Supercritical CO2 solvent

Aside from the difficulties at the upper and lower ends of the liquid s vibrational band, the INM ideas do seem to work and to work quantitatively. The ability of the liquid-mode concept to account for the absolute magnitude of the vibrational friction, including the factor of 2 difference between liquid and supercritical CO2 solvents, is worth noting (52). But does this success mean that vibrational energy relaxation is really a collective process To answer this question, we need to carry out precisely the kind of mechanistic investigation we discussed in Section II.C. 

UV photolysis of CpMn(CO)3 in toluene leads to loss of CO and formation of CpMn(CO)2( ] -toluene). Kinetic studies suggest that the binding energy of the toluene is ca. 60kJmor. The binding of H2 to CpMn(CO)2 has been studied in supercritical CO2 solvent. It has been proposed that pyrylium and pyridinium salts such as (35) can be used to label proteins and thereby aid in the detection and characterization of receptor sites. Cymantrene bound to lysine residues of bovine serum albumin (BSA) has been used as a redox label. Electrochemical reduction of the label established an impressive BSA detection limit of 2 x 10 M. 

Trivedi, A.H. Kwak, S. Lee, S. Grafting of poly (vinyl chloride) and polypropylene with styrene in a supercritical CO2 solvent medium synthesis and characterization. Polym. Eng. Sci. 2001, 41, 1923-1937. 

Grierson S, StrezovV, Bray S, Mummacari R, Danh LT, Foster N. Assessment of bio-oil extraction from Tetrasehnis chui microalgae comparing supercritical CO2, solvent extraction, and thermal processing. Energy Fuels 2012 26 248. 

The most common mobile phase for supercritical fluid chromatography is CO2. Its low critical temperature, 31 °C, and critical pressure, 72.9 atm, are relatively easy to achieve and maintain. Although supercritical CO2 is a good solvent for nonpolar organics, it is less useful for polar solutes. The addition of an organic modifier, such as methanol, improves the mobile phase s elution strength. Other common mobile phases and their critical temperatures and pressures are listed in Table 12.7. 

Solvent extraction removes chlorophyll and other pigments to give a light-colored product but increases processing costs. Furthermore, solvent extraction removes p-carotene and reduces vitamin A activity (89) (see Terpenoids Vitamins). Supercritical CO2 extraction at 30 and 70 MPa (4,350 and 10,150 psi) and 40°C removed 90 and 70% carotene and lutein, respectively, from alfalfa LPC (96). This process avoids organic solvent residues and recovers valuable by-products. 

Conventional nitrocellulose lacquer finishing leads to the emission of large quantities of solvents into the atmosphere. An ingeneous approach to reducing VOC emissions is the use of supercritical carbon dioxide as a component of the solvent mixture (172). The critical temperature and pressure of CO2 are 31.3°C and 7.4 MPa (72.9 atm), respectively. Below that temperature and above that pressure, CO2 is a supercritical fluid. It has been found that under these conditions, the solvency properties of CO2 ate similar to aromatic hydrocarbons (see Supercritical fluids). The coating is shipped in a concentrated form, then metered with supercritical CO2 into a proportioning airless spray gun system in such a ratio as to reduce the viscosity to the level needed for proper atomization. VOC emission reductions of 50% or more are projected. 

Numerous half-sandwich compounds of the type [M()7 -C5R5)L2], M = Rh, Ir R = H, Me L = CO, phosphine etc.) are known and are useful reagents. [Ir()7 -C5Me5)(CO)2] for instance is an excellent nucleophile and is also used in the photochemical activation of C-H in alkanes. It is particularly effective in the latter role when supercritical CO2 is the solvent. ... 

Many transition metal complexes dissolve readily in ionic liquids, which enables their use as solvents for transition metal catalysis. Sufficient solubility for a wide range of catalyst complexes is an obvious, but not trivial, prerequisite for a versatile solvent for homogenous catalysis. Some of the other approaches to the replacement of traditional volatile organic solvents by greener alternatives in transition metal catalysis, namely the use of supercritical CO2 or perfluorinated solvents, very often suffer from low catalyst solubility. This limitation is usually overcome by use of special ligand systems, which have to be synthesized prior to the catalytic reaction. 

When ionic liquids are used as replacements for organic solvents in processes with nonvolatile products, downstream processing may become complicated. This may apply to many biotransformations in which the better selectivity of the biocatalyst is used to transform more complex molecules. In such cases, product isolation can be achieved by, for example, extraction with supercritical CO2 [50]. Recently, membrane processes such as pervaporation and nanofiltration have been used. The use of pervaporation for less volatile compounds such as phenylethanol has been reported by Crespo and co-workers [51]. We have developed a separation process based on nanofiltration [52, 53] which is especially well suited for isolation of nonvolatile compounds such as carbohydrates or charged compounds. It may also be used for easy recovery and/or purification of ionic liquids. 

It is noted that the Diels-Alder reaction has been done with supercritical CO2 as a solvent. Diels-Alder reactions on solid supports have also been reported, and zeolites have been used in conjunction with catalytic agents.Alumina has been used to promote Diels-Alder reactions. 

Although critical pressures are many times greater than atmospheric pressure, supercritical fluids have important commercial applications. The most important of these is the use of supercritical carbon dioxide as a solvent. Supercritical CO2 diffuses through a solid matrix rapidly, and it transports materials well because it has a lower... 

Gas-expanded liquids (GXLs) are emerging solvents for environmentally benign reactive separation (Eckert et al., op. cit.). GXLs, obtained by mixing supercritical CO2 with normal liquids, show intermediate properties between normal liquids and SCFs both in solvation power and in transport properties and these properties are highly tunable by simple pressure variations. Applications include chemical reactions with improved transport, catalyst recycling, and product separation. 

Supercritical fluid extraction (SFE) is a technique in which a supercritical fluid [formed when the critical temperature Tf) and critical pressure Pf) for the fluid are exceeded simultaneously] is used as an extraction solvent instead of an organic solvent. By far the most common choice of a supercritical fluid is carbon dioxide (CO2) because CO2 has a low critical temperature (re = 31.1 °C), is inexpensive, and is safe." SFE has the advantage of lower viscosity and improved diffusion coefficients relative to traditional organic solvents. Also, if supercritical CO2 is used as the extraction solvent, the solvent (CO2) can easily be removed by bringing the extract to atmospheric pressure. Supercritical CO2 itself is a very nonpolar solvent that may not have broad applicability as an extraction solvent. To overcome this problem, modifiers such as methanol can be used to increase the polarity of the SFE extraction solvent. Another problem associated with SFE using CO2 is the co-extraction of lipids and other nonpolar interferents. To overcome this problem, a combination of SFE with SPE can be used. Stolker et al." provided a review of several SFE/SPE methods described in the literature. 

Vasapollo G, Longo L, Rescio L and Ciurlia L 2004. Innovative supercritical CO2 extraction of lycopene from tomato in the presence of vegetable oil as co-solvent. J Supercrit Fluids 29(1-2) 87-96. 

The preferred solvent is supercritical CO2. The reasons for this choice are many and various. Firstly, the CO2 is not hot (CO2 first becomes critical at 31 °C and 73 atm pressure see Figure 5.5), so no charring of the coffee occurs during decaffeination. Furthermore, at such a low temperature, all the components within the coffee that impart the flavour and aroma remain within the solid coffee - try soaking coffee beans in cold water and see how the water tastes afterwards Caffeine is removed while retaining a full flavour. 

D. J. Adam, J. Mainwaring and Michael N. Quigley have described a simple experiment to remove caffeine from coffee with a Soxhlet apparatus see Journal of Chemical Education, 1996, 73, 1171. Their solvent was a chlorinated organic liquid rather than supercritical CO2. The abstract is available at http //jchemed.chem.wisc.edu/ journal/issues/1996/Dec/absll71.html. 

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