FEATURE

S
upercritical carbon dioxide is emerging as
Supercritical a "green" chemical alternative in a vari-
ety of industrial and analytical pro-
cesses. Industrial managers, researchers,

Carbon Dioxide: and analytical chemists view it as offer-

ing a benign, environmentally friendly
alternative to a variety of organic solvents (2). Al-

The "Greener" though already established in such diverse applica-

tions as decaffeinating coffee, wastewater treat-
ment, and chemical analysis, supercritical C0 2 is
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currently being investigated for use in polymer man-

Solvent ufacturing, pharmaceuticals, and soil remediation.
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Much of the interest in the technology is at a very

early stage, with industry and government funding
a number of fundamental R&D projects to find out
It's not toxic and it doesn't more about the suitability of supercritical C0 2 in spe-
cific applications. Barriers do exist to its wide-
harm the ozone layer, but spread acceptance, not the least of which is the sub-
stantial capital investment in new equipment it
can supercritical C O 2 do the requires. But advocates for the technology believe that
it is only a matter of time and further research be-
job in major industrial fore the advantages of supercritical C0 2 are widely
recognized.
applications? Supercritical C0 2 attracts all this interest be-
cause of what it is not. It is not toxic, it is not flam-
mable, it is not expensive, and it does not threaten
HARVEY BLACK the ozone layer as do chlorofluorocarbons (CFCs),
which until the recent ban were used extensively in
polymer manufacturing. Carbon dioxide becomes su-
percritical at pressures above 1100 psi and at tem-
peratures at or above 88 °F. Making C0 2 supercriti-
cal is hardly the stuff of cutting-edge technology, but
capitalizing on its characteristics is. The focus of much
industrial activity to date has been R&D as op-
posed to use in production processes.

Polymerization solvent
In the supercritical state, C0 2 is nonreactive for many
chemistries and has zero surface tension and low vis-
cosity, explains Joseph DeSimone, professor of chem-
istry at the University of North Carolina-Chapel Hill,
who is a leader in exploring the properties and po-
tential of supercritical C0 2 . In the lab DeSimone is
conducting basic research on using supercritical C02's
properties as a solvent in polymerization. He has used
it to make fluoropolymers (2) and has developed a
technique to use it in making micrometer-sized
acrylic polymers (3). His work is supported by a num-
ber of major chemical and technology companies in-
cluding DuPont, Hoechst-Celanese, BF Goodrich, Air
Products, Eastman Chemical, and Xerox; he has re-
ceived federal support from the National Science
Foundation and EPA.
According to DeSimone, supercritical C02's fea-
tures help make it an ideal solvent in producing com-
mercially important fluoropolymers, whose major ad-

1 2 4 A • VOL. 30, NO. 3, 1996 / ENVIRONMENTAL SCIENCE & TECHNOLOGY / NEWS 0013-936X/96/0929-124AS12.00/0 © 1996 American Chemical Society
vantage is waterproofness.
Jackie Savoca, a former manager of technology as-
sessment and acquisition at BF Goodrich, an aero-
space and specialty chemicals company in Cleve-
land, Ohio, also promotes the advantages of
supercritical C0 2 in making fluoropolymers. "I'm very
sanguine about the process," she says, describing her-
self as a cheerleader for research in the area at the
firm. She declined to discuss the extent to which the
firm is exploring supercritical C0 2 , but acknowl-
edges that the company is supporting DeSimone's re-
search.
Hoechst-Celanese, the chemical and advanced
materials manufacturer in Charlotte, N.C., is also ex-
ploring supercritical C0 2 . "If you can use it in place
of organic solvents, you have fewer environmental
concerns," says technology manager George Serad.
Serad said the firm also has used supercritical C0 2
to purify polymers for recycling, but declined to dis-
cuss that process in detail because the firm wants to
patent the process.
DeSimone also talks of using supercritical C0 2 as
a replacement for benzene and toluene in polymer-
izing acrylic acid, which is used as a thickener in
toothpaste and foods. "Very often the polymeriza-
tion is done in the organic solvents to precipitate it,"
he says. In 1994 he reported successfully polymer-
izing acrylic acid in supercritical C0 2 .

"Superior" in chiral drug manufacture

Pharmaceuticals may be another industry ripe for us-
ing supercritical C0 2 . William Tumas at Los Alamos
National Laboratory, Mark Burk of Duke University,
and their colleagues report that supercritical C0 2 can
be superior to conventional hazardous solvents for
making chiral or "handed" molecules using asym-
metric catalysts (transition metals with chiral li-
gands). Many drugs are chiral; they come in left- or
right-handed forms (enantiomers). One active form
may have desired properties; the other may be del-
eterious. "We've shown that you can get more of the
handed molecule that you want by reducing carbon-
carbon double bonds with either hydrogen or hy-
drogen transfer agents in supercritical C0 2 using
ruthenium and rhodium catalysts with chiral li-
gands," Tumas says. Tumas, who presented these find-
ings at the August 1995 meeting of the American
Chemical Society (4), says using supercritical C0 2 in
drug and specialty chemical manufacture can not
only replace hazardous solvents, but could also bring
economic benefits because it could "increase selec-
tivity," meaning that more of the desired product is Carbon dioxide goes supercritical in a 60 mL stainless steel reactor at Los Alamos
produced compared to an undesired one. National Laboratory. C0 2 is in both a liquid and gas phase at 30 °C and 1000 psi
(top photo) and begins the phase transition to the supercritical state as tem-
He gives this example: Naproxen, a widely used perature increases (middle photo). The single-phase supercritical C0 2 solu-
anti-inflammatory drug, has a handed molecule that tion (bottom photo) is being used by Los Alamos researcher William Tumas to
is a liver toxin. The maker of the drug separates the investigate new methods of synthesizing chiral molecules.

VOL. 30, NO. 3, 1996 / ENVIRONMENTAL SCIENCE & TECHNOLOGY / NEWS • 1 2 5 A


Industrial wastewater meets supercritical C0 2 in the 32-foot-
tall counter-current liquid-liquid extraction column at the Clean
Harbors treatment facility in Baltimore. C0 2 is pumped into
the bottom of the column and dissolves organic contami-
nants as it percolates up through the water.
two and gets rid of the toxin. "What you'd like to do
is avoid costly separations by making only one en-
antiomer," says Tumas.
But pharmaceutical makers don't seem to be rush-
ing to embrace this method. Representatives of Merck
and Boehinger Ingleheim deny any strong interest in
supercritical C0 2 . However, according to one long-
time entrepreneur involved in the supercritical C0 2
business, that view is not universal. John Moses, pres-
1 2 6 A • VOL. 30, NO. 3, 1996 / ENVIRONMENTAL SCIENCE & TECHNOLOGY / NEWS
ident of CF Technologies, Inc., a process develop-
ment firm in Hyde Park, Mass., says that in Europe
supercritical C0 2 is the primary means used for phar-
maceutical separations.
But Tumas says the technology to produce syn-
thetic chemicals might not be completely ready for
full-scale use. "Synthetic and catalytic reactions in
C0 2 represent a fairly new field, and there needs to
be more exploration into the effects of the solvent
(supercritical C02) to understand what kind of chem-
istry can be carried out," he says. A lot more re-
search needs to be done, he believes, noting that the
Los Alamos work is directed to answer such ques-
tions.
"We believe that for supercritical C0 2 to be more
broadly applicable, reactions have to go faster and
better, which would provide the necessary eco-
nomic incentive in addition to the environmental
benefits," Tumas says. "That's what we can't predict
yet."
Beyond such fundamental questions is the issue
of equipment. Using supercritical C0 2 requires new,
expensive equipment to keep the material under high
pressure. "Switching to something that uses whole
new 'pots and pans' is expensive. There's a big cap-
ital expense, hundreds of thousands to several mil-
lions of dollars, depending on the size of the busi-
ness," says Savoca.
Industrial wastewater treatment
Supercritical C0 2 has also been put to use in a va-
riety of industrial waste treatment applications. Clean
Harbors Environmental Services, Inc., has used su-
percritical C0 2 in Baltimore since 1989 to treat waste-
water from chemical and pharmaceutical manufac-
turers. In its plant with a capacity to treat 1.2 million
gallons of water a day, supercritical C0 2 removes or-
ganic contaminants including ketones, chlorinated
solvents, and oils from wastewater shipped to the
plant. The contaminants are separated from the C02,
which is recycled, and then incinerated off site, ex-
plains Alex Schultheiss, Clean Harbors technology de-
velopment manager.
"As wastewater streams reach a certain level in
terms of organic content, traditional treatments don't
work, so we fill a unique market niche with the pro-
cess in Baltimore," says Schultheiss.
In the process the wastewater is pumped into the
top of a 32-foot high, 2-ft. diameter column, while
the C0 2 is pumped in from the bottom and perco-
lates up. 'As the C0 2 percolates up it dissolves the
organics. So at the top of the column you have C0 2
contaminated with organics, and at the bottom you
have clean water," he says. The water from the plant,
which Schultheiss says typically runs at 75% capac-
ity, is sent to the Baltimore municipal sewage treat-
ment plant.
According to Schultheiss, the technology is the
"leading edge" of a new process, and the firm is ex-
ploring a number of "market opportunities in the
chemical industry."
Supercritical fluid extraction
Supercritical C0 2 is also being used in a variety of
analytical settings. Hewlett-Packard, for example,
manufactures two supercritical fluid extractors. They
use supercritical C0 2 instead of organic solvents to
extract compounds of interest for analysis.
"There's a drive in the analytical industry to speed
up the process and get away from toxic solvents," says
Steven Hutt, Hewlett-Packard's project manager for
supercritical equipment. Last year the company and
other manufacturers of analytical instruments us-
ing supercritical C0 2 had about $35 million in sales
of such instruments, according to Strategic Direc-
tions International, a Los Angeles-based marketing
firm that tracks the analytical market. Thefirm'spres-
ident, Lawrence Schmid, estimates that sales in 1996
will grow to about $40 million.
Supercritical C0 2 can extract compounds in 30-45
minutes; conventional processes, such as Soxhlet ex-
traction, can take hours to days. "It's a faster, more
selective extraction solvent because it has the vis-
cosity of a gas and the density of a liquid. And you
can control the selectivity by changing the pressure
and the temperature," says Steven Lehotay, an ana-
lytical chemist with the U.S. Department of Agricul-
ture. Lehotay uses supercritical C0 2 in the analysis
of pesticide residues in food [5-6).
Because supercritical C0 2 is under high pres-
sure, it acts like a liquid and can dissolve the mate-
rials of interest. Simply by changing the pressure, the
solvent strength can be changed—a key advantage
for Lehotay and other analytical chemists. "You can
tailor the solvency with pressure," says DeSimone. 'There's a drive in the analytical industry to speed up the pro-
"If you were to do this with organic solvents, you cess and get away from toxic solvents," according to Steven
Hutt, Hewlett-Packard product manager for supercritical equip-
would have to use co-solvents, and that would bring
ment. The HP 7680T Supercritical Fluid Extractor is part of a
up problems due to specific solvent-solute interac- $35 million annual market for supercritical analytical instru-
tions because of the changing composition of the sol- ments.
vent."
Supercritical C0 2 is also being used to better un-
derstand the distribution of nonvolatile organics such about $1000 for the glassware and solvents needed
as dioxins and polychlorinated biphenyls (PCBs) in for conventional Soxhlet extraction. Another poten-
contaminated soils. Thomas Harmon at the Univer- tial problem is that the sample size obtained in su-
sity of California-Los Angeles is planning National percritical C0 2 extraction is very small—only 2-6
Science Foundation-funded research to use super- grams, according to Lehotay. "If your instrument for
critical fluid extraction to study how these contam- detection is not sensitive enough, that would be a
inants behave in subsurface soil, air, and water. In problem," he says.
laboratory-contaminated samples, supercritical C0 2 Boosters of supercritical C0 2 see a bright future
will be used to extract these chemicals and allow Har- for it in a variety of applications. "But the broad po-
mon to explore how they are distributed. The goal tential is only going to be seen with more re-
is to develop better remediation strategies. search," says Paul Anastas of EPA's Office of Pollu-
tion Prevention and Toxics. Just how far it can be
Faster, cleaner, but expensive developed depends on what that research uncovers
"There are three primary advantages that I see in su- as well as how much interest can be generated in
percritical C02," says John Rankin, a chemist with the industry.
New York State Department of Environmental Con-
servation, who uses it to extract PCBs from soil sam-
ples. "Speed, the extracts are inherently cleaner, and
References
(1) Kiran, E.; Levelt Sengers, J.M.H., Eds. Supercritical Flu-
the use of solvents is drastically reduced from up to ids: Fundamentals for Applications; Kluwer: Dordrecht,
one liter down to 10 to 15 mL." 1994.
EPA has accepted the use of supercritical C0 2 in (2) Shaffer, K. M.; DeSimone, J. M. Trends in Polymer Sci-
ence 1995, 3, 146-53.
extracting total petroleum hydrocarbons (Refer- (3) DeSimone, J.M. et al. Science 1994, 265, 356-59.
ence Method 35603 and polycyclic aromatic hydro- (4) Borkowsky, S. L. et al. Presented at the 210th Meeting of
carbons (Method 3561) under SW846. The proto- the American Chemical Society, August 1995.
cols have gone from draft to proposal and are (5) Lehotay, S. J.; Eller, K. I./. AOACInt. 1995, 78, 821-30.
(6) Lehotay, S. J.; Ibrahim, M. A. /. AOAC Int. 1995, 78, 445-
expected to be promulgated in 1996. EPA is ex- 52.
pected to propose supercritical C0 2 as a method to
extract PCBs in 1996 (Method 3562.)
However, supercritical C0 2 is not without its draw-
backs. One is cost. Rankin says the equipment can Harvey Black is a freelance science writer based in
cost between $20,000 and $50,000 compared with Madison, Wis.

VOL. 30, NO. 3, 1996 / ENVIRONMENTAL SCIENCE & TECHNOLOGY / NEWS • 1 2 7 A