SUPERCRITICAL FLUID
TECHNOLOGY
SUPERCRITICAL FLUID EXTRACTION
What are supercritical fluids?
• A SCF is defined as a substance above its critical
temperature (TC) and critical pressure (PC).
• The critical point represents the highest
temperature and pressure at which the substance
can exist as a vapour and liquid in equilibrium.
• The phenomenon can be easily explained with
reference to the phase diagram for pure carbon
dioxide
• Supercritical Fluid: Fluid over its critical temperature
and pressure, exhibiting good solvent power ; in
most applications, carbon dioxide is used pure or
added with a co-solvent ; the main interest of
supercritical fluids is related to their “ tunable ”
properties, that can be changed easily by monitoring
pressure and temperature :
• good solvent power at high densities (temperature
near critical temperature and pressure much over
critical pressure) to very low solvent power at low
densities (temperature near or higher critical
temperature and pressure lower critical pressure).
Carbon dioxide and other fluids
• Carbon dioxide : CO2 is a very attractive supercritical
fluid for many reasons :
– very cheap and abundant in pure form (food grade)
worldwide ;
– non flammable and not toxic ;
– environment-friendly, as non polluting gas and as most of
CO2 is manufactured from waste streams (mainly fertilizer
plants gaseous effluents) ;
– critical temperature at 31°C, permitting operations at
near-ambient temperature, avoiding product alteration ;
– critical pressure at 74 bar, leading to “acceptable”
operation pressure, generally between 100 and 350 bar.
• However, carbon dioxide always behaves as a
“non-polar ” solvent that selectively dissolves
the lipids that are water-insoluble compounds
like vegetal oils, butter, fats, hydrocarbons
Carbon dioxide does not dissolve the
hydrophilic compounds like sugars and
proteins, and mineral species like salts,
metals,…
• Co-solvent : Organic solvent added to the
main fluid (generally carbon dioxide) to
modify its solvent power vis-à-vis “ polar ”
molecules as the fluid itself is only able to
dissolve “ nonpolar ” molecules ; generally,
the co-solvent is chosen between short-chain
alcohols, esters or ketones. For obvious
reasons, ethanol is preferred in many cases as
it is abundant and cheap in pure forms (food
grade, pharmacopoeia grade), not
environment hazardous and not very toxic (as
it is well known ! ).
PROPERTIES OF SUPERCRITICAL FLUIDS
1. Density Considerations
2. Thermodynamic Properties
3. Polarity
4. Solvent power
5. Thermodynamic cycle
6. Diffusivity /Viscosity Considerations
7. Transport Properties
8. Biological Properties
9. Solvating Strength
SUPERCRITICAL FLUID EXTRACTION
• Supercritical fluid extraction is defined as the use
of SFs to selectively remove analytes from solid,
semisolid, and liquid matrices.
• The significant properties of SFs that relate to
extraction processes are:
– solvating power directly related to density (which near
the critical point is pressure and temperature
dependent),
– relatively high diffusivity and low viscosity, and
– minimal surface tension.
• The performance goals of SFE are to reduce
the use of hazardous chemicals, the amount
of glassware, and the labor/time involved in
extraction.
• In SFE a key question is whether to conduct
the extraction in the
– off-line or
– on-line mode.
• Off-line SFE refers to any method in which the
extracted analytes are collected in a device
independent of the measurement instrument.
Utilization of the offline mode of SFE offers
many advantages to the analyst who is
inexperienced in SFE.
• The on-line mode is more efficient because it
involves the combination of the extraction
step with another analytical technique such as
gas chromatogra-phy, SF chromatography, or
IR spectrometry.
• The advantages of the off-line mode are:
– Only the SFE step need be optimized
– Larger samples can be processed
– Extracted analytes can be analyzed on multiple
instruments at anytime
– Measurement instrumentation is free for other
analyses
– Chromatography column overload can be avoided
• The on-line mode:
– Affords the greatest extractant concentration to
the measurement instrument since 100% of the
analyte may be directly transferred
– Demands fewer sample manipulations
– Increases the speed of analysis
– Protects air/light sensitive samples from the
environment
• The equipment for off-line and on-line SFE has
many common features. It is not advisable to
perform on-line SFE without optimizing
extraction parameters using off-line SFE
initially. The basic components of an off-line
analytical SF extractor are:
– Supply of CO2 or some other fluid
– Gas compressor or pump
– Heated zone or oven
– Extraction vessel or thimble
– Outlet restrictor or valve
– Extract accumulator or trap (e.g., collector)
There are a number of automated commercial extraction units available which
incorporate many or all of these features. Currently, major suppliers are Applied
Separations, Dionex, Hewlett Packard, Isco, Supelco, and Suprex. Less expensive home-
built systems can easily be assembled from components.
• high-purity CO2 serves as the fluid of choice
for all extractions. Replacement choices for
pure CO2 will, in over 90% of the cases,
employ CO2 with an organic modifier added
(to increase the fluid polarity) rather than an
alternate fluid such as propane or sulfur
hexafluoride. At this point alternate pure
fluids have seen limited applicability in
analytical SFE.
• The advantages of using CO 2-based fluids are:
• it is nonflammable,
• it is nontoxic,
• it is less expensive than reagent grade liquid
solvents,
• it is available in a high state of purity, and
• it can be vented to the atmosphere or
recycled without harm.
• In analytical SFE procedures,
• gas purity is a prime issue because the process
concentrates the nonvolatile impurities along with the
analyte during the extraction.
• For these extractions to yield quantitative results at the
parts per billion level, impurities introduced by the
extraction fluid must be minimal.
• It has been reported that impurities in CO2 caused
background interference with trace analysis. In this case,
the limit of detection was determined by CO2 purity rather
than the detector employed.
• If one cannot obtain highly pure CO2, detectors that are
insensitive to the impurities should be used.
• This option has been employed in the extraction and
assay of drugs from animal feed via HPLC/UV since
many of extractable feed components are not UV
active.
• Since the impurities in CO2 can vary, utilization of this
option can be somewhat limited.
• SFC grade, which may have as much as 100 ppb
nonvolatile hydrocarbon. An extraction requiring 20 g
of SFC-grade CO2 would, for example, deposit 2 jxg of
hydrocarbon impurity along with the analyte.
• The SFE-grade CO2 would typically contain no more
than 1 ppb nonvolatile hydrocarbon residue, 0.1 ppb
halo-genated residue, and 100 ppb moisture.
