Lewis acids catalyzed ring-opening reactions of methylenecyclopropanes and epoxides in supercritical carbon dioxide or modified supercritical carbon dioxide with perfluorocarbon

The reactions of methylenecyclopropanes (MCPs) and epoxides with alcohols and aromatic amines can be carried out in supercritical carbon dioxide (scCO₂) or modified scCO₂ with perfluorocarbon which offer a way to synthesize various alcohols, amino-alcohols, homoallylic ethers, and amines under an environmentally benign condition.     

Investigation of AOT reverse microemulsions in supercritical carbon dioxide

Bis(2-ethylhexyl) sodium sulphosuccinate (AOT) was successfully solubilised in supercritical carbon dioxide (scCO₂), with ethanol or pentanol as co-solvent. Three molecular spectroscopic probes: methyl orange (MO), 8-hydroxy-1,3,6-pyrenetrisulphonic acid trisodium salt (HPTS), and riboflavin (RF) were used to examine the solubilisation characteristics of the water/scCO₂ microemulsions formed with AOT. MO was extracted at various operating conditions, although the wavelength of its solvatochromic absorption maximum was not indicative of bulk water properties. Instead, the spectral results imply that MO may be located at the surfactant/water interface. The highly water-soluble dye HPTS was unable to be extracted into scCO₂/AOT/water systems, suggesting that the water in the reverse micelle core was not as polar under supercritical conditions as those at ambient conditions. Finally, RF was extracted into the supercritical phase (40°C, 175 bar) with pentanol co-solvent, with an apparent enhanced uptake compared with the value at 40°C and ambient pressure in bulk water. This appears to be due to the presence of microcrystals dispersed in the supercritical phase.     

Liquid trapping after supercritical fluid extraction with modified carbon dioxide

A polarity test mix consisting of acetophenone, N,N-dimethylaniline, naphthalene, 2-naphthol, and n-tetracosane was spiked onto sand and extracted with carbon dioxide modified with acetonitrile, methanol, or toluene. The extracts were collected in chloroform, hexane, methanol, or a mixed collection solvent consisting of equal parts chloroform-hexane-methanol. The mixed collection solvent which showed excellent recoveries for pure CO₂, had the worst recoveries of all the collection solvents with modified CO₂. Overall hexane was the best collection solvent studied for these analytes under these extraction conditions.     

Seed oil extraction with supercritical carbon dioxide modified with pentane

Chromatographia - Soybean, wheat germ, sunflower and peanut oils were extracted with supercritical carbon dioxide modified with pentane. The extractions were optimized by chemometric methods using...     

Metallic nanoparticle production utilizing a supercritical carbon dioxide flow process

Metallic nanoparticles of palladium and silver ranging in size from 1 to 15 nm were produced entirely within carbon dioxide by spraying a carbon dioxide carrier solution containing CO2-soluble metal precursors into a CO2 receiving solution containing a reducing agent (NaBH(OAc)3 or H2) and fluorocarbon thiol stabilizing ligands. The process uses the benign solvent CO2 while also allowing for the production of nanoparticles with a limited number of chemical components. Particles were characterized by transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS).     

Direct coupling of capillary supercritical fluid chromatography with supercritical fluid extraction using modified carbon dioxide

Capillary supercritical fluid chromatography has been directly coupled with supercritical fluid extraction using modified carbon dioxide. The mixed fluids were prepared with a single pump on-line mixing system. The most important step in the SFE-SFC interface was the elimination of the modifier solvent. This was achieved by use of a coupled trap, 0.1 mm i.d. and 0.53 mm i.d. capillary tubing connected in series, with the collected solutes refocused on the second (0.53 mm i.d.) trap before transfer into the separation column. This enabled complete elimination of various modifier solvents and high efficiency collection of the solutes. The effect of the modifier on trapping efficiency was investigated using methanol, ethanol, dichloromethane, hexane, and toluene at a variety of concentrations. n-Eicosane was, for example, trapped quantitatively by modified carbon dioxide containing up to 13 % (w/w) methanol. The use of the technique has been demonstrated by selective extraction of n-paraffins, fatty acid methyl esters, and alcohols from a silica matrix; the effect of different modifiers on the extraction of a mixture of pesticides from soil has also been investigated.     

Diffusion coefficients of solids in supercritical carbon dioxide: Modelling of near critical behaviour

Most of the models proposed in literature for binary diffusion coefficients of solids in supercritical fluids are restricted to infinite dilution; this can be explained by the fact that most of experimental data are performed in the dilute range. However some industrial processes, such as supercritical fluid separation, operate at finite concentration for complex mixtures. In this case, the concentration dependence of diffusion coefficients must be considered, especially near the upper critical endpoint (UCEP) where a strong decrease of diffusion coefficients was experimentally observed. In order to represent this slowing down, a modified version of the Darken equation was proposed in literature for naphthalene in supercritical carbon dioxide. In this paper, the conditions of application of such a modelling are investigated. In particular, we focus on the order of magnitude of the solubility of the solid and on the vicinity of the critical endpoint. Various equations proposed in literature for the modelling of the infinite dilution diffusion coefficients of the solutes are also compared. Ten binary mixtures of solids with supercritical carbon dioxide were considered for this purpose.     

Diaryl ether synthesis in supercritical carbon dioxide in batch and continuous flow modes

A high yielding, batch mode synthesis of diaryl ethers and sulfides by an S(N)Ar fluoride-mediated process in scCO(2) has been developed; the use of a polymer-supported imidazolium fluoride reagent in batch mode led to the development of a fixed-bed continuous flow process, with high conversions.     

Dissolution of uranium dioxide in supercritical fluid carbon dioxide

Uranium dioxide can be dissolved in supercritical CO2 with a CO2-philic TBP-HNO3 complexant to form a highly soluble UO2(NO3)(2).2TBP complex; this new method of dissolving UO2 that requires no water or organic solvent may have important applications for reprocessing of spent nuclear fuels and for treatment of nuclear wastes.     

Synthesis of fluorinated oligomers for supercritical carbon dioxide applications

Syntheses of various fluorine‐based surfactants, namely fluorinated‐segment‐containing block co‐oligomers, were achieved by the radical polymerization of mainly acrylate‐based monomers. These types of surfactants serve as stabilizers for supercritical carbon dioxide (scCO₂) media based applications, for which the effective solubilization of materials in the supercritical phase is generally not possible because of solubility problems faced when CO₂ is involved. Initially, a difunctional fluorinated initiator was synthesized in two steps. First, 4,4′‐azobis‐4‐cyanovaleric acid was chlorinated with SOCl₂, and then the product, 4,4′‐azobis‐4‐cyanovaleryl chloride, was reacted with a fluorinated alcohol to obtain the initiator for the polymerization reactions. The synthesized triblock co‐oligomers consisted of fluorinated side blocks and a hydrocarbon intermediate block. Efficient solubilization of the materials in scCO₂ was observed. It was experimentally shown that the solubility efficiency was affected by specific interactions between CO₂ and the oligomers, and these were determined by the nature and size of the inner block and by the chain length of the fluorinated side blocks in comparison with the inner block. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5312–5322, 2005     

Biocatalytic reduction of ketones by a semi-continuous flow process using supercritical carbon dioxide

The immobilized resting-cell of Geotrichum candidum was used as a catalyst for the reduction of a ketone in a semi-continuous flow process using supercritical carbon dioxide for the first time; it was also applied for the asymmetric reduction of a ketone and resulted in excellent enantioselectivity (ee > 99%) and a higher space-time yield than that of the corresponding batch process.     

超临界CO_2萃取甾醇的研究(1)

本文用超临界ＣＯ＿２对高酸价麦胚油进行选择住萃取，结果表明，萃取温度和压力不同时，萃取物中甾醇的含量不同．且甾醇混合物主要为β－谷甾醇和菜籽甾醇。萃取物的酸价也明显高于高酸价麦胚油。     

Epoxidation of olefins with a silica-supported peracid in supercritical carbon dioxide under flow conditions

Anhydrous 2-percarboxyethyl-functionalized silica (2b), a recyclable supported peracid, is a suitable reagent to perform the epoxidation of alkenes 1 in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions. This procedure simplifies the isolation of the reaction products and uses only carbon dioxide as a solvent under mild conditions. The solid reagent 2b can be easily recycled by a reaction with 30% hydrogen peroxide in an acid medium.     

Regeneration of cobalt-contaminated activated carbon by supercritical carbon dioxide extraction

A mixture of Di-(2-ethylhexyl) phosphoric acid (D2EPHA) and n-hexane or methanol is used as the extractant solution for extracting cobalt from activated carbon using supercritical carbon dioxide extraction technology. In this work, a semi-continuous pilot unit of SFE is employed to conduct the extraction. In order to feed the viscous extractant by HPLC pump, n-hexane or methanol is added as a diluent to reduce the viscosity of the extractant. The amount of cobalt removed along the time course of the extraction is recorded and plotted as an extraction curve. A kinetic model is also established and fit to the extraction curve, and the obtained parameters of the model are used to explain the regeneration mechanism. The effects of temperature ranged from?40 to?80?°C and the effect of the concentration of diluents on the extraction are investigated and discussed based on the established model. It is also found that the removal of cobalt ions reaches a maximum; this varies with the operational conditions and is known as maximum removal efficiency. It is presumed that the maximum removal efficiency is affected by the adsorption kinetics of the extractant and the rate of ion exchange between the extractant and metal ions on the surface of the activated carbon. After increasing the extraction temperature from?60 to?80?°C it is observed that the maximum removal efficiency is greatly increased, presumably resulting from the diminishing competitive adsorption between the extractant and diluents. The established model can help to reveal the extraction mechanism and to promote maximum removal efficiency for regenerating activated carbon without secondary pollution.     

Solubility and micronisation of phenacetin in supercritical carbon dioxide

The rapid expansion of a supercritical solution (RESS) process represents an attractive prospect for producing sub-micron and nano-particles of medical compounds with low solubility. The solubility of phenacetin in supercritical carbon dioxide was measured by the analytical-isothermal method at pressures ranging from 9.0 MPa to 30.0 MPa and temperatures ranging from 308.0 K to 328.0 K. The results show that the mole fraction solubility of phenacetin in supercritical carbon dioxide is up to 10^?5. Four density-based semi-empirical models were introduced to correlate the experimental data. Agreement between the model predictions and experimental data is greater with the Adachi-Lu-modified Chrastil model than with the Chrastil model, Méndez-Santiago-Teja model, and the Bartle model and the average absolute relative deviation (AARD) observed is 0.0483. The preparation of fine phenacetin particles by the RESS process under different conditions of extraction temperatures (308.0–328.0 K), extraction pressures (9.0–30.0 MPa), nozzle temperatures (373.0–393.0 K), nozzle diameters (0.1–0.8 mm), and collection distance (20.0–40.0 mm) was investigated. The size and morphology of the resultant particles were analysed by SEM. A remarkable modification in size and morphology can be obtained by condition-optimisation.     

Effect of supercritical carbon dioxide on nanoporous polyhexafluoropropylene

The effect of supercritical CO₂ (sc-CO₂) on the size distribution of free volume holes (nanopores) in a polyhexafluoropropylene (PHFP) polymer matrix has been studied. Residual (after CO₂ release) swelling improves gas transport properties of the material. Relaxation of these properties over time has been compared with changes in permeability and nanoporosity. For PHFP samples with different histories, the data on nanoporosity have been obtained using positron annihilation lifetime spectroscopy (micropores) and the lowtemperature gas sorption technique (mesopores and part of micropores). Matching of the data is intended to reveal the role of pores of different sizes in permeability of membrane materials to different gases and determine the specifics of application of the positron annihilation technique to studying sc-CO₂-modified objects.     

Ab initio molecular-dynamics study of supercritical carbon dioxide

Car-Parrinello molecular-dynamics simulations of supercritical carbon dioxide (scCO(2)) have been performed at the temperature of 318.15 K and at the density of 0.703 g/cc in order to understand its microscopic structure and dynamics. Atomic pair correlation functions and structure factors have been obtained and good agreement has been found with experiments. In the supercritical state the CO(2) molecule is marginally nonlinear, and thus possesses a dipole moment. Analyses of angle distributions between near neighbor molecules reveal the existence of configurations with pairs of molecules in the distorted T-shaped geometry. The reorientational dynamics of carbon dioxide molecules, investigated through first- and second-order time correlation functions, exhibit time constants of 620 and 268 fs, respectively, in good agreement with nuclear magnetic resonance experiments. The intramolecular vibrations of CO(2) have been examined through an analysis of the velocity autocorrelation function of the atoms. These reveal a red shift in the frequency spectrum relative to that of an isolated molecule, consistent with experiments on scCO(2). The results have also been compared to classical molecular-dynamics calculations employing an empirical potential.     

Rheology of polydimethylsiloxane swollen with supercritical carbon dioxide

Viscosity curves were measured for polydimethyl siloxane (PDMS) melts swollen with dissolved carbon dioxide at 50 and 80°C for shear rates ranging from 40 to 2300 s⁻¹, and for carbon dioxide contents ranging from 0 to 21 wt %. The measurements were performed with a capillary extrusion rheometer modified for sealed, high-pressure operation to prevent degassing of the melt during extrusion. The concentration-dependent viscosity curves for these systems are self-similar in shape, exhibiting low-shear rate Newtonian plateau regions followed by shear-thinning “power-law” regions. Considerable reduction of viscosity is observed as the carbon dioxide content is increased. Classical viscoelastic scaling methods, employing a composition-dependent shift factor to scale both viscosity and shear rate, were used to reduce the viscosity data to a master curve at each temperature. The dependence of the shift factors on polymer chain density and free volume were investigated by comparing the shift factors for PDMS-CO₂ systems to those obtained by iso-free volume dilutions of high molecular weight PDMS. This comparison suggests that the free volume added to PDMS upon swelling with dissolved carbon dioxide is the predominant mechanism for viscosity reduction in those systems. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 523–534, 1997