SUPERCRITICAL

FLUID EXTRACTION

BAMGBOSE Timothy
Oluwaseyi
First Year M.Sc.
CONTENT
Introduction
Supercritical Fluid
Supercritical Fluid Extraction (SFE)
Optimization of SFE
Advantages of Supercritical Fluid Extraction
Disadvantages of Supercritical Fluid Extraction
Conclusion
References
INTRODUCTION

• Supercritical fluids (SCFs) are increasingly replacing

the organic solvents that are used in industrial
purification and recrystallization operations because
of regulatory and environmental pressures on
hydrocarbon and ozone-depleting emissions.

• SCF-based processes has helped to eliminate the use of

hexane and methylene chloride as solvents.

• With increasing scrutiny of solvent residues in

pharmaceuticals and medical products the use of SCFs
is rapidly proliferating in all industrial sectors.
INTRODUCTION

• Supercritical Fluid Extraction (SFE) is based on the

fact that, near the critical point of the solvent, its
properties change rapidly with only slight variations of
pressure.

• Its advantage includes the use of moderate

temperatures, and that several cheap and non-toxic
fluids are available.

• The technique of supercritical fluid extraction

utilizes the dissolution power of supercritical fluids,
i.e. fluids above their critical temperature and pressure.
 SUPERCRITICAL FLUID
• The critical point (CP) marks the end of
the vapour liquid coexistence curve.

• A fluid is termed supercritical when the

temperature and pressure are higher than
the corresponding critical values.

• Above the critical temperature, there is no

phase transition in that the fluid cannot
undergo a transition to a liquid phase,
regardless of the applied pressure.
SUPERCRITICAL FLUID
In the supercritical
domain, the SCF
increases in
density as the
pressure is
raised whilst
other physical
properties,
including
diffusivity, change
but remain gas-
like.
 SUPERCRITICAL FLUID
• A supercritical fluid (SCF) is defined as “non-
compressible and high density fluid”. The
temperature and pressure are higher than critical
temperature (Tc) and Critical Pressure (Pc).

• SCF has high thermal motion, and it is possible to

change the density widely (from low like a gas to
high like a liquid), therefore many properties whose
function is expressed by density can be controlled.

• Under these conditions, the molar volume is

the same whether the original form was a liquid
or a gas.
 SUPERCRITICAL FLUID
• Supercritical fluids have densities, viscosities and
other properties that are intermediate between those
of the substance in its gaseous and in its liquid
state.

• Carbon dioxide is the most commonly used

supercritical fluid because of its low critical
temperature (31oC), inertness, low toxicity and
reactivity and high purity at low cost.

• In summary, a supercritical fluid is any substance

at a temperature and pressure above its critical point,
where distinct liquid and gas phases do not exist. It can
effuse through like a gas, and dissolve materials like a
SUPERCRITICAL FLUID
Critical Fluid technology Timeline
SUPERCRITICAL FLUID EXTRACTION (SFE)

• Supercritical Fluid
Extraction (SFE) is the process of
separating one component (the
extractant) from another (the
matrix) using supercritical
fluids as the extracting solvent.

• Extraction is usually from a solid matrix,

but can also be from liquids.
SUPERCRITICAL FLUID EXTRACTION (SFE)

• SFE can be used as a sample

preparation step for
analytical purposes,

• or on a larger scale to either strip

unwanted material from a product
(e.g. decaffeination) or collect a
desired product (e.g. essential
oils).
SUPERCRITICAL FLUID EXTRACTION (SFE)

Carbon dioxide (CO2) is the most

used supercritical fluid,
sometimes modified by co-
solvents such as ethanol or
methanol. Extraction conditions
for supercritical carbon
dioxide are above the critical
temperature of 31°C and critical
pressure of 74bar.
SUPERCRITICAL FLUID EXTRACTION (SFE)

• The main advantages of

using supercritical fluids for
extractions is that they are
inexpensive, extract the
analytes faster and more
environmentally friendly than
organic solvents.
SUPERCRITICAL FLUID EXTRACTION (SFE)

It is based on the principle

that solubility in a
supercritical fluid increase
dramatically with increasing
density, and different solutes
have different solubility at the
same condition.
SUPERCRITICAL FLUID EXTRACTION (SFE)

The major advantage of this

method over liquid-liquid
extraction is that the
supercritical fluid can easily
be removed after extraction
by lowering the temperature or
pressure or both.
SUPERCRITICAL FLUID EXTRACTION (SFE)

• It has also been shown experimentally that

the extraction of certain steroids and
chemotherapeutic drugs can be achieved
using supercritical fluids.

• Other current and potential uses include the

removal of undesirable substances such
as pesticide residues, removal of bacteriostatic
agents from fermentation broths, the recovery
of organic solvent from aqueous solution, cell
disintegration, destruction and treatment of
industrial wastes and liposome preparation.
INSTRUMENTATION

• A supercritical-fluid extractor consists of

a tank of the mobile phase, usually CO2, a
pump to pressurize the gas, an oven
containing the extraction vessel, a restrictor
to maintain a high pressure in the extraction
line, and a trapping vessel.

• Analytes are trapped by letting the solute-

containing supercritical fluid decompress into
an empty vial, through a solvent, or onto a
solid sorbent material.
INSTRUMENTATION

• Extractions are done in dynamic,

static, or combination modes.

• In a dynamic extraction the

supercritical fluid continuously
flows through the sample in the
extraction vessel and out the
restrictor to the trapping vessel.
INSTRUMENTATION

• In static mode the supercritical fluid

circulates in a loop containing the
extraction vessel for some period of
time before being released through the
restrictor to the trapping vessel.

• In combination mode, a static

extraction is performed for some period
of time, followed by a dynamic
extraction.
INSTRUMENTATION

Typical examples of
Supercritical Fluid
Extractors.
PROCEDURE
PROCEDURE
• The main components of the SFE instrument are
a pump, an extraction chamber, a recovery
chamber and a collection device.

• In order to generate a supercritical fluid, carbon

dioxide is pressurized above its critical
pressure in a pump.

• The mixture to be separated is placed in the extraction

chamber and put in contact with the supercritical fluid.

• One of the elements in the mixture dissolves better in the

critical fluid and leaves the residue enriched in the other
components.
PROCEDURE
• The loaded solvent is then transferred to a recovery
chamber, where earlier component is recovered by
lowering the solvent's density.

• This density can be achieved by raising the

temperature at constant pressure but more often it
is achieve by reducing the pressure at constant
temperature.

• After depressurizing, two methods have been

adopted for collection of the extracted analyses,
these are on-line or off-line SFE.
PROCEDURE

• In on-line SFE, the extracted analytes are

directly coupled to a chromatographic
separation system such as SFC, gas
chromatography (GC) or high performance
liquid chromatography (HPLC) with
appropriate detection.

• In off-line SFE, it allows direct collection of the

extracted analytes either in a solvent or passing the
SCF through a column packed with
Chromatography adsorbent or can be collected in a
cryogenic vessel for subsequent analysis.
 OPTIMIZATION OF SFE
• Optimization is dependent on the purpose of the
extraction.

• For an analytical extraction e.g antioxidant content of a

polymer, then the essential factors are complete extraction in
the shortest time.

• For production of an essential oil extract from a plant, then

quantity of CO2 used will be a significant cost, and
"complete" extraction not required, a yield of 70 - 80%
perhaps being sufficient to provide economic returns.

• In another case, the selectivity may be more important,

and a reduced rate of extraction will be preferable if it
provides greater discrimination.
OPTIMIZATION OF SFE
Maximizing diffusion

• This can be achieved by increasing the

temperature, swelling the matrix, or reducing
the particle size.

• Matrix swelling can sometimes be increased by

increasing the pressure of the solvent, and by
adding modifiers to the solvent.

• Some polymers and elastomers in particular are

swelled dramatically by CO2, with diffusion being
increased by several orders of magnitude in some
cases.
OPTIMIZATION OF SFE
Maximizing Solubility
• Generally, higher pressure will increase
solubility.

• The effect of temperature is less certain, as

close to the critical point, increasing the
temperature causes decreases in density, and
hence dissolving power.

• At pressures well above the critical pressure, solubility

is likely to increase with temperature.

• Addition of low levels of modifiers, such as methanol

and ethanol, can also significantly increase solubility,
particularly of more polar compounds.
OPTIMIZATION OF SFE
Optimizing flow rate

• The flow rate of Supercritical carbon

dioxide should be measured in terms of
mass flow rather than by volume because
the density of the CO2 changes according
to the temperature both before entering the
pump heads and during compression.

• To maximize the rate of extraction, the flow

rate should be high enough for the extraction
to be completely diffusion limited.
OPTIMIZATION OF SFE
Optimizing flow rate

• However, to minimize the amount of solvent used,

the extraction should be completely solubility
limited.

• Flow rate must therefore be determined depending

on the competing factors of time and solvent costs,
and also capital costs of pumps, heaters and heat
exchangers.

• The optimum flow rate will probably be somewhere

in the region where both solubility and diffusion are
significant factors.
Advantages of Supercritical Fluid Extraction
• SCFs have solvating powers similar to liquid
organic solvents, but with higher diffusivities,
lower viscosity, and lower surface tension.

• Since the solvating power can be adjusted

by changing the pressure or temperature
separation of analytes from solvent is fast
and easy.

• By adding modifiers to a SCF (like methanol

to CO2) its polarity can be changed for
having more selective separation power.
Advantages of Supercritical Fluid Extraction
• In industrial processes involving food or
pharmaceuticals, one does not have to
worry about solvent residuals as you
would if a "typical" organic solvent were
used.

• Selectivity: The properties of a

supercritical fluid can be altered by
varying the pressure and temperature,
allowing selective extraction.
Advantages of Supercritical Fluid Extraction
• Speed: Extraction is a diffusion-
based process, with the solvent
required to diffuse into the matrix,
and the extracted material to
diffuse out of the matrix into the
solvent. Diffusivities are much
faster in supercritical fluids than
in liquids, and therefore
extraction can occur faster.
Disadvantages of Supercritical Fluid Extraction
There are, however, a number of significant disadvantages
in the utilization of this technology:

• Phase equilibrium of the solvent/solute

system is complex, making design of
extraction conditions difficult.

• The most popular solvent (carbon dioxide) is

non-polar and is therefore most useful in the
extraction of non-polar solutes. Though co-
solvents can be added for the extraction
of polar compounds, they will complicate
further downstream processing.
Disadvantages of Supercritical Fluid Extraction
There are, however, a number of significant disadvantages
in the utilization of this technology:

• Phase equilibrium of the solvent/solute

system is complex, making design of
extraction conditions difficult.

• The most popular solvent (carbon dioxide) is

non-polar and is therefore most useful in the
extraction of non-polar solutes. Though co-
solvents can be added for the extraction
of polar compounds, they will complicate
further downstream processing.
Disadvantages of Supercritical Fluid Extraction

• The use of high pressures leads to

capital costs for plant, and operating
costs may also be high.

• The requirement for high pressures

increases the cost compared to
conventional liquid extraction, so
SFE will only be used where there are
significant advantages.
Disadvantages of Supercritical Fluid Extraction
• Carbon dioxide itself is non-polar, and has
somewhat limited dissolving power, so cannot
always be used as a solvent on its own,
particularly for polar solutes.

• The use of modifiers increases the range of

materials which can be extracted.

• Food grade modifiers such as ethanol can often be

used, and can also help in the collection of the
extracted material, but reduces some of the
benefits of using a solvent which is gaseous at
room temperature.
Disadvantages of Supercritical Fluid Extraction

Thus, the number of commercial

processes utilizing supercritical fluid
extraction is relatively small, due mainly to
the existence of more economical
processes.

However, its use is likely to increase in

some sectors, for example the recovery of
high value biological, when conventional
extractions are inappropriate, and in the
treatment of toxic wastes.
CONCLUSION

Extraction by means of
supercritical carbon dioxide can be
Thank you
expected to improve efficiency,
including shorter extraction times
and simplified procedures when
compared with extraction
techniques that employ organic
solvents.
REFERENCES
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“Supercritical fluid extraction of biological products. In Recovery Processes for
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CLIFFORD, TONY (1999). “Fundamentals of Supercritical Fluids”. Oxford:

Oxford Science Publications.

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EKHTERA, M.R., Mansoori, G.A., Mensinger, M.C., Rehmat, A. and Deville, B.
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of State - Applications for Supercritical Fluid Extraction Modelling", Chemical
Eng. Science, 41, 5, pp.1303-1309, 1986.
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Kwon, Y.J. and. Mansoori, G.A. "Solubility modeling of solids in

supercritical fluids using the Kirkwood-Buff fluctuation integral with the
hard-sphere expansion (HSE) theory", The Journal of Supercritical
Fluids, Vol. 6, pp. 173-180, 1993.

Mansoori, G.A. and Ely, J.F. "Density Expansion (DEX) Mixing Rules

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(Thermodynamic Modeling of Supercritical Extraction)", J. Chem. Phys.,
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Peter F. Stanbur, Allan Whitaker, Stephen J. Hall “Principles of

fermentation technology” 2nd edition.

Skoog (2007) [1998]. "29". Principles of Instrumental Analysis. David

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Tanaka, Y.; Takeshi, O (2004). “Extraction of Phospholipids from salmon

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Thank you