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4442 Ind. Eng. Chem. Res.

2000, 39, 4442-4444

Commentary on Supercritical Fluids: Research and Applications


About 20 years ago, a meeting of the High Pressure There are also cases where environmental or health
Committee of the AIChE almost went out of business considerations dictate the use of benign supercritical
because it appeared unlikely that high-pressure re- solvents and some where the marketability of the
search would lead to new commercial processes. Low- product (coffee that is “naturally decaffeinated with
pressure catalysts had been developed for making sparkling effervescence”) or its quality are enhanced by
polyethylene, the air and ammonia industries were supercritical processing. Finally, there are some cases
mature, and all that appeared to be left was hot isostatic where the traditional processes are simply inadequate
pressingsand that was not exactly big business. Su- and the use of supercritical fluids offers a viable
percritical fluids were known only from some patent solution. This may be because the product is thermally
literature from Germany, and they did not appear to labile or morphologically unique or when solvent con-
be of significant commercial interest to justify an tamination must be avoided.3
extensive research effort. Nevertheless, one of the Until the early 1980s, large-scale applications of
younger memberssDick Grieger-Block of Wisconsins supercritical fluids were confined to fossil fuel process-
convinced the Committee that sessions on supercritical ing (the ROSE process) and food processing (coffee and
fluids would be of some interest to AIChE members, and tea decaffeination and hops extraction), the latter
a few sessions were therefore planned for a future mainly in Germany. Toward the end of this period, the
AIChE Meeting. German companies had expanded into smaller volume
Those first sessions were held in New Orleans in applications in the food industry (aromas and additives)
1980sunfortunately without Dick Greiger-Block, who and the drug/cosmetics industries. Also by the late
had passed away. The AIChE Meeting Program Com- 1980s, large plants dedicated to coffee decaffeination
mittee was apparently unimpressed by the potential of and hops extraction were built in the U.S., and there
supercritical fluids and assigned a small room for the were several small-scale plants related to drugs/cosmet-
sessions. To everyone’s surprise, more than 200 people ics/natural products in Japan, Korea, India, and else-
tried to jam into that small room; supercritical fluids where. The emphasis in all cases was on the ability of
had obviously “arrived”! The discussions in those first supercritical fluids to extract components from complex
sessions were devoted mainly to phase equilibria and substrates, aided by government regulations and con-
extractions.1 However, there were also papers on mak- sumer demands that encouraged the replacement of
ing silica aerogels and carrying out organic reactions. organic solvents.
More recently, plants have been constructed in the
After New Orleans came the halcyon days of super-
Far East for the extraction of phytochemicals and
critical fluids, when many university and industrial
neutraceuticals from natural products such as ginseng.
laboratories started research in this area. These labo-
In these applications, supercritical fluids provide better
ratories had to fabricate their own high-pressure equip-
quality products by also selectively separating contami-
ment because very little high-pressure equipment was
nants such as pesticides. New applications such as dry
available commercially. Nevertheless, many papers on
cleaning and degreasing of precision parts and electron-
supercritical fluid extraction were published, with the
ics are also on the verge of being commercialized. In
majority reporting solubility data and measurements of
these applications, chlorinated solvents are being re-
physical properties. New applications were proposed
placed by supercritical carbon dioxide because of in-
and, perhaps unfortunately, supercritical fluids were
creasing environmental and health concerns. Also, foam
offered as a panacea for many industrial problems. Here
expansion and particle generation have been developed
was a classic case of a solution in search of problems!
commercially and do not employ the extractive capabili-
Many of the proposed applications were proprietary, ties of supercritical fluids. CO2 is an excellent substitute
some were not even patented, and some were quite for chlorofluorohydrocarbons in swelling polymers and
speculative. It soon became quite clear that there would has been utilized to expand foams. Particle generation
be no particular advantage to using supercritical fluids using supercritical fluids has been employed in phar-
in many of the proposed processes. Distillation, solvent maceutical process development and in the making of
extraction, adsorption, fractional crystallization, mem- paints and coatings. In addition, the dyeing of textiles
brane separation, preparatory-scale chromatography, or using supercritical fluids has also been commercialized.
even zone refining were often cheaper than supercritical These examples of supercritical processing are likely
fluid extraction for several reasons: (i) the obvious one to become increasingly common in the future, particu-
that high-pressure equipment is more expensive, and larly in the case of particle production, solvent replace-
(ii) the other methods were more established and ment, and reactions to obtain “tailor-made” materials
required little research and development effort in order with desired properties, morphology, and purity. Some
to apply them. Nevertheless, the flood of research of these are discussed below.
continued unabated. Despite this effort, however, su-
percritical fluid extraction remains a relatively “new” Extraction and Purification
technology even today. Each supercritical process es-
sentially requires a new design, with concomitant front- Extraction and purification of nutraceuticals, food
end costs and contingency factors.2 There are cases, of supplements, and active ingredients for pharmaceuti-
course, when the supercritical process is more economi- cals will continue to be areas of importance in research
cal and some when processing cost is not a major as well as the application of supercritical fluids.3 As a
consideration (high-value-added products, for example). result, the knowledge base in solubility, extractability,
10.1021/ie000915m CCC: $19.00 © 2000 American Chemical Society
Published on Web 12/04/2000
Ind. Eng. Chem. Res., Vol. 39, No. 12, 2000 4443

purity, and quality of these materials will continue to reactions has been demonstrated in many studies.9
expand as more products are commercialized. The phase What is more interesting is that polymer molecular
behavior of the solute species in the supercritical fluid weight and molecular weight distribution, as well as
must be known precisely for reliable process design, and microstructure and morphology, can be controlled in
the considerable effort in this area is likely to continue. these reactions. Supercritical fluids such as CO2 also
However, there will be an increasing need for mass- lower the glass transition temperature of the polymer,
transfer, process design, and simulation studies for which can facilitate the impregnation of the polymer by
these supercritical processes. Moreover, the need for additives, drugs, dyes, and other polymers. The viscosity
acceptance of these sometimes “new” products by the of the polymer in the molten or dissolved states can be
consumer will determine their commercial success. lowered in the presence of supercritical fluids, which
can lead to new methodologies for the production of
Solvent Replacement and Green Chemistry polymer films, coatings, fibers, foams, membranes,
composites, and porous structures.10 Finally, supercriti-
A significant amount of research on supercritical cal fluids also offer the potential for the processing of
fluids has been devoted to their use as alternative inorganic materials, via synthesis reactions or from
solvents that are environmentally benign. In particular, decomposition of soluble precursors. Thin metal films,
the use of water and CO2 as solvents for traditional magnetic oxides, silicon nanowires, and other materials
organic syntheses is receiving and will continue to have been produced by deposition, microemulsion, and
receive much attention. The design of new chemical sol-gel techniques using supercritical fluids.11
pathways using these and other supercritical solvents
will also be of much interest. The potential for exploiting Analytical Applications
the “tunable” nature of the properties of supercritical
solvents (with and without cosolvents) will probably be The use of supercritical fluids as mobile phases in a
realized commercially in applications other than the chromatograph was demonstrated almost 40 years ago.
oxidation of organic wastes in supercritical water.4 Since then, commercial chromatographs have been
Supercritical fluids are promising media for homoge- marketed and supercritical fluid chromatography has
neous as well heterogeneous reactions. In particular, found its place as an analytical technique in many
reactions in near-critical and supercritical fluids will be applications.12 Furthermore, supercritical fluid extrac-
able to exploit the enhanced rates, improved mass tion is extensively used in sample preparation. There
transfer, increased selectivity and yield, and ease of is an extensive literature on the development of pack-
separation of reaction products.5,6 The technical feasibil- ings, columns, modifiers, detectors, and methods, dis-
ity of phase-transfer catalysis, selective oxidations, cussion of which is beyond the scope of this brief
cycloadditions, enzymatic reactions, and enantioselec- commentary. It is sufficient to note here that research
tive syntheses has already been demonstrated and will and development in this area will continue to flourish
likely be exploited in commercial applications in the in the future.
future.
Other Applications
Particle Production
Mechanisms by which molecules are solubilized in
The manufacture of uniform-sized organic and inor- supercritical CO2 have been studied extensively and are
ganic particles using the RESS process has already been being increasingly understood. It has been demon-
commercialized on a pilot-plant scale. The supercritical strated that fluoroalkanes, fluoroethers, poly(dimeth-
antisolvent process (and its many variations including ylsiloxane), and even carbonates offer special opportu-
GAS, SAS, PCA, SEDS, etc.) has also been the subject nities for CO2-philicity.13 This can be exploited in the
of many studies to make uniform particles.7 These synthesis of fluorochemicals and fluoropolymers and in
processes are of considerable interest in the pharma- the design of amphiphilic molecules specifically for
ceutical, paint, and polymer industries. Supercritical supercritical CO2. The latter include surfactants to
fluids offer a wide range of possibilities in the making promote water/CO2 macro- and microemulsions that
of particles. Active fragrance and flavor agents, as well offer many opportunities to do aqueous chemistry in the
as drugs, can be microencapsulated within a coating of supercritical phase. As a result, bioreactions involving
protective material using RESS. The supercritical pro- enzymes, peptides, and proteins can now be carried out
cess eliminates the potential for solvent contamination in supercritical CO2. These techniques can also be used
and is able to microencapsulate many materials that to make chelating agents to recover metal atoms, to
are difficult to treat with existing techniques. It has also carry out heterogeneous reactions such as phase-
been demonstrated that morphology can be controlled transfer catalysis and biphasic chemistry in fluorous
by adjusting nucleation and growth during the synthesis systems, and to develop new synthesis routes for na-
of nanoparticles of inorganic materials in supercritical nomaterials in supercritical CO2.
fluids,8 and this is an area that is likely to receive much Finally, investigations are underway to use super-
attention in the future. critical CO2 to improve the uniformity, purity, and
feature size of microelectronic devices. These investiga-
Materials Processing tions include the use of chemical fluid deposition from
CO2-soluble precursors to make thin metal films and
Processing in supercritical fluids offers routes to core-shell materials for magnetic recording.
“novel” materials, especially in the case of polymeric It has been suggested that the future of supercritical
materials, where properties such as morphology can be fluid processing depends on the technology going beyond
tailored to specific applications. The use of supercritical these niche markets and into mainstream processing.2
fluids as polymerization media to replace conventional The argument is that this technology would never
organic solvents and as reactants in polymerization gain acceptance in chemical manufacturing until it was
4444 Ind. Eng. Chem. Res., Vol. 39, No. 12, 2000

applied to high-volume products with low capital costs. (6) Brennecke, J. F.; Chateauneuf, J. E. Homogeneous Organic
Although we would welcome such applications, it seems Reactions as Mechanistic Probes in Supercritical Fluids. Chem.
more likely that the “niche” markets described in this Rev. 1998, 99, 433-452.
commentary will make up a significant fraction of the (7) Debenedetti, P. G.; Tom, J. W.; Yeo, S.-D.; Lim, G. B.
manufacturing sector in the future. Supercritical fluids Application of Supercritical Fluids for Production of Sustained
Delivery Devices. J. Controlled Release 1993, 24, 27-34.
have already made inroads into these markets, and
their contributions are likely to continue to increase. (8) Hakuta, Y.; Adschiri, T.; Hirakoso, H.; Arai, K. Chemical
Equilibria and Particle Morphology of Boehmite in Sub- and
The variety of these “niche” applications and the in- Supercritical Water. Fluid Phase Equilib. 1999, 158-160, 733-
creasing amount of research devoted to understanding 739.
the mechanisms of supercritical processes attest to the (9) DeSimone, J. M.; Maury, E. E.; Menceloglu, Y. Z.; McClain,
“maturing” of this technology and to the increasing J. B.; Romack, T. J.; Combes, J. R. Dispersion Polymerizations in
likelihood that it will be a significant contributor to Supercritical Carbon Dioxide. Science 1994, 265, 356-357.
manufacturing in the future. (10) Watkins, J. J.; Rao, V. S.; Pollard, M. A.; Russell, T. P. In
Phase Transitions in Polymer Blends and Block Copolymers
Literature Cited Induced by Selective Dilation with Supercritical Carbon Dioxide;
Kiran, E., Debenedetti, P. G., Peters, C. J., Eds.; NATO Advanced
(1) Paulaitis, M. E., Penninger, J. M. L., Gray, R. D., Davidson, Study Institute Series; Kluwer Academic Publishers: Dordrecht,
P., Eds. Chemical Engineering at Supercritical Conditions; Ann The Netherlands, 1999.
Arbor Science: Ann Arbor, MI, 1983. (11) Johnston, K. P.; Jacobsen, G. B.; Lee, C. T.; Meredith, C.;
(2) Chordia, L. 8th International Symposium on Supercritical Da Rocha, S. R. P.; Yates, M. Z.; DeGrazia, J.; Randolph, T. W.
Chromatography and Extraction, St. Louis, MO, July 1998. Microemulsions, Emulsions, and Latexes in Supercritical Fluids.
(3) Perrut, M. New Challenges for Supercritical Fluids. Pro- In Chemical Synthesis in Supercritical Fluids; Jessup, P., Leitner,
ceedings of the 5th Meeting on Supercritical Fluids, Nice, France, E., Eds.; Wiley-VCH: Weinheim, Germany, 1999.
1998; Instituto National Polytechnique De Lorraine: Vandoeuvre
Cedex, France, 1998; Vol. 1, pp 1-4. (12) Taylor, L. The Future Impact of Supercritical Fluid Chro-
(4) Tester, J. W.; Marrone, P. A.; DiPippo, M. M.; Sako, K.; matography on Packed Columns, Modified Fluids, and Detectors;
Reagan, M. T.; Arias T.; Peters, W. A. Chemical Reactions and ACS Symposium Series 670; American Chemical Society: Wash-
Phase Equilibria of Model Halocarbons in Sub- and Supercritical ington, DC, 1997; pp 134-153.
Water. J. Supercrit. Fluids 1998, 13, 225-240. (13) Beckman, E. J.; Sarbu, T.; Styranec, T. J. CO2-Philic
(5) Savage, P. E.; Gopalan, S.; Mizan, T. I.; Martino, C. J.; Polymers: Beyond Fluoropolymers and Silicones. The 5th Inter-
Brock, E. E. Reactions at Supercritical Conditions: Applications national Symposium on Supercritical Fluids, Atlanta, GA, April
and Fundamentals. AIChE J. 1995, 41, 1723-1778. 2000.

Amyn S. Teja and Charles A. Eckert*

School of Chemical Engineering


Georgia Institute of Technology
Atlanta, Georgia 30332-0100
IE000915M

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