conditions in conventional catalytic processes in liquid-phase, gas-liquid interface., or even some gas-phase reactions. basically, a supercritical solvent can diminish the reactant's transport resistance from the bulk region to the catalyst surface due to enhancement of liquid diffusivity values and better solubility than those in different phases. Another advantage is that supercritical solvents permit prompt and easy changes in intermolecular properties in order to modify reaction parameters, such as conversion or selectivity, or even proceed with the separation of reaction products. Diesel fractions from petroleum frequently have larger than desirable quantities of aromatic compounds. Diesel hydrogenation is intended to decrease these quantities, to increase the quantity of paraffin present in this petroleum fraction. In this work, the hydrogenation of tetralin was studied as a model reaction for the aromatic hydrogenation process. A conventional gas-liquid-solid catalytic process was compared with that of supercritical carbon dioxide substrate under similar conditions. Additionally, an equilibrium conversion diagram was calculated for this reaction in a wide range of temperature and reactant ratios, so as to optimize the operational conditions and improve the results of subsequent experiments. An increase in the rate of reaction at 493 K in supercritical fluid, as compared to that in the conventional process, was observed. (author)

  3. Supercritical extraction of lycopene from tomato industrial wastes with ethane.

    Science.gov (United States)

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

    2012-07-11

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

  4. Hydrogen bond driven chemical reactions: Beckmann rearrangement of cyclohexanone oxime into epsilon-caprolactam in supercritical water.

    Science.gov (United States)

    Boero, Mauro; Ikeshoji, Tamio; Liew, Chee Chin; Terakura, Kiyoyuki; Parrinello, Michele

    2004-05-26

    Recent experiments have shown that supercritical water (SCW) has the ability to accelerate and make selective synthetic organic reactions, thus replacing the common but environmentally harmful acid and basic catalysts. In an attempt to understand the intimate mechanism behind this observation, we analyze, via first-principles molecular dynamics, the Beckmann rearrangement of cyclohexanone oxime into epsilon-caprolactam in supercritical water, for which accurate experimental evidence has been reported. Differences in the wetting of the hydrophilic parts of the solute, enhanced by SCW, and the disrupted hydrogen bond network are shown to be crucial in triggering the reaction and in making it selective. Furthermore, the enhanced concentrations of H(+) in SCW play an important role in starting the reaction.

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

    Energy Technology Data Exchange (ETDEWEB)

    Holcomb, Gordon [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Tylczak, Joseph [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Carney, Casey [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Dogan, Omer N. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)

    2017-02-26

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

  6. Reactions of supercritical water and supercritical methanol with benzaldehyde; Chorinkaisui oyobi chorinkai methanol to benzaldehyde tono hanno

    Energy Technology Data Exchange (ETDEWEB)

    Yokoyama, C.; Yasuda, T.; Nishi, K.; Takahashi, S. [Tohoku University, Sendai (Japan). Institute for Chemical Reaction Science

    1996-11-01

    The reactions of supercritical water and supercritical methanol with benzaldehyde have been examined in the temperature range from 553 to 693 K, and the reaction pathways have been examined from the temporal variations of the reaction products. For the reaction of benzaldehyde with supercritical water, the major product was benzene, which was formed from the pyrolysis of benzaldehyde. The benzoic acid and benzyl alcohol were the by-products, produced from the Cannizzaro-type disproportionation reaction of benzaldehyde with the hydrate formed from the reaction with water and benzaldehyde. The major product for the reaction of benzaldehyde with supercritical methanol was benzyl alcohol, and the by-product were dimethylacetal, benzene, and methyl benzoic acid. Under the reaction conditions of this study, a significant amount of acetal was produced from benzaldehyde and methanol. The pyrolysis of acetal yielded benzyl alcohol. 29 refs., 6 figs., 4 tabs.

  7. Thermodynamic properties of superheated and supercritical steam

    Energy Technology Data Exchange (ETDEWEB)

    Malhotra, A. [Indian Inst. of Technology, New Delhi (India). Dept. of Mechanical Engineering; Panda, D.M.R. [Dadri Gas Power Station, NTPC, Gautam Buddha Nagar (India)

    2001-07-01

    An existing formulation for steam properties is due to Irvine and Liley. Their equations are convenient to program and do not require excessive computational time to produce results. The properties computed from these equations compare favourably with standard data. An additional advantage of these equations is that they follow prescribed theoretical trends by reducing to perfect-gas behaviour away from the saturation dome. However, a difficulty with these equations is that, at pressures above 10 MPa and close to the saturation dome, unacceptably large errors (above 10%) are produced. These equations are examined in the present work with a view towards enhancing their range of application through the use of additional functions. It is shown that the errors may be reduced to within 1% over the entire range of pressures (both sub-critical and super-critical pressures) required in steam-plant calculations. (author)

  8. Electromagnetic Whistler Precursors at Supercritical Interplanetary Shocks

    Science.gov (United States)

    Wilson, L. B., III

    2012-01-01

    We present observations of electromagnetic precursor waves, identified as whistler mode waves, at supercritical interplanetary shocks using the Wind search coil magnetometer. The precursors propagate obliquely with respect to the local magnetic field, shock normal vector, solar wind velocity, and they are not phase standing structures. All are right-hand polarized with respect to the magnetic field (spacecraft frame), and all but one are right-hand polarized with respect to the shock normal vector in the normal incidence frame. Particle distributions show signatures of specularly reflected gyrating ions, which may be a source of free energy for the observed modes. In one event, we simultaneously observe perpendicular ion heating and parallel electron acceleration, consistent with wave heating/acceleration due to these waves.

  9. Gasification of cyanobacterial in supercritical water.

    Science.gov (United States)

    Zhang, Huiwen; Zhu, Wei; Xu, Zhirong; Gong, Miao

    2014-01-01

    Cyanobacterial collected from eutrophic freshwater lakes constituted intractable waste with a rich algae biomass content. Supercritical water gasification (SCWG) was proposed to treat the cyanobacterial and to produce hydrogen for energy. The H 2 yield reached 2.92 mol/kg at reaction conditions of 500 °C, 30 min and 22 MPa; this yield accounted for 26% of the total gaseous products. Abundant ammonia and dissolved reactive phosphorous were concentrated in the liquid product, which could be recovered and used as a liquid fertilizer. Solid residue, which accounted only for about 1% of the wet weight, was mainly composed of coke and ash. The efficiency of H 2 production was better than that from other biomass, because of the abundant organic matter in cyanobacterial. Thus, cyanobacterial are an ideal biomass feedstock for H 2 production from SCWG.

  10. Supercritical droplet combustion and related transport phenomena

    Science.gov (United States)

    Yang, Vigor; Hsieh, K. C.; Shuen, J. S.

    1993-01-01

    An overview of recent advances in theoretical analyses of supercritical droplet vaporization and combustion is conducted. Both hydrocarbon and cryogenic liquid droplets over a wide range of thermodynamic states are considered. Various important high-pressure effects on droplet behavior, such as thermodynamic non-ideality, transport anomaly, and property variation, are reviewed. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influence on fluid transport, gas-liquid interfacial thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibit a considerable change in the combustion mechanism at the criticl pressure, mainly as a result of reduced mass diffusivity and latent heat of vaporization with increased pressure. The influence of droplet size on the burning characteristics is also noted.

  11. Fractionation for Biodiesel Purification Using Supercritical Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Chao-Yi Wei

    2014-02-01

    Full Text Available In recent years, biodegradable and alternative biodiesel has attracted increased attention worldwide. Producing biodiesel from biomass involves critical separation and purification technology. Conventional technologies such as gravitational settling, decantation, filtration, water washing, acid washing, organic solvent washing and absorbent applications are inefficient, less cost effective and environmentally less friendly. In this study supercritical carbon dioxide (SC-CO2 with few steps and a low environmental impact, was used for biodiesel fractionation from impure fatty acid methyl ester (FAME solution mixes. The method is suitable for application in a variety of biodiesel production processes requiring subsequent stages of purification. The fractionation and purification was carried out using continuous SC-CO2 fractionation equipment, consisting of three columns filled with stainless steel fragments. A 41.85% FAME content solution mix was used as the raw material in this study. Variables were a temperature range of 40–70 °C, pressure range of 10–30 MPa, SC-CO2 flow rate range of 7–21 mL/min and a retention time range of 30–90 min. The Taguchi method was used to identify optimal operating conditions. The results show that a separated FAME content of 99.94% was verified by GC-FID under optimal fractionation conditions, which are a temperature of 40 °C of, a pressure level of 30MPa and a flow rate of 7 mL/min of SC-CO2 for a retention time of 90 min.

  12. Supercritical water oxidation of landfill leachate.

    Science.gov (United States)

    Wang, Shuzhong; Guo, Yang; Chen, Chongming; Zhang, Jie; Gong, Yanmeng; Wang, Yuzhen

    2011-01-01

    In this paper, ammonia as an important ingredient in landfill leachate was mainly studied. Based on Peng-Robinson formulations and Gibbs free energy minimization method, the estimation of equilibrium composition and thermodynamic analysis for supercritical water oxidation of ammonia (SCWO) was made. As equilibrium is reached, ammonia could be totally oxidized in SCW. N(2) is the main product, and the formation of NO(2) and NO could be neglected. The investigation on SCWO of landfill leachate was conducted in a batch reactor at temperature of 380-500 °C, reaction time of 50-300s and pressure of 25 MPa. The effect of reaction parameters such as oxidant equivalent ratio, reaction time and temperature were investigated. The results showed that COD and NH(3) conversion improved as temperature, reaction time and oxygen excess increased. Compared to organics, NH(3) is a refractory compound in supercritical water. The conversion of COD and NH(3) were higher in the presence of MnO(2) than that without catalyst. The interaction between reaction temperature and time was analyzed by using response surface method (RSM) and the results showed that its influence on the NH(3) conversion was relatively insignificant in the case without catalyst. A global power-law rate expression was regressed from experimental data to estimate the reaction rate of NH(3). The activation energy with and without catalyst for NH(3) oxidation were 107.07 ± 8.57 kJ/mol and 83.22 ± 15.62 kJ/mol, respectively.

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

    Science.gov (United States)

    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.

  14. Solid-state flurbiprofen and methyl-β-cyclodextrin inclusion complexes prepared using a single-step, organic solvent-free supercritical fluid process.

    Science.gov (United States)

    Rudrangi, Shashi Ravi Suman; Kaialy, Waseem; Ghori, Muhammad U; Trivedi, Vivek; Snowden, Martin J; Alexander, Bruce David

    2016-07-01

    The aim of this study was to enhance the apparent solubility and dissolution properties of flurbiprofen through inclusion complexation with cyclodextrins. Especially, the efficacy of supercritical fluid technology as a preparative technique for the preparation of flurbiprofen-methyl-β-cyclodextrin inclusion complexes was evaluated. The complexes were prepared by supercritical carbon dioxide processing and were evaluated by solubility, differential scanning calorimetry, X-ray powder diffraction, scanning electron microscopy, practical yield, drug content estimation and in vitro dissolution studies. Computational molecular docking studies were conducted to study the possibility of molecular arrangement of inclusion complexes between flurbiprofen and methyl-β-cyclodextrin. The studies support the formation of stable molecular inclusion complexes between the drug and cyclodextrin in a 1:1 stoichiometry. In vitro dissolution studies showed that the dissolution properties of flurbiprofen were significantly enhanced by the binary mixtures prepared by supercritical carbon dioxide processing. The amount of flurbiprofen dissolved into solution alone was very low with 1.11±0.09% dissolving at the end of 60min, while the binary mixtures processed by supercritical carbon dioxide at 45°C and 200bar released 99.39±2.34% of the drug at the end of 30min. All the binary mixtures processed by supercritical carbon dioxide at 45°C exhibited a drug release of more than 80% within the first 10min irrespective of the pressure employed. The study demonstrated the single step, organic solvent-free supercritical carbon dioxide process as a promising approach for the preparation of inclusion complexes between flurbiprofen and methyl-β-cyclodextrin in solid-state.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. Preliminary Design of In-Pile Supercritical Pressurized Water Test Loop

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>Based on two proven technologies, current light water reactors (LWRs) and the supercritical coal-fired power plants, the supercritical water-cooled reactor (SCWR) is one of the six Generation-Ⅳ

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

    Science.gov (United States)

    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 ...

  18. Oxidation of substituted phenols in supercritical water. Final technical report, September 1992--August 1996

    Energy Technology Data Exchange (ETDEWEB)

    Savage, P.E.

    1996-11-01

    Wastewaters from coal-conversion processes contain phenolic compounds in appreciable concentrations. These compounds need to be removed so that the water can be discharged or reused. Oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of model pollutants in supercritical water. The decomposition of cresols, hydroxybenzaidehydes, nitrophenols, and benzenediols was studied in dilute aqueous solutions in both the presence and absence of oxygen at 460{degrees}C and 250 atm. Experimental data from the oxidation of these compounds were fit to global, power-law rate expressions. The resulting rate laws showed that the reactivity of the different isomers at 460{degrees}C was in the order of ortho > para > meta for cresols and hydroxybenzaldehydes. Moreover, the CHO-substituted phenol was more reactive than the analogous CH{sub 3}-substituted phenol, and all of these substituted phenols were more reactive than phenol itself. Identifying and quantifying the reaction products of incomplete oxidation allowed us to assemble a general reaction network for the oxidation of cresols in supercritical water. This network comprises parallel primary paths to phenol, to a hydroxybenzaldehyde, and to ring-opening products. The hydroxybenzaldehyde reacts through parallel paths to phenol and to ring-opening products. Phenol also reacts via two parallel paths, but these lead to phenol dimers; and ring-opening products. The dimers are eventually converted to ring-opening products, and the ring-opening products are ultimately converted to CO{sub 2} The relative rates of the different paths in the reaction network are strong functions of the location of the substituent on the phenolic ring.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  1. Modified Korteweg-de Vries solitons at supercritical densities in two-electron temperature plasmas

    CERN Document Server

    Verheest, Frank; Hereman, Willy A

    2016-01-01

    The supercritical composition of a plasma model with cold positive ions in the presence of a two-temperature electron population is investigated, initially by a reductive perturbation approach, under the combined requirements that there be neither quadratic nor cubic nonlinearities in the evolution equation. This leads to a unique choice for the set of compositional parameters and a modified Korteweg-de Vries equation (mKdV) with a quartic nonlinear term. The conclusions about its one-soliton solution and integrability will also be valid for more complicated plasma compositions. Only three polynomial conservation laws can be obtained. The mKdV equation with quartic nonlinearity is not completely integrable, thus precluding the existence of multi-soliton solutions. Next, the full Sagdeev pseudopotential method has been applied and this allows for a detailed comparison with the reductive perturbation results. This comparison shows that the mKdV solitons have slightly larger amplitudes and widths than those obta...

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

    Science.gov (United States)

    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)

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

    Science.gov (United States)

    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. 10 MW Supercritical CO2 Turbine Test

    Energy Technology Data Exchange (ETDEWEB)

    Turchi, Craig

    2014-01-29

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

  5. Supercritical fluid processing: opportunities for new resist materials and processes

    Science.gov (United States)

    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.

  6. Experimental study of elliptical jet from sub to supercritical conditions

    Science.gov (United States)

    Muthukumaran, C. K.; Vaidyanathan, Aravind

    2014-04-01

    The jet mixing at supercritical conditions involves fluid dynamics as well as thermodynamic phenomena. All the jet mixing studies at critical conditions to the present date have focused only on axisymmetric jets. When the liquid jet is injected into supercritical environment, the thermodynamic transition could be well understood by considering one of the important fluid properties such as surface tension since it decides the existence of distinct boundary between the liquid and gaseous phase. It is well known that an elliptical liquid jet undergoes axis-switching phenomena under atmospheric conditions due to the presence of surface tension. The experimental investigations were carried out with low speed elliptical jet under supercritical condition. Investigation of the binary component system with fluoroketone jet and N2 gas as environment shows that the surface tension force dominates for a large downstream distance, indicating delayed thermodynamic transition. The increase in pressure to critical state at supercritical temperature is found to expedite the thermodynamic transition. The ligament like structures has been observed rather than droplets for supercritical pressures. However, for the single component system with fluoroketone jet and fluoroketone environment shows that the jet disintegrates into droplets as it is subjected to the chamber conditions even for the subcritical pressures and no axis switching phenomenon is observed. For a single component system, as the pressure is increased to critical state, the liquid jet exhibits gas-gas like mixing behavior and that too without exhibiting axis-switching behavior.

  7. Experimental study of elliptical jet from sub to supercritical conditions

    Energy Technology Data Exchange (ETDEWEB)

    Muthukumaran, C. K.; Vaidyanathan, Aravind, E-mail: aravind7@iist.ac.in [Department of Aerospace Engineering, Indian Institute of Space Science and Technology, Trivandrum, Kerala 695547 (India)

    2014-04-15

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

  8. Supercritical fluid extraction: Application in the food industry

    Directory of Open Access Journals (Sweden)

    Skala Dejan U.

    2002-01-01

    Full Text Available Supercritical fluid extraction is an extraction process realized with supercritical fluids, which are at a temperature and pressure above their critical temperature and critical pressure. This process has shown to be very efficient one for the isolation of different substances of medium molecular weights and molecules of relatively low polarity. The solubility of more polar substances in supercritical fluids can be improved by the addition of small amounts of other polar solvents (cosolvent to the supercritical fluids, which is the main solvent in extraction process. The advantage of supercritical extraction compared to other extraction procedures (the application of classical organic solvents hydrodistillation, distillation with steam is that SFE is usually performed at moderate temperature (e.g. with SF CO2 at 40-70°C so it can be applied for the separation of different substances which are thermally unstable and have a larger vapour pressure. All of these facts indicate that SFE is of special interest for the food and pharmaceutical industry.

  9. Oxidation behavior of Incoloy 800 under simulated supercritical water conditions

    Energy Technology Data Exchange (ETDEWEB)

    Fulger, M. [Institute for Nuclear Research Pitesti, POB 78, Campului Street, No. 1, 115400 Mioveni (Romania)], E-mail: manuela.fulger@nuclear.ro; Ohai, D.; Mihalache, M.; Pantiru, M. [Institute for Nuclear Research Pitesti, POB 78, Campului Street, No. 1, 115400 Mioveni (Romania); Malinovschi, V. [University of Pitesti, Research Center for Advanced Materials, Targul din Vale Street, No. 1, 110040 Pitesti (Romania)

    2009-03-31

    For a correct design of supercritical water-cooled reactor (SCWR) components, data regarding the behavior of candidate materials in supercritical water are necessary. Corrosion has been identified as a critical problem because the high temperature and the oxidative nature of supercritical water may accelerate the corrosion kinetics. The goal of this paper is to investigate the oxidation behavior of Incoloy 800 exposed in autoclaves under supercritical water conditions for up to 1440 h. The exposure conditions (thermal deaerated water, temperatures of 723, 773, 823 and 873 K and a pressure of 25 MPa) have been selected as relevant for a supercritical power plant concept. To investigate the structural changes of the oxide films, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and electrochemical impedance spectroscopy (EIS) analyses were used. Results show changes in the oxides chemical composition, microstructure and thickness versus testing conditions (pressure, temperature and time). The oxide films are composed of two layers: an outer layer enriched in Fe oxide and an inner layer enriched in Cr and Ni oxides corresponding to small cavities supposedly due to internal oxidation.

  10. Microencapsulation and characterization of liposomal vesicles using a supercritical fluid process coupled with vacuum-driven cargo loading.

    Science.gov (United States)

    Tsai, Wen-Chyan; Rizvi, Syed S H

    2017-06-01

    A new technique of liposomal microencapsulation, consisting of supercritical fluid extraction followed by rapid expansion of the supercritical solution and vacuum-driven cargo loading, was successfully developed. It is a continuous flow-through process without usage of any toxic organic solvent. For use as a coating material, the solubility of soy phospholipids in supercritical carbon dioxide was first determined using a dynamic equilibrium system and the data was correlated with the Chrastil model with good agreement. Liposomes were made with D-(+)-glucose as a cargo and their properties were characterized as functions of expansion pressure, temperature, and cargo loading rates. The highest encapsulation efficiency attained was 31.7% at the middle expansion pressure of 12.41MPa, highest expansion temperature of 90°C, and lowest cargo loading rate of 0.25mL/s. The large unilamellar vesicles and multivesicular vesicles were observed to be a majority of the liposomes produced using this eco-friendly process. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Experimental study on supercritical phenomena of WO3 solubility in NaCl-H2O system

    Institute of Scientific and Technical Information of China (English)

    GONG; Qingjie(龚庆杰); CEN; Kuang(岑况); YU; Chongwen(於崇文)

    2003-01-01

    The solubility measurements of WO3 in NaCl-H2O system with 4.0% by weight salt were carried out to study the supercritical phenomena of solubility. These experiments were carried out using rapid-quench pressure vessels, with quantitative Na2WO4(2H2O, HCl, NaCl and H2O in Pt capsule to determine the solubility of WO3 from supersaturated solution. The pressure was kept at 34 MPa, which was near the critical pressure 31.4 MPa and the temperatures varied from 250℃ to 550℃. The experimental results indicate that the solubility of WO3 has the features of supercritical phenomenon in critical region and is sensitive to the change of system temperature and solvent density. The temperature and pressure in this experiment are close to those of ore-forming fluids in many tungsten deposits, so the features of supercritical geofluids can be helpful to investigating the ore-forming mechanism of tungsten deposit.

  12. Effect of supercritical water treatment on porous structure, liquid-phase adsorption and regeneration characteristics of activated anthracite

    Energy Technology Data Exchange (ETDEWEB)

    Tanthapanichakoon, W.; Sittipraneed, S.; Japthong, P.; Charinpanitkul, T.; Boon-Amnuayvitaya, V.; Nakagawa, K.; Tamon, H. [National Nanotechnological Centre, Pathumthani (Thailand)

    2006-06-15

    Microporous activated anthracite was produced from waste anthracite powders by the conventional steam activation. The activated anthracite was also treated by supercritical water reaction (SWR) by using distilled water and hydrogen peroxide solution as a liquid medium for SWR treatment. It was found that SWR treatment can improve the mesoporosity of the activated anthracite though the micropore volume was reduced by the treatment. In liquid-phase adsorption and supercritical water regeneration studies, phenol and organic dye RED 31 were selected as the representative adsorbates. The adsorption and regeneration characteristics of activated anthracite were compared with those of a commercial activated carbon. The results indicate that the activated anthracite prepared showed comparable phenol adsorption capacity but significantly lower dye adsorption capacity than the commercial one. However, supercritical water regeneration efficiency was remarkably high. The first/second regeneration efficiencies of commercial activated carbon and activated anthracite exhausted with phenol were 55/55 and 65/65%, respectively, and in the case of RED 31, 78/79 and 338/317%, respectively, with losses of activated carbon less than 4% per regeneration. Because of little loss of activated carbon during successive regenerations, this SWR regeneration method was suitable for regenerating spent activated carbon or anthracite.

  13. Chiral separation of amides using supercritical fluid chromatography.

    Science.gov (United States)

    Xiang, Yanqiao; Dunetz, Joshua R; Lovdahl, Michael

    2013-06-07

    Nine amide derivatives bearing α-stereocenters as well as different substitutions on the amide nitrogen were synthesized via an n-propanephosphonic acid cyclic anhydride (T3P)-mediated coupling, and their enantiomeric pairs were separated using supercritical fluid chromatography (SFC). Five polysaccharide-based chiral stationary phases (CSPs), Chiralcel OD-H, and OJ-H, and Chiralpak AD-H, AS-H and IC columns were explored for the chiral separation of these compounds. None of the compounds could be resolved on all five columns, and no single column could separate all nine pairs of enantiomers. Comparatively, the IC and OD-H columns showed the best results for this group of amides, yielding baseline separations for eight of nine pairs. The type of polar functional group and aromatic substitution in the CSPs and the substitutions on the amide nitrogen had a significant impact on the enantiomeric resolution of the compounds in the interaction between the analyte and the stationary phases. The potential separation mechanism and the effect of substitutions in the CSPs and amide solutes on the separation are discussed. The effects of the organic modifiers, modifier composition, mobile phase additives, and temperature were investigated for the separation of these amides on the IC or the OD-H column. Baseline resolution was achieved under optimized chromatographic conditions using an IC or an OD-H column. Linearity, reproducibility, and limit of quantitation were also demonstrated for the compound 9. Approximately three-fold improvement in signal-to-noise was observed using a SFC system with better instrument design.

  14. Preparation and characterization of Tripterygium wilfordii multi-glycoside nanoparticle using supercritical anti-solvent process.

    Science.gov (United States)

    Chen, Fengli; Li, Tong; Li, Shuangyang; Hou, Kexin; Liu, Zaizhi; Li, Lili; Cui, Guoqiang; Zu, Yuangang; Yang, Lei

    2014-02-17

    The aim of this study was to prepare nanosized Tripterygium wilfordii multi-glycoside (GTW) powders by the supercritical antisolvent precipitation process (SAS), and to evaluate the anti-inflammatory effects. Ethanol was used as solvent and carbon dioxide was used as an antisolvent. The effects of process parameters such as precipitation pressure (15-35 MPa), precipitation temperature (45-65 °C), drug solution flow rates (3-7 mL/min) and drug concentrations (10-30 mg/mL) were investigated. The nanospheres obtained with mean diameters ranged from 77.5 to 131.8 nm. The processed and unprocessed GTW were characterized by scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy and thermal gravimetric analysis. The present study was designed to investigate the beneficial effect of the GTW nanoparticles on adjuvant-induced arthritis in albino rats. The processed and unprocessed GTW were tested against Freund's complete adjuvant-induced arthritis in rats. Blood samples were collected for the estimation of interleukins (IL-1α, IL-1β) and tumor necrosis factor-α (TNF-α). It was concluded that physicochemical properties and anti-inflammatory activity of GTW nanoparticles could be improved by physical modification, such as particle size reduction using supercritical antisolvent (SAS) process. Further, SAS process was a powerful methodology for improving the physicochemical properties and anti-inflammatory activity of GTW.

  15. Burst wait time simulation of CALIBAN reactor at delayed super-critical state

    Energy Technology Data Exchange (ETDEWEB)

    Humbert, P. [Commissariat a l' Energie Atomique CEA, Centre de Bruyeres-le-Chatel, 91297 Arpajon (France); Authier, N.; Richard, B.; Grivot, P.; Casoli, P. [Commissariat a l' Energie Atomique CEA, Centre de Valduc, 21120 Is-sur-Tille (France)

    2012-07-01

    In the past, the super prompt critical wait time probability distribution was measured on CALIBAN fast burst reactor [4]. Afterwards, these experiments were simulated with a very good agreement by solving the non-extinction probability equation [5]. Recently, the burst wait time probability distribution has been measured at CEA-Valduc on CALIBAN at different delayed super-critical states [6]. However, in the delayed super-critical case the non-extinction probability does not give access to the wait time distribution. In this case it is necessary to compute the time dependent evolution of the full neutron count number probability distribution. In this paper we present the point model deterministic method used to calculate the probability distribution of the wait time before a prescribed count level taking into account prompt neutrons and delayed neutron precursors. This method is based on the solution of the time dependent adjoint Kolmogorov master equations for the number of detections using the generating function methodology [8,9,10] and inverse discrete Fourier transforms. The obtained results are then compared to the measurements and Monte-Carlo calculations based on the algorithm presented in [7]. (authors)

  16. Modeling the supercritical desorption of orange essential oil from a silica-gel bed

    Directory of Open Access Journals (Sweden)

    Silva E.A.

    2000-01-01

    Full Text Available One of the most important byproducts of the orange juice industry is the oil phase. This is a mixture of terpenes, alcohols, and aldehydes, dissolved in approximately 96% limonene. To satisfactorily use oil phase as an ingredient in the food and cosmetics industries separation of the limonene is required. One possibility is to use a fixed bed of silica gel to remove the light or aroma compounds from the limonene. The aroma substances are then extracted from the bed of silica gel using supercritical carbon dioxide. This work deals with the modeling of the desorption step of the process using mass balance equations coupled with the Langmuir equilibrium isotherm. Data taken from the literature for the overall extraction curves were used together with empirical correlations to calculate the concentration profile of solute in the supercritical phase at the bed outlet. The system of equations was solved by the finite volume technique. The overall extraction curves calculated were in good agreement with the experimental ones.

  17. MICROPOROUS PVDF-HFP-BASED POLYMER MEMBRANES FORMED FROM SUPERCRITICAL CO2 INDUCED PHASE SEPARATION

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Microporous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membranes following supercritical CO2 induced phase separation process were prepared using four solvents.The solid electrolytes of PVDF-HFP were formed by microporous PVDF-HFP membranes filled and swollen by a liquid electrolyte.The effect of the solvents on the morphology and structure,electrolyte absorptions and lithium ionic conductivity of the activated membranes were investigated.It was approved that all the membrane had the similar"sponge-like"and asymmetric structure when different solvent was used.As the mutual affinity between solvent and supercritical CO2 decreased,the membrane porosity and the average pore diameter increased.The PVDF-HFP membrane with porosity at 88% and pore size at 10 μm were successfully prepared.The uptake of electrolyte solution and lithium ionic conductivity could reach 487 wt% and 3.09×10-3 S/cm respectively for obtained membrane.

  18. The structure and appearance of winds from supercritical accretion disks. I - Numerical models

    Science.gov (United States)

    Meier, D. L.

    1979-01-01

    Equations for the structure and appearance of supercritical accretion disks and the radiation-driven winds which emanate from them are derived and solved by a steady-state hydrodynamic computer code with a relaxation technique used in stellar structure problems. The present model takes into account the mass of the accreting star, the total accretion rate, a generalization of the disk alpha parameter which accounts for heating by processes in addition to viscosity, and the ratio of the total luminosity to the Eddington luminosity. Solutions indicate that for accretion onto a hard-surfaced star, steady, optically thick winds result for even slightly supercritical accretion, and the object will appear as a supergiant star with a high mass loss rate and a nonblackbody spectrum. Winds from black hole accretion disks are expected to depend on the form of the accretion interior to the critical radius, possibly consisting of no ejection at all, a wind similar to that of a hard-surfaced star, or a column of material ejected from a hole in the accretion disk.

  19. Preparation and Characterization of Tripterygium wilfordii Multi-Glycoside Nanoparticle Using Supercritical Anti-Solvent Process

    Directory of Open Access Journals (Sweden)

    Fengli Chen

    2014-02-01

    Full Text Available The aim of this study was to prepare nanosized Tripterygium wilfordii multi-glycoside (GTW powders by the supercritical antisolvent precipitation process (SAS, and to evaluate the anti-inflammatory effects. Ethanol was used as solvent and carbon dioxide was used as an antisolvent. The effects of process parameters such as precipitation pressure (15–35 MPa, precipitation temperature (45–65 °C, drug solution flow rates (3–7 mL/min and drug concentrations (10–30 mg/mL were investigated. The nanospheres obtained with mean diameters ranged from 77.5 to 131.8 nm. The processed and unprocessed GTW were characterized by scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy and thermal gravimetric analysis. The present study was designed to investigate the beneficial effect of the GTW nanoparticles on adjuvant-induced arthritis in albino rats. The processed and unprocessed GTW were tested against Freund’s complete adjuvant-induced arthritis in rats. Blood samples were collected for the estimation of interleukins (IL-1α, IL-1β and tumor necrosis factor-α (TNF-α. It was concluded that physicochemical properties and anti-inflammatory activity of GTW nanoparticles could be improved by physical modification, such as particle size reduction using supercritical antisolvent (SAS process. Further, SAS process was a powerful methodology for improving the physicochemical properties and anti-inflammatory activity of GTW.

  20. Water/oil repellent property of polyester fabrics after supercritical carbon dioxide finishing

    Directory of Open Access Journals (Sweden)

    Xu Yan-Yan

    2015-01-01

    Full Text Available The strong permeability and driving force of supercritical carbon dioxide renders it an ideal medium for fabrics finishing. This paper is to use supercritical carbon dioxide medium with a solution of organic fluorine to fabricate water/oil repellent polyester fabrics. A series of characterization methods including Fourier transform infrared spectrometry, energy dispersive spectrometry, and scanning electron microscopy were carried out to evaluate the fabrics finishing. Fourier transform infrared spectrometry showed that the transmittance peak appeared at 1202.4 and 1147.4 cm-1, indicating the presence of -CF2- group on the surface of polyester fabrics. The results of energy dispersive spectrometer and scanning electron microscopy showed that the fluorine was evenly distributed on the fibers surface. In addition, a series of physical properties were detected, including contact angel, air permeability, breaking strength, and wearing resistance. The average water and hexadecane contact angles were 147.58° and 143.78°, respectively. Compared with the initial fabrics, the treated one has little change in air permeability, while its strength increased greatly. The treated fabrics gained good water/oil repellent properties while keeping good air permeability and improving mechanical property.

  1. PREPARATION OF MESOPOROUS TITANIA-SILICA AEROGELS BY CO2 SUPERCRITICAL EXTRACTION

    Directory of Open Access Journals (Sweden)

    Silvester Tursiloadi

    2010-06-01

    Full Text Available Stable anatase is attractive because of its notable functions for photocatalysis and photon-electron transfer.  TiO2-nanoparticles dispersed SiO2 wet gels were prepared by hydrolysis of Ti(OC4H9n4 and Si(OC2H54 in a 2-propanol solution with acid catalyst.  The solvent in the wet gels was supercritically extracted using CO2 at 60 oC and 22 Mpa in one-step.  Thermal evolution of the microstructure of the extracted gels (aerogels was evaluated by XRD measurements, TEM and N2 adsorption measurements. The as-extracted aerogel with a large specific surface area, more than 365 m2g-1, contained anatase nanoparticles, about 5 nm in diameter.  The anatase phase was stable after calcinations at temperatures up to 1000 oC, and BET specific surface area, total pore volume and average pore diameter did not change significantly after calcinations at temperature up to 800 oC.   Keywords: Stable anatase, sol-gel, CO2 supercritical extraction.

  2. Conceptual design of a thermalhydraulic loop for multiple test geometries at supercritical conditions named Supercritical Phenomena Experimental Test Apparatus (SPETA)

    Science.gov (United States)

    Adenariwo, Adepoju

    The efficiency of nuclear reactors can be improved by increasing the operating pressure of current nuclear reactors. Current CANDU-type nuclear reactors use heavy water as coolant at an outlet pressure of up to 11.5 MPa. Conceptual SuperCritical Water Reactors (SCWRs) will operate at a higher coolant outlet pressure of 25 MPa. Supercritical water technology has been used in advanced coal plants and its application proves promising to be employed in nuclear reactors. To better understand how supercritical water technology can be applied in nuclear power plants, supercritical water loops are used to study the heat transfer phenomena as it applies to CANDU-type reactors. A conceptual design of a loop known as the Supercritical Phenomena Experimental Apparatus (SPETA) has been done. This loop has been designed to fit in a 9 m by 2 m by 2.8 m enclosure that will be installed at the University of Ontario Institute of Technology Energy Research Laboratory. The loop include components to safely start up and shut down various test sections, produce a heat source to the test section, and to remove reject heat. It is expected that loop will be able to investigate the behaviour of supercritical water in various geometries including bare tubes, annulus tubes, and multi-element-type bundles. The experimental geometries are designed to match the fluid properties of Canadian SCWR fuel channel designs so that they are representative of a practical application of supercritical water technology in nuclear plants. This loop will investigate various test section orientations which are the horizontal, vertical, and inclined to investigate buoyancy effects. Frictional pressure drop effects and satisfactory methods of estimating hydraulic resistances in supercritical fluid shall also be estimated with the loop. Operating limits for SPETA have been established to be able to capture the important heat transfer phenomena at supercritical conditions. Heat balance and flow calculations have

  3. Chemistry and catalysis in supercritical media

    Energy Technology Data Exchange (ETDEWEB)

    Tumas, W.; Morgenstern, D.; Feng, S. [and others

    1997-07-01

    This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The aim of this research is to explore the potential of supercritical fluids as reaction media for stoichiometric and catalytic chemical transformations in an effort to develop new, environmentally-friendly methods for chemical synthesis or processing. This approach offers the possibility of opening up substantially different chemical pathways, increasing selectivity while enhancing reaction rates, facilitating downstream separations and mitigating the need for hazardous solvents. The authors describe investigations into a number of catalytic processes for which carbon dioxide represents a viable solvent replacement. In several cases they have observed significant enhancements in selectivity and/or reactivity relative to conventional organic solvents. They have investigated the following catalytic processes: (a) selective oxidation including dihydroxylation and epoxidation, (b) asymmetric hydrogenation and hydrogen transfer reduction, (c) Lewis acid catalyzed acylation and alkylation, and (c) coupling of amines with carbon dioxide to make isocyanates.

  4. Coal gasification with water under supercritical conditions

    Energy Technology Data Exchange (ETDEWEB)

    A.A. Vostrikov; S.A. Psarov; D.Yu. Dubov; O.N. Fedyaeva; M.Ya. Sokol [Russian Academy of Sciences, Novosibirsk (Russian Federastion). Kutateladze Institute of Thermophysics, Siberian Division

    2007-08-15

    The conversion of an array of coal particles in supercritical water (SCW) was studied in a semibatch reactor at a pressure of 30 MPa, 500-750{sup o}C, and a reaction time of 1-12 min. The bulk conversion, surface conversion, and random pore models were used to describe the conversion. The quantitative composition of reaction products was determined, and the dependence of the rate of reaction on the degree of coal conversion, reaction time, and reaction temperature was obtained on the assumption of a first-order reaction and the Arrhenius function. It was found that the gasification of coal under SCW conditions without the addition of oxidizing agents is a weakly endothermic process. The addition of CO{sub 2} to SCW decreased the rate of conversion and increased the yield of CO. It was found that, at a 90% conversion of the organic matter of coal (OMC) in a flow of SCW in a time of 2 min, the process power was 26 W/g per gram of OMC.

  5. Kinetics of coal conversion in supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Anatoli A. Vostrikov; Sergey A. Psarov; Dmitri Yu. Dubov; Oxana N. Fedyaeva; Mikhail Ya. Sokol [Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation). Institute of Thermophysics

    2007-09-15

    Conversion of the coal particle pack in supercritical water (SCW) was studied in the semibatch reactor under the pressure of P = 30 MPa, in the temperature range of T = 500-750{sup o}C, and in the reaction time of t = 60-720 s. The experimental results were analyzed within the framework of homogeneous, nonreacted core, and random pore models. The quantitative composition of conversion products was determined. Dependences of the conversion rate on the degree of coal conversion, reaction time, and temperature were described in an assumption of the first-order reaction and Arrhenius dependence. It was found that activation energy of conversion is E = 103 kJ/mol and the pre-exponential factor is A{sub 0} = 1.3 x 10{sup 3.1} s{sup -1}. It was revealed that coal gasification in SCW without oxidants is the weakly endothermic process. The addition of CO{sub 2} into SCW decreases the conversion rate and increases the CO yield. 20 refs., 8 figs.

  6. Supercritical fluids technology for clean biofuel production

    Institute of Scientific and Technical Information of China (English)

    Dongsheng Wen; H.Jiang; Kai Zhang

    2009-01-01

    Biofuels are liquid or gaseous fuels that are predominantly produced from biomass for transport sector applications.As biofuels are renewable,sustainable,carbon neutral and environmentally benign,they have been proposed as promising alternative fuels for gasoline and diesel engines.This paper reviews state-of-the-art application of the supercritical fluid(SCF)technique in biofuels production that includes biodiesel from vegetable oils via the transesterification process,bio-hydrogen from the gasification and bio-oil from the lique-faction of biomass,with biodiesel production as the main focus. The global biofuel situation and biofuel economics are also reviewed.The SCF has been shown to be a promising technique for future large-scale biofuel production,especially for biodiesel production from waster oil and fat.Compared with conventional biofuel production methods,the SCF technology possesses a number of advantages that includes fast inetics,high fuel production rate,ease of continuous operation and elimination of the necessity of catalysts.The harsh operation environment,i.e. the high temperature and high pressure,and its request on the materials and associated cost are the main concerns for its wide application.

  7. Some Organic Reactions in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    JIANG Huan-feng; YANG Xiao-yue; LI Guo-ping; ZOU Gang

    2004-01-01

    Organic reactions in supercritical carbon dioxide (scCO2) have facilitated great progress in recent years 1. ScCO2, as an environmentally friendly reaction medium, may be a substitute for volatile and toxic organic solvents and show some special advantages. Firstly, CO2 is inexpensive,nonflammable, nontoxic and chemical inert under many conditions. Secondly, scCO2 possesses hybrid properties of both liquid and gas, to the advantage of some reactions involving gaseous reagents. Control of the solvent density by variation of the temperature and pressure enables the solvent properties to be "tuned" to reactants. Finally, separating of CO2 from the reaction mixture is energy-efficient and simple. Here we disclose our new work on some organic reactions involving small molecules in scCO2.The results showed that the upper reactions in scCO2 could be carried out smoothly and thepressure of CO2 had a remarkable effect on the conversion and selectivity.

  8. Towards Overhauser DNP in supercritical CO2

    Science.gov (United States)

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

    2016-06-01

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

  9. The Supercritical Pile Model for GRBs

    Science.gov (United States)

    Kazanas, Demos

    2006-01-01

    We present the spectral and temporal radiative signatures expected within the Supercritical Pile model of Gamma Ray Bursts (GRB). This model is motivated by the need for a process that provides the dissipation necessary in GRB and presents a well defined scheme for converting the energy stored in the relativistic protons of the Relativistic Blast Waves (RBW) associated with GRB into radiation; at the same time it leads to spectra which exhibit a peak in the burst nuF(sub nu) distribution at an energy E(sub p) approximately equal to 1 MeV in the observer s frame, in agreement with observation and largely independent of the Lorentz factor GAMMA of the associated relativistic outflow. Furthermore, this scheme does not require (but does not preclude) acceleration of particles at the shock other than that provided by the isotropization of the flow bulk kinetic energy on the RBW frame. In the present paper we model in detail the evolution of protons, electrons and photons from a RBW to produce detailed spectra of the prompt GRB phase as a function of time from across a very broad range spanning roughly 4 log10 GAMMA decades in frequency. The model spectra are in general agreement with observations and provide a means for the delineating of the model parameters through direct comparison with trends observed in GRB properties.

  10. Towards Overhauser DNP in supercritical CO2.

    Science.gov (United States)

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

    2016-06-01

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

  11. Digested sewage sludge gasification in supercritical water.

    Science.gov (United States)

    Zhai, Yunbo; Wang, Chang; Chen, Hongmei; Li, Caiting; Zeng, Guangming; Pang, Daoxiong; Lu, Pei

    2013-04-01

    Digested sewage sludge gasification in supercritical water was studied. Influences of main reaction parameters, including temperature (623-698 K), pressure (25-35 Mpa), residence time (10-15 min) and dry matter content (5-25 wt%), were investigated to optimize the gasification process. The main gas products were methane, carbon monoxide, carbon dioxide and traces of ethene, etc. Results showed that 10 wt% dry matter content digested sewage sludge at a temperature of 698 K and residence time of 50 min, with a pressure of 25 MPa, were the most favorable conditions for the sewage sludge gasification and carbon gasification efficiencies. In addition, potassium carbonate (K2CO3) was also employed as the catalyst to make a comparison between gasification with and without catalyst. When 2.6 g K2CO3 was added, a gasification efficiency of 25.26% and a carbon gasification efficiency of 20.02% were achieved, which were almost four times as much as the efficiencies without catalyst. K2CO3 has been proved to be effective in sewage sludge gasification.

  12. Welding immiscible polymers with a supercritical fluid.

    Science.gov (United States)

    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. Synthesis of biodiesel from edible and non-edible oils in supercritical alcohols and enzymatic synthesis in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Vivek Rathore; Giridhar Madras [Indian Institute of Science, Bangalore (India). Department of Chemical Engineering

    2007-12-15

    Biodiesel is an attractive alternative fuel because it is environmentally friendly and can be synthesized from edible and non-edible oils. The synthesis of biodiesel from edible oils like palm oil and groundnut oil and from crude non-edible oils like Pongamia pinnata and Jatropha curcas was investigated in supercritical methanol and ethanol without using any catalyst from 200 to 400{sup o}C at 200 bar. The variables affecting the conversion during transesterification, such as molar ratio of alcohol to oil, temperature and time were investigated in supercritical methanol and ethanol. Biodiesel was also synthesized enzymatically with Novozym-435 lipase in presence of supercritical carbon dioxide. The effect of reaction variables such as temperature, molar ratio, enzyme loading and kinetics of the reaction was investigated for enzymatic synthesis in supercritical carbon dioxide. Very high conversions (>80%) were obtained within 10 min and nearly complete conversions were obtained at within 40 min for the synthesis of biodiesel in supercritical alcohols. However, conversions of only 60-70% were obtained in the enzymatic synthesis even after 8 h. 48 refs., 8 figs., 1 tab.

  14. Producing Polymer Fibers by Electrospinning in Supercritical Fluids

    Directory of Open Access Journals (Sweden)

    Lu Li

    2013-01-01

    Full Text Available Nanofibers have a wide range of applications, including filtration and biomedical engineering. Porous or hollow fibers with large surface-to-volume ratios are more popular in some fields than the common nanofibers. Porous nanofibers can be obtained through electrospinning with highly volatile solvents or through special treatment following electrospinning. A new process where electrospinning is conducted in supercritical or near-critical CO2 to produce porous or hollow nanofibers has been summarized. In addition, a process entailing compressed N2-assisted electrospinning was attempted to produce PVP nanofibers in this work, but it was proved to be unsuccessful. Since the fiber morphologies are dependent on the phase behavior of organic solvents in supercritical fluids, ASPEN PLUS 2006 was used to simulate the phase equilibrium of the solvent-supercritical fluid system to explain why porous or hollow fibers can be obtained in compressed CO2, but not in compressed N2.

  15. Research Progress on Preparation of Graphene by Supercritical Fluid Exfoliation

    Directory of Open Access Journals (Sweden)

    HU Sheng-fei

    2017-03-01

    Full Text Available As a new type of two-dimensional carbonaceous material, graphene has excellent physical properties and great application potential. The key problem to realize graphene industrialization is to find a large-scale preparing method of graphene with high quality and low cost. In this paper, the advantages and disadvantages of preparation methods for graphene were first reviewed, and then the mechanism, research status and characterization methods of supercritical fluids exfoliated method were introduced in details. And the features of supercritical fluids exfoliated method with the assistance of ultrasonication and pyrene-polymers were summarized. The advantages of supercritical fluids exfoliated method are simple equipment, processing conditions easy to achieve and products with high quality, and a new way of thinking for the industrial production of graphene is provided.

  16. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol

    Energy Technology Data Exchange (ETDEWEB)

    Saka, S.; Kusdiana, D. [Kyoto University, Kyoto (Japan). Dept. of Socio-Environmental Energy Science, Graduate School of Energy Science

    2001-01-01

    Transesterification reaction of rapeseed oil in supercritical methanol was investigated without using any catalyst. An experiment has been carried out in the batch-type reaction vessel preheated at 350 and 400{degree}C and at a pressure of 45-65 MPa, and with a molar ratio of 1:42 of the rapeseed oil to methanol. It was consequently demonstrated that, in a preheating temperature of 350{degree}C, 240 s of supercritical treatment of methanol was sufficient to convert the rapeseed oil to methyl esters and that, although the prepared methyl esters were basically the same as those of the common method with a basic catalyst, the yield of methyl esters by the former was found to be higher than that by the latter. In addition, it was found that this supercritical methanol process requires the shorter reaction time and simpler purification procedure because of the unused catalyst. 16 refs., 9 figs., 2 tabs.

  17. Application of supercritical antisolvent method in drug encapsulation: a review

    Directory of Open Access Journals (Sweden)

    Kalani M

    2011-07-01

    Full Text Available Mahshid Kalani, Robiah YunusChemical and Environmental Engineering, Faculty of Engineering, University Putra Malaysia, Selangor Darul Ehsan, MalaysiaAbstract: The review focuses on the application of supercritical fluids as antisolvents in the pharmaceutical field and demonstrates the supercritical antisolvent method in the use of drug encapsulation. The main factors for choosing the solvent and biodegradable polymer to produce fine particles to ensure effective drug delivery are emphasized and the effect of polymer structure on drug encapsulation is illustrated. The review also demonstrates the drug release mechanism and polymeric controlled release system, and discusses the effects of the various conditions in the process, such as pressure, temperature, concentration, chemical compositions (organic solvents, drug, and biodegradable polymer, nozzle geometry, CO2 flow rate, and the liquid phase flow rate on particle size and its distribution.Keywords: supercritical antisolvent method, drug encapsulation, particle size, drug release mechanisms, drug delivery

  18. A note on the total domination supercritical graphs

    Directory of Open Access Journals (Sweden)

    Abdollah Alimadadi

    2012-09-01

    Full Text Available Let $G$ be a connected spanning subgraph of $K_{s,s}$ and let $H$ be the complement of $G$ relative to $K_{s,s}$. The graph $G$ is {it $k$-supercritical} relative to $K_{s,s}$ if $gamma_t(G=k$ and $gamma_t(G+e=k-2$ for all $ein E(H$. The 2002 paper by T.W. Haynes, M.A. Henning and L.C. van der Merwe, "Total domination supercritical graphs with respect to relative complements" that appeared in Discrete Mathematics, 258 (2002, 361-371, presents a theorem (Theorem 11 to produce $(2k + 2$-supercritical graphs relative to $K_{2k+1, 2k+1}$ of diameter $5$, for each $kgeq 2$. However, the families of graphs in their proof are not the case. We present a correction of this theorem.

  19. The latent heat of vaporization of supercritical fluids

    Science.gov (United States)

    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 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.

  20. Bioactive insulin microparticles produced by supercritical fluid assisted atomization with an enhanced mixer.

    Science.gov (United States)

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

    2013-09-15

    Supercritical fluid assisted atomization introduced by a hydrodynamic cavitation mixer (SAA-HCM) was used to micronize insulin from aqueous solution without use of any organic solvents. Insulin microparticles produced under different operating conditions including solution type, solution concentration and precipitator temperature presented distinct morphologies such as highly folded, partly deflated, corrugated or smooth hollow spherical shape. Solution concentration had a striking influence on particle size, and insulin microparticles produced from acidic solution had mean diameters increasing from 1.4 μm to 2.7 μm when protein concentration increased from 3g/L to 50 g/L. HPLC chromatograms showed no degradation of insulin after SAA-HCM processing and FTIR, CD and fluorescence data further confirmed the structural stability. TGA analysis revealed that insulin microparticles remained moderate moisture content compared with raw material. In vivo study showed that insulin processed by SAA-HCM from acidic solution retained identical bioactivity. SAA-HCM is demonstrated to be a very promising process for insulin inhaled formulation development.

  1. Supercritical Extraction of Lycopene from Tomato Industrial Wastes with Ethane

    Directory of Open Access Journals (Sweden)

    Rui L. Mendes

    2012-07-01

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

  2. Destruction of energetic materials by supercritical water oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Beulow, S.J.; Dyer, R.B.; Harradine, D.M.; Robinson, J.M.; Oldenborg, R.C.; Funk, K.A.; McInroy, R.E.; Sanchez, J.A.; Spontarelli, T.

    1993-10-01

    Supercritical water oxidation is a relatively low-temperature process that can give high destruction efficiencies for a variety of hazardous chemical wastes. Results are presented examining the destruction of high explosives and propellants in supercritical water and the use of low temperature, low pressure hydrolysis as a pretreatment process. Reactions of cyclotrimethylene trinitramine (RDX), cyclotetramethylene tetranitramine (HMX), nitroguanidine (NQ), pentaerythritol tetranitrate (PETN), and 2,4,6-trinitrotoluene (TNT) are examined in a flow reactor operated at temperatures between 400{degrees}C and 650{degrees}C. Explosives are introduced into the reactor at concentrations below the solubility limits. For each of the compounds, over 99.9% is destroyed in less than 30 seconds at temperatures above 600{degrees}C. The reactions produce primarily N{sub 2}, N{sub 2}O,CO{sub 2}, and some nitrate and nitrite ions. The distribution of reaction products depends on reactor pressure, temperature, and oxidizer concentration. Kinetics studies of the reactions of nitrate and nitrite ions with various reducing reagents in supercritical water show that they can be rapidly and completely destroyed at temperatures above 525{degrees}C. The use of slurries and hydrolysis to introduce high concentrations of explosives into a supercritical water reactor is examined. For some compounds the rate of reaction depends on particle size. The hydrolysis of explosives at low temperatures (<100{degrees}C) and low pressures (<1 atm) under basic conditions produces water soluble, non-explosive products which are easily destroyed by supercritical water oxidation. Large pieces of explosives (13 cm diameter) have been successfully hydrolyzed. The rate, extent, and products of the hydrolysis depend on the type and concentration of base. Results from the base hydrolysis of triple base propellant M31A1E1 and the subsequent supercritical water oxidation of the hydrolysis products are presented.

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

    Science.gov (United States)

    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.

  4. Exp6-polar thermodynamics of dense supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Bastea, S; Fried, L E

    2007-12-13

    We introduce a simple polar fluid model for the thermodynamics of dense supercritical water based on a Buckingham (exp-6) core and point dipole representation of the water molecule. The proposed exp6-polar thermodynamics, based on ideas originally applied to dipolar hard spheres, performs very well when tested against molecular dynamics simulations. Comparisons of the model predictions with experimental data available for supercritical water yield excellent agreement for the shock Hugoniot, isotherms and sound speeds, and are also quite good for the self-diffusion constant and relative dielectric constant. We expect the present approach to be also useful for other small polar molecules and their mixtures.

  5. Measurement of flow in supercritical flow regime using cutthroat flumes

    Indian Academy of Sciences (India)

    Shrikant A Tekade; Avinash D Vasudeo; Aniruddha D Ghare; Ramesh N Ingle

    2016-02-01

    Cutthroat flume is commonly used for measurement of subcritical flow in open channel because of its simplicity and ease of construction. No experimental data is available in literature for measurement of flow in supercritical regime using cutthroat flume. The present paper finds the feasibility of cutthroat flume as a measurement device for flow in supercritical regime. Experimental data are generated to develop the relation between discharge and observed head at a specified location on upstream of throat section. Regression analysis for discharge and head indicated a good correlation. Based on all the experimental data generated, a relationship between discharge and head is proposed.

  6. Supercritical CO2 extraction of essential oils from Thymus vulgaris

    Directory of Open Access Journals (Sweden)

    S.A.B. Vieira de Melo

    2000-09-01

    Full Text Available Supercritical CO2 extraction of essential oil from Thymus vulgaris leaves was studied using experimental data recently obtained in the Florys S.p.A. laboratory. Mass transfer coefficients in the supercritical and solid phases from extraction curves at 40°C and 20 MPa were evaluated using a mathematical model based on the local adsorption equilibrium of essential oil on lipid in leaves. The adsorption equilibrium constant was fitted to these experimental data, and internal and external mass transfer resistances were calculated, allowing identification of the mechanism controlling the extraction process.

  7. AN INTERIM THERMODYNAMIC PROPERTY FORMULATION FOR SUPERCRITICAL n-HEXANE

    Directory of Open Access Journals (Sweden)

    Azzedine Abbaci

    2010-07-01

    Full Text Available Accurate information on the thermodynamic properties of supercritical fluids is highly sought for the chemical technology, especially, supercritical extraction technology. The thermodynamic properties of fluids near the critical region are strongly affected by the presence of fluctuations and therefore, can not be described by conventional equation. We have investigated an interim formulation for the behavior of the thermodynamic properties of n-hexane in the vicinity of the critical region. For this reason we have used the so-called “crossover model” to describe the thermodynamic properties of n-hexane in a wide range of temperatures and densities around the critical point.

  8. Supercritical carbon dioxide-based sterilization of decellularized heart valves.

    Science.gov (United States)

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

    2017-02-01

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

  9. Solubilities of triolein in supercritical CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, M.A.; Bernardo-Gil, M.G. [Instituto Superior Tecnico, Lisboa (Portugal). Dept. de Engenharia Quimica

    1995-11-01

    A vegetable oil typically consists of a range of triglycerides, approximately 10% diglycerides, and a small fraction of free fatty acids and other minor constituents. The use of supercritical carbon dioxide for solvent extraction is currently the subject of numerous investigations. The solubilities of triolein in supercritical carbon dioxide were measured over a temperature range of 308--328 K and at pressures between 8 and 20 MPa by the static method. The data were correlated by the model proposed by Chrastil and the modification proposed by Adachi and Lu and Del Valle and Aguilera.

  10. SOLID PHASE TRANSITION OF SYNDIOTACTIC POLYSTYRENE IN SUPERCRITICAL CO2

    Institute of Scientific and Technical Information of China (English)

    Yu-ying Li; Jia-song He

    2002-01-01

    Solid phase transition of the a form crystals to the β form crystals in syndiotactic polystyrene (sPS) samples has occurred in supercritical CO2. This transformation is different from those detected under other conditions. The effects of some factors (e.g. time, temperature, and pressure) on the solid phase transformation of sPS in supercritical CO2 were analyzed in detail. Experimental results show that longer time, higher temperature or higher pressure favors the transformation of the α form crystals to the β form crystals.

  11. Supercritical water oxidation - Concept analysis for evolutionary Space Station application

    Science.gov (United States)

    Hall, John B., Jr.; Brewer, Dana A.

    1986-01-01

    The ability of a supercritical water oxidation (SCWO) concept to reduce the number of processes needed in an evolutionary Space Station design's Environmental Control and Life Support System (ECLSS), while reducing resupply requirements and enhancing the integration of separate ECLSS functions into a single Supercritical Water Oxidation process, is evaluated. While not feasible for an initial operational capability Space Station, the SCWO's application to the evolutionary Space Station configuration would aid the integration of eight ECLSS functions into a single one, thereby significantly reducing program costs.

  12. Neural networks for predicting mass transfer parameters in supercritical extraction

    Directory of Open Access Journals (Sweden)

    A.P. Fonseca

    2000-12-01

    Full Text Available Neural networks have been investigated for predicting mass transfer coefficients from supercritical Carbon Dioxide/Ethanol/Water system. To avoid the difficulties associated with reduce experimental data set available for supercritical extraction in question, it was chosen to use a technique to generate new semi-empirical data. It combines experimental mass transfer coefficient with those obtained from correlation available in literature, producing an extended data set enough for efficient neural network identification. With respect to available experimental data, the results obtained to benefit neural networks in comparing with empirical correlations for predicting mass transfer parameters.

  13. Extraction of oil from wheat germ by supercritical CO2.

    Science.gov (United States)

    Piras, Alessandra; Rosa, Antonella; Falconieri, Danilo; Porcedda, Silvia; Dessì, Maria A; Marongiu, Bruno

    2009-07-15

    This study examined the supercritical fluid extraction of wheat germ oil. The effects of pressure (200-300 bar at 40 degrees C) and extraction time on the oil quality/quantity were studied. A comparison was also made between the relative qualities of material obtained by SFE and by organic solvent extraction. The extracts were analyzed for alpha-tocopherol and polyunsaturated fatty acid content. The maximum wheat germ oil yield at about 9% was obtained with supercritical carbon dioxide extraction at 300 bar, while fatty acid and alpha-tocopherol composition of the extracts was not remarkable affected by either pressure or the extraction method.

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

    Science.gov (United States)

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

    2014-11-01

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

  15. Molecular dynamics simulation of the key characteristics of the supercritical CO2-pentaerythritol tetraacetate system

    Science.gov (United States)

    Lei, Peiyu; Jin, Zunlong; Liu, Hong; Wang, Dingbiao; Liu, Donglai

    2016-12-01

    Supercritical CO2 is widely used in many fields of industry. Investigation of statistical mechanics of CO2 fluid under quasi critical and supercritical state has great significance. Equilibrium molecular dynamics (EMD) simulations are carried out to investigate the statistical mechanics and macroscopic performance of CO2 fluid under the quasi critical and supercritical state. The results show that the bond length and bond angle distributions for supercritical CO2 are Gaussian distribution basically. The dimers' proportion of supercritical CO2 system changes with pressure increasing. T-type dimer has high share within the system when pressure is higher than 9MPa. It can be inferred that T-type dimer leads to CO2 physical properties changing tempestuously under supercritical state. The effect that lubricating oil has on microstructure and heat transfer of supercritical CO2 is also investigated in the present work. The results show the lubricating oil produces significant effect on the dimers' structure under low pressure.

  16. Treatment of sewage sludge in supercritical water and evaluation of the combined process of supercritical water gasification and oxidation.

    Science.gov (United States)

    Qian, Lili; Wang, Shuzhong; Xu, Donghai; Guo, Yang; Tang, Xingying; Wang, Longfei

    2015-01-01

    Influences of temperature and oxidation coefficient (n) on sewage sludge treatment in supercritical water and its corresponding reaction mechanism were studied. Moreover, the combined process of supercritical water gasification (SCWG) and supercritical water oxidation (SCWO) was also investigated. The results show that ammonia nitrogen, phenols and pyridines are main refractory intermediates. The weight of solid products at 873K and n=4 is only 3.5wt.% of the initial weight, which is lower than that after combustion. Volatile organics in solid phase have almost released at 723K and n=0. Highest yield of combustible gases was obtained at n=0, and H2 yield can reach 11.81mol/kg at 873K. Furthermore, the combination of SCWG at 723K and SCWO at 873K with a total n=1 is feasible for its good effluent quality and low operation costs.

  17. Hydrothermal conversion of chrysotile asbestos using near supercritical conditions

    Energy Technology Data Exchange (ETDEWEB)

    Anastasiadou, Kalliopi; Axiotis, Dimosthenis [Laboratory of Toxic and Hazardous Waste Management, Department of Environmental Engineering, Technical University of Crete, Chania, P.C. 73100 (Greece); Gidarakos, Evangelos, E-mail: gidarako@mred.tuc.gr [Laboratory of Toxic and Hazardous Waste Management, Department of Environmental Engineering, Technical University of Crete, Chania, P.C. 73100 (Greece)

    2010-07-15

    The present research investigates, develops and evaluates the transformation of chrysotile asbestos into a non-hazardous material, such as forsterite, using an economically viable and safe method. The aim of this study is to convert fibrous chrysotile asbestos into an anhydrous magnesium silicate with a non-hazardous lamellar morphology using supercritical steam. The treatment method is characterized as hydrothermal in a temperature and pressure range of 300-700 deg. C and 1.75-5.80 MPa, respectively. Small amounts of asbestos (2.5 g) were treated in each experiment. Deionised water was used as the treatment solution. The treatment duration varied from approximately 1-5 h. Additional experiments took place using solutions of distilled water and small amounts of acetic acid, with the aim of attaining optimal treatment conditions. Crystal phases of the samples were determined by X-ray diffraction (XRD). The main phases present in the treated samples were forsterite, enstatite, and chrysotile asbestos. Lizardite and periclase were also found. The morphology of the treated chrysotile asbestos fibers was identified by scanning electron microscope (SEM). The fibrous form of chrysotile asbestos was converted into non-fibrous form of forsterite. In fact, none of the fibrous-needle-like morphology, with length equal to or greater than 5 {mu}m and diameter less than 3 {mu}m, which was responsible for the toxicity of the original material, was visible in the solid phase. The dissolution of magnesium from chrysotile asbestos was measured using volumetric determination by titration with EDTA. Leaching of magnesium into the liquid phase was observed. Clearly, the highest concentrations of dissolved magnesium are observed after hydrothermal treatment of chrysotile asbestos using acetic acid 1% (8.4-14.6%). Lowest concentrations of dissolved magnesium are obtained after hydrothermal treatment of chrysotile asbestos without using additives. Observing the results of the hydrothermal

  18. Hydrothermal conversion of chrysotile asbestos using near supercritical conditions.

    Science.gov (United States)

    Anastasiadou, Kalliopi; Axiotis, Dimosthenis; Gidarakos, Evangelos

    2010-07-15

    The present research investigates, develops and evaluates the transformation of chrysotile asbestos into a non-hazardous material, such as forsterite, using an economically viable and safe method. The aim of this study is to convert fibrous chrysotile asbestos into an anhydrous magnesium silicate with a non-hazardous lamellar morphology using supercritical steam. The treatment method is characterized as hydrothermal in a temperature and pressure range of 300-700 degrees C and 1.75-5.80 MPa, respectively. Small amounts of asbestos (2.5 g) were treated in each experiment. Deionised water was used as the treatment solution. The treatment duration varied from approximately 1-5 h. Additional experiments took place using solutions of distilled water and small amounts of acetic acid, with the aim of attaining optimal treatment conditions. Crystal phases of the samples were determined by X-ray diffraction (XRD). The main phases present in the treated samples were forsterite, enstatite, and chrysotile asbestos. Lizardite and periclase were also found. The morphology of the treated chrysotile asbestos fibers was identified by scanning electron microscope (SEM). The fibrous form of chrysotile asbestos was converted into non-fibrous form of forsterite. In fact, none of the fibrous-needle-like morphology, with length equal to or greater than 5 microm and diameter less than 3 microm, which was responsible for the toxicity of the original material, was visible in the solid phase. The dissolution of magnesium from chrysotile asbestos was measured using volumetric determination by titration with EDTA. Leaching of magnesium into the liquid phase was observed. Clearly, the highest concentrations of dissolved magnesium are observed after hydrothermal treatment of chrysotile asbestos using acetic acid 1% (8.4-14.6%). Lowest concentrations of dissolved magnesium are obtained after hydrothermal treatment of chrysotile asbestos without using additives. Observing the results of the

  19. Supercritical water pyrolysis of sewage sludge.

    Science.gov (United States)

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

    2017-01-01

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

  20. The structure of the homogeneous oxidation catalyst, Mn(II)(Br(-1))x, in supercritical water: an X-ray absorption fine-structure study.

    Science.gov (United States)

    Chen, Yongsheng; Fulton, John L; Partenheimer, Walter

    2005-10-12

    Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure about Mn(II) and Br(-1) ions that exist as contact ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr2 in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene as well as a number of other methylaromatic compounds. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne National Laboratory. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH2 and Mn-Br are 2.14 and 2.46 A, respectively. Direct contact ion pairs form with about 2 Br(-1) ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr2, below 1.0 m, changes from essentially [Mn(II)(H2O)6]+2 to [Mn(II)(H2O)2(Br(-1))2] in supercritical water (scH2O). When an excess of Br(-1) ion is added, the bromide coordination number increases and the number of water molecules decreases. The results show that the initial MnBr2 catalyst in scH2O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO.

  1. The structure of the homogeneous oxidation catalyst, Mn(II)-Br(-I)x, in supercritical water: An x-ray absorption fine structure study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yongsheng; Fulton, John L.; Partenheimer, Walt

    2005-10-12

    Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure of Mn(II) and Br(-I) ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr2 in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH2 and Mn-Br are 2.11 and 2.46 ?, respectively. Direct contact ion pairs form with about 2 Br(-I) ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr2, below 1.0 m, changes from essentially [Mn(II)(H2O)6]+2 to [Mn(II)(H2O)2(Br)2] in supercritical water (scH2O). When an excess of a Br(-I) ion is added, the bromide coordination increases and the number of water molecules decreases. The results show that the initial MnBr2 catalyst in scH2O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO.

  2. The Structure of the Homogeneous Oxidation Catalyst, Mn(II)(Br[superscript -1])[subscript x], in Supercritical Water: An X-ray Absorption Fine-Structure Study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yongsheng; Fulton, John L.; Partenheimer, Walter (PNNL)

    2008-09-25

    Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure about Mn(II) and Br{sup -1} ions that exist as contact ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr{sub 2} in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene as well as a number of other methylaromatic compounds. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne National Laboratory. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH{sub 2} and Mn-Br are 2.14 and 2.46 {angstrom}, respectively. Direct contact ion pairs form with about 2 Br{sup -1} ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr{sub 2}, below 1.0 m, changes from essentially [Mn(II)(H{sub 2}O){sub 6}]{sup +2} to [Mn(II)(H{sub 2}O){sub 2}(Br{sup -1}){sub 2}] in supercritical water (scH{sub 2}O). When an excess of Br{sup -1} ion is added, the bromide coordination number increases and the number of water molecules decreases. The results show that the initial MnBr{sub 2} catalyst in scH{sub 2}O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO.

  3. Supercritical gel drying: a powerful tool for tailoring symmetric porous PVDF-HFP membranes.

    Science.gov (United States)

    Cardea, S; Gugliuzza, A; Sessa, M; Aceto, M C; Drioli, E; Reverchon, E

    2009-01-01

    In this work, poly(vinylidene fluoride) copolymer with hexafluoropropylene (PVDF-HFP) membrane-like aerogels have been generated for the first time. PVDF-HFP gels have been prepared from polymer-acetone solutions by adding various amounts of ethanol. A series of supercritical drying experiments have been performed at different pressures (from 100 to 200 bar) and temperatures (from 35 to 45 degrees C) and at various polymer concentrations (from 5 to 12 wt %). The effects of the process conditions on the membrane morphology have been evaluated, and structure-property relationships have been found. In all cases, the membranes exhibit interconnected structures with nanosized pores and high porosity, leading to reduced resistance to the gas mass transfer and high hydrophobic character of the surfaces. These membrane-like aerogels promise to form a new class of highly hydrophobic porous interfaces, potentially suitable to be used in membrane operations based, for example, on the contactor technology.

  4. 3-D loaded scaffolds obtained by supercritical CO2 assisted process

    Science.gov (United States)

    Cardea, S.; Reverchon, E.

    2014-08-01

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

  5. Binary Diffusion Coefficients of Platinum(II) Acetylacetonate in Supercritical Carbon Dioxide.

    Science.gov (United States)

    Kong, Chang Yi; Siratori, Tomoya; Wang, Guosheng; Sako, Takeshi; Funazukuri, Toshitaka

    2013-11-14

    Binary diffusion coefficients (D12) and retention factors (k) of platinum(II) acetylacetonate at infinitesimal concentration in supercritical (sc) carbon dioxide (CO2) were measured by the chromatographic impulse response method with a poly(ethylene glycol) coated capillary column at temperatures from (308.15 to 343.15) K and pressures from (8.5 to 40.0) MPa, and D12 in liquid ethanol at temperatures from (298.15 to 333.15) K and atmospheric pressure by the Taylor dispersion method. As has been seen for our previously reported data on other metal complexes measured in sc CO2 and organic solvents, the D12 data in sc CO2 and liquid ethanol were represented by a function of temperature and solvent viscosity. The D12 values for metal complexes were not related to the solute molecular weights. The k values in sc CO2 were expressed by a function of temperature and CO2 density.

  6. Experimental evidence of a helical, supercritical instability in pipe flow of shear thinning fluids

    Science.gov (United States)

    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.

  7. Physicochemical properties and oral bioavailability of ursolic acid nanoparticles using supercritical anti-solvent (SAS) process.

    Science.gov (United States)

    Yang, Lei; Sun, Zhen; Zu, Yuangang; Zhao, Chunjian; Sun, Xiaowei; Zhang, Zhonghua; Zhang, Lin

    2012-05-01

    The objective of the study was to prepare ursolic acid (UA) nanoparticles using the supercritical anti-solvent (SAS) process and evaluate its physicochemical properties and oral bioavailability. The effects of four process variables, pressure, temperature, drug concentration and drug solution flow rate, on drug particle formation during SAS process, were investigated. Particles with mean particle size ranging from 139.2±19.7 to 1039.8±65.2nm were obtained by varying the process parameters. The UA was characterised by scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, thermal gravimetric analysis, specific surface area, dissolution test and bioavailability test. It was concluded that physicochemical properties and bioavailability of crystalline UA could be improved by physical modification, such as particle size reduction and generation of amorphous state using SAS process. Further, SAS process was a powerful methodology for improving the physicochemical properties and bioavailability of UA.

  8. Survival Time of a Censored Supercritical Galton-Watson Process

    CERN Document Server

    Couronné, Olivier

    2011-01-01

    We study the asymptotic behavior of the survival time of a supercritical Galton-Watson process censored at a certain level. As a byproduct we obtain the asymptotics for the speed of a particular case of a particle system with branching and selection introduced by B\\'erard and Gou\\'er\\'e (2010).

  9. Research activities on supercritical fluid science in food biotechnology.

    Science.gov (United States)

    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.

  10. Solubilities of sub- and supercritical carbon dioxide in polyester resins

    NARCIS (Netherlands)

    Nalawade, SP; Picchioni, F; Janssen, LPBM; Patil, VE; Keurentjes, JTF; Staudt, R; Nalawade, Sameer P.; Patil, Vishal E.; Keurentjes, Jos T.F.

    In supercritical carbon dioxide (CO2) assisted polymer processes the solubility of CO2 in a polymer plays a vital role. The higher the amount of CO2 dissolved in a polymer the higher is the viscosity reduction of the polymer. Solubilities Of CO2 in polyester resins based on propoxylated bisphenol

  11. Reforming of methanol and glycerol in supercritical water

    NARCIS (Netherlands)

    van Bennekom, J. G.; Venderbosch, R. H.; Assink, D.; Heeres, H. J.

    2011-01-01

    Reforming of pure glycerol, crude glycerin, and methanol (pure and in the presence of Na(2)CO(3)) in supercritical water was investigated. Continuous experiments were carried out at temperatures between 450 and 650 degrees C, residence times between 6 and 173 s, and feed concentrations of 3-20 wt%.

  12. Large Deviation for Supercritical Branching Processes with Immigration

    Institute of Scientific and Technical Information of China (English)

    Jing Ning LIU; Mei ZHANG

    2016-01-01

    In this paper, we study the large deviation for a supercritical branching process with immigration controlled by a sequence of non-negative integer-valued independently identical distributed random variables, improving the previous results for non immigration processes. We rely heavily on the detail description and limit property of the generating function of immigration processes.

  13. Stability of wheat germ oil obtained by supercritical carbon dioxide ...

    African Journals Online (AJOL)

    심정은

    with 1,3-regiospecific lipase at different temperatures (40 to 70°C) to produce diglycerides and ... Key words: Supercritical carbon dioxide, wheat germ oil, ethanolysis, .... Methanol (1 mL), replacing the extract, was used as the blank. The.

  14. Supercritical carbon dioxide process for pasteurization of fruit juices

    Science.gov (United States)

    Supercritical carbon dioxide (SCCO2) nonthermal processing inactivates microorganisms in juices using non-toxic and non-reactive CO2. However, data is lacking on the inactivation of E. coli K12 and L. plantarum in apple cider using pilot plant scale SCCO2 equipment. For this study, pasteurized pres...

  15. Supercritical Fluid Chromatography- A Hybrid of GC and LC

    Directory of Open Access Journals (Sweden)

    Kaushal K Chandrul

    2010-03-01

    Full Text Available

    High performance specifications and unique functionality of chromatographic techniques is a demand of pharmaceutical industry and research. This leads to the origin of Supercritical Fluid Chromatography (SFC. It is a rapidly expanding analytical technique. The main feature that differentiates SFC from other chromatographic techniques is the replacement of either the liquid or gas mobile phase with a supercritical fluid mobile phase. It is considered a hybrid of GC and LC technique. High diffusion coefficient and low viscosity of supercritical fluids is responsible for high speed analysis, high efficiency and high sensitivity. Low mobile-phase flow rate, density programming and compatability with GC and LC detectors make SFC a versatile chromatographic technique in analytical research and development. It has a unique characteristic of analyzing thermo labile or non-volatile substances. This review highlights the role of supercritical fluid chromatography in the separation of polymers, thermally labile pesticides, fatty acids, metal chelates and organometallic compounds, chiral and achiral molecules, identification and analysis of polar samples, explosives, drugs of abuse and application of SFC in forensic science (fingerprinting. 

  16. Supercritical fluid chromatography-A Hybrid of GC and LC

    Directory of Open Access Journals (Sweden)

    Neha Sethi

    2010-01-01

    Full Text Available High performance specifications and unique functionality of chromatographic techniques is a demand of pharmaceutical industry and research. This leads to the origin of Supercritical Fluid Chromatography (SFC. It is a rapidly expanding analytical technique. The main feature that differentiates SFC from other chromatographic techniques is the replacement of either the liquid or gas mobile phase with a supercritical fluid mobile phase. It is considered a hybrid of GC and LC technique. High diffusion coefficient and low viscosity of supercritical fluids is responsible for high speed analysis, high efficiency and high sensitivity. Low mobile-phase flow rate, density programming and compatability with GC and LC detectors make SFC a versatile chromatographic technique in analytical re-search and development. It has a unique characteristic of analyzing thermo labile or non-volatile substances. This review highlights the role of supercritical fluid chromatography in the separation of polymers, thermally labile pesticides, fatty acids, metal chelates and organometallic compounds, chiral and achiral molecules, identification and analysis of polar samples, explosives, drugs of abuse and application of SFC in forensic science (fingerprint-ing.

  17. Preparation of PMMA Foam by Supercritical CO2 with Ethanol

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Supercritical CO2 with ethanol as blowing agent foamed poly(methylmethacrylate) (PMMA) fiber at 308.15K and in the pressure range from 12-15MPa. The foam structure was detected using scanning electron microscope. It was found that the concentration of ethanol in the fluid is a major parameter to affect the foam structure.

  18. WaiGao Qiao: taking supercritical technology to new heights

    Energy Technology Data Exchange (ETDEWEB)

    Kessel, W.; Weiss, G.; Kawa, P. [Alstom, Stuttgart (Germany)

    2006-06-15

    In their first two years of commercial life the two supercritical boilers of Wai Gao Qiao Phase II, at 900 MWe each the largest operating coal fired units in China and the largest tangentially fired bituminous coal fired boilers in the world have performed reliably and efficiently. 11 figs., 1 tab.

  19. Extraction of heavy oil by supercritical carbon dioxide

    DEFF Research Database (Denmark)

    Rudyk, Svetlana Nikolayevna; Spirov, Pavel; Søgaard, Erik Gydesen

    2010-01-01

    The present study deals with the extraction of heavy oil by supercritical carbon dioxide at the pressure values changing from 16 to 56 MPa at the fixed value of temperature: 60oC. The amount of the recovered liquid phase of oil was calculated as a percentage of the extracted amount to the initial...

  20. Solubilities of ferrocene and acetylferrocene in supercritical carbon dioxide

    DEFF Research Database (Denmark)

    Kazemi, Somayeh; Belandria, Veronica; Janssen, Nico

    2012-01-01

    In this work, the solubilities of ferrocene and acetylferrocene in supercritical carbon dioxide (scCO2) were measured using an analytical method in a quasi-flow apparatus. High-performance liquid chromatography was applied through an online sampling procedure to determine the concentration...

  1. Capillary supercritical fluid chromatography-mass spectrometry (SFC-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Kalinoski, H.T.; Udseth, H.R.; Chess, E.K.; Smith, R.D.

    1986-10-01

    The physical and chemical characteristics of supercritical fluids have prompted the development of supercritical fluid chromatography (SFC) for the analysis of labile and less volatile compounds. High resolution chromatographic separations with efficiencies approaching those of gas chromatography and high speed analyses are possible in capillary SFC using pressure programming methods and narrow bore columns. Further refinement of the SFC-mass spectrometry interface (SFC-MS) provides the basis for extension to more polar fluid systems with greater solvating power and the selectivity and sensitivity of mass spectrometric detection. The use of polar modified fluids has been facilitated by advances in understanding of supercritical fluid phase behavior. Fluid mixtures have been prepared for analysis of more polar, higher molecular weight analytes, that allow mild chromatographic temperatures and allow full exploitation of selectivity offered through control of fluid pressure (i.e., density). Continuing development of the SFC-MS interface has led to designs which can be near routinely applied with fluids such as CO/sub 2/, and providing enhanced transport of truly nonvolatile compounds to the mass spectrometer ionization regions. These advances also include an SFC interface to a high resolution, dual electric magnetic sector instrument, allowing supercritical fluid solvents to be explited for on-line extraction-mass spectrometry for characterization of complex, often otherwise intractable, materials. 26 refs., 5 figs., 1 tab.

  2. Manometric determination of supercritical gas sorption in coal

    NARCIS (Netherlands)

    Van Hemert, P.

    2009-01-01

    The characteristics of the manometric method are investigated so that it can be used to obtain accurate data of sorption of supercritical gas in coal. Furthermore, data of the sorption of carbon dioxide, methane and nitrogen in coal at in situ conditions have been determined. Accurate data are req

  3. THE UNIQUENESS OF BIFURCATION TO SEPARATRIX LOOPS IN SUPERCRITICAL CASES

    Institute of Scientific and Technical Information of China (English)

    SUNJIANHUA

    1994-01-01

    In paper[4] the existence of bifurcation to separatrix loops in supercritical cases on the plane is studied.This note is a continuation of [4].The author proves the uniqueness of limit cycles in a neighb-orhood of the separatrix loop,and the results strengthen the relevant conclusions in[1-6].

  4. Promising flame retardant textile in supercritical carbon dioxide

    Science.gov (United States)

    Since carbon dioxide is non-toxic, non-flammable and cost-effective, supercritical carbon dioxide (scCO2) is widely used in textile dyeing applications. Due to its environmentally benign character, scCO2 is considered in green chemistry as a substitute for organic solvents in chemical reactions. O...

  5. Supercritical fluid chromatography for lipid analysis in foodstuffs.

    Science.gov (United States)

    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.

  6. Supercritical fluid extraction and bioactivity of cedarwood oil

    Science.gov (United States)

    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...

  7. SUPERCRITICAL WATER OXIDATION MODEL DEVELOPMENT FOR SELECTED EPA PRIORITY POLLUTANTS

    Science.gov (United States)

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

  8. Up-Scaled Supercritical Flow Synthesis of Hybrid Materials

    DEFF Research Database (Denmark)

    Hellstern, Henrik Christian; Becker, Jacob; Hald, Peter

    A new, up-scaled supercritical flow synthesis apparatus is currently under construction in Aarhus. A module based system allows for a range of parameter studies with improved parameter control. The dual-reactor setup enables both single phase and core-shell nanoparticle synthesis, and the large...

  9. Treatment of municipal sewage sludge in supercritical water: A review.

    Science.gov (United States)

    Qian, Lili; Wang, Shuzhong; Xu, Donghai; Guo, Yang; Tang, Xingying; Wang, Laisheng

    2016-02-01

    With increasing construction of wastewater treatment plants and stricter policies, municipal sewage sludge (MSS) disposal has become a serious problem. Treatment of MSS in supercritical water (SCW) can avoid the pre-drying procedure and secondary pollution of conventional methods. SCW treatment methods can be divided into supercritical water gasification (SCWG), supercritical water partial oxidation (SCWPO) and supercritical water oxidation (SCWO) technologies with increasing amounts of oxidants. Hydrogen-rich gases can be generated from MSS by SCWG or SCWPO technology using oxidants less than stoichiometric ratio while organic compounds can be completely degraded by SCWO technology with using an oxidant excess. For SCWG and SCWPO technologies, this paper reviews the influences of different process variables (MSS properties, moisture content, temperature, oxidant amount and catalysts) on the production of gases. For SCWO technology, this paper reviews research regarding the removal of organics with or without hydrothermal flames and the changes in heavy metal speciation and risk. Finally, typical systems for handling MSS are summarized and research needs and challenges are proposed.

  10. The solubilities of phosphate and sulfate salts in supercritical water

    NARCIS (Netherlands)

    Leusbrock, Ingo; Metz, Sybrand J.; Rexwinkel, Glenn; Versteeg, Geert F.

    2010-01-01

    Inorganic compounds are regularly present in aqueous streams. To understand their influence and behavior on these streams at supercritical conditions, little to no property data is available, which can be used as starting point for further research or application design. Since inorganic compounds te

  11. Supercritical Water Gasification of Biomass: A Literature and Technology Overview

    NARCIS (Netherlands)

    Yakaboylu, O.; Harinck, J.; Smit, K.G.; De Jong, W.

    2014-01-01

    The supercritical water gasification process is an alternative to both conventional gasification as well as anaerobic digestion as it does not require drying and the process takes place at much shorter residence times; a few minutes at most. The drastic changes in the thermo-physical properties of w

  12. Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

    Science.gov (United States)

    Rathke, Jerome W.; Klingler, Robert J.

    1993-01-01

    A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

  13. Green dyeing of cotton fabrics by supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    Zhang Juan

    2015-01-01

    Full Text Available Green dyeing process with zero waste water emission is a hot topic recently. This paper reveals that supercritical carbon dioxide is the best candidate for this purpose. Effects of thermodynamic parameters, such as enthalpy and entropy of activation, on dyeing process are studied experimentally.

  14. Supercritical water oxidation data acquisition testing. Final report, Volume I

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-11-01

    This report discusses the phase one testing of a data acquisition system for a supercritical water waste oxidation system. The system is designed to destroy a wide range of organic materials in mixed wastes. The design and testing of the MODAR Oxidizer is discussed. An analysis of the optimized runs is included.

  15. Solubilities of sub- and supercritical carbon dioxide in polyester resins

    NARCIS (Netherlands)

    Nalawade, SP; Picchioni, F; Janssen, LPBM; Patil, VE; Keurentjes, JTF; Staudt, R; Nalawade, Sameer P.; Patil, Vishal E.; Keurentjes, Jos T.F.

    2006-01-01

    In supercritical carbon dioxide (CO2) assisted polymer processes the solubility of CO2 in a polymer plays a vital role. The higher the amount of CO2 dissolved in a polymer the higher is the viscosity reduction of the polymer. Solubilities Of CO2 in polyester resins based on propoxylated bisphenol (P

  16. Aerobic Oxidation of Methyl Vinyl Ketone in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    OUYANG,Xiao-Yue(欧阳小月); JIANG,Huan-Feng(江焕峰); CHENG,Jin-Sheng(程金生); ZHANG,Qun-Jian(张群健)

    2002-01-01

    Aerobic oxidation of methyl vinyl ketone to acetal in supercritical carbon dioxide are achieved in high conversion and high selectivity when oxygen pressure reaches 0.5MPa. The effects of cocatalysts,additive, pressure and temperature of the reaction are studied in detail.

  17. Preparation of Aromatic Polycarbonate Nanoparticles using Supercritical Carbon Dioxide

    Science.gov (United States)

    Lee, Jun-Young; Song, Cheong-Hun; Kim, Joong-In; Kim, Jung-Hyun

    2002-04-01

    A novel synthetic process for producing aromatic polycarbonate (PC) nanoparticles using supercritical CO2 was developed. The objective of the present research work was to synthesize high molecular weight PC nanoparticles using transesterification between bisphenol-A (BPA) and diphenyl carbonate (DPC) in supercritical CO2 which is an excellent plasticizing agent and a good solvent for phenol, a by-product of the reaction. Poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) tri-block copolymer with CO2-phobic anchor and CO2-philic tail group was used as a stabilizer for the preparation of stable dispersions of BPA-DPC mixture in a CO2 continuous phase. As the reaction was proceeding, phenol formed from the reaction was dissolved and diffused into supercritical CO2 phase. The PC nanoparticles were isolated by simple venting of the supercritical CO2 from the reactor. Spherical morphology of PC particles was confirmed by scanning electron microscopy. Particle size and morphology of PC particles were modified upon variation of the process conditions. The resulting PC particles with a nano-size of 30-140 nm have a high molecular weight ( M w) of 3.1×105 (g/mol).

  18. Synthesis of fatty acid starch esters in supercritical carbon dioxide

    NARCIS (Netherlands)

    Muljana, Henky; van der Knoop, Sjoerd; Keijzer, Danielle; Picchioni, Francesco; Janssen, Leon P. B. M.; Heeres, Hero J.

    2010-01-01

    This manuscript describes an exploratory study on the synthesis of fatty acid/potato starch esters using supercritical carbon dioxide (scCO(2)) as the solvent. The effects of process variables such as pressure (6-25 MPa), temperature (120-150 degrees C) and various basic catalysts and fatty acid der

  19. Supercritical flows past a square cylinder with rounded corners

    Science.gov (United States)

    Cao, Yong; Tamura, Tetsuro

    2017-08-01

    Large-eddy simulations were used to investigate the supercritical aerodynamics of a square cylinder with rounded corners in comparison with those in the subcritical regime. First, the numerical methods, especially the dynamic mixed model, were validated on the basis of their prediction of supercritical flows past a circular cylinder. Then, the supercritical flows past a rounded-corner square cylinder were simulated and systematically clarified. Strong Reynolds number (Re) effects existed in the forces and local pressures as Re increased from o(104) to o(106). Changeover of flow patterns occurred as Re increased. At the supercritical Re, the free stream overall flowed along the cross sections of the cylinder, separated from the leeward corners and generated Karman vortices behind the cylinder. This pattern resulted in a much smaller recirculation region behind the cylinder compared with the subcritical flow. At the micro level, the flow experienced laminar separation and flow reattachment near the frontal corners, followed by the spatial development of turbulent boundary layers (TBLs) on the side faces and turbulent separation near the leeward corners. The feedback by large-scale primary vortex shedding and the small-scale turbulent motions in the high-frequency region with a slope of -5/3 were detected in the TBL. Their interaction affected the spanwise correlations of wall pressure fluctuations. The TBL on the side face differed from the zero-pressure-gradient flat-plate one; it was subjected to pressure gradients varying in space and time.

  20. Hydrogel Nanoparticles from Supercritical Technology for Pharmaceutical and Seismological Applications

    Science.gov (United States)

    Hemingway, Melinda Graham

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

  1. X65钢在含超临界CO2的NaCl溶液中腐蚀机制的讨论%CORROSION MECHANISM DISCUSSION OF X65 STEEL IN NaCl SOLUTION SATURATED WITH SUPERCRITICAL CO2

    Institute of Scientific and Technical Information of China (English)

    魏亮; 庞晓露; 高克玮

    2015-01-01

    利用高温高压反应釜研究了X65管线钢在含有超临界CO2(supercritical CO.SC CO2)的3.5%NaC1溶液、去离子水以及溶解有NaC1溶液的超临界CO2相中的腐蚀行为.结果表明,C1-的存在导致X65钢在含有饱和SC CO2的NaC1溶液中的腐蚀速率显著升高,腐蚀产物膜的晶粒形貌发生改变.X65钢在超临界CO2相中的腐蚀速率远远低于在NaCl溶液中的腐蚀速率,但出现局部腐蚀.X65钢在含有SC CO2的NaC1溶液中的腐蚀分为3个阶段:第一个阶段为基体快速溶解阶段,表面没有FeCO3生成;第二阶段为FeCO3开始沉积阶段,形成的FeCO3腐蚀产物膜不完整,增大了阴极还原反应面积,导致腐蚀加速;第三阶段为腐蚀产物膜保护阶段,形成的腐蚀产物膜致密性逐渐提高,保护性好,但C1-仍然可以穿过腐蚀产物膜到达膜基界面,从而加速钢的腐蚀.建立了普通管线钢在含C1-溶液中的超临界CO2腐蚀模型.

  2. 超临界氨合成%AMMONIA SYNTHESIS AT SUPERCRITICAL CONDITIONS

    Institute of Scientific and Technical Information of China (English)

    刘化章; 唐浩东; 李小年

    2004-01-01

    Ammonia synthesis at supercritical conditions was first studied over iron and active carbonsupported ruthenium catalysts in a fixed-bed reactor. The influences of 15 kinds of different supercritical media, such as alkanes of C7-C13, 1, 2, 3, 4-tetrahydronaphthalene, cis-decalin, o-xylene,ethylbenzene, quinolin, n-hexane and aniline etc. and reaction conditions (catalyst, temperature, space velocity, particial pressure of media) on ammonia at supercritical condition were investigated.Supercritical medium was decomposed under reaction conditions over Fe and Ru/AC catalysts. The decomposition products deactivated the catalysts. Alkane decomposed the least, and the rate of deactivation was the slowest. Therefore alklane was a relatively good medium. The decomposion of supercritical medium was the key for the deactivation of catalysts. Another important reason for the decrease of ammonia concentration was that the effective pressure of syngas decreased because of the presence of supercritical media. The active temperature of catalyst was the decisive factor in supercritical ammonia synthesis. Supercritical catalytic reaction was viable only at a lower temperature. Ammonia ynthesis at supercritical conditions is possible if a catalyst with active temperature lower than 573 K could e developed and the decomposition of supercritical media could be prevented.

  3. Dense CO2 as a Solute, Co-Solute or Co-Solvent in Particle Formation Processes: A Review

    Directory of Open Access Journals (Sweden)

    Ana V. M. Nunes

    2011-11-01

    Full Text Available The application of dense gases in particle formation processes has attracted great attention due to documented advantages over conventional technologies. In particular, the use of dense CO2 in the process has been subject of many works and explored in a variety of different techniques. This article presents a review of the current available techniques in use in particle formation processes, focusing exclusively on those employing dense CO2 as a solute, co-solute or co-solvent during the process, such as PGSS (Particles from gas-saturated solutions®, CPF (Concentrated Powder Form®, CPCSP (Continuous Powder Coating Spraying Process, CAN-BD (Carbon dioxide Assisted Nebulization with a Bubble Dryer®, SEA (Supercritical Enhanced Atomization, SAA (Supercritical Fluid-Assisted Atomization, PGSS-Drying and DELOS (Depressurization of an Expanded Liquid Organic Solution. Special emphasis is given to modifications introduced in the different techniques, as well as the limitations that have been overcome.

  4. Pulsed corona discharge at atmospheric and supercritical conditions

    Science.gov (United States)

    Lock, Evgeniya Hristova

    Pulsed corona discharge is one of the non-equilibrium plasma techniques, by which electrical power is mainly utilized to generate high-energy electrons. These react further with the background gas to produce radicals, which can be further employed in chemically selective reactions. Study of the initiation of pulsed corona discharge in carbon dioxide and air was conducted. Furthermore due to its high removal efficiency, energy yields and good economy, the pulsed corona discharge was employed for removal of methanol and dimethyl sulfide. These compounds are part of the volatile organic compounds (VOC) air pollutants, which are subject of severe environmental regulations due to their toxicity, environmental persistence and intensity of smell. The study provides experimental data for the destruction of methanol and dimethyl sulfide from dry and humid air streams. The effects of the process parameters, including applied voltage, pulse repetition rate, initial concentration of pollutants, temperature and humidity on the destruction and removal efficiency and energy cost are analyzed. Specific consideration is given to the formation of unwanted byproducts. The study on plasma application for pollution control showed that small amounts of dispersed liquid droplets increase the efficiency of the chemical utilization of the high-energy electrons and reduce the required power. So media that could facilitate homogeneous and heterogeneous chemistry at the same time would enhance the efficiency of the removal process. Such medium that has properties intermediate between the gas and liquid phase is the supercritical fluid. Generation of plasma in supercritical fluids is an unexplored area in plasma science. The generation of plasma at elevated pressures usually requires high voltages or small interelectrode distances. The supercritical phase is characterized by extensive cluster formation in the vicinity of the critical point. Typically the clusters have lower ionization

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

    Science.gov (United States)

    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

  6. Regulation of Renewable Energy Sources to Optimal Power Flow Solutions Using ADMM

    Energy Technology Data Exchange (ETDEWEB)

    Dall-Anese, Emiliano [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Zhang, Yijian [Iowa State University; Hong, Mingyi [Iowa State University; Dhople, Sairaj [University of Minnesota; Xu, Zi [Shanghai University

    2017-07-03

    This paper considers power distribution systems featuring renewable energy sources (RESs), and develops a distributed optimization method to steer the RES output powers to solutions of AC optimal power flow (OPF) problems. The design of the proposed method leverages suitable linear approximations of the AC-power flow equations, and is based on the Alternating Direction Method of Multipliers (ADMM). Convergence of the RES-inverter output powers to solutions of the OPF problem is established under suitable conditions on the stepsize as well as mismatches between the commanded setpoints and actual RES output powers. In a broad sense, the methods and results proposed here are also applicable to other distributed optimization problem setups with ADMM and inexact dual updates.

  7. Regulation of Renewable Energy Sources to Optimal Power Flow Solutions Using ADMM: Preprint

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yijian; Hong, Mingyi; Dall' Anese, Emiliano; Dhople, Sairaj; Xu, Zi

    2017-03-03

    This paper considers power distribution systems featuring renewable energy sources (RESs), and develops a distributed optimization method to steer the RES output powers to solutions of AC optimal power flow (OPF) problems. The design of the proposed method leverages suitable linear approximations of the AC-power flow equations, and is based on the Alternating Direction Method of Multipliers (ADMM). Convergence of the RES-inverter output powers to solutions of the OPF problem is established under suitable conditions on the stepsize as well as mismatches between the commanded setpoints and actual RES output powers. In a broad sense, the methods and results proposed here are also applicable to other distributed optimization problem setups with ADMM and inexact dual updates.

  8. Solubility of 1:1 Alkali Nitrates and Chlorides in Near-Critical and Supercritical Water : 1 Alkali Nitrates and Chlorides in Near-Critical and Supercritical Water

    NARCIS (Netherlands)

    Leusbrock, Ingo; Metz, Sybrand J.; Rexwinkel, Glenn; Versteeg, Geert F.

    2009-01-01

    To increase the available data oil systems containing supercritical water and inorganic compounds, all experimental setup was designed to investigate the solubilities of inorganic compounds Ill supercritical water, In this work, three alkali chloride salts (LiCl, NaCl, KCl) and three alkali nitrate

  9. On the supercritical KdV equation with time-oscillating nonlinearity

    CERN Document Server

    Panthee, M

    2011-01-01

    For the initial value problem (IVP) associated the generalized Korteweg-de Vries (gKdV) equation with supercritical nonlinearity, u_{t}+\\partial_x^3u+\\partial_x(u^{k+1}) =0,\\qquad k\\geq 5, numerical evidence \\cite{BDKM1, BSS1} shows that there are initial data $\\phi\\in H^1(\\mathbb{R})$ such that the corresponding solution may blow-up in finite time. Also, with the evidence from numerical simulation \\cite{ACKM, KP}, the physicists claim that a periodic time dependent term in factor of the nonlinearity would disturb the blow-up solution, either accelerating or delaying it. In this work, we investigate the IVP associated to the gKdV equation u_{t}+\\partial_x^3u+g(\\omega t)\\partial_x(u^{k+1}) =0, where $g$ is a periodic function and $k\\geq 5$ is an integer. We prove that, for given initial data $\\phi \\in H^1(\\R)$, as $|\\omega|\\to \\infty$, the solution $u_{\\omega}$ converges to the solution $U$ of the initial value problem associated to U_{t}+\\partial_x^3U+m(g)\\partial_x(U^{k+1}) =0, with the same initial data, wh...

  10. Symmetry and decay of traveling wave solutions to the Whitham equation

    Science.gov (United States)

    Bruell, Gabriele; Ehrnström, Mats; Pei, Long

    2017-04-01

    This paper is concerned with decay and symmetry properties of solitary-wave solutions to a nonlocal shallow-water wave model. An exponential decay result for supercritical solitary-wave solutions is given. Moreover, it is shown that all such solitary-wave solutions are symmetric and monotone on either side of the crest. The proof is based on the method of moving planes. Furthermore, a close relation between symmetric and traveling-wave solutions is established.

  11. Comparison between s-CO2 and other supercritical working Fluids (s-Ethane, s-SF6, s-Xe, s-CH4, s-N2) in Line-Focusing Solar Power Plants with supercritical Brayton power cycles

    OpenAIRE

    Coco Enríquez, Luis; Muñoz Antón, Javier; Martínez-Val Peñalosa, Jose Maria

    2016-01-01

    Thermosolar power plants with linear solar collectors and Rankine or Brayton power cycles are maturing as a competitive solution for reducing CO2 emissions in power plants as an alternative to traditional fossil and nuclear fuels. In this context, nowadays a great effort is being invested in supercritical Carbon Dioxide Brayton (s-CO2) power cycles for optimizing the line-focusing solar plants performance and reducing the cost of renewable energy. However, there are other working fluids with ...

  12. Supercritical Water Reactor Cycle for Medium Power Applications

    Energy Technology Data Exchange (ETDEWEB)

    BD Middleton; J Buongiorno

    2007-04-25

    Scoping studies for a power conversion system based on a direct-cycle supercritical water reactor have been conducted. The electric power range of interest is 5-30 MWe with a design point of 20 MWe. The overall design objective is to develop a system that has minimized physical size and performs satisfactorily over a broad range of operating conditions. The design constraints are as follows: Net cycle thermal efficiency {ge}20%; Steam turbine outlet quality {ge}90%; and Pumping power {le}2500 kW (at nominal conditions). Three basic cycle configurations were analyzed. Listed in order of increased plant complexity, they are: (1) Simple supercritical Rankine cycle; (2) All-supercritical Brayton cycle; and (3) Supercritical Rankine cycle with feedwater preheating. The sensitivity of these three configurations to various parameters, such as reactor exit temperature, reactor pressure, condenser pressure, etc., was assessed. The Thermoflex software package was used for this task. The results are as follows: (a) The simple supercritical Rankine cycle offers the greatest hardware simplification, but its high reactor temperature rise and reactor outlet temperature may pose serious problems from the viewpoint of thermal stresses, stability and materials in the core. (b) The all-supercritical Brayton cycle is not a contender, due to its poor thermal efficiency. (c) The supercritical Rankine cycle with feedwater preheating affords acceptable thermal efficiency with lower reactor temperature rise and outlet temperature. (d) The use of a moisture separator improves the performance of the supercritical Rankine cycle with feedwater preheating and allows for a further reduction of the reactor outlet temperature, thus it was selected for the next step. Preliminary engineering design of the supercritical Rankine cycle with feedwater preheating and moisture separation was performed. All major components including the turbine, feedwater heater, feedwater pump, condenser, condenser pump

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  14. Estimation of the Isotherms of Phenol on Activated Carbons and Polymeric Adsorbents under Supercritical Condition

    Institute of Scientific and Technical Information of China (English)

    奚红霞; 谢兰英; 李祥斌; 李忠

    2003-01-01

    A method named as "volume-expanding and pressure-reducing adsorption" is proposed. It can be used to measure the isotherms under supercritical condition. The adsorption isotherms of phenol on activated carbons and polymeric adsorbents are estimated and compared respectively for the systems of "phenol-activated carbon-supercritical fluid CO2" and "phenol-polymeric adsorbent-supercritical fluid CO2". The results show that the amount of phenol adsorbed on the activated carbons and the polymeric adsorbents under the supercritical condition is much less than that under the general condition, which can be utilized to develop a technology regenerating the activated carbon with supercritical fluid. Moreover, the effects of ethyl alcohol, used as the third component, on the isotherms of phenol on the activated carbons and polymeric adsorbents under the supercritical condition are also investigated.

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

    Science.gov (United States)

    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.

  16. Recent Progress in the Development of Supercritical Carbon Dioxide-Soluble Metal Ion Extractants: Aggregation, Extraction, and Solubility Properties of Silicon-Substituted Alkylenediphosphonic Acids

    Energy Technology Data Exchange (ETDEWEB)

    Dietz, Mark L.; McAlister, Daniel R.; Stepinski, Dominique C.; Zalupski, Peter R.; Dzilawa, Julie A.; Barrans, Richard E.; Hess, J.N.; Rubas, Audris V.; Chiarizia, Renato; Lubbers, Christopher M.; Scurto, Aaron M.; Brennecke, Joan F.; Herlinger, Albert W.

    2003-09-11

    Partially esterified alkylenediphosphonic acids (DPAs) have been shown to be effective reagents for the extraction of actinide ions from acidic aqueous solution into conventional organic solvents. Efforts to employ these compounds in supercritical fluid extraction have been hampered by their modest solubility in unmodified supercritical carbon dioxide (SC-CO2). In an effort to design DPAs that are soluble in SC-CO2, a variety of silicon-substituted alkylenediphosphonic acids have been prepared and characterized, and their behavior compared with that of conventional alkyl-substituted reagents. Silicon substitution is shown to enhance the CO2-philicity of the reagents, while other structural features, in particular, the number of methylene groups bridging the phosphorus atoms of the extractant, are shown to exert a significant influence on their aggregation and extraction properties. The identification of DPAs combining desirable extraction properties with adequate solubility in SC-CO2 is shown to be facilitated by the application of molecular connectivity indices.

  17. Application of aluminum-supported Pd, Rh, and Rh-Pd nanoparticles in supercritical carbon dioxide system for hydrodebromination of polybrominated diphenyl ethers.

    Science.gov (United States)

    Wu, Ben-Zen; Sun, Yu-Jie; Chen, Yan-Hua; Yak, Hwa Kwang; Yu, Jya-Jyun; Liao, Weisheng; Chiu, KongHwa; Peng, Shie-Ming

    2016-08-01

    Al-powder-supported Pd, Rh, and Rh-Pd catalysts were synthesized through a spontaneous redox reaction in aqueous solutions. These catalysts hydrodebrominated 4- and 4,4'-bromodiphenyl ethers in supercritical carbon dioxide at 200 atm CO2 containing 10 atm H2 and 80 °C in 1 h. Diphenyl ether was the major product of Pd/Al. Rh/Al and Rh-Pd/Al further hydrogenated two benzene rings of diphenyl ether to form dicyclohexyl ether. The hydrogenolysis of CO bonds on diphenyl ether over Rh/Al and Rh-Pd/Al was observed to generate cyclohexanol and cyclohexane (Rh-Pd/Al among three catalysts is suggested to be used for ex situ degradation of polybrominated diphenyl ethers in supercritical carbon dioxide. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Supercritical and Transcritical Real-Fluid Mixing in Diesel Engine Applications

    Science.gov (United States)

    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

  19. Molecular Dynamics Simulation of Diffusion Coefficients of Oxygen, Nitrogen and Sodium Chloride in Supercritical Water

    Institute of Scientific and Technical Information of China (English)

    肖吉; 陆九芳; 陈健; 李以圭

    2001-01-01

    Molecular dynamics simulation has been performed to determine the infinite-dilution diffusion coefficients of oxygen and nitrogen, and the diffusion coefficients of NaCl in supercritical water from 703.2- 763.2 K and 30-45 MPa.The results obtained show that the diffusion coefficients in supercritical water increase with temperature, while decreasing with pressure. Nevertheless, the diffusion coefficients in supercritical water are much larger than those in normal water.

  20. Development of a Facility for Combustion Stability Experiments at Supercritical Pressure

    Science.gov (United States)

    2013-12-01

    Supercritical Pressure 5a. CONTRACT NUMBER In-House 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Wegener, Leyva, Forliti, Talley 5d... supercritical pressures that are relevant to high-performance liquid rocket engines, accurately-controlled and cryogenically-conditioned propellants, and... Supercritical Pressure Jeffrey L. Wegener1 University of California at Los Angeles, CA 90095 Ivett A. Leyva2 AFRL/RQRE, Edwards AFB, CA 93524

  1. Supercritical Carbon Dioxide Extraction of Benzene in Poly(vinyl acetate) and Polystyrene

    OpenAIRE

    佐々木, 正和; 滝嶌, 繁樹; 舛岡, 弘勝

    1989-01-01

    In order to test the applicability of the supercritical fluid extraction technique to the separation of impurities in polymers, separation of benzene from two polymers of poly(vinyl acetate) and polystyrene was carried out using supercritical carbon dioxide. Figure 1 shows a schematic diagram of the supercritical fluid extraction apparatus. It consists of the following sections: (1) compression of carbon dioxide, (2) extraction, and (3) control and measurement of carbon dioxide flow rates...

  2. [Effect of entrainer on supercritical CO2 for extraction of tradition and herbal drugs].

    Science.gov (United States)

    Xi, Yanbin; Xia, Xiaohui; Jin, Ran; Zhang, Yu; Yang, Liqin; Tang, Shihuan

    2009-06-01

    Type, mode of affiliating, mechanism of action of entrainer in Supercritical CO2 on extraction of Chinese traditional and herbal drugs were briefly reviewed. Application of entrainer in Supercritical CO2 on extraction of flavones, terpenes, sterols, and saponins in Chinese traditional and herbal drugs were recommended in particular. Some problems and directions in research of entrainer in Supercritical CO2 on extraction of Chinese traditional and herbal drugs were shown in this paper.

  3. Applications of Supercritical Fluid Extraction (SFE) of Palm Oil and Oil from Natural Sources

    OpenAIRE

    Mohd Omar Ab Kadir; Sahena Ferdosh; Mohd Yazid Abdul Manap; Nik Norulaini Nik Ab Rahman; Mohammed Jahurul Haque Akanda; Mohammed Zaidul Islam Sarker

    2012-01-01

    Supercritical fluid extraction (SFE), which has received much interest in its use and further development for industrial applications, is a method that offers some advantages over conventional methods, especially for the palm oil industry. SC-CO2 refers to supercritical fluid extraction (SFE) that uses carbon dioxide (CO2) as a solvent which is a nontoxic, inexpensive, nonflammable, and nonpolluting supercritical fluid solvent for the extraction of natural products. Almost 100% oil can be ext...

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

    National Research Council Canada - National Science Library

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

    2015-01-01

    Supercritical carbon dioxide (SCCO2) extraction and fractionation of Spirulina platensis was carried out to obtain functional compounds with antioxidant, antimicrobial and enzyme inhibitory activities...

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

    Science.gov (United States)

    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.

  6. Research and application of multiple model predictive control in Ultra-supercritical boiler-turbine system

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Hengfeng; Yan, Weiwu; Wang, Guoliang; Hu, Yong; Li, Nan [Shanghai Jiao Tong Univ., Shanghai (China). Dept. of Automation; Ministry of Education of China, Shanghai (China). Key Lab. of System Control and Information Processing; Chen, Shihe; Zhang, Xi [Guangdong Electric Power Research Institute, Guangzhou (China)

    2013-07-01

    Based on analyzing the characteristics of Ultra-supercritical unit, this paper introduced a multiple model MCPC (Multivariable Constrained Predictive Control) structure with three inputs and three outputs for coordination control of Ultra-supercritical unit. In the structure, double-layer structure of optimization was used to obtain good steady and dynamic performance, and piecewise linear models at the different operating points of Ultra-supercritical unit were used to deal with nonlinearity. In the real-time simulation, nonlinear model of 1000MW Ultra-supercritical unit in was considered. Finally, the result of real-time simulation was given in the paper.

  7. Preparation and characterization of foxtail millet bran oil using subcritical propane and supercritical carbon dioxide extraction

    National Research Council Canada - National Science Library

    Shi, Yuzhong; Ma, Yuxiang; Zhang, Ruitin; Ma, Hanjun; Liu, Benguo

    2015-01-01

    ...), supercritical carbon dioxide extraction (SCE) and subcritical propane extraction (SPE) and analyzed the yield, physicochemical property, fatty acid profile, tocopherol composition, oil oxidative stability in this study...

  8. Formation of methotrexate-PLLA-PEG-PLLA composite microspheres by microencapsulation through a process of suspension-enhanced dispersion by supercritical CO2

    Directory of Open Access Journals (Sweden)

    Chen AZ

    2012-06-01

    Full Text Available Ai-Zheng Chen,1,2 Guang-Ya Wang,1 Shi-Bin Wang,1,2 Li Li,1 Yuan-Gang Liu,1,2 Chen Zhao11College of Chemical Engineering, 2Institute of Pharmaceutical Engineering, Institute of Biomaterials and Tissue Engineering, Huaqiao University, Xiamen 361021, ChinaBackground: The aim of this study was to improve the drug loading, encapsulation efficiency, and sustained-release properties of supercritical CO2-based drug-loaded polymer carriers via a process of suspension-enhanced dispersion by supercritical CO2 (SpEDS, which is an advanced version of solution-enhanced dispersion by supercritical CO2 (SEDS.Methods: Methotrexate nanoparticles were successfully microencapsulated into poly (L-lactide-poly(ethylene glycol-poly(L-lactide (PLLA-PEG-PLLA by SpEDS. Methotrexate nanoparticles were first prepared by SEDS, then suspended in PLLA-PEG-PLLA solution, and finally microencapsulated into PLLA-PEG-PLLA via SpEDS, where an "injector" was utilized in the suspension delivery system.Results: After microencapsulation, the composite methotrexate (MTX-PLLA-PEG-PLLA microspheres obtained had a mean particle size of 545 nm, drug loading of 13.7%, and an encapsulation efficiency of 39.2%. After an initial burst release, with around 65% of the total methotrexate being released in the first 3 hours, the MTX-PLLA-PEG-PLLA microspheres released methotrexate in a sustained manner, with 85% of the total methotrexate dose released within 23 hours and nearly 100% within 144 hours.Conclusion: Compared with a parallel study of the coprecipitation process, microencapsulation using SpEDS offered greater potential to manufacture drug-loaded polymer microspheres for a drug delivery system.Keywords: drug loading, encapsulation efficiency, methotrexate, nanoparticles, poly(L-lactide, supercritical CO2 sustained release

  9. Experimental study of choking flow of water at supercritical conditions

    Science.gov (United States)

    Muftuoglu, Altan

    Future nuclear reactors will operate at a coolant pressure close to 25 MPa and at outlet temperatures ranging from 500°C to 625°C. As a result, the outlet flow enthalpy in future Supercritical Water-Cooled Reactors (SCWR) will be much higher than those of actual ones which can increase overall nuclear plant efficiencies up to 48%. However, under such flow conditions, the thermal-hydraulic behavior of supercritical water is not fully known, e.g., pressure drop, forced convection and heat transfer deterioration, critical and blowdown flow rate, etc. Up to now, only a very limited number of studies have been performed under supercritical conditions. Moreover, these studies are conducted at conditions that are not representative of future SCWRs. In addition, existing choked flow data have been collected from experiments at atmospheric discharge pressure conditions and in most cases by using working fluids different than water which constrain researchers to analyze the data correctly. In particular, the knowledge of critical (choked) discharge of supercritical fluids is mandatory to perform nuclear reactor safety analyses and to design key mechanical components (e.g., control and safety relief valves, etc.). Hence, an experimental supercritical water facility has been built at Ecole Polytechnique de Montreal which allows researchers to perform choking flow experiments under supercritical conditions. The facility can also be used to carry out heat transfer and pressure drop experiments under supercritical conditions. In this thesis, we present the results obtained at this facility using a test section that contains a 1 mm inside diameter, 3.17 mm long orifice plate with sharp edges. Thus, 545 choking flow of water data points are obtained under supercritical conditions for flow pressures ranging from 22.1 MPa to 32.1 MPa, flow temperatures ranging from 50°C to 502°C and for discharge pressures from 0.1 MPa to 3.6 MPa. Obtained data are compared with the data given in

  10. Neutron scattering characterization of homopolymers and graft-copolymer micelles in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Chillura-Martino, D; Triolo, R. [Palermo Univ. (Italy). Ist. di Chimica Fisica; McClain, J.B. [North Carolina Univ., Chapel Hill, NC (United States)] [and others

    1995-12-31

    Supercritical fluids are becoming an attractive alternative to the liquid solvents traditionally used as polymerization media. As the synthesis proceeds, a wide range of colloidal aggregates form, but there has hitherto been no way to measure such structures directly. We have applied small-angle neutron scattering (SANS) to characterize such systems, and although SCF polymerizations are carried out at high pressures, the penetrating power of the neutron beam means that typical cell windows are virtually transparent. Systems studied include molecules soluble in CO{sub 2} (e.g. polyfluoro-octyl acrylate or PFOA) and this polymer has previously been shown to exhibit a positive second virial coefficient (A{sub 2}). Other CO{sub 2}-soluble polymers include hexafluoro-polypropylene oxide (HFPPO), which appears to have a second virial coefficient which is close to zero (10{sup 4}A{sub 2} {approx_equal} 0 +{+-} 0.2 cm{sup 3} g{sup -2} mol). Polydimethylsiloxane (PDMS), is soluble on the molecular level only in the limit of dilute solution and seems to form aggregates as the concentration increases (c > 0.01 g cm{sup -3}). Other polymers (e.g. polystyrene) are insoluble in CO{sub 2}, though polymerizations may be accomplished via the use of PS-PFOA blockcopolymer stabilizers, which are also amenable to SANS characterization, and have been shown to form micelles in CO{sub 2}. Other amphiphilic surfactant molecules that form micelles include PFOA-polyethylene oxide (PFOA-PEO) graft copolymers, which swell as the CO{sub 2} medium is saturated with water. These systems have been characterized by SANS, by taking advantage of the different contrast options afforded by substituting D{sub 2}O for H{sub 2}O. This paper illustrates the utility of SANS to measure molecular dimensions, thermodynamic variables, molecular weights, micelle structures etc. in supercritical CO{sub 2}.

  11. Near-membrane refractometry using supercritical angle fluorescence

    CERN Document Server

    Brunstein, Maia; Oheim, Martin

    2016-01-01

    Total internal reflection fluorescence (TIRF) microscopy and its variants are key technologies for visualizing the dynamics of single molecules or organelles in live cells. Yet, truely quantitative TIRF remains problematic. One unknown hampering the interpretation of evanescent-wave excited fluorescence intensities is the undetermined cell refractive index (RI). Here, we use a combination of TIRF excitation and supercritical angle fluorescence emission detection to directly mea-sure the average RI in the 'footprint' region of the cell, during imaging. Our RI measurement is based on the determination on a back-focal plane image of the critical angle separating supercritical and undercritial fluorescence emission components. We validate our method by imaging mouse embryonic fibroblasts. By targeting various dyes and fluorescent-protein chimerae to vesicles, the plasma membrane as well as mitochondria and the ER, we demonstrate local RI measurements with subcellular resolution on a standard TIRF microscope with ...

  12. Application of supercritical antisolvent method in drug encapsulation: a review.

    Science.gov (United States)

    Kalani, Mahshid; Yunus, Robiah

    2011-01-01

    The review focuses on the application of supercritical fluids as antisolvents in the pharmaceutical field and demonstrates the supercritical antisolvent method in the use of drug encapsulation. The main factors for choosing the solvent and biodegradable polymer to produce fine particles to ensure effective drug delivery are emphasized and the effect of polymer structure on drug encapsulation is illustrated. The review also demonstrates the drug release mechanism and polymeric controlled release system, and discusses the effects of the various conditions in the process, such as pressure, temperature, concentration, chemical compositions (organic solvents, drug, and biodegradable polymer), nozzle geometry, CO(2) flow rate, and the liquid phase flow rate on particle size and its distribution.

  13. Supercritical Fluid Parameters in Organic Rankine Cycle Applications

    Directory of Open Access Journals (Sweden)

    Andreas Schuster

    2008-09-01

    Full Text Available Nowadays, the use of Organic Rankine Cycle (ORC in decentralised applications is linked with the fact that this process allows to use low temperature heat sources and offers an advantageous efficiency in small-scale applications. Many state of the art applications like geothermal and biomass fired power plants as well as new applications like solar desalination with reverse osmosis, waste heat recovery from biogas digestion plants or micro-Combined Heat and Power (micro-CHP systems can successfully use the ORC process. The investigation of supercritical parameters in ORC applications seems to bring promising results in decentralised energy production. This paper presents the results from the simulation of the ORC process in normal and supercritical fluid parameters and discusses the efficiency variation in various applications.

  14. Supercritical Saltwater Spray for Marine Cloud Brightening (MCB)

    Science.gov (United States)

    Neukermans, A.; Cooper, G. F.; Foster, J.; Galbraith, L. K.; Johnston, D.; Ormond, B.; Wang, Q.

    2012-12-01

    Solar Radiation Management (SRM), including both stratospheric sulfur aerosol delivery and MCB, has emerged as the leading contender for geoengineering. Field research in MCB would require a technique capable of producing 1017 salt nuclei/sec from a single source on a seagoing vessel. Spraying supercritical saltwater has emerged as a viable technology, at least for research purposes. Under optimum conditions a single 50-μm nozzle produces 1014 suitable nuclei/sec. Power consumption is high (1-2 MW), but 95% of the required energy is in the form of heat that can probably be obtained from wasted ship-engine heat. While its implementation is conceptually simple, the corrosive nature of supercritical saltwater makes the material requirements very demanding. Progress on this work is detailed.

  15. The Supercritical Pile Model: Prompt Emission Across the Electromagnetic Spectrum

    Science.gov (United States)

    Kazanas, Demos; Mastichiadis, A.

    2008-01-01

    The "Supercritical Pile" GRB model is an economical model that provides the dissipation necessary to convert explosively the energy stored in relativistic protons in the blast wave of a GRB into radiation; at the same time it produces spectra whose luminosity peaks at 1 MeV in the lab frame, the result of the kinematics of the proton-photon - pair production reaction that effects the conversion of proton energy to radiation. We outline the fundamental notions behind the "Supercritical Pile" model and discuss the resulting spectra of the prompt emission from optical to gamma-ray energies of order Gamma^2 m_ec^2, (Gamma is the Lorentz factor of the blast wave) present even in the absence of an accelerated particle distribution and compare our results to bursts that cover this entire energy range. Particular emphasis is given on the emission at the GLAST energy range both in the prompt and the afterglow stages of the burst.

  16. Solubility of the sesquiterpene alcohol patchoulol in supercritical carbon dioxide.

    Science.gov (United States)

    Hybertson, Brooks M

    2007-01-01

    The solubility of the sesquiterpene alcohol patchoulol in supercritical carbon dioxide was measured at P ranging from 10.0 MPa to 25.0 MPa and T of 40.0 and 50.0 °C using a simple microsampling type apparatus with a 100.5 µL sample loop to remove aliquots for off-line analysis. The system was first validated using vanillin with off-line spectrophotometric analysis, then utilized for patchoulol measurements with off-line GC-MS analysis. The measured solubility of patchoulol in supercritical CO(2) ranged from mole fractions of 0.43 × 10(-3) at 10.0 MPa and 50.0 °C to 9.45 × 10(-3) at 25.0 MPa and 40.0 °C.

  17. Extraction of tannin by Acacia mearnsii with supercritical fluids

    Directory of Open Access Journals (Sweden)

    Marcia Regina Pansera

    2004-11-01

    Full Text Available Studies were carried out on solvent and supercritical extraction to obtain natural tannins. The results showed that the best co-solvent to extract tannin with CO2 supercritical was water with a concentration of 5.0% and the best trap rinse solvent was methanol.Neste trabalho foram utilizados dois processos de extração de tanino vegetal: extração a quente em aparelho Soxhlet e extração com CO2 supercítico. Os resultados mostraram que o melhor co-solvente para extração de taninos com CO2 supercrítico foi a água na concentração de 5% e o melhor solvente para lavagem do trap foi o metanol.

  18. Extraction of copper ions by supercritical carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Complexation combined with supercritical fluid extraction was used to extract Cu2+ in this study. The effects of pressure, temperature, volume of CO2 on the efficiency of extraction were systematically investigated. At the optimum condition a 57.32% recovery was achieved. Addition of suitable amount of methanol(v/v = 5 % ) to the supercritical CO2 can increase in the extraction of Cu2+ (72.69 %, RSD = 2.12 %, n = 3). And the recovery can further increase in the presence of non-ionic surfactant Triton X-100 because of its function of solubilization. Surfactant was first used in the extraction of metal ions in the present study, and the results are satisfied (90.52%, RSD=2.20%, n =3).

  19. Exploration of the gasification of Spirulina algae in supercritical water.

    Science.gov (United States)

    Miller, Andrew; Hendry, Doug; Wilkinson, Nikolas; Venkitasamy, Chandrasekar; Jacoby, William

    2012-09-01

    This study presents non-catalytic gasification of Spirulina algae in supercritical water using a plug flow reactor and a mechanism for feeding solid carbon streams into high pressure (>25 MPa) environments. A 2(III)(3-1) factorial experimental design explored the effect of concentration, temperature, and residence time on gasification reactions. A positive displacement pump fed algae slurries into the reactor at a temperature range of 550-600°C, and residence times between 4 and 9s. The results indicate that algae gasify efficiently in supercritical water, highlighting the potential for a high throughput process. Additional experiments determined Arrhenius parameters of Spirulina algae. This study also presents a model of the gasification reaction using the estimated activation energy (108 kJ/mol) and other Arrhenius parameters at plug flow conditions. The maximum rate of gasification under the conditions studied of 53 g/Ls is much higher than previously reported.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-09-01

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

  1. Methanolysis of Poly(ethylene terephthalate) in Supercritical Phase

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The depolymerization of poly(ethylene terephthalate, PET) in supercritical methanol is studied using a stainless stirred autoclave at temperature of 255~260℃, pressure of 8.5~14.0 MPa, and methanol/PET weight ratio of 3~8. Under the optimal conditions, the PET is depolymerized completely to its monomers in 60 min. The main products of the reaction are dimethyl terephthalate and ethylene glycol. There are still some small amounts of byproducts, such as methyl-(2-hydroxyethyl) terephthalate, bis(hydroxyethyl) terephthalate, dimers and oligomers. Reversed-phase high performance liquid chrom- atography and gas chromatography are used to analyze solid products and liquid products respectively. The results of depolymerization show that the yield of dimethyl terephthalate and the degree of PET depolymerization are dependent on the reaction temperature, weight ratio of methanol to PET and reaction time. But the reaction pressure has little influence on the depolymerization as long as methanol is in supercritical state.

  2. The Supercritical Pile Model: Prompt Emission Across the Electromagnetic Spectrum

    Science.gov (United States)

    Kazanas, Demos; Mastichiadis, A.

    2008-01-01

    The "Supercritical Pile" GRB model is an economical model that provides the dissipation necessary to convert explosively the energy stored in relativistic protons in the blast wave of a GRB into radiation; at the same time it produces spectra whose luminosity peaks at 1 MeV in the lab frame, the result of the kinematics of the proton-photon - pair production reaction that effects the conversion of proton energy to radiation. We outline the fundamental notions behind the "Supercritical Pile" model and discuss the resulting spectra of the prompt emission from optical to gamma-ray energies of order Gamma^2 m_ec^2, (Gamma is the Lorentz factor of the blast wave) present even in the absence of an accelerated particle distribution and compare our results to bursts that cover this entire energy range. Particular emphasis is given on the emission at the GLAST energy range both in the prompt and the afterglow stages of the burst.

  3. ABRUPT DEFLECTED SUPERCRITICAL WATER FLOW IN SLOPED CHANNELS

    Institute of Scientific and Technical Information of China (English)

    LIU Ya-kun; NI Han-gen

    2008-01-01

    The effect of the bottom slope on abrupt deflected supercritical water flow was experimentally and theoretically studied. Model tests were conducted in a flume of 1.2 m wide and 2.6 m long with sloped bottom at an angle 35.54o, its length of deflector was 0.2 m and the deflection angles were 15o and 30o. An approximate method for calculatjng the shock wave angle and depth ratio of the abrupt deflected supercritical water flow was suggested, and a correction coefficient for the hydrodynamic pressure was introduced to generalize the momentum equation in the direction perpendicular to the shock front. It must be noticed that in the sloped channel the shock wave angle and the depth ratio are no longer constant as those in the horizontal channels, but slowly change along the shock front. The calculated results are in good agreement with measured data.

  4. Prediction of the viscosity of supercritical fluid mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Vesovic, V. [Imperial Coll., London (United Kingdom). T.H. Huxley School of Environment, Earth Sciences and Engineering; Assael, M.J.; Gallis, Z.A. [Aristotle Univ., Thessaloniki (Greece). Faculty of Chemical Engineering

    1998-09-01

    A method for predicting the viscosity of supercritical, multicomponent fluid mixtures, at any density, from the zero-density viscosity of pure components is presented. The method is based upon the results for a rigid-sphere model, suitably interpreted to apply to real fluids, and on the finding that the excess viscosity of pure supercritical fluids can be adequately described by a density function independent of temperature. The density range of the method extends to twice the critical density of the pure component with the smallest critical density. The only exception is for the methane-rich mixtures where the mixture density should not exceed 12000 mol{center_dot}m{sup {minus}3}. The uncertainty ascribed to the predictions made by this method is of the order of {+-}5%.

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

    Science.gov (United States)

    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.

  6. [Extraction of lobetyolin from codonopsis with supercritical CO2].

    Science.gov (United States)

    Liu, Tongju; Li, Shufen; Min, Jiang; Bao, Xiaomei

    2009-03-01

    To develop a green and rapid method for extraction of lobetyolin from C. pilosula. Extraction of lobetyolin from C. pilosula with supercritical carbon dioxide in the presence of ethanol was studied. The effects of pressure, temperature, volume of cosolvent and extraction time on efficiency and their interactive relationships were discussed, based on central composite design and response surface methodology (RSM). The key effect factor was volume of cosolvent. The extraction yield of lobetyolin was 0.078 6 mg x g(-1) when C. pilosula (40-60 mesh) was extracted at 30 MPa, 60 degrees C and 2 L x min(-1) (as CO2 in normal pressure and temperature) for 100 minutes with supercritical CO2 and 1 mL x min(-1) ethanol as dynamic cosolvent. This result is better than that obtained from traditional method. Therefore, the optimized process is valuable for extraction of lobetyolin from C. pilosula.

  7. Design of Supercritical Carbon Dioxide Compressor Testing Loop

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seong Gu; Lee, Jeong Ik; Ahn, Yoon Han; Lee, Je Kyoung [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of); Yoon, Ho Joon; Addad, Yacine [KUSTAR, Abu Dhabi (United Arab Emirates)

    2012-05-15

    For small and medium-sized reactors and Generation IV reactors such as sodium-cooled fast reactor are recently under development actively. The supercritical CO{sub 2} Brayton cycle is considered as an attractive cycle for the above mentioned nuclear systems. This is because the supercritical CO{sub 2} Brayton cycle (S-CO{sub 2} cycle) is especially effective to reduce the volume of power generation system, which occupies 1.5{approx}2 times more space than the primary nuclear system in general. Comparing to traditional water-vapor cycle and helium cycle, the S-CO{sub 2} system has relatively much less volume and component size. Therefore, S-CO{sub 2} cycle can be used for many purposes such as nuclear ship propulsion where volume requirement is strict, or a small nuclear reactor when it is constructed on geographically limited area

  8. Modification and processing of polymers using supercritical fluids

    CERN Document Server

    Webb, P B

    2000-01-01

    This thesis describes the application of supercritical CO sub 2 to the modification and processing of polymeric materials. Chapter 1 begins by outlining the physical properties of supercritical fluids (SCF's) and the characteristic signatures of critical point phase transitions. This chapter then goes on to describe some of the current applications of SCF's and the advantages that can be gained by working in such media with particular reference to applications involving polymers. Whilst SCF's may offer several advantages compared to conventional liquid solvents, the switch to a SCF process is by no means a straightforward task and requires consideration of several factors in its development. Such considerations are discussed in the first part of chapter 2, again with particular reference to the modification and processing of polymers. Chapter 3 details the preliminary results obtained from experiments performed with the new high-pressure IR cell; initial experiments were carried out to study the effectiveness...

  9. Homogeneous catalysis of valeronitrile hydrolysis under supercritical conditions.

    Science.gov (United States)

    Sarlea, Michael; Kohl, Sabine; Blickhan, Nina; Vogel, Herbert

    2012-01-01

    Supercritical nitrile hydrolysis can be used for both, amide and acid production as well as waste water treatment, as the hydrolysis products show good biodegradability. The conventional process at ambient conditions requires large amounts of mineral acid or base. Approaches that use supercritical water as a green solvent without a catalyst have been investigated over recent years. Findings for valeronitrile hydrolysis presented recently showed promising reaction rates and valeric acid yields. In an attempt to further maximize product yield and to better understand the impact of the pH, reactions in dilute sulfuric acid (0.01 mol L(-1)) were performed in a continuous high-pressure laboratory-scale apparatus at 400-500 °C, 30 MPa, and a maximum residence time of 100 s. Results from both reaction media were compared with regard to productivity and sustainability.

  10. Scalable organic solvent free supercritical fluid spray drying process for producing dry protein formulations.

    Science.gov (United States)

    Nuchuchua, O; Every, H A; Hofland, G W; Jiskoot, W

    2014-11-01

    In this study, we evaluated the influence of supercritical carbon dioxide (scCO2) spray drying conditions, in the absence of organic solvent, on the ability to produce dry protein/trehalose formulations at 1:10 and 1:4 (w/w) ratios. When using a 4L drying vessel, we found that decreasing the solution flow rate and solution volume, or increasing the scCO2 flow rate resulted in a significant reduction in the residual water content in dried products (Karl Fischer titration). The best conditions were then used to evaluate the ability to scale the scCO2 spray drying process from 4L to 10L chamber. The ratio of scCO2 and solution flow rate was kept constant. The products on both scales exhibited similar residual moisture contents, particle morphologies (SEM), and glass transition temperatures (DSC). After reconstitution, the lysozyme activity (enzymatic assay) and structure (circular dichroism, HP-SEC) were fully preserved, but the sub-visible particle content was slightly increased (flow imaging microscopy, nanoparticle tracking analysis). Furthermore, the drying condition was applicable to other proteins resulting in products of similar quality as the lysozyme formulations. In conclusion, we established scCO2 spray drying processing conditions for protein formulations without an organic solvent that holds promise for the industrial production of dry protein formulations.

  11. Effect of solvent type on the nanoparticle formation of atorvastatin calcium by the supercritical antisolvent process.

    Science.gov (United States)

    Kim, Min-Soo; Song, Ha-Seung; Park, Hee Jun; Hwang, Sung-Joo

    2012-01-01

    The aims of this study were to identify how the solvent selection affects particle formation and to examine the effect of the initial drug solution concentration on mean particle size and particle size distribution in the supercritical antisolvent (SAS) process. Amorphous atorvastatin calcium was precipitated from seven different solvents using the SAS process. Particles with mean particle size ranging between 62.6 and 1493.7 nm were obtained by varying organic solvent type and solution concentration. By changing the solvent, we observed large variations in particle size and particle size distribution, accompanied by different particle morphologies. Particles obtained from acetone and tetrahydrofuran (THF) were compact and spherical fine particles, whereas those from N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO) were agglomerated, with rough surfaces and relatively larger particle sizes. Interestingly, the mean particle size of atorvastatin calcium increased with an increase in the boiling point of the organic solvent used. Thus, for atorvastatin particle formation via the SAS process, particle size was determined mainly by evaporation of the organic solvent into the antisolvent phase. In addition, the mean particle size was increased with increasing drug solution concentration. In this study, from the aspects of particle size and solvent toxicity, acetone was the better organic solvent for controlling nanoparticle formation of atorvastatin calcium.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Ultra-Supercritical Pressure CFB Boiler Conceptual Design Study

    Energy Technology Data Exchange (ETDEWEB)

    Zhen Fan; Steve Goidich; Archie Robertson; Song Wu

    2006-06-30

    Electric utility interest in supercritical pressure steam cycles has revived in the United States after waning in the 1980s. Since supercritical cycles yield higher plant efficiencies than subcritical plants along with a proportional reduction in traditional stack gas pollutants and CO{sub 2} release rates, the interest is to pursue even more advanced steam conditions. The advantages of supercritical (SC) and ultra supercritical (USC) pressure steam conditions have been demonstrated in the high gas temperature, high heat flux environment of large pulverized coal-fired (PC) boilers. Interest in circulating fluidized bed (CFB) combustion, as an alternative to PC combustion, has been steadily increasing. Although CFB boilers as large as 300 MWe are now in operation, they are drum type, subcritical pressure units. With their sizes being much smaller than and their combustion temperatures much lower than those of PC boilers (300 MWe versus 1,000 MWe and 1600 F versus 3500 F), a conceptual design study was conducted herein to investigate the technical feasibility and economics of USC CFB boilers. The conceptual study was conducted at 400 MWe and 800 MWe nominal plant sizes with high sulfur Illinois No. 6 coal used as the fuel. The USC CFB plants had higher heating value efficiencies of 40.6 and 41.3 percent respectively and their CFB boilers, which reflect conventional design practices, can be built without the need for an R&D effort. Assuming construction at a generic Ohio River Valley site with union labor, total plant costs in January 2006 dollars were estimated to be $1,551/kW and $1,244/kW with costs of electricity of $52.21/MWhr and $44.08/MWhr, respectively. Based on the above, this study has shown that large USC CFB boilers are feasible and that they can operate with performance and costs that are competitive with comparable USC PC boilers.

  14. Supercritical carbon dioxide: a solvent like no other

    Directory of Open Access Journals (Sweden)

    Jocelyn Peach

    2014-08-01

    Full Text Available Supercritical carbon dioxide (scCO2 could be one aspect of a significant and necessary movement towards green chemistry, being a potential replacement for volatile organic compounds (VOCs. Unfortunately, carbon dioxide has a notoriously poor solubilising power and is famously difficult to handle. This review examines attempts and breakthroughs in enhancing the physicochemical properties of carbon dioxide, focusing primarily on factors that impact solubility of polar and ionic species and attempts to enhance scCO2 viscosity.

  15. Valorization of horse manure through catalytic supercritical water gasification.

    Science.gov (United States)

    Nanda, Sonil; Dalai, Ajay K; Gökalp, Iskender; Kozinski, Janusz A

    2016-06-01

    The organic wastes such as lignocellulosic biomass, municipal solid waste, sewage sludge and livestock manure have attracted attention as alternative sources of energy. Cattle manure, a waste generated in surplus amounts from the feedlot, has always been a chief environmental concern. This study is focused on identifying the candidacy of horse manure as a next generation feedstock for biofuel production through supercritical water gasification. The horse manure was gasified in supercritical water to examine the effects of temperature (400-600°C), biomass-to-water ratio (1:5 and 1:10) and reaction time (15-45min) at a pressure range of 23-25MPa. The horse manure and resulting biochar were characterized through carbon-hydrogen-nitrogen-sulfur (CHNS), inductively coupled plasma-mass spectrometry (ICP-MS), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy and scanning electron microscopy (SEM). The effects of alkali catalysts such as NaOH, Na2CO3 and K2CO3 at variable concentrations (1-2wt%) were investigated to maximize the hydrogen yields. Supercritical water gasification of horse manure with 2wt% Na2CO3 at 600°C and 1:10 biomass-to-water ratio for 45min revealed maximum hydrogen yields (5.31mmol/g), total gas yields (20.8mmol/g) with greater carbon conversion efficiency (43.1%) and enhanced lower heating value of gas products (2920kJ/Nm(3)). The manure-derived biochars generated at temperatures higher than 500°C also demonstrated higher thermal stability (weight loss 70wt%) suggesting their application in enhancing soil fertility and carbon sequestration. The results propose that supercritical water gasification could be a proficient remediation technology for horse manure to generate hydrogen-rich gas products.

  16. Destruction of Navy Hazardous Wastes by Supercritical Water Oxidation

    Science.gov (United States)

    1994-08-01

    voltmeters and scanning thermocouple meters. The data are acquired, analyzed, filed, and displayed using software written for the LabWindows data...acquisition software from National Instruments Corporation. The code was written by NFESC in the C computer language and compiled to achieve rapid program...Hazards and operability ( HAZOP ) study of a supercritical water oxidation (SCWO) bench scale system. Cambridge, MA, Aug 1992. 8. Arthur D. Little, Inc

  17. Supercritical water oxidation of wastewater and sludges - design considerations

    Energy Technology Data Exchange (ETDEWEB)

    Alonso, M.J.C.; Sanchez, E.A.; Fernandez-Polanco, F. [Dept. Ingenieria Quimica, Univ. de Valladolid, Valladolid (Spain)

    2002-07-01

    The supercritical water oxidation (SCWO) process is a promising technology for the treatment of industrial wastewaters and sludges. It has been shown to be effective in destroying recalcitrant, xenobiotic or nonbiodegradable compounds and is an interesting alternative to conventional chemical and biological oxidation processes. This paper describes the basic concepts and state of the art of the SCWO technology and presents the flow sheets and energy and mass balances for diluted wastewater and sludge treatment. (orig.)

  18. Droplet turbulence interactions under subcritical and supercritical conditions

    Science.gov (United States)

    Coy, E. B.; Greenfield, S. C.; Ondas, M. S.; Song, Y.-H.; Spegar, T. D.; Santavicca, D. A.

    1993-01-01

    The goal of this research is to experimentally characterize the behavior of droplets in vaporizing liquid sprays under conditions typical of those encountered in high pressure combustion systems such as liquid fueled rocket engines. Of particular interest are measurements of droplet drag, droplet heating, droplet vaporization, droplet distortion, and secondary droplet breakup, under both subcritical and supercritical conditions. The paper presents a brief description of the specific accomplishments which have been made over the past year.

  19. Heat Transfer Phenomena in Supercritical Water Nuclear Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Mark H. Anderson; MichaelL. Corradini; Riccardo Bonazza; Jeremy R. Licht

    2007-10-03

    A supercritical water heat transfer facility has been built at the University of Wisconsin to study heat transfer in ancircular and square annular flow channel. A series of integral heat transfer measurements has been carried out over a wide range of heat flux, mas velocity and bulk water temperatures at a pressure of 25 MPa. The circular annular test section geometry is a 1.07 cm diameter heater rod within a 4.29 diameter flow channel.

  20. Supercritical Flow Synthesis of TiO2

    DEFF Research Database (Denmark)

    Hellstern, Henrik Christian; Becker, Jacob; Hald, Peter

    2014-01-01

    A new, up-scaled supercritical flow synthesis apparatus has been constructed in Aarhus. A module based system allows for a range of parameter studies with improved parameter control. The dual-reactor setup enables both single phase and core-shell nanoparticle synthesis. TiO2 is a well......-known material and has been synthesized to evaluate the performance of the new super critical reactor setup. TiO2 will form the basis for planned core-shell syntheses....

  1. Supercritical extraction of carqueja essential oil: experiments and modeling

    Directory of Open Access Journals (Sweden)

    R. M. F. Vargas

    2006-09-01

    Full Text Available Baccharis trimera is a native Brazilian plant which has medicinal properties. In this work a method of supercritical extraction was studied to obtain the popularly essential oil from Baccharis trimera, known as carqueja. The aim was to obtain experimental data and to compare two mathematical models used in the simulation of carqueja (Baccharis trimera oil extraction by supercritical CO2. The two mathematical models are based on mass transfer. One of the models, proposed by Reverchon, is solved numerically and requires two adjustable parameters from the experimental data. The other model chosen is the one proposed by Sovová. This model is solved analytically and requires four adjustable parameters. Numerical results are presented and discussed for the adjusted parameters. The experimental results are obtained in a temperature range of 313.15 K to 343.15 K at 90 bar. The extraction yield of carqueja essential oil using supercritical carbon dioxide ranged between 1.72 % (w/w at 323.15 K and 2.34 % (w/w at 343.15 K, 90 bar with a CO2 flow rate of 3.34.10-8 m³/s for a 0.0015 kg sample of Baccharis trimera.

  2. Subchannel analysis with turbulent mixing rate of supercritical pressure fluid

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jianhui, E-mail: wjianhui1985@gmail.com [Department of Applied Physics, Waseda University, Tokyo 169-8555 (Japan); Oka, Yoshiaki [Emeritus Professor the University of Tokyo, Tokyo (Japan)

    2015-06-15

    Highlights: • Subchannel analysis with turbulent mixing rate law of supercritical pressure fluid (SPF) is carried out. • Turbulent mixing rate is enhanced, compared with that calculated by the law of pressurized water reactor (PWR). • Increase in maximum cladding surface temperature (MCST) is smaller comparing with PWR model. • The sensitivities of MCST on non-uniformity of subchannel area and power peaking are reduced by using SPF model. - Abstract: The subchannel analysis with turbulent mixing rate law of supercritical pressure fluid (SPF) is carried out for supercritical-pressurized light water cooled and moderated reactor (Super LWR). It is different from the turbulent mixing rate law of pressurized water reactor (PWR), which is widely adopted in Super LWR subchannel analysis study, the density difference between adjacent subchannels is taken into account for turbulent mixing rate law of SPF. MCSTs are evaluated on three kinds of fuel assemblies with different pin power distribution patterns, gap spacings and mass flow rates. Compared with that calculated by employing turbulent mixing rate law of PWR, the increase in MCST is smaller even when peaking factor is large and gap spacing is uneven. The sensitivities of MCST on non-uniformity of the subchannel area and power peaking are reduced.

  3. Solubility in supercritical solvents: A comparison of theory and simulation

    Science.gov (United States)

    Tomberli, Bruno Luca

    1998-12-01

    Solubility at supercritical conditions is studied using thermodynamics and statistical mechanics. The Redlich- Kwong equation of state, virial equation of state and fluctuation theory are used to predict the chemical potential for pure and mixed Lennard-Jones fluids. Where literature results are unavailable, Monte Carlo simulations employing the Widom particle insertion method are also carried out to determine the chemical potential at the same conditions. Several methods are shown to achieve an accuracy on the order of five percent. Based on the success of these theories, qualitative studies of cavity-interaction contributions to the chemical potential and the effect of clustering in supercritical solvation are conducted. Finally, fluctuation theory is shown to be the only available method suitable for ab initio calculations of the chemical potential involving anisotropic potentials. A suitable potential for naphthalene-carbon dioxide systems is developed from existing multi-site exp-6-1 potentials and predictions of the chemical potential of infinitely- dilute naphthalene in supercritical carbon dioxide are made as an example of a possible application of this method.

  4. Biodiesel production from rice bran oil and supercritical methanol.

    Science.gov (United States)

    Kasim, Novy Srihartati; Tsai, Tsung-Han; Gunawan, Setiyo; Ju, Yi-Hsu

    2009-04-01

    In this study, production of biodiesel from low cost raw materials, such as rice bran and dewaxed-degummed rice bran oil (DDRBO), under supercritical condition was carried out. Carbon dioxide (CO2) was employed as co-solvent to decrease the supercritical temperature and pressure of methanol. The effects of different raw materials on the yield of biodiesel production were investigated. In situ transesterification of rice bran with supercritical methanol at 30MPa and 300 degrees C for 5 min was not a promising way to produce biodiesel because the purity and yield of fatty acid methyl esters (FAMEs) obtained were 52.52% and 51.28%, respectively. When DDRBO was reacted, the purity and yield were 89.25% and 94.84%, respectively. Trans-FAMEs, which constituted about 16% of biodiesel, were found. They were identified as methyl elaidate [trans-9], methyl linoleaidate [trans-9, trans-12], methyl linoleaidate [cis-9, trans-12], and methyl linoleaidate [trans-9, cis-12]. Hydrocarbons, which constituted about 3% of the reaction product, were also detected.

  5. Supercritical fluids technology in bioprocess industries: A review

    Directory of Open Access Journals (Sweden)

    Kianoush Khosravi Darani

    2009-12-01

    Full Text Available This article reviews the fundamentals of supercritical fluid (SCF science and moves on to the biotechnological applications of them e.g. removal of biostatic agents from fermentation broths, SCF disruption of microorganisms, destruction of industrial waste, the gas-antisolvent crystallization and micron-size particle formation. Also gaining ground is enzymatic catalysis in supercritical carbon dioxide (SC-CO2, which offers the possibility of integrated synthesis product recovery processes. The paper is structured as follows: first, the effects of dense SC-CO2 on the extraction of biomaterials and disruption of cells are thoroughly reported and discussed. Then the application of SC-CO2 in particle formation and modifications of biopolymers and enzymes are described. In general, the article is focused on potential bio-industrial applications and future research needs of the SCF technology. Keywords: Biotechnology, Supercritical Fluids (SCF, disruption, inactivation, extraction, downstream, particle formation Received: 10 October 2009 / Received in revised form: 30 January 2010, Accepted: 30 January 2010, Published online: 10 March 2010

  6. Supercritical Fluid Extraction of Plutonium and Americium from Soil

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-05-23

    Supercritical fluid extraction (SFE) of plutonium and americium from soil was successfully demonstrated using supercritical fluid carbon dioxide solvent augmented with organophosphorus and beta-diketone complexants. Spiked Idaho soils were chemically and radiologically characterized, then extracted with supercritical fluid carbon dioxide at 2,900 psi and 65 C containing varying concentrations of tributyl phosphate (TBP) and thenoyltrifluoroacetone (TTA). A single 45 minute SFE with 2.7 mol% TBP and 3.2 mol% TTA provided as much as 88% {+-} 6.0 extraction of americium and 69% {+-} 5.0 extraction of plutonium. Use of 5.3 mol% TBP with 6.8 mol% of the more acidic beta-diketone hexafluoroacetylacetone (HFA) provided 95% {+-} 3.0 extraction of americium and 83% {+-} 5.0 extraction of plutonium in a single 45 minute SFE at 3,750 psi and 95 C. Sequential chemical extraction techniques were used to chemically characterize soil partitioning of plutonium and americium in pre-SFE soil samples. Sequential chemical extraction techniques demonstrated that spiked plutonium resides primarily (76.6%) in the sesquioxide fraction with minor amounts being absorbed by the oxidizable fraction (10.6%) and residual fractions (12.8%). Post-SFE soils subjected to sequential chemical extraction characterization demonstrated that 97% of the oxidizable, 78% of the sesquioxide and 80% of the residual plutonium could be removed using SFE. These preliminary results show that SFE may be an effective solvent extraction technique for removal of actinide contaminants from soil.

  7. Thermodynamic Analysis of a Supercritical Mercury Power Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, A.S. Jr.

    1969-04-15

    An heat engine is considered which employs supercritical mercury as the working fluid and a magnetohydrodynamic (MHD) generator for thermal to electrical energy conversion. The main thrust of the paper is power cycle thermodynamics, where constraints are imposed by utilizing a MHD generator operating between supercritical, electrically conducting states of the working fluid; and, pump work is accomplished with liquid mercury. The temperature range is approximately 300 to 2200 K and system pressure is > 1,500 atm. Equilibrium and transport properties are carefully considered since these are known to vary radically in the vicinity of the critical point, which is found near the supercritical states of interest. A maximum gross plant efficiency is 20% with a regenerator effectiveness of 90% and greater, a cycle pressure ratio of two, and with highly efficient pump and generator. Certain specified cycle irreversibilities and others such as heat losses and heat exchanger pressure drops, which are not accounted for explicitly, reduce the gross plant efficiency to a few per cent. Experimental efforts aimed at practical application of the power cycle are discouraged by the marginal thermodynamic performance predicted by this study, unless such applications are insensitive to gross cycle efficiency.

  8. Supercritical nitrogen processing for the purification of reactive porous materials.

    Science.gov (United States)

    Stadie, Nicholas P; Callini, Elsa; Mauron, Philippe; Borgschulte, Andreas; Züttel, Andreas

    2015-05-15

    Supercritical fluid extraction and drying methods are well established in numerous applications for the synthesis and processing of porous materials. Herein, nitrogen is presented as a novel supercritical drying fluid for specialized applications such as in the processing of reactive porous materials, where carbon dioxide and other fluids are not appropriate due to their higher chemical reactivity. Nitrogen exhibits similar physical properties in the near-critical region of its phase diagram as compared to carbon dioxide: a widely tunable density up to ~1 g ml(-1), modest critical pressure (3.4 MPa), and small molecular diameter of ~3.6 Å. The key to achieving a high solvation power of nitrogen is to apply a processing temperature in the range of 80-150 K, where the density of nitrogen is an order of magnitude higher than at similar pressures near ambient temperature. The detailed solvation properties of nitrogen, and especially its selectivity, across a wide range of common target species of extraction still require further investigation. Herein we describe a protocol for the supercritical nitrogen processing of porous magnesium borohydride.

  9. Phase behaviour of sterols and vitamins in supercritical CO2

    Directory of Open Access Journals (Sweden)

    Gerszt R.

    2000-01-01

    Full Text Available Extraction with supercritical solvents has been used in different areas, such as petroleum desasphaltation, descaffeination of coffee and tea and in the separation of other types of natural products. The supercritical solvent most frequently utilized in the extraction of natural products is carbon dioxide (CO2 due to its several advantages over other solvents such as low cost, atoxicity and volatility. The design, evaluation and optimization of a supercritical extraction that is based on phase equilibrium require phase equilibrium data. This type of data is very scarce for natural compounds like sterols and vitamins. These natural compounds are produced synthetically, but nowadays interest in their extraction from natural sources is increasing. Therefore, the objective of this work is to study the thermodynamic modelling equilibrium of systems containing vitamins A, D, E and K, using the predictive LCVM model. The sensitivity of critical properties in the calculation of the phase behavior was also studied. This study proved that the choice of a group contribution method to calculate thermodynamic properties is very important for obtaining good results in the phase equilibrium calculations.

  10. Supercritical Fluid Extraction of Metal Chelate: A Review.

    Science.gov (United States)

    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.

  11. Intermolecular interactions and the thermodynamic properties of supercritical fluids.

    Science.gov (United States)

    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.

  12. Efficient decomposition of a new fluorochemical surfactant: perfluoroalkane disulfonate to fluoride ions in subcritical and supercritical water.

    Science.gov (United States)

    Hori, Hisao; Saito, Hiroki; Sakai, Hidenori; Kitahara, Toshiyuki; Sakamoto, Takehiko

    2015-06-01

    Decomposition of (-)O3SC3F6SO3(-) in subcritical and supercritical water was investigated, and the results were compared with the results for C3F7SO3(-). This is the first report on the decomposition of perfluoroalkane disulfonates, which are being introduced in electronics industry as greener alternatives to environmentally persistent and bioaccumulative perfluoroalkyl surfactants. Addition of zerovalent iron to the reaction system dramatically increased the yield of F(-) in the reaction solution: when the reaction of (-)O3SC3F6SO3(-) was carried out in subcritical water at 350°C for 6h, the F(-) yield was 70%, which was 23times the yield without zerovalent iron. Prolonged reaction increased the F(-) formation: after 18h, the F(-) yield from the reaction of (-)O3SC3F6SO3(-) reached 81%, which was 2.1times the F(-) yield from the reaction of C3F7SO3(-). Although the reactivity of FeO toward these substrates was lower than zerovalent iron in subcritical water, the reactivity was enhanced when the reaction temperature was elevated to supercritical state, at which temperature FeO underwent in situ disproportionation to form zerovalent iron, which acted as the reducing agent. When the reaction of (-)O3SC3F6SO3(-) was carried out in the presence of FeO in supercritical water at 380°C for 18h, the F(-) yield reached 92%, which was the highest yield among tested.

  13. Can supercritical oxidation of sewage sludge be an alternative for supercritical gasification?; Kan superkritische oxidatie van zuiveringsslib een alternatief zijn voor superkritische vergassing?

    Energy Technology Data Exchange (ETDEWEB)

    Rulkens, W. [Wageningen UR, Wageningen (Netherlands); Wentink, J. [Horizon Solutions, Leiden (Netherlands)

    2013-05-15

    In the context of the development of The Energy Factory a number of technologies has been identified that may be interesting to develop further. Two of these techniques relate to the conversion of sludge in supercritical water: supercritical gasification of sludge and supercritical oxidation of sludge [Dutch] In het kader van de ontwikkeling van De Energiefabriek is een aantal technologieen geidentificeerd die mogelijk interessant zijn om verder te ontwikkelen. Twee van deze technieken hebben betrekking op de conversie van slib in superkritisch water: superkritische slibvergassing en superkritische sliboxidatie.

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

    Science.gov (United States)

    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.

  15. Supercritical Fluids: Nanotechnology and Select Emerging Applications

    Science.gov (United States)

    2006-01-01

    reducing agent) solution. A stable suspension of nano-sized Ag in ethanol was formed under the protection of a stabilizing agent. An intense UV-vis...of applications such as new cancer fighting methods, drug delivery, and nano-biodevices. For example, in nanofluidic chips, tiny channels (50 nm) on...silver-containing nanocrystalline particles in stable suspensions . J. Phy. Chem. B, 103, 77. Takashi, I. and Shinji O. (2000) Pushing the limits of

  16. Global existence and blowup of solutions for the multidimensional sixth-order "good" Boussinesq equation

    Science.gov (United States)

    Runzhang, Xu; Yanbing, Yang; Bowei, Liu; Jihong, Shen; Shaobin, Huang

    2015-06-01

    This paper is concerned with the Cauchy problem of solutions for some nonlinear multidimensional "good" Boussinesq equation of sixth order at three different initial energy levels. In the framework of potential well, the global existence and blowup of solutions are obtained together with the concavity method at both low and critical initial energy level. Moreover by introducing a new stable set, we present some sufficient conditions on initial data such that the weak solution exists globally at supercritical initial energy level.

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

    Science.gov (United States)

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

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

    Science.gov (United States)

    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

  19. Application of Parallel Processing to the Investigation of Supercritical Droplet Evaporation and Combustion Using Molecular Dynamics

    Science.gov (United States)

    2007-11-02

    Molecular dynamics (MD) implemented on parallel processors was used to model supercritical droplet phenomena occurring in combustion devices. The use...of molecular dynamics allows the modeling of supercritical phenomena without an a priori knowledge of the equation of state or transport properties

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

    Science.gov (United States)

    Muthukumaran, C. K.; Vaidyanathan, Aravind

    2015-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Muthukumaran, C. K.; Vaidyanathan, Aravind, E-mail: aravind7@iist.ac.in [Department of Aerospace Engineering, Indian Institute of Space Science and Technology, Trivandrum, Kerala 695547 (India)

    2015-03-15

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

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

    Science.gov (United States)

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

  3. Study on Supercritical Fluid Extraction of Pu(Ⅳ)in Simulative Contaminated Soils

    Institute of Scientific and Technical Information of China (English)

    SONG; Zhi-jun; DING; You-qian; ZHOU; Li-qiang

    2015-01-01

    Supercritical fluid has advantages of rapid mass transfer and high solubility,which can extract different substance through changing the extracting temperature and pressure.So in comparison to conventional solvent extraction process,supercritical fluid extraction do not need to pretreatment of the matrix,minimizes the amount of secondary waste,and the extraction

  4. Improved manometric setup for the accurate determination of supercritical carbon dioxide sorption

    NARCIS (Netherlands)

    Van Hemert, P.; Bruining, H.; Rudolph, E.S.J.; Wolf, K.H.A.A.; Maas, J.G.

    2009-01-01

    An improved version of the manometric apparatus and its procedures for measuring excess sorption of supercritical carbon dioxide are presented in detail with a comprehensive error analysis. An improved manometric apparatus is necessary for accurate excess sorption measurements with supercritical car

  5. Improved manometric setup for the accurate determination of supercritical carbon dioxide sorption

    NARCIS (Netherlands)

    Van Hemert, P.; Bruining, H.; Rudolph, E.S.J.; Wolf, K.H.A.A.; Maas, J.G.

    2009-01-01

    An improved version of the manometric apparatus and its procedures for measuring excess sorption of supercritical carbon dioxide are presented in detail with a comprehensive error analysis. An improved manometric apparatus is necessary for accurate excess sorption measurements with supercritical car

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

    Science.gov (United States)

    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.

  7. System model for gasification of biomass model compounds in supercritical water – a thermodynamic analysis

    NARCIS (Netherlands)

    Withag, Jan A.M.; Smeets, Jules R.; Bramer, Eddy A.; Brem, Gerrit

    2012-01-01

    This article presents a system model for the process of gasification of biomass model compounds in supercritical water. Supercritical water gasification of wet biomass (water content of 70 wt% or more) has as the main advantage that conversion may take place without the costly drying step. The therm

  8. System model for gasification of biomass model compounds in supercritical water - A thermodynamic analysis

    NARCIS (Netherlands)

    Withag, J.A.M.; Smeets, Jules R.; Bramer, E.A.; Brem, G.

    2012-01-01

    This article presents a system model for the process of gasification of biomass model compounds in supercritical water. Supercritical water gasification of wet biomass (water content of 70 wt% or more) has as the main advantage that conversion may take place without the costly drying step. The therm

  9. Supercritical water gasification of biomass: an experimental study of model compounds and potential biomass feeds

    NARCIS (Netherlands)

    Chakinala, Anand Gupta

    2013-01-01

    Gasification of biomass in supercritical water is a complex process. In supercritical water ideally the biomass structure and the larger molecules are broken down into smaller, gaseous components under the influence of radicals. However, the biomass is normally fed to the system at low temperature a

  10. Lewis-acid catalyzed depolymerization of Protobind lignin in supercritical water and ethanol

    NARCIS (Netherlands)

    Guvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Ernie J. M.

    2016-01-01

    The use of metal acetates, metal chlorides and metal triflates as Lewis acid catalysts for the depolymerization of soda lignin under supercritical conditions was investigated. The reactions were carried out at 400 degrees C in water and ethanol. Lignin conversion in supercritical water led to format

  11. Modeling the outflow of liquid with initial supercritical parameters using the relaxation model for condensation

    Directory of Open Access Journals (Sweden)

    Lezhnin Sergey

    2017-01-01

    Full Text Available The two-temperature model of the outflow from a vessel with initial supercritical parameters of medium has been realized. The model uses thermodynamic non-equilibrium relaxation approach to describe phase transitions. Based on a new asymptotic model for computing the relaxation time, the outflow of water with supercritical initial pressure and super- and subcritical temperatures has been calculated.

  12. Palladium-Catalyzed Carbonylation of Primary Amines in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    李金恒; 江焕峰; 陈鸣才

    2001-01-01

    The chemoselectity of the palladimm-catalyzed carbonylation of amines was affected by the addition of MeOH in supercritical carbon dioxide. The results show different selectivity in supercritical carbon dioxide CO2(sc) from that in alcohol.Methyl carbamate and its derivatives were obtained in high yields in CO2(sc).

  13. Metal Ions Extraction with Glucose Derivatives as Chelating Reagents in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    Guo Chen YANG; Hai Jian YANG

    2006-01-01

    A series of glucose derivatives have been used as chelating reagents to extract metal ions in supercritical carbon dioxide. With perfluoro-1-octanesulfonic acid tetraethylammonium salt as additive, glucose derivatives were selective for Sr2+ and Pb2+ extraction in supercritical carbon dioxide.

  14. Morphodynamics and sedimentary structures of bedforms under supercritical-flow conditions: new insights from flume experiments

    NARCIS (Netherlands)

    Cartigny, M.J.B.; Ventra, D.; Postma, G.; Berg, J.H. van den

    2012-01-01

    Particulate density currents, such as pyroclastic flows and turbidity currents, are prone to flow in a supercritical state, due to their small density difference in relation to the ambient fluid. Facies deposited in supercritical-flow conditions are therefore likely to be common, yet their recogniti

  15. Lewis-acid catalyzed depolymerization of Protobind lignin in supercritical water and ethanol

    NARCIS (Netherlands)

    Guvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Ernie J. M.

    2016-01-01

    The use of metal acetates, metal chlorides and metal triflates as Lewis acid catalysts for the depolymerization of soda lignin under supercritical conditions was investigated. The reactions were carried out at 400 degrees C in water and ethanol. Lignin conversion in supercritical water led to

  16. Synthesis of niobium pentoxide nanoparticles in single-flow supercritical water

    Science.gov (United States)

    Fuchigami, Teruaki; Kakimoto, Ken-ichi

    2016-10-01

    The development of a new synthesis method is still required for very fine oxide nanoparticles. In this study, a single-flow supercritical fluid system has been developed for the synthesis of highly crystalline nanosized oxide particles. Niobium oxide particles were synthesized by single-flow supercritical water treatment, batch-type supercritical water treatment and subcritical water treatment. Niobium pentoxide nanoparticles synthesized by single-flow supercritical water treatment at 673 K, 24.5 MPa, and 15 ml min-1 flow rate had a pseudohexagonal structure. The morphology of the nanoparticle was a rod, and it has a smaller particle size and larger crystallite size than those of the oxide particles synthesized by the other methods, because the particle growth and the decomposition of surfactant were rapidly suppressed in the single-flow supercritical water treatment. The nanosized niobium pentoxide is useful as a catalyst in harsh environments and as a precursor powder of lead-free piezoelectric materials.

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

    Science.gov (United States)

    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.

  18. Successively separation method of uranium and rare earth element having supercritical fluid as extracting medium

    Energy Technology Data Exchange (ETDEWEB)

    Iso, Shuichi; Meguro, Yoshihiro; Yoshida, Yoshiyuki

    1996-08-30

    In a method of separating by extraction of coolants uranium and rare earth elements by using supercritical fluid in a supercritical state and a hydrophobic organic chelating agent, a plurality of extraction steps having different extraction efficiencies are provided. As the fluid in the supercritical state, carbon dioxide, carbon monoxide, ammonia, sulfur tetrafluoride and nitrogen are mentioned. A hydrophobic organic chelating agent can form a chelating compound with uranium and rare earth elements, and the formed complex compounds are easily dissolved into the supercritical fluid thereby enabling to provide an excellent extraction effect. A suitable hydrophobic organic chelating agent includes organic phosphor compounds, {beta}-diketone compounds and microcyclic compounds. Then, there can be provided an extraction method using a supercritical liquid as an extraction medium capable of successively separating uranium and rare earth elements selectively having high safety and performed safely and also performed in a case where a plurality of rare earth elements exist together. (N.H.)

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

    Science.gov (United States)

    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.

  20. Fischer-Tropsch synthesis in supercritical fluids. Quarterly technical progress report, April 1, 1996--June 30, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Akgerman, A.; Bukur, D.B. [Texas A and M Univ., College Station, TX (United States). Dept. of Chemical Engineering

    1996-12-31

    For the task on diffusion coefficients of F-T products in supercritical fluids, we attempted to find a model for the {beta} parameter to predict the molecular diffusion coefficients to a high degree of accuracy so we may be able to predict both the molecular diffusion coefficient and thus the effective diffusivity a priori. The dependency of solvent/solute interactions on the {beta} parameter was analyzed and a correlation developed to predict the functionality. This allowed us to develop an empirical formula to correlate the molecular diffusion coefficient to ratios of mass, size, and density. Thus finally allowing for supercritical fluid diffusion predictions a priori. Figure 6 shows our predictions of the data available on the self diffusion coefficient of carbon dioxide (Chen, 1983; Takahashi and Iwasaki, 1966) ethylene (Arends et al., 1981; Baker et al., 1984), toluene (Baker et al., 1985) and chlorotrifuoromethane (Harris, 1978). The predictions, with no parameters adjusted from the data, are excellent with an average absolute error of 3.64%.