Separation with supercritical solvents

Supercritical fluids are effective at much lower temperatures than distillation, and their application in separation avoids degradation and decomposition of heat-labile compounds. Attractiveness of supercritical extraction processes are due to the sensitivity of responses to process variables, promise of complete and versatile regeneration of solvents, energy savings, enhanced solute volatilities, solvent selectivities, favorable transport properties for solvents, and state governed effectiveness of solvents which enables the use of low cost, non-toxic, environmentally acceptable solvents. The impact of inherent characteristics of supercritical fluids on separations is summarized in Table 21.1.5. 

Inherent characteristics of systems snpercritical conditions Resnlting promise Challenges to be met 

Enhanced solubility Effective at lower temperatures Recovery of substances inadvertently extracted 

Favorable transport properties High mass transfer rates especially in porous media  

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One of the most studied technologies is supercritical fluid extraction with SC-CO2. The advantages of SC-CO2 include its low processing temperature, which minimizes thermal degradation the ease of separation with no solvent residue left in the final product and minimization of undesirable oxidation reactions. 

Table II. Operating Conditions for Separation of n-Paraffins from C16-C32 Wax Distillate With Supercritical Solvent Volatility Application and 5A Molecular Sieves...

Matsuyama H, Yamamoto A, Yano H, Maki T, Teramoto M, Mishima K, and Matsuyama K. Effect of organic solvents on membrane formation by phase separation with supercritical CO2. J. Membr. Sci. 2002 204(l-2) 81-87. 

Due to possible environmental problems with acetone, new technologies are being developed for the production of deoiled lecithins involving treatment of Hpid mixtures with supercritical gases or supercritical gas mixtures (10—12). In this process highly viscous cmde lecithin is fed into a separation column at several levels. The supercritical extraction solvent flows through the column upward at a pressure of 8 MPa (80 bar) and temperature between 40 and 55°C. The soy oil dissolves together with a small amount of lecithin. 

The combination of ionic liquids with supercritical carbon dioxide is an attractive approach, as these solvents present complementary properties (volatility, polarity scale.). Compressed CO2 dissolves quite well in ionic liquid, but ionic liquids do not dissolve in CO2. It decreases the viscosity of ionic liquids, thus facilitating mass transfer during catalysis. The separation of the products in solvent-free form can be effective and the CO2 can be recycled by recompressing it back into the reactor. Continuous flow catalytic systems based on the combination of these two solvents have been reported [19]. This concept is developed in more detail in Section 5.4. 

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. 

To date most of the work which has been done with supercritical fluid extraction has concentrated on the extraction of analytes from solid matrices or liquids supported on an inert solid carrier matrix. The extraction of aqueous matrices presents particular problems [276-278]. The co-extraction of water causes problems with restrictor plugging, column deterioration, and phase separation if a nonpolar solvent is used for sample collection. Also, carbon dioxide isay have limited extraction efficiency for many water soluble compounds. 

A subsequent picosecond electronic absorption spectroscopic study of TPE excited with 266- or 355-nm, 30-ps laser pulses in cyclohexane found what was reported previously. However, in addition to the nonpolar solvent cyclohexane, more polar solvents such as THF, methylene chloride, acetonitrile, and methanol were employed. Importantly, the lifetime of S lp becomes shorter as the polarity is increased this was taken to be evidence of the zwitterionic, polar nature of TPE S lp and the stabilization of S lp relative to what is considered to be a nonpolar Sop, namely, the transition state structure for the thermal cis-trans isomerization. Although perhaps counterinmitive to the role of a solvent in the stabilization of a polar species, the decrease in the S lp lifetime with an increase in solvent polarity is understood in terms of internal conversion from to So, which should increase in rate as the S -So energy gap decreases with increasing solvent polarity. Along with the solvent-dependent hfetime of S lp, it was noted that the TPE 5ip absorption band near 425 nm is located where the two subchromophores— the diphenylmethyl cation and the diphenylmethyl anion—of a zwitterionic 5ip should be expected to absorb hght. A picosecond transient absorption study on TPE in supercritical fluids with cosolvents provided additional evidence for charge separation in 5ip. 

Extraction of 25 different binary mixtures of racemic acids (2-(4-isobutylphenyl)-propionic acid (1), and cis- and trans-chrysanthemic (2)), and various chiral bases with supercritical carbon dioxide permitted the conclusion that molecular chiral differentiation in a supercritical fluid is more efficient than in conventional solvents. In the majority of cases, however, complete separation could not be achieved. In five cases, remarkable partial resolutions were realized (30-75% ee) and resolution was possible on a preparative scale. The pair ds-chrysanthemic acid and (S)-(-i-)-2-(benzylamino)-1-butanol (3) was studied in detail. Pressure, temperature, and time, as well as the molar ratio of base and acid, had a marked influence on the quantity and quality of the products. Increasing pressure or decreasing temperature resulted in higher ee values. (-)-cw-Chrysanthemic acid in 99% ee was obtained from the raffinate in a single extraction step. Multiple extractions produced the (-i-)-cA-acid in 90% ee (see fig. 6.3) (Simandi et al., 1997). 

The supercritical solvent is expanded with the throttling valve (9) in order to remove the caffeine (separator 8) and to bring the solvent back to the liquid state (condenser 10). The gasrecycling (dry running) reciprocating compressor (7), the C02 and the co-solvent feed (2, 3 diaphragm pumps) represent variable process components if required. Heat exchangers (4) maintain the suitable thermodynamic conditions. 

The countercurrent extraction method is the most common one for separation of liquid mixtures with supercritical fluids as solvents. The extraction is performed in pressure columns where the liquid feed and the supercritical fluid flow in countercurrent way. 

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