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Submitted to:
Professor Jeff Sczechowski
Civil and Environmental Engineering Department
Cal Poly, San Luis Obispo, CA
Submitted by:
Leslie Harrison
Tracie Mustain
Bryan Williams
March 7, 1997
Overview
A fluid becomes supercritical when compressed to a pressure and elevated to a
temperature greater than that of its critical point (see figure 1). Although a
supercritical fluid (SCF) is at single phase, it exhibits properties of both a liquid and a
gas. A SCF has a relatively high liquid-like density. Solubility increases with density
and pressure, thus, SCFs have a high absorption capacity (at high pressures, solubility
increases with temperature as well). The gas-like properties of high diffusivity and
low viscosity allow for high mass transfer rates between a solute and a SCF. Fluids in
their supercritical states, having a high rate of absorbtion, are widely used in organic
contaminant extraction from soil, water and precipitates.
Carbon dioxide (CO2) is the most beneficial SCF used in extraction. Its non-toxic and
non-combustible properties make it environmentally friendly. Supercritical CO2 has a
higher density (thus solubility) and lower critical parameters than most of the other
SCFs. With a critical temperature of 31�C and critical pressure of 73 atm,
supercritical CO2 extraction energy costs are lower than those of other fluids (water's
critical temperature and pressure are 374�C and 218.4 atm). CO2 is readily available
in high purity and is therefore, inexpensive to purchase. Supercritical CO2 is the most
popular and inexpensive solvent used in industry today.
The food and beverage industry was the first to make commercial use of supercritical
carbon dioxide extraction. Three examples of this are as follows:
Coffee decaffeination stands out as the most successful use thus far of SCF-CO2
extraction. "�(I)t is the first example of a supercritical fluid process that has reached
the commercial processing level and whose primary step is, indeed, supercritical
extraction (McHugh (1986) 185)." The use of SCF-CO2 replaced dichloromethane, a
solvent that has been proven to cause cancer, and was previously used to remove
caffeine from coffee beans. In November 1991, OSHA "proposed lowering from 500
ppm to 25 ppm the permitted hourly industrial exposure to methylene chloride
(dichloromethane) � (Chemical & Engineering News vol. 69 8)." The three
advantage to using SCF-CO2 instead of the traditional solvent methods are:
Dichloromethane extraction is a carcinogenic process.
SCF-CO2 extracts caffeine only in green coffee beans and does not remove the
precious aroma oils.
No post-decaffeination treatment is needed to remove the solvent from the beans.
The actual decaffeination process using SCF-CO2 is a simple one. Basically, green
coffee beans are saturated with water and exposed to humidified SCF-CO2.
"Saturating the raw beans with water and humidifying the supercritical CO2 are
essential if high extraction rates are to be realized (AIChE Journal 762)." "Extraction
rates increase at higher temperatures and pressures due to the increased value of the
partition coefficient for caffeine between supercritical carbon dioxide and water
(AIChE Journal 763)." An efficiency of up to 95% can be expected with the use of
SCF-CO2. It should be noted that once the SCF-CO2 has passed through the bed of
beans and stripped the caffeine, it is depressurized. However, the carbon dioxide must
be either water stripped or passed through a carbon bed to remove all of the caffeine.
This is the only disadvantage to the SCF-CO2 process as opposed to the traditional
solvent method.
New Technology
Soon after recognizing that supercritical carbon dioxide had a future as a solvent,
scientists began seeking ways to get a larger variety of molecules (contaminants) to
mingle with the CO2. However, since SCF-CO2 is nonpolar, many contaminants will
not stick to it. Thus, to find a CO2-loving surfactant (a surface active solution) with
one end adhering to CO2 and the other end to the contaminant of concern, creative
chemical research was needed.
Researchers looking for solutions to the surfactant solution have recently found that
by using a co-solvent with the CO2, contaminants can be easily extracted. Currently,
fluorine has been found to be the most effective co-solvent. One research team
(DeSimone's group at Oak Ridge National Laboratory in Tennessee) has linked a
fluorinated CO2-loving compound to the removal of polystyrene. The team tested the
fluorocarbon compound by dumping it into a CO2 filled vat containing a plate coated
with polystyrene pieces. Alone, polystyrene won't dissolve in SF-CO2, but with the
help of fluorine, researchers expected the plate to be cleaned. They found that the
surfactant's polystyrene loving ends of the molecules picked up the polystyrene from
the plate. The polystyrene ends then slipped into a ball configuration (a micelle) with
the CO2 loving ends sticking out and polystyrene was trapped in the middle: the plate
became clean. The flourocarbon surfactant connected the polystyrene with the CO2
and when later depressurized, the solvent and contaminant separate. The CO2 is
recycled for other uses. An advantage of dissolving fluorocarbon polymers in the fluid
is that the critical point is lowered, making it supercritical at lower economically
viable pressures. The team is currently creating other surfactants for compounds other
than polystyrene.
The mechanisms by which the highly electronegative fluorinated groups combine with
supercritical CO2 are leading researchers to believe radioactive elements, thornium
and uranimum, can also be extracted from nitric acid solutions or from solid materials.
Previously, radioactive wastes had to be dissolved in acid, extracted into an organic
solvent, and then it became a waste. In addition to producing a waste, solvents left
traces in the treated solids.
Industry is still using many hazardous organic solvents each year, because nonpolar
SCF-CO2 can not dissolve many substances on its own. Once researchers develop co-
solvents to cure this problem, SCF-CO2 will become the ideal environmentally and
economically friendly solvent. But in general, while fluorine has been found to
expand the use of supercritical carbon dioxide for extraction, it is also costly. Though
fluorinated compounds may likely be too expensive to be used on a large scale,
researchers are hoping that once developed, the surfactants can be mass produced
much more inexpensively.
Conclusion
Engineering practices that require traditional solvents are no longer the only option.
Through new focuses, such as pollution prevention, solvent use is being steadily
replaced with more environmentally friendly methods. Supercritical carbon dioxide
offers many advantages over traditional solvents. Extraction processes can achieve the
same results without the negative side effects of large waste streams and work place
hazards from working with carcinogenic materials. These advantages have been
encompassed by the food and beverage industry and are making their way into more
technical fields.
References
Bright, Frank V., and Mary Ellen P. McNally. Supercritical Fluid Technology. New
York: Maple Press, 1992.
"Caffeine Extraction from Coffee Beans Using Supercritical Carbon Dioxide." AIChE
Journal vol. 38 no. 5. May 1992: 761-70.
Kaiser, Jocelyn. "Supercritical Solvent Comes Into Its Own." Science 274 (1996):
2013.
McHugh, Mark, and Val Krukonis. Supercritical Fluid. MA: Butterworth Publishers,
1986.
McHugh, Mark, and Val Krukonis. Supercritical Fluid. second edition. MA:
Butterworth-Heinemann, 1994.
"National Science Foundation Grant Will Lead to Better Soil Contamination Clean Up
Techniques." Http://cct.seas.ucla.edu/cct.supercritical.html.
"New Role for Supercritical Carbon Dioxide." Chemistry & Industry no. 3. 15
February 1996: 73.
"OSHA Changes Exposure Levels for Methylene Chloride." Chemical & Engineering
News vol. 69, no. 46. 18 November 1991: 8.
Paulaitis, Michael E., Johan M. L. Penninger, Ralph D. Gray, Jr., and Phillip
Davidson. Chemical Engineering at Supercritical Fluid Conditions. Michigan: Ann
Arbor Science Publishers, 1983.
Taylor, Larry T. Supercritical Fluid Extraction. New York: John Wiley & Sons, Inc,
1996.