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DOI: 10.1106/108201302029451
2002 8: 269 Food Science and Technology International
M. Ravents, S. Duarte and R. Alarcn
Application and Possibilities of Supercritical CO2 Extraction in Food Processing Industry: An Overview

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Application and Possibilities of Supercritical CO
2
Extraction in
Food Processing Industry: An Overview
M. Ravento s,* S. Duarte and R. Alarco n
Escola Universitaria dEnginyeria Te`cnica Agrcola de Barcelona, Urgell 187, 08036 Barcelona, Spain
The food industry is always looking for the best separation technology to obtain natural compounds of
high purity, healthy products of excellent quality with several industrial applications. The conventional
extraction process for those compounds has some limitations regarding the solvent toxicity, flammability
and wastefulness. Research into energetically less costly technologies with respect to the environment is
required. Supercritical fluid extraction (SFE) is a relatively new extraction process that has attracted great
interest in many industries. Supercritical fluid properties are used selectively to extract specific components.
This paper overviews the applications of supercritical fluid technology in food processing using carbon
dioxide as the ideal supercritical fluid because of its non-flammable, non-toxic, non-polluting and
recoverable characteristics. A summary of commercial applications and examples of recent developments
illustrate the different possibilities that SFE has in industrial food processes.
Key Words: supercritical CO
2
, extraction
PRINCIPLES OF SUPERCRITICAL
FLUID EXTRACTION
Many technologies have been developed for the
separation and fractionation of different food com-
pounds in the food industry. Conventional processes
such as crystallisation, filtration, distillation or precipi-
tation are being substituted by new processes that use
membranes or supercritical fluids.
Supercritical fluid extraction (SFE) is a separation
process where the substances are dissolved in a fluid
which is able to modify its dissolving power under
specific conditions above their critical temperature
and pressure (supercritical region). The properties of a
supercritical fluid are used to extract selectively a
specific compound or to fractionate mixtures by
changing the temperature and pressure without any
phase change.
A supercritical fluid is a liquid or a gas at atmospheric
conditions which is operational when compressed above
its critical pressure (50250 bar) and heated above its
critical temperature (2060

C). The most important


property of these fluids is the dissolving power in their
supercritical region.
In the phase diagram for a pure compound (Figure 1,
based on a phase diagram for water) it is possible to
distinguish the three material states: solid, liquid and
vapour. These are separated by a fusion curve or solid
liquid equilibrium, sublimation curve or solidvapour
equilibrium, and vapourisation curve or liquidvapour
equilibrium. There are also two important points: the
triple point and the critical point. The triple point is the
point at which the three states coexist. The critical point
lies at the end of vapourisation curve, where the gas and
liquid phase merge to form a single homogeneous fluid
phase, and beyond this point is the supercritical fluid
region.
A supercritical fluid exhibits physicochemical proper-
ties between those of a gas and a liquid, and has the
capacity to dissolve compounds that may only dissolve
poorly or not at all in the gas or liquid state. The
dissolving power of a supercritical fluid varies with
density, which can be as high as a liquid or as low as a
gas depending on small changes in pressure and/or in
temperature. These properties of supercritical fluids
provide a good extraction of the compounds due to their
high dissolving power at high densities, and conse-
quently a good fractionation and separation of the
compound from the fluid (at lower densities) by
reducing the pressure or changing the temperature in a
separator.
Another important factor is the penetrating power
based in the high mass transfer rate of the solutes into
the fluid. The low viscosity and high diffusivity of the
supercritical fluid enhance this property allowing an
efficient extraction of the compounds from the raw
material.
The process of SFE consists of two essential steps:
extraction and separation. The material to be extracted
is placed in a extractor together with the supercritical
fluid at specific pressure and temperature conditions.
For solid materials extraction can be batchwise (Figure 2)
*To whom correspondence should be sent
(e-mail: merce.raventos@upc.es).
Received 23 November 2001; revised 10 April 2002.
Food Sci Tech Int 2002;8(5):026916
2002 Sage Publications
ISSN: 1082-0132
DOI: 10.1106/108201302029451
269
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and for liquid materials extractions can be continuous
(Figure 3). After extraction, both the fluid and
compound extracted are passed through a separator
and by reducing pressure and/or changing temperature
the dissolving power of the supercritical fluid is reduced
and the separation or fractionation of the compound
occurs.
Carbon dioxide (CO
2
) has become the ideal super-
critical fluid in the food industry due to its character-
istics: the critical temperature is 31.06

C, the critical
pressure is 73.83 bar and the critical density is 0.460 g/
cm
3
. The many advantages of CO
2
over conventional
organic solvents justifies the use of this fluid in food
processing to obtain an excellent extraction and an
Figure 1. Phase diagram of carbon dioxide as a function of temperature and pressure.
Figure 2. Batchwise supercritical fluid extraction process (solidfluid).
Figure 3. Continuous supercritical extraction process (liquidfluid).
270 M. RAVENTO

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optimal final product. CO
2
is non-toxic, non-flammable,
non-polluting, completely recoverable, inexpensive
and inert, and its critical conditions are relatively safe
and easy to reach, making it appropriate for the
extraction of volatile or heat labile compounds.
Supercritical CO
2
tends to be selective towards lower
molecular weight compounds (<250) or weakly polar
groups such as lipids, cholesterol, aldehydes, ethers,
esters and ketones, while high molecular weight
( >400) or polar groups such as hydroxyl, carboxyl,
and sugars, polysaccharides, amino acids, proteins,
phosphatides, glycosides, inorganic salts, are relatively
insoluble in dense carbon dioxide (Table 1). It is possible
to extend and modify the selectivity and solubility of
these compounds in carbon dioxide by the addition of
co-solvents or adsorbents.
A co-solvent has intermediate volatility between the
supercritical fluid and the compound to be extracted. It
is miscible with the supercritical fluid and constitutes a
small percentage of the total fluid composition.
Normally, all co-solvents at ambient conditions are
liquids, but gases can also be used. Co-solvents can
improve the selectivity and solute solubility by physical
interactions with the solvent (by increasing the density)
as well as by specific chemical interaction with the solute
(by hydrogen bonds). The co-solvents facilitate the
solubility in carbon dioxide of materials such as egg yolk
lipids, fish oils, gluten lipids, carrot, tomato and annatto
pigments, tamarind antioxidants, etc. However, many
co-solvent systems present difficulties in separating the
co-solvent from the product after extraction.
In food processing applications, ethanol, water and
various gases are particularly suitable co-solvents. For
Moyler (1993) only water and ethanol, are natural
co-solvents for the food industry.
Adsorbents have frequently been used in supercritical
carbon dioxide extraction and fractionation, and have
the potential to greatly improve the selectivity and
efficiency of separations by a variety of mechanisms,
usually by specific interactions with solutes or solute
impurities at the extraction, separation or collection/
evaporation stages.
The advantages of SFE over other conventional
processes such as extraction by solvents and separa-
tion by distillation are automation, the reduction in
operational steps, safe operation due to the use of non-
organic solvents and the use of moderate temperature in
the critical range favourable for heat labile foods. The
main advantage of SFE is the excellent quality of the
resulting product.
The disadvantage of SFE at the beginning of its use
was the investment cost of its implantation in the food
industry. However, in the 1970s this cost was offset by
the establishment of several commercial plants for the
decaffeination of coffee at high pressures producing a
valuable extract (caffeine) as well as a valuable raffinate
(decaffeinated coffee beans).
The successful commercial developments involves the
processing of a high-value product, relatively simple
extraction processes, that has finally brought about the
level of growth that was initially forecast for SFE.
APPLICATIONS OF
SUPERCRITICAL FLUID
EXTRACTION IN THE FOOD
INDUSTRY
The main objective of this work was to collect in
different tables, examples about SFE process using CO
2
with application in food industry related to meat and
meat products and vegetables. The information has been
summarised to list the process and food type, the
extracted product obtained, equipment characteristics,
process conditions, and final results process with all the
information available to the authors. There are some
examples of the many developments with SFE, repre-
senting all fields where this technology may be applied
(Tables 212).
The first commercial supercritical fluid extraction was
performed in Germany in 1978 by Hag A.G (Palmer and
Ting, 1995) for the decaffeination of green coffee beans.
Two years later Carlton and United Breweries in
Australia developed a process for the extraction of
hop flavours using liquid carbon dioxide (Palmer and
Ting, 1995). Both applications were commercially
successful and have given rise to numerous variations
and improvements which have also been developed on
an industrial scale (Kazlas et al., 1994).
Table 1. Solubility of different compounds in supercritical CO
2
.
Highly Soluble Moderately Soluble Almost Insoluble
Organic compounds of low polarity
and low molecular weight (<250)
Polar organic compounds of
molecular weight lower than 400
Highly polar organic compounds of
molecular weight above 400
Highly volatile substances, used
for aromas and flavouring in foods
Substances with low volatility Non-volatile substances
Thiols, pyrazines, thiazoles, acetic acid,
benzaldehyde, hexanol, glycerol and acetates
Water, terpenes, oleic acid, glycerol
and saturated lipids with chains
of up to 12 carbons
Proteins, sugars, olysaccharides, amino acids,
inorganic salts, nitrates, waxes
Supercritical CO
2
Extraction in Food Processing 271
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Other important applications of SFE are decaffeina-
tion of tea, flavour extraction from herbs (Diaz et al.,
1997b; Saldan a et al., 1999), extraction of fats and oils
(Fujimoto et al., 1989; Froning et al., 1990, 1998),
cholesterol extraction (Chao et al., 1991; Froning
et al.,1998), fractionation of fats and oils (Arul et al.,
1987; Lim and Rizvi, 1995; Diaz et al., 1997a; King,
2000) and dealcoholisation of alcoholic beverages (Diaz
et al.,1997b; Sen ora ns et al., 2001). On a lesser scale, the
extraction of aromas in juices (Spanos et al., 1993; Vega
et al., 1996, Favati et al., 1998; Ollanketo et al., 2000),
extraction of colourants, refinement of fats and oils,
extraction of antioxidants (Tsuda et al., 1995; Fadel
et al., 1999), deacidification of oil (Robin et al., 1996;
Dunford and King, 2000a, b, 2001), and inactivation of
orange juice pectinesterase have also some importance
(Palmer and Ting, 1995).
Some developments in the production of industrial
powders and thin film by the rapid expansion of
supercritical solution (RESS) processes, may also find
application in food processing (Palmer and Ting, 1995).
In RESS processes, a non-volatile solute is dissolved in a
supercritical fluid at high pressure as in a normal SFE
process and then mechanically precipitated, rather than
thermally, by fast decompression or expansion. This
allows rapid establishment of uniform nucleation con-
ditions within the solution, minimising temperature and
pressure gradients, and results in particles with a narrow
size distribution. Supercritical fluids are very sensitive to
small changes in temperature and pressure in the critical
region, and this property offers the possibility of
controlling both particle size and morphology over a
wide range, with only a small adjustment to process
conditions.
In a related application, gas anti-solvent (GAS)
crystallisation, solids may be dissolved in a liquid, and
the precipitation of the solids is produced with the
addition of a supercritical fluid (having low dissolving
power regarding the solids, but miscible with the liquid).
Rapid addition of the supercritical fluid results in a
sudden reduction in liquid density, and the rapid
precipitation of small uniform particles. This technique
is especially useful in processing solids such as polypep-
tides and proteins, which are difficult to dissolve in
supercritical carbon dioxide or are sensitive to mechan-
ical handling.
Table 2. Extraction of cholesterol and other lipids from egg yolk.
Process-reference Process Conditions Effects/results
Extraction of
cholesterol
and other
lipids without
removing polar
lipids responsible
for sensory
characteristics,
(Froning et al.,
1990)
Extractor: Capacity 300mL
P
max
: 713 bar
Separator: Capacity 103mL
Sample: 115g dried egg yolk
Extraction (P-T-Density CO
2
):
186bar-40

C-0.81g/cm
3
271bar-45

C-0.86g/cm
3
349bar-45

C-0.90g/cm
3
426bar-55

C-0.90g/cm
3
CO
2
flow-rate: 510L/min
Separation: 393 bar
Total lipids are reduced on increasing the pressure and the temperature at the
extractor. Under the most extreme conditions (426 bar/55

C) 36% of the total


lipids and nearly 66% of the cholesterol is extracted.
At 349 bar/45

CC and at 426 bar/55

CC substantial amounts of phospholipids


(largely responsible for the desired emulsifying characteristics) are not extracted.
The emulsion stability of the mayonnaise only suffers a significant ( p<0.005)
negative effect at 426 bar/55

C.
The volume of bakery products is only affected under conditions of 426 bar/55

C.
After extraction the colour of the yolk is lighter and less red and yellow.
Excellent results under conditions of 349 bar and 45

C providing a higher
quality product.
Extraction of
cholesterol
and lipids,
(Froning et al.,
1990; Hung and
Unger, 1994)
Extraction: 300 bar,
40 and 50

C
Co-solvent: ethanol
A 6674% extraction of cholesterol and a total elimination of the neutral lipids
are obtained.
There is no extraction of phospholipids.
The product obtained is indistinguishable from non-extracted yolk when used in
custard and mayonnaise. Bakery products have an increased volume and omelettes
have improved sensory characteristics.
An interesting by-product is obtained: egg oil. It contains cholesterol (4%) and
triglycerides with a high monounsaturated fatty acid content, which could be used
in the cosmetic and pharmaceutical industries.
Co-solvent increased yield but reduced the selectivity in comparison with pure CO
2
.
Produces a high extraction of phospholipids and a loss of many useful properties.
Extraction of
cholesterol
and lipids at
optimum particle
size and moisture
content (Froning
et al., 1998)
Sample: 100g dried egg yolk
Moisture: 24 (control),
7 and 12%
Extraction: 3103.5 bar,
451

C
Particle size: 45g CO
2
/g sample
Moisture: 30g CO
2
/g sample
Separation: 34.43.5 bar
Flow rate CO
2
: 510L/min
Density CO
2
: 0.90g/cm
3
Fat extraction significantly improved as the moisture of dried yolk increased
to 7%; a further increase in moisture to 12% did not improve fat extraction but
extraction is recommended above 7% moisture to achieve a higher lipid removal.
The SCE of dried egg yolk samples with a large particle size (32.2%, >25mm)
significantly removed more fat and cholesterol than the small particle size
(0.6%, >25 mm) due to the easier and uniform penetration of CO
2
throughout the
sample.
Sponge cake volume seemed to be lowered as moisture content of dried
egg yolk increased prior to SCE, related to a possible protein denaturation, and it
was significantly higher with large particle size samples.
Colour, and emulsion stability are not significantly affected by moisture content
or by the particle size.
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An other important application of supercritical fluids
in food processing is the combined application of
supercritical fluid and extrusion (SCFX) technology
(Rizvi et al., 1995). The supercritical extrusion fluid has
the potential to produce a range of puffed food
products, such as ready-to-eat cereals, pasta and
confectionery with improved texture, colour and taste.
Supercritical fluid extrusion involves the introduction of
a supercritical fluid, preferably CO
2
, carrying micro-
nutrients, flavouring and colourants. Conventional
extrusion technology has some limitations with regard
to the process product characteristics, but SCFX has
been successful in overcoming some of these limitations,
making extrusion a more versatile and controllable
process.
It is clear from this review that the application of
supercritical fluid technology in the food industry is a
field in which there is much research and development at
present. In some cases, such as the extraction of caffeine
from tea and coffee or aromas from spices and hops,
SFE is already being used in industry. In other cases we
could soon see its practical application, particularly in
the case of food colourings and the refining of seed oils
(Table 7) due to its economic potential.
In general, the extraction yields are good for the
majority of products studied and comparable to those
Table 3. Milk fat fractionation.
Process Process Conditions Effects/Results
Fractionation of
milk fat into 8
fractions (Arul
et al., 1987)
Extractor: 2 cm diameter 30cm high.
Separator: heated micrometering valve
and two U-tubes for precipitating and
capturing the solute.
Sample: 6.05g
Extraction: 100350 bar, 50

C
and 70

C
CO
2
flow-rate: 10L/min.
Five fractions (2, I1, I2 and I3) at:
100250 bar, 50

C.
Three fractions (S1, S2 and S3) at:
250350 bar and 70

C.
Fractions: L1 and L2, liquid at room temperature (20

C),
represent 12.2% of the fat. S 13, semi-solid at room temperature,
represent 38.2% of the fat. S13, solid at room temperature, represent
49.5% of the fat.
The concentration of short-chain triglycerides
falls progressively from fractions L1 to S3. Fractions L2 and I13 are rich
in medium-chain triglycerides. Fractions S2 and S3 are low in short-
and medium-chain triglycerides and contain most of the long-chain
triglycerides.
Fractions L1 and L2 are rich in cholesterol while S2 and S3
contain less than the original milk fat. The cholesterol content of
I1 and S1 is comparable to that of milk fat.
Fractions obtained offer the possibility
of meeting many of the industrial requirements, such as the production
of butter which is spreadable at low temperatures and butter rich in short-
and medium-chain triglycerides.
Four stage
fractionation of
milk fat
(Lim and Rizvi, 1995)
Continuous counter-current system with
an extraction section and an adsorption,
desorption and separation section
Extraction column: 61cm high
and 1.75cm diameter
Extraction: 241 bar, 40

C.
Nominal velocities:
CO
2
: 20.6cm/min
Milk fat: 0.42cm/min
Four stage fractionation:
60

C-241bar
80

C-207bar
80

C-172bar
60

C-69bar
Recovery of 4 fractions (S14) and refining (R):
Fractions S14: Containmost of the short- and
medium-chain fatty acids, and the quantity
decreases with increasing separation pressure.
Refined product (R): Most of the short-chain fats are contained in the
refined product, and the amount decreases with decreasing separation
pressure.
Long-chain unsaturated fatty acids are concentrated in the refined
product while the saturates remain evenly constant.
The solid triglyceridecontent in the extracted fractions is
higher than that in the original fat.
The refined product has the lowest content.
The fraction with a low melting point may be used in
bakery and ice-cream products.
Fractionation of
the fat of
anhydrous milk
(Rizvi et al., 1995)
Continuous counter-current system:
1 extractor (knitted mesh packed column)
4 separators
Extractionseparation: 24134bar,
4075

C
Recovery of 5 fractions: The proportion of short-chain fatty acids
increased from the first to the fifth fraction and that of long-chain fatty
acids from the fifth to the first.
The refined product reduced 51% cholesterol, increased 10%
unsaturated fatty acids and 145% -carotene. It can be used in the
production of low-cholesterol butter, in the chocolate, confectionery and
baking industries, as an additive to skimmed milk to achieve higher
nutritional quality semi-skimmed and full-fat milk, in ice-creams
and cheeses.
The fraction rich in short-chain fatty acids can be used
by people who have problems absorbing long-chain
fatty acids.
The fraction rich in medium-chain fatty acids can be used
in baby milks to make them more similar to human milk.
Supercritical CO
2
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obtained using conventional methods. For example,
when extracting oil from oil-seeds, the yields may be
slightly lower than those obtained using organic solvents,
but this is due to the fact that CO
2
is much more selective
and does not extract undesired compounds.
The successful commercial application of SFE
requires intensive research since, unlike conventional
extraction techniques, SFE is not an established
technology which can be applied directly to any
product. According to Palmer and Ting (1995), the
commercial use of CO
2
as a solvent depends on
the development of supplementary processes for
manipulating and applying new products. One impor-
tant factor to bear in mind is that it is necessary to
pre-treat some foodstuffs so that the supercritical
extraction is efficient. Among these pre-treatments are,
for example, the need to reduce the water content of
samples, mill them, or form pellets in order to obtain
extracts from hops.
Consumer pressure will probably force the food
industry to use a greater proportion of natural ingre-
dients in the future, even though these are less stable and
more expensive than synthetic alternatives. This bodes
well for SFE in the field of flavourings (Table 8). The
sensory characteristics of natural products are too
complicated to be imitated by a combination of artificial
products. Furthermore, the increased cost of CO
2
extraction will be balanced by higher extract prices,
since the extracts are of a higher quality. The flavours
and fragrances industry is a field of SFE application
which has developed considerably and which now has
extraction plants in several countries.
Colourings are in a similar situation to aromas and
flavours. Given the growing interest which exists in using
natural colourings, SFE is also well placed in this sector
(Table 6), especially considering the high prices that these
products fetch on the market. -carotene is widely used
in food processing to give foodstuffs a uniform colour,
Table 4. Extraction of lipids and cholesterol from meat and meat products.
Foodstuff Process Conditions Effects/Results
Frozen ground beef
(19% fat) (Chao et al.,
1991)
Extractor:
Capacity: 1L
P
max
689bar (at 100

C)
Separator: Capacity: 0.5 L
P
max
414bar (at 100

C)
Sample: 200g
Extraction:103310bar,
3050

C.
Separation: 34.5bar, 40

C
CO
2
flow-rate: 1.72.1kg/h
Total CO
2
: 820kg
Time: 48 h
The maximum extraction of lipids (27.8 g) is achieved under
the conditions of 310 bar, 51

C and 15.4kg of CO
2
.
The extraction of lipids increased with increasing pressure
up to 310 bar.
By using more than 89 kg of CO
2
, lipid extraction
is increased considerably.
Maximum extraction of cholesterol (39.8%) is achieved at 172
bar, 50

C and 20.1kg of CO
2
. However, a similar reduction in
cholesterol (36.9%) is reached at 310 bar, 50

C and 15.4kg
of CO
2
, with a much higher reduction in lipids (71.2% as
opposed to 37.9% obtained at 196 bar).
Higher pressure conditions could be used to obtain
maximum extraction of lipids. The lowest pressures could be
used for the specific concentration of cholesterol.
High-fat pork (Chao
et al., 1991)
Extraction: 100310bar, 3050

C A 10% reduction in lipids.


A reduction in the WRC (water retention capacity) of 60% in
comparison with untreated meat.
The functional properties are appreciably altered.
Dried pork (Clarke,
1991)
Co-solvent: ethanol More than a 71.9% reduction in fatty acids.
A 78% reduction in cholesterol.
Co-solvent:
The reduction in cholesterol increased but that of the fat did
not (less efficient).
Re-hydrated meat displays worse properties for sausage
making. This can be corrected by adding other ingredients to
the product.
Dehydrated chicken
meat (Froning et al.,
1994)
95% reduction in lipids.
-84% reduction in cholesterol.
Beef fat (Merkle and
Larick, 1993, 1994,
1995)
Extraction: 103276bar, 40

C Selective separation of saturated and monounsaturated


triglycerides (reduced selectivity for polyunsaturates).
The saturated fatty acids can be extracted at low pressure,
while the extraction of the unsaturates requires an increase in
the density of the solvent. There are differences in the
fractions but the fatty acids are not separated
from each other.
The volatile substances obtained can be used as
flavourings.
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which is why the main objective of recent developments
was its extraction. In general, extraction is greatly
improved by using ethanol as the co-solvent.
Extraction times are less than with organic solvents.
The extraction yields for lutein and lycopene are slightly
lower than those for -carotene under the same proces-
sing conditions. When dealing with bixin, the yield
increases when soya bean oil is added to the extractor.
The natural antioxidants produced by SFE are also of
interest to the food industry because they do not alter
the aroma, flavour or colour of foodstuffs (Table 9).
They are very easily dispersed since they are highly
soluble, and they do not evaporate during frying or
baking, unlike other synthetic antioxidants. There is
a large increase in the yield of antioxidants extracted
from tamarind seeds when ethanol is used as a co-solvent
and when the temperature and pressure of the process
are increased. Antioxidants could also be extracted from
eucalyptus leaves, although their use in the industry is
not yet regulated. Apart from these two products, SFE
has also been successfully used for other products such
as sage and labiate plants.
Table 5. Extraction of lipids and cholesterol from fish.
Foodstuff Process Conditions Effects/Results
Trout (Hardardottir
and Kinsella, 1988)
Extraction: 130350bar, 4050

C Protein solubility is reduced.


The concentrated protein product had few emulsifying
properties (it did not form a gel).
Antarctic krill
(Yamaguchi et al., 1986)
Extraction: 250bar, 4080

C Extraction of non-polar lipids with a low phospholipids content


and a high content of astaxantin and derivates.
High temperatures (6080

C) produced a decomposition of the


astaxantin and its compounds.
Tuna oil (Yoon, 1993) Extraction: 100200bar, 5075

C Fractionation and concentration of polyunsaturated fatty acids n-3.


12% increase in the EPA concentration and 85% in the DHA.
Sardine oil
(Lucien et al., 1993)
Extraction system with a reflux
column and a urea column
Fractionation and concentration of polyunsaturated fatty acids n-3.
Purities of 58% for EPA and 67% for DHA.
Sardine oil (Riha
and Brunner, 2000) Extraction column: 68 mm inner
diameter 12m effective height
Separator: backpressure valve (1 bar)
Two samples:
M1: C14-C18 main components
M2: C20C22 main components
Extraction M1: 14, 14.5 and
15 bar; 60

C
CO
2
flow-rate: 297.0300 kg/h
Extraction M2: 9.6, 14.5, 17.0 and
19.5 bar; 40, 60, 70 and 80

C
CO
2
flow-rate: 209.3303.0kg/h
Separation: pressure reduction below
the critical pressure of CO
2
M1: better extraction conditions were 60

C and 145 bar.


M2: better extraction conditions were 40

C and 96 bar for C14C16,


60

C and 145 bar for C18C20 and 70

C and 170 bar for C22.


With this sample less amount is required at higher temperatures
to fractionate a given amount of feed.
The more volatile C14 and C16 components are easily
enriched in the extract fraction, while the high volatile C22
components remain in the liquid raffinate fraction.
Mackerel fillets
(Temelli et al., 1995) Extractor:
Capacity: 50mL.
2 separators
Sample: 1214g
(freeze-dried fillets up to 1.6%
water content).
Extraction: 207345bar, 3555

C
CO
2
flow-rate: 1.6L/min
Time: 5 h
Separator: Extract collected in two
glass tubes in an ice bath after passing
through a depressurisation valve
The maximum solubility of mackerel lipids (g of oil/100L CO
2
)
in SC CO
2
is obtained at 345 bar and 35

C.
Recovery of lipids under the maximum solubility conditions was
58% after 5 h. An increase in CO
2
flow-rate under these
conditions would increase recovery.
The maximum concentration of EPADHA (polyunsaturated
fatty acids !-3) was got with 345 bar and 55

C (18%), but at 345 bar


and 35

C was similar (17.7%).


Conventional extraction using hexane, produces a lower
concentration of EPADHA (14.7%).
There is a slight fall in pH after SFE, similar to that produced after
extraction using hexane.
The water binding potential of the proteins increases with SFE,
but slightly less than with hexane extraction.
After extraction of the lipids, the mackerel muscle protein can
be used in food products.
Sardine meat powder
(Fujimoto et al., 1989)
Extraction SC CO
2
: 285bar, 40

C
Using liquid CO
2
: 285bar, 12

C.
Time: 68h.
Co-solvent: Ethyl acetate (10%)
SC CO
2
extracted more lipids than liquid CO
2
.
Sardine meat deffated with SC-CO
2
is less likely to form
kamaboko (class C) than that sardine meat deffated with liquid
CO
2
(class A). This showed that temperature has a greater
influence on sardine meat protein than pressure.
Supercritical CO
2
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Alcohol-free drinks are another product with a
growing market. Traditional methods of extracting
alcohol (ethanol) after fermentation pose the problem
that some of the components of flavour and/or aroma
may become denatured or eliminated, changing
the sensory characteristics of the product. Also,
distillation requires large amounts of energy.
Furthermore, alcoholic drinks do not develop their
Table 6. Extraction of natural colourings from several foodstuffs.
Foodstuff-reference Process Conditions Effects/Results
Carrot (Barth
et al., 1995)
Extraction of carotenes
Extractor:
Capacity: 150mL
P
max
345 bar
Sample (residual pulp; -carotene:
67200mg/g pulp): 6 g. Average
particle diameter: 0.93mm
Extraction: 207, 276 and 345 bar,
40, 55 and 70

C
Co-solvent: Ethanol (5 and 10%)
Total CO
2
volume: 250L
CO
2
flow-rate: 1.5L/min
The highest extraction percentages (nearly 100%) are achieved using
10% ethanol and temperatures of 55 and 70

C.
The concentration of ethanol and the temperature are the two
most important factors in increasing the degree of extraction.
Pressure variations have no effect on the percentage extracted.
The recovery percentage increased with % of ethanol. Extractions
without ethanol produce a recovery of 3040%, while those with a
5 and 10% ethanol content result in a 5065% recovery.
Extraction using ethanol is an economically viable method for
achieving high efficiencies in the extraction of -carotene from
the carrot pulp by-product.
Carrot (freeze dried,
(Vega et al., 1996)
Extraction of carotenes
Extractorcapacity: 5 mL
Sample: 0.5g
Extraction: 342, 456 and 570 bar,
30, 40 and 50

C
Co-solvent: ethanol (5 and 10%)
Volume of CO
2
ethanol: 500mL/min
Time: 1 h
Optimum conditions: 50

C , 342 bar and 10% ethanol.


Under these conditions were extracted 605mg/g of -carotene
and 485mg/g of -carotene compared to dry weight.
The time required for SCE is 1 h compared to the 6 h of the
traditional extraction using liquid solvents.
The quantity of solvent used in the extraction of a sample is 40mL
using SCE, compared to 200mL needed for conventional extraction.
Leaf protein
concentrates (alfalfa
Favati et al., 1998)
Extraction of carotene and lutien
Extractor:
Dimensions: 1.75cm diameter
55.9cm high
P
max
760 bar
Sample: 4550g.
Extraction: 100, 300, 500 and 700 bar,
40

C
CO
2
flow-rate: 56L/min
Volume of CO
2
: 3000L
At a pressure of 100 bar a very small amount of carotene and
a negligible amount of lutien were extracted.
At pressure above 300 bar an extraction of 90% of the carotene
is achieved. At 500 and 700 bar, the recovery of carotene is
completed after only 800L of CO
2
has been used.
The extraction of lutein required pressures above 700 bar
and greater volumes of gas to achieve 70% recovery.
SCE did not affect the nutritional value of the protein supplement.
The extracts obtained could be used directly in industrial
processes as colourings, since there are no traces of solvent.
Bixa Orellana tree
seeds (Degnan
et al., 1991)
Extraction of bixin
Extractor capacity: 11.8mL.
Separator capacity: 6.8mL.
Sample: 3 g (whole seeds)
Extraction: 207483 bar, 4055

C
Co-solvent: Soya bean oil
Separation: The gas is eliminated at
atmospheric pressure and the
extract is precipitated. Then CHCl
3
is added to clean the extract
from the recipient
The extract obtained only contains and -bixin and
no degradation compounds.
The extraction efficiency increases when soya bean oil is
added to the extractor.
Sweet potatoes
(Spanos et al., 1993) Extraction of -carotene
Continuous system
Extractor:
6.5cm I.D. 25.4cm long
Samples:
Cubes or powder dried in a forced
air oven or freeze-dried: 1 g
Raw sample: 3 g
Extraction:
P: 138, 276 and 414 bar
T: 38

C (and 48

C at 414 bar)
CO
2
flow-rate: 1418L/min
Vol. CO
2
: 1000L
Pre-treatments:
Extraction from the raw samples is not very efficient due to their
high water content of the dried samples, those that are freeze-dried
exhibit a higher yield (228 mg/g sample) than those that are dried
in a forced air oven (77mg/g sample). 50% of the carotenoids
are lost during oven drying due to oxidisation.
The optimum conditions for extraction: 48

C and 414 bar.


The extraction yield and recovery increased when the
volume of CO
2
used, but never exceeded 90%. It seemed that 20%
of the carotenoids present cannot be extracted using SC CO
2
.
(continued)
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sensory characteristics fully when alcohol production is
limited by restricting the fermentation process. In de-
alcoholisation using SFE the separation efficiency is far
greater than in distillation. Furthermore, extraction
temperatures are moderate (between 15 and 40

C)
which means that the thermolabile components, which
are largely responsible for the aroma and flavour, do not
break down (Calabuig, 1998).
Ethanol is reduced between 0.5 and 1% by SFE
technology without losing the characteristics of the final
product. Research has also been carried out on
flavoured and aromatic drinks, as well as the drinks
shown in Table 12 (wine, beer and cider).
Research is also being focused on the extraction of oil
from seeds. But SFE is not only useful for obtaining oils,
in many instances it is desirable to separate out fats in
order to obtain flour or other products which are low in
lipids.
In general, oils extracted using CO
2
have the dis-
advantage of being less resistant to oxidation than those
produced using hexane, as it does not extract most of the
phospholipids. However, the losses during refining are
reduced and they need less caustic soda since they do not
contain polar lipids and their colours are lighter than
those of oils produced using organic solvents.
The particle diameter and the characteristics of the
preparation of the substrate are also very important in
the extraction of oils, and it may be necessary to mill
samples or alter their water content (del Valle and
Aguilera, 1999)
SFE can also be used as a method of refining
vegetable oils previously extracted using hexane, instead
of conventional refining, as in the case of the
de-acidification of rice bran oil. As well as this use,
de-gumming of soya bean oil and olive oil refining have
been investigated. On the other hand, given that oils are
liquids, there is a possibility of using continuous systems
which are economically much more interesting.
With regard to foodstuffs of animal origin, the
relationship between cholesterol consumption and the
likelihood of suffering cardiovascular disease has led to
an increased consumer demand for low-cholesterol
products. The experiments carried out on milk (Table 3),
meat (Table 4), fish (Table 5) and eggs (Table 2) show
that SFE is an effective way of reducing cholesterol levels
and other lipids contained in these foodstuffs.
Table 6. Continued.
Foodstuff-reference Process Conditions Effects/Results
Tomato paste
waste (Baysal
et al., 2000)
Extraction of -carotene and lycopene
1 extractor and two separators (S1 and S2).
Sample: 53g (ground)
Extraction temperature and pressure
variations to find the optimum conditions:
P: 200, 250 and 300 bar
T: 35, 45, 55 and 65

C
CO
2
flow-rate: 2, 4 and 8 kg/h
t: 4, 2 and 1 h
Co-solvent: Ethanol (0, 5, 10 and 15%).
Separation:
Separator 1: 80 bar, 35

C
Separator 2: 1 bar, 35

C
Extraction in the absence of ethanol achieves recoveries of 20 and
40% of lycopene and -carotene respectively, while the addition of
ethanol recovery reached 50% of the substances.
It is necessary to mill the paste in order to achieve
a greater extraction efficiency.
The maximum extraction of carotenes from 3 mm
milled tomato paste waste was under the following
conditions:
Extractor: 300 bar, 65

C
Separator 1: 80 bar, 35

C
Separator 2: 35

C
CO
2
flow-rate: 4 kg/h
Extraction time: 2 h
Ethanol: 5%.
Temperatures above 65

C could increase the extraction efficiency


but they could also cause an increase in the degradation
of the carotenes.
Pressures up to 400 bar can increase extraction.
Tomato skin
(Ollanketo et al., 2001)
Extraction of lycopene (carotenoids)
Sample: 0.3g powdered tomato skin.
Extraction: 405.2 bar, at 60,85 and 110

C.
Extraction times: 5, 12, 19, 26, 38,
50, 62, 79min.
Addition of modifier: 500mm of
solvent to the sample.
Solvents: acetone, methanol, ethanol,
hexane, dichloromethane and water.
CO
2
flow rate: 1.5mL/min
Relative recovery of 100% of total lycopene was
achieved at 110

C, 405.2 bar, in 50min, both without


modifier and with acetone, but with acetone speeded
up the beginning of the extraction, leading to a
relative recovery of 94% in just 15 min.
The maximum recovery was higher than with
conventional solid-liquid extraction (SLE)
Red grape skin
(Blasco et al., 1999)
Extraction of anthocyanins
Extraction: 70150 bar, 80

C
CO
2
: equivalent flow-rate at 80 bar
A good use for this wine production by-product
from an economic point of view.
The extract contains very interesting products such
as reservatrol.
Extraction is achieved very quickly. In just 30min
the majority of the anthocyanine is extracted.
Supercritical CO
2
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Table 7. Extraction, refining and fractionation of oils and vegetable fats.
Foodstuff-reference Process Conditions Effects/Results
Grape seeds
(Molero et al., 1995)
Tubular extractor:
Capacity: 75 mL
P
max
: 400 bar
T
max
: 340

C
Separator capacity: 100mL
Sample: 40g (drained, ground,
sieved and dried)
Extraction: 50350 bar, 1060

C
CO
2
flow-rate: 0.52.0L/min
The extraction yield (the percentage relationship between the
amounts of oil extracted and seeds loaded into the extractor)
is 6.9 using SFE and 7.5 using hexane because the CO
2
is
much more selective and does not extract other undesired
compounds.
The extraction yield using liquid CO
2
is lower than
that using SC-CO
2
.
Maximum extraction is achieved at 350 bar and 40

C.
With a CO
2
flow-rate of 1.5L/min maximum yield
with minimum solvent use is achieved. The optimum time
under these conditions is 2 h.
The characteristics of the oil extracted allow the
omission of two of the refining stages of extraction
using solvent.
Soya bean
(Stahl et al., 1980)
Extraction: 200 bar, 40

C SFE allows the distillation and flour dissolving stages


to be eliminated.
The yield (% by weight) was 19.9%.
Dry-milled corn
germ (Christianson
et al., 1984)
Extractor Capacity: 2 L
Sample: 4501000g [Raw samples
(3.5% water content), hydrated
samples (8% water content) and
hexane soaked samples]
Extraction: 345552 bar, 50

C
CO
2
flow-rate: 1518L/min
Co-solvent: Hexane
The water content did affect the extraction efficiency.
Pressure from 345 to 552 bar increased the extraction
efficiency. Oil recovery from the sample is almost total.
Soaking the samples in hexane increases the extraction
of lipids but does not reduce the peroxidase activity.
The flour obtained using SFE is of a higher quality (less
residual lipids and peroxidase activity) than that obtained
using hexane and it is more stable during storage.
The oil experiences fewer losses during refining
and has a lighter colour than that of the oil obtained
using hexane.
The disadvantage of SFE is that the oil does not
contain the natural antioxidants and therefore oxidises
more easily.
Roasted and
deskinned
peanuts (49% fat)
(Robin et al., 1996)
Systems:
SCP: Semi-continuous process
IDP: Intermittent depressurisation process
Extractor: 13mL
Samples:
M1.Skinless roasted peanut flour (2g)
M2. Skinless roasted peanut: 1 g (2 units)
SCP Extraction:
M1:
P: 207, 276, 414 and 552 bar at 80

C
T: 40, 60 and 80

C at 552 bar
M2:
P: 552 bar
T: 80

C
Volume of CO
2
: 14mL
CO
2
flow-rate: 4.0 mL/min
Time: 3 min
IDP Extraction: 552138 bar, 80

C
Volume of CO
2
: 13mL
Time: 3 min
In the flour samples (M 1):
SCP: When the pressure and temperature are increased,
the quality of the oil recovered (weight of oil extracted
divided by the weight of CO
2
used) and the percentage of
fat reduction (weight of oil extracted divided by weight of
flour or peanuts multiplied by 100) also increase. The most
effective combination is 552 bar and 80

C(80% oil recovery


efficiency). The percentage of fat reduction increases to 95%
if the flour is subjected to additional extractions.
Whole peanuts (M 2):
SCP: There is less oil extraction than with the flour due to the
greater particle size.
IDP: The highest oil recovery based on the weight of CO
2
used is achieved at 138 bar and 80

C.
The SCP system is the most adequate for fat reduction
of peanut flour.
The IDP system is the most suitable for fat reduction of
whole peanuts. The appearance and texture are maintained
or improved.
The fatty acid composition of the oils only varies for oils
extracted from whole peanuts by IDP, depending on the
conditions used.
Diatomaceous
earth as a
by-product
of oil refining
(Blasco et al., 1999)
Sample (4050% oil): 200g
Extraction: 280 bar, 50

C
CO
2
flow-rate: 4 kg/h
Using extraction by hexane (conventional method) 45% of
the oil remains in the sample and the oil recovered contains
traces of hexane.
Complete oil recovery without using hexane. Earth can be
reused. This treatment reduces waste intake into the
environment.
(continued)
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Table 7. Continued.
Foodstuff-reference Process Conditions Effects/Results
Canola flakes
(Dunford and
Tamelli et al., 1995)
Extraction of phospholipids
Extraction: 552 bar, 70

C
Co-solvent: Ethanol (10%)
Up to 20.8% recovery of phospholipids.
The extracted phospholipids are used as
emulsifiers in the food industry.
The yield increases to 30% when the flour is cleaned with
SC-CO
2
and ethanol before extraction.
The extraction of lecithin using SC-CO
2
can compete
economically with conventional systems such as extraction
using acetone.
Rice bran oil
(extracted using
hexane; 7% of free
fatty acids) (Dunford
et al., 2000b)
De-acidification of the oil
(extraction of free fatty acids)
at pilot scale fractionation
column:
Height: 164cm
Capacity: 260cm
3
Semi-continuous
Fractionation: 136340 bar, 4590

C
CO
2
flow-rate: 1.2L/min
Time: 3 h
Conventional rice bran oil refining processes cause
important losses of phytosterols which are very valuable
because of their beneficial nutritional properties.
The results show that rice bran oil can be de-acidified using
SC-CO
2
fractionation without affecting the phytosterol content.
Processing at low pressures and high temperatures
favours a higher concentration of the extract and less
phytosterol and triglyceride loss.
Supercritical fractionation is shown to be an alternative for
de-acidification and the production of vegetable oils rich
in phytosterols.
Rice bran oil
(extracted with
hexane; 7% of free
fatty acids) (Dunford
et al., 2001)
Packed column:
Dimensions: 1.70m high1.43cm
diameter
Pre-heater and 4 heating zones
at different temperatures
Extraction: 136205 bar, 4090

C
CO
2
flow-rate: 1.22L/min
Time: 120480min
Applying a temperature gradient along the column favours
the reduction of triacylglycerol (TAG) losses with
the extracted fraction.
The concentration of free fatty acids in the extract increases
with increasing temperature in the area of the column.
Increasing the CO
2
flow-rate from 1.2 to 2 L/min did not
significantly affect the composition of the extract.
Fractions of rice bran oil with a total sterol ester content
of 23%, similar to that of margarine enriched in this
substance.
The sterol esters can be introduced into foodstuffs as
cholesterol reducing ingredients.
Evening primrose
seeds (Oenothera
biennis) (Favati
et al., 1991)
Tubular extractor: 1.75cm i.d. 30 cm
Sample (ground): 50g
Extraction: 200, 300, 500 and 700 bar,
40, 50 and 60

C
CO
2
flow-rate: 18g/min (2.5kg per test)
Separation: extract fractions are diluted
with diethyl ether and dried with
anhydrous sodium sulphate, cooled
at room temperature and depressurised
At 200 bar was got a low recovery. After the 2.5 kg of CO
2
has been passed through, the extraction yields at 40, 50
and 60

C were 65.6, 59.1 and 34.2% respectively.


Increasing the pressure to 500 bar the extraction of oil
increased about ten fold, allowing a rapid extraction,
at 700 bar an even faster extraction is achieved, reaching
a 94% extraction in less than 14 min.
No appreciable differences in the composition of the oil
from the different samples are observed.
Table 8. Extraction and fractionation of natural flavourings.
Foodstuff Process Conditions Effects/Results
Oil from bitter
orange peel
(Chouchi
et al., 1996)
Fractionation of terpenes. Elimination
of high molecular weight compounds
Sample: 20 g
Desorption column: 0.18dm
3
Max. CO
2
flow-rate: 3.6dm
3
/h
P
max
: 250 bar
Adsorbent: silica gel (100g)
Extraction: 77120 bar, 40

C
Separator 1: 30 bar, 40

C
Separator 2: 20 bar, 15

C
The hydrocarbon terpenes in the oil are unstable and tend to break down,
lowering the quality of the oil.
The extraction of this fraction is achieved in 30min at 77 bar and 40

C.
The fractions recovered between 30 and 140min of the process are
rich in oxygenated terpenes with a limonin content of 88.79%. 80%
of the oxygenated fraction of the oil is recovered in this fraction.
The non-volatile high molecular weight fraction, which causes
cloudiness in the oil, remained in the column after the
fractionation process.
The SC-CO
2
fractionation reduced largely hydrocarbon terpenes
content and eliminated high molecular weight components.
The oxygenated fraction did not exhibit formation of undesired
perceptions from the terpenes even after long storage.
(continued)
Supercritical CO
2
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Table 8. Continued.
Foodstuff Process Conditions Effects/Results
Dried orange
peel (Blasco
et al., 1999)
Extraction of essential oils
Extraction: 100280 bar, 4050

C
CO
2
flow-rate: 0.53.5kg/h
The CO
2
flow-rate used has little effect on the extraction percentage.
Limonin is the main component extracted (up to 99.5%).
Particle size affected extract composition.
With 0.11nm at 160 bar, 50

C and 2.5kg CO
2
limonin
extraction is 560mg/kg orange peel.
With 12nm at 160 bar, 50

C and 2.5kg CO
2
limonin
extraction is 200mg/kg orange peel.
Juice from citrus fruit
(Kimball, 1987)
Extraction of limonin
Extractor: 300mL
Extraction: 207414 bar, 3060

C
Time: 14h
Limonin reduction of 25% is achieved after an hour.
From 40 to 45

C at 207 bar a large increase in limonin extraction


is reached.
In 4 h limonin is reduced from the initial 17.5ppm to about 7.0ppm
without altering the levels of ascorbic acid, pulp, citric acids or
amino acids.
Aromatic Plants
Melissa officinalis
and Lippia citriodora
(Blasco et al., 1999)
Extraction of essential oils.
Sample: 80g (ground).
Extraction: 200 bar, 40

C
CO
2
flow-rate: 2 kg/h
When the particle size is reduced more essential oils are released.
The extraction of essential oils from aromatic plants such as
Melissa officinalis and Lippia citriodora is economically viable,
but for both plants liquefaction represents the majority of the
costs (6070% of total costs).
Mushrooms
(del Valle and
Aguilera., 1989)
Extraction of mushrooms oleoresins
Extractor: Capacity: 3.785 L
Ground dried sample (mushroom
powder)
Extraction (dimensionless parameters):
Reduced pressure, p
r
: 1.151.49
Reduced temperature, T
r
: 1.1051.195
Sample compacting. Specific
volume (
d
): 0.8251.125mL/g
Time: 6 h
The degree of solubility of the oleoresins increased with increasing
p
r
and T
r
and with decreasing
r
.
The compacting of the mushroom particles produces a porous
structure which varies according to the degree of compacting.
Consequently, the oleoresins can be found in two states: available,
in broken cells orientated towards the pores; and confined, in
undamaged cells or cells connected to closed pores.
The fraction of available oleoresins is extracted at a rate similar to
that of the diffusivity of a solute in supercritical fluid.
The fraction of confined oleoresins is extracted at a lower rate,
numerically similar to that of the diffusion of supercritical fluid
through solids.
Table 9. Extraction of antioxidants.
Foodstuff Process Conditions Effects/Results
Tamarind seed
coat (Tsuda
et al., 1995)
Extractor: 10 or 50 mL
Sample: 2 g (ground)
Extraction: 100, 200 and 300 bar,
40, 60 and 80

C
CO
2
flow-rate: 5 mL/min
Time: 5 h
Separation: extracts dissolved in ethanol
and then evapored to dryness in vacuum
Co-solvent: Ethanol (0.5mL/min)
At a constant pressure of 300 bar the maximum extraction is at 40

C.
At a constant temperature of 40

C the extraction increased with


increasing pressure.
The extraction yield reaches a maximum after 3 h under all
conditions studied.
The quantity of extract obtained with SFE is less than with ethyl
acetate, which gave a value of 740mg/100g of sample.
At a constant pressure of 300 bar extraction increased with
decreasing temperature.
At a constant temperature of 40

C extraction increased
with increasing pressure.
The amount of extract obtained with ethanol was greater than
with pure CO
2
. The combination of SC-CO
2
and ethanol is an
effective technique for extracting the antioxidants.
The extract can be used to prevent lipid peroxidation in foodstuff.
Leaves from
Eucalyptus
Camaldulensis var.
brevirostris
(Fadel et al., 1999)
Extraction of the oil (high antioxidant activity)
SFE compared with HD (hydrodistillation)
Sample: 1 g (crushed)
Extraction: 200 bar, 50

C
CO
2
flow-rate: 2 mL/min
Time: 2 h
Separation: Extract trapped in ethanol
(96%) in recipient submerged in
crushed ice. The CO
2
is freed
The oil obtained by SFE showed greater antioxidant activity
than that obtained by hydro-distillation due to the different
concentrations of some components.
SCE: oil with more -phellandrene, e-cymene, cryptone,
spathulenol. Less 1,8-cineole is obtained (the main compound in the
majority of eucalyptus with high volatility) because it might be
trapped at the separation stage.
More detailed toxicology studies are required to confirm the
safety of these extracts and therefore their use as a new
antioxidant food additive.
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For milk, the possibility of separating the fat into
extracts with different fusion points and chemical
compositions meets many of the requirements of the
industry, such as the production of butter which is
spreadable at low temperatures and low in cholesterol,
products to add to skimmed milk to make higher
quality semi-skimmed milk or full fat milk, or its use
in the chocolate, baking, ice-cream and cheese industries.
Furthermore, the separation of milk fat also has the
advantage of being a potentially continuous process.
FINAL REMARKS
Supercritical fluid extraction applied in the food
industry using CO
2
as a solvent, is totally established
especially in decaffeinating of coffee and tea, hop
extraction, aromatic herbs extraction, and cholesterol
separation from egg yolk, meat, or milk fat.
The many advantages of the SFE can be summarised
as follows: high quality and purity of the obtained
product; quick extraction and separation phases; extract
free of residues; selective extraction by a specific
compound; reduction in separation cost.
But the use of SFE in the food industry also has some
disadvantages. The lack of continuous systems for
extracting solid substrates imposes serious capacity
restrictions on installed apparatus. The fact that
continuous processes cannot be used for solid substrates
means that, from an economic perspective, SFE could
be more attractive for refining conventional extracts
than for treating solid substrates directly. But the most
Table 10. Decaffeinating of coffee and tea.
Foodstuff Process Conditions Effects/Results
Coffee
(Zosel, 1980;
Williams, 1981)
Extraction of caffeine from green beans
Extraction: 160220 bar, 90

C
Separation: water, activated carbon or
decompression
Co-solvent: water
Separation using water or activated carbon represents an important
energy saving compared to decompression.
The separation of the caffeine from the SC-CO
2
with water is
performed by distillation or reverse osmosis. Water is also added
in the extraction process to increase the size of the cell wall pores
and to release the caffeine from the compounds it forms with other
substances.
Activated carbon is added to the extractor together with the
coffee beans, and separated by sieving at the end of the process.
Tea (Vitzthum
and Hubert, 1973)
Extraction of caffeine from the fermented
dry leaves
Extraction 1st stage. 250300 bar, 4575

C
Extraction 2nd stage: 250 bar, 50

C
Separation: Water and vacuum drying
An aromatic extract is obtained and collected.
The caffeine is extracted.
The leaves are vacuum dried at 50

C.
Then the aromatised CO
2
from the 1st stage is expanded
through the dried, de-aromatised, decaffeinated leaves, resulting
in a tea very similar to normal tea.
Tea (Klima
et al., 1990 see
Calabuig A. J. J.
(1998))
Extraction of caffeine
Extractor with layers of activated carbon
Extraction: 250350 bar, 5080

C
Time: 14h
A 15 to 50% water content is introduced to the tea.
The caffeine is extracted in less time and using less CO
2
.
Mate (Saldana
et al., 1999)
Extraction of alkaloids
(caffeine, theobromine and theophylline)
Semicontinuous-flow high-pressure system,
designed for working pressures
up to 370 bar at 200

C
Sample: 10g, 10% moisture content
Extraction: 255 bar, 70.2

C
Time: 7 h
Separation: depressurisation of the saturated
supercritical fluid at 0

C
A finely divided fraction with an average diameter of 0.0046mm
and a moisture content of 10% was used in all the experiments.
High caffeine removal rates were obtained in the earlier stages
of the extraction. Extraction rates diminished at later stages.
Solubilities of caffeine in supercritical carbon dioxide are about 2
orders of magnitude higher than those of theobromine and
theophylline.
After 7 h of extraction at 70.2

C and 255 bars and a CO


2
flow
rate of 0.91.2g/min 94, 68 and 57% of all extractable caffeine,
theobromine and theophylline, respectively, were successfully
removed from mate tea.
Table 11. Extraction of hop.
Foodstuff Process Conditions Effects/Results
Hops
(Langezaal
et al., 1990)
Extraction of humulone, lupulone and
essential oils
Sample: ground with pellet formation
Extraction: 200 bar, 40

C
Separation: decompression
Given the high selectivity of SFE, the pesticides used in the cultivation
of hops are not extracted.
No alterations, such as oxidisation or polymerisation, are
produced in the humulone.
The extract can be separated during decompression.
An extract with nearly 99% of the humulone was obtained.
Supercritical CO
2
Extraction in Food Processing 281
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important restriction on SFE is the cost associated with
the high-pressure equipment. At present only high-cost
low-volume products are being processed, but in the
future the technique could be economically competitive
for larger volume products, although expansion of the
process is limited by patents available.
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C
Time: 80min
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S1: 90,150 and 120 bar,40

C
S2: 20 and 30 bar, 25

C
CO
2
flow rate: 2700mL/h
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ext
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C, P
ext
: 300 bar, T
S1
: 40

C,
T
S2
: 25

C, P
S1
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S2
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from 40 to 85%, whereas the residue contained less alcohol and
no appreciable aroma.
The content in ethanol of the aromatic extracts can be modified
by tuning the extraction/fraction conditions, rendering from
15 to 95% recovery.
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