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20.2.1. INTRODUCTION
Fluids above their critical temperatures and pressures, called supercritical fluids
(SCFs), exhibit properties intermediate between those of gases and liquids.
Consequently, each of these two boundary conditions sheds insight into the
nature of these fluids. Unlike gases, SCFs possess a considerable solvent
strength, and transport properties are more favorable. In regions where a SCF is
highly compressible, its density and hence its solvent strength may be adjusted
over a wide range with modest variations in temperature and pressure. This
tunability may be used to control phase behavior, separation processes (e.g., SCF
extraction), rates and selectivities of chemical reactions, and morphologies in
materials processing. For SCF separation processes to be feasible, the
advantages (Table 20-10) must compensate for the costs of high pressure;
examples of commercial applications are listed in Table 20-11.
The two SCFs most often studiedCO2 and waterare the two least expensive of
all solvents. CO2 is nontoxic and nonflammable and has a near-ambient critical
temperature of 31.1C. CO2 is an environmentally friendly substitute for organic
solvents including chlorocarbons and chlorofluorocarbons. Supercritical water (Tc
= 374C) is of interest as a substitute for organic solvents to minimize waste in
extraction and reaction processes. Additionally, it is used for hydrothermal
oxidation of hazardous organic wastes (also called supercritical water oxidation)
and hydrothermal synthesis. (See also Sec. 15 for additional discussion of
supercritical fluid separation processes.)
Diffusion coefficients are higher and viscosities lower, compared with liquids.
There is rapid diffusion of CO2 through condensed phases, e.g., polymers and
ionic liquids.
Reactive separations
Table 20-12. Physical Proper ties of a Supercritical Fluid Fall between Those
of a Typical Gas and Liquid
Water, a key SCF, undergoes profound changes upon heating to the critical point.
It expands by a factor of 3, losing about two-thirds of the hydrogen bonds, the
dielectric constant drops from 80 to 5 (Shaw et al., op. cit.), and the ionic product
falls several orders or magnitude (see Fig. 20-18). At lower densities, supercritical
water (SCW) behaves as a nonaqueous solvent, and it dissolves many organics
and even gases such as O2. Here it does not solvate ions significantly.
Solid-Fluid Equilibria The solubility of the solid is very sensitive to pressure and
temperature in compressible regions, where the solvents density and solubility
parameter are highly variable. In contrast, plots of the log of the solubility versus
density at constant temperature often exhibit fairly simple linear behavior (Fig.
20-19). To understand the role of solute-solvent interactions on solubilities and
selectivities, it is instructive to define an enhancement factor E as the actual
solubility y2 divided by the solubility in an ideal gas, so that , where
is the vapor pressure. The solubilities in CO2are governed primarily by vapor
pressures, a property of the solid crystals, and only secondarily by solute-solvent
interactions in the SCF phase. For example, for a given fluid at a particular T and
P , the Es are similar for the three sterols, each containing one hydroxyl group,
even though the actual solubilities vary by many orders of magnitude (Fig. 20-
19).
Figure 20-19. Solubility of sterols in pure CO2 at 35C [Wong and Johnston,
Biotech. Prog., 2, 29 (1986)].
Phase Equilibria Models Two approaches are available for modeling the
fugacity of a solute in a SCF solution. The compressed gas approach includes a
fugacity coefficient which goes to unity for an ideal gas. The expanded liquid
approach is given as
(20-9)
where xi is the mole fraction, i is the activity coefficient, P and fi are the
reference pressure and fugacity, respectively, and is the partial molar volume
of component i. A variety of equations of state have been applied in each
approach, ranging from simple cubic equations such as the Peng-Robinson
equation of state to the more complex statistical associating fluid theory (SAFT)
(Prausnitz et al., op. cit.). SAFT is successful in describing how changes in H
bonding of SCF water influence thermodynamic and spectroscopic properties.
Figure 20-20 shows a one-stage extraction process that utilizes the adjustability
of the solvent strength with pressure or temperature. The solvent flows through
the extraction chamber at a relatively high pressure to extract the components of
interest from the feed. The products are then recovered in the separator by
depressurization, and the solvent is recompressed and recycled. The products
can also be precipitated from the extract phase by raising the temperature after
the extraction to lower the solvent density. Multiple extractions or multiple stages
may be used with various profiles, e.g., successive increases in pressure or
decreases in pressure. Solids may be processed continuously or semicontinuously
by pumping slurries or by using lock hoppers. For liquid feeds, multistage
separation may be achieved by continuous countercurrent extraction, much as in
conventional liquid-liquid extraction. In SCF chromatography, selectivity may be
tuned with pressure and temperature programming, with greater numbers of
theoretical stages than in liquid chromatography and lower temperatures than in
gas chromatography.
Figure 20-20. Idealized diagram of a supercritical fluid extraction process
for solids.
20.2.6. APPLICATIONS
*Mukhopadhyay, Natural Extracts Using Supercritical Carbon Dioxide, CRC Press, Boca
Raton, Fla., 2000; Moyler, Extraction of flavours and fragrances with compressed CO 2, in
Extraction of Natural Products Using Near-Critical Solvents, King and Bott (eds.), Blackie
Academic & Professional, London, 1993.
Figure 20-21. Schematic diagram of the Kerr-McGee ROSE process.
Cleaning SCFs such as CO2 can be used to clean and degrease quartz rods
utilized to produce optical fibers, products employed in the fabrication of printed-
circuit boards, oily chips from machining operations, precision bearings in military
applications, and so on. Research is in progress for removing residues in etch/ash
processes in microelectronics.
Citation
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Don W. Green; Robert H. Perry: Perry's Chemical Engineers' Handbook, Eighth
Edition. SUPERCRITICAL FLUID SEPARATION PROCESSES, Chapter (McGraw-Hill
Professional, 2008 1997 1984 1973 1963 1950 1941 1934), AccessEngineering
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