Search results for "SUPERCRITICAL CARBON DIOXIDE"

Synthesis of dimethyl carbonate in supercritical carbon dioxide

2006

The reactivity of carbon dioxide with methanol to form dimethyl carbonate was studied in the presence of the n-butylmethoxytin compounds n-Bu3SnOCH3, n-Bu2Sn(OCH3)2 , and [n-Bu2(CH3O)Sn]2 O. The reaction occurred under solventless conditions at 423 K and was produced by an increase in CO2 pressure. This beneficial effect is primarily attributed to phase behavior. The mass transfer under liquid-vapor biphasic conditions was not limiting when the system reached the supercritical state for a CO2 pressure higher than 16 MPa. Under these conditions, CO2 acted as a reactant and a solvent.

Transesterification of rapeseed oil over acid resins promoted by supercritical carbon dioxide

2011

The methanolysis of rapeseed oil catalyzed by commercial styrene-divinylbenzene macroporous acid resins was performed in a batch reactor at 100-140 °C and 10-46 MPa to study the effect of supercritical carbon dioxide (scCO2) on the performances of the process. Reaction temperatures of 120-140 °C were necessary to obtain high enough yields of fatty acid methyl esters. Upon addition of scCO2 faster transesterification kinetics was obtained also at the lowest investigated operating pressure (10-11 MPa), working in two fluid phase systems. Experiments performed changing the reaction time indicated that most of the esters were formed during the first 3 h. When the pressure was increased at 38-46…

Supercritical Carbon Dioxide: A Promoter of Carbon-Halogen Bond Heterolysis

2013

as the leaving groupdeparts from the carbon atom prior to the entrance of thenucleophile. Polar protic solvents with high dielectric con-stants promote polar bond heterolysis by providing effectiveH-bonding and electron-pair donation interactions to theleaving group and the incipient carbocation, respectively.Then, the solvent captures the carbocation intermediate togive the corresponding S

Inclusion complexes of triphenylphosphine derivatives and peracetylated-β-cyclodextrin in supercritical carbon dioxide

2008

The supramolecular chemistry of peracetylated-β-CD (perAc-β-CD) as a host for triphenyphosphine derivatives has been studied in supercritical (scCO2) using UV absorption spectroscopy. It was found that the association constant in scCO2 at 40°C and 300 bar is 10 to 1000 times smaller compared to analogous systems in aqueous solvent. Studies of the thermodynamics of the inclusion process found an enthalpy of association of -30 kJ/mole and an entropy of -55 J/moleK. This difference with respect to water is attributed to the absence of the hydrophobic effect in scCO2 due to the much smaller polarity of scCO2 versus water. To further explore the effect of the solvent on the association constant,…

Utilization of dense carbon dioxide as an inert solvent for chemical syntheses

2010

Supercritical CO2 extraction of essential oil from orange peel. Effect of operation conditions on the extract composition

1999

Abstract The supercritical fluid extraction (SFE) of orange essential oil was studied using dehydrated orange peel (0.0538 kg H2O/kg dm) from naveline cultivars as raw material and CO2 as solvent. The effect of operation conditions was analyzed in a series of experiments at temperatures between 293 and 323 K and pressures between 8 and 28 MPa. The collected extracts were analyzed and the relative composition of the essential oil was determined. Limonene was the principal component extracted, the optimum conditions for limonene extraction were 12.5 MPa and 308 K, in these conditions limonene represents more than 99.5% of the essential oil. Within the operating range conditions, the optimum f…

Solubilities of Essential Oil Components of Orange in Supercritical Carbon Dioxide

2000

The solubilities of pure limonene and linalool in compressed carbon dioxide have been measured using a flow apparatus at 318.2 K and 328.2 K and pressures ranging from 69 bar to 111 bar. The solubilities were successfully modeled using equations of state (Peng−Robinson, Soave−Redlich−Kwong, 3P1T, Dohrn and Prausnitz nopolar) and a semiempirical equation (Chrastill model). The generalized parameters for the Peng−Robinson EOS were obtained for each system. These parameters were independent of temperature, and they reproduce successfully all data available in the literature. The results show that the solubility of limonene in supercritical carbon dioxide was bigger than the solubility of linal…

Effect of interfacial area on heterogeneous free radical grafting of vinyl monomers in supercritical carbon dioxide: Grafting of acrylic acid on poly…

2014

The role of the polymer interfacial area on free radical grafting of acrylic acid (AA) onto poly(vinylidenefluoride) (PVDF) was studied at 65°C using supercritical carbon dioxide (scCO2) as a solvent and swelling agent, benzoylperoxide (BPO) as chemical initiator and PVDF nanoparticles as polymer matrix. Under adopted conditions PVDF particles do not melt neither dissolve in the reaction medium and FTIR analyses performed on carefully washed nanoparticles confirmed the achievement of high grafting levels. The mass fraction of grafted AA increased with the grafting time and the BPO concentration while it decreased when the density of the fluid phase was enhanced. Collected results suggest th…

The rate of polymerization in two loci reaction systems: VDF-HFP precipitation copolymerization in supercritical carbon dioxide

2011

When the copolymerization of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) is carried out in supercritical carbon dioxide (scCO 2) under heterogeneous conditions, the reaction occurs both in the continuous CO 2-rich phase and in the dispersed polymer-rich phase. The two phases being characterized by different values of reactant concentrations and kinetic parameters, one would expect that the reaction kinetics is affected by the polymer phase holdup in the reactor. However, the reaction rate is almost insensitive to the amount of produced polymer, at least at specific reaction conditions. This apparent contradiction is discussed and clarified in this paper by a series of comparativ…

A one-pot method to enhance dissolution rate of low solubility drug molecules using dispersion polymerization in supercritical carbon dioxide

2009

The surfactant assisted polymerization of 1-vinyl-2-pyrrolidone in supercritical carbon dioxide in the presence of Piroxicam, selected as a model of a low aqueous solubility drug, was studied in order to prepare in a single step a polymeric composite to enhance the rate of dissolution of the pharmaceutical compound. Reactive entrapping was carried out at 65 degrees C in the P range 21-38MPa. Under proper operative conditions we obtained the composite under the form of sub-micron spherical particles with relatively narrow particle size distribution. Drug loadings higher than 12% (w/w) were obtained and XRD and Raman spectroscopy suggest that the anti-inflammatory agent is dispersed in the ma…