J.

of Supercritical Fluids 47 (2009) 583590

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Review

Perspectives on supercritical uid processing of fats and oils

Feral Temelli
Department of Agricultural, Food and Nutritional Science, University of Alberta, Edmonton, Alberta, Canada T6G 2P5

a r t i c l e i n f o a b s t r a c t

Article history: Over the past two decades, fats and oils processing using supercritical carbon dioxide (SC-CO2 ) has devel-
Received 8 July 2008 oped from focusing only on extraction to fractionation of complex lipid mixtures, conducting reactions in
Received in revised form 13 October 2008 supercritical uid media and particle formation techniques for the delivery of bioactive lipid components.
Accepted 13 October 2008
Extraction of specialty oils and column fractionation of deodorizer distillates to concentrate tocopherols
have reached commercial scale. Even though signicant progress has been made in fundamental aspects,
Keywords:
many challenges lie ahead to better understand the phase behavior and solubility of multicomponent
Extraction
lipid mixtures in SC-CO2 and to generate the much needed fundamental data, including transport proper-
Fractionation
Lipids
ties, density and interfacial tension. Considering the increasing consumer demand for natural products
Reactions and stricter government regulations on the use of organic solvents like hexane, the future of SC-CO2 pro-
Particle formation cessing of lipids is bright. Based on the know-how accumulated, integrated processes can be developed,
Supercritical CO2 targeting ingredients for both food and non-food industrial applications, which would t well into a larger
biorenery approach.
2008 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
2. Fundamental aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
3. Process development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
3.1. Separation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
3.1.1. Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
3.1.2. Fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
3.1.3. Coupling with membrane systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
3.2. Conversion processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
3.3. Delivery systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
4. Commercialization and future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589

1. Introduction cosmetic, pharmaceutical, oleochemical and other industries. The

rapidly growing functional food and nutraceutical market is target-
Fats and oils are complex mixtures of lipid components. Even ing bioactive lipid components, such as -3 fatty acids, physterols,
though the main components are triglycerides, fats and oils also tocopherols and tocotrineols for their health benets. On the other
contain mono- and diglycerides, free fatty acids, phospholipids, hand, recent developments in biofuels also depend on the use of fats
glycolipids, sterols, and other fat-soluble components includ- and oils as the raw material for biodiesel and other fuel applications.
ing tocopherols, tocotrienols, carotenoids and squalene. These The sources of fats and oils are plant and animal materials. Con-
compounds have different physical, chemical and physiological ventional processing involves a series of separation processes to
properties. Fats and oils and their various lipid components are extract the lipids from the complex plant or animal tissue matrix
used quite extensively not only in the food industry but also in the and rene them to produce various ingredients for use in a wide
range of products as well as conversion processes to convert the
lipids to other forms for different applications. Organic solvents
Tel.: +1 780 492 3829; fax: +1 780 492 8914. such as hexane are used extensively and the use of hexane is facing
E-mail address: feral.temelli@ualberta.ca. greater government restrictions due to safety and environmental

0896-8446/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.supu.2008.10.014
584 F. Temelli / J. of Supercritical Fluids 47 (2009) 583590
concerns. Therefore, the use of supercritical carbon dioxide (SC-
CO2 ) is being evaluated more favorably as an alternative to organic
solvents used in fats and oils processing. This is especially true for
the functional food and nutraceutical market since the consumers
are demanding natural products without the use of organic sol-
vents. The use of SC-CO2 can fulll this demand. Even though other
supercritical uids, such as ethane [1] and propane [2], have also
been evaluated as a potential extraction solvent for fats and oils
due to the higher solubility of lipids in supercritical ethane and
propane compared to SC-CO2 , the major drawback of these u-
ids is their ammability. On the contrary, CO2 is not ammable,
cheap and abundant with moderate critical temperature (31 C) and
pressure (7.4 MPa). Thus, SC-CO2 has been the solvent of choice for
fats and oils processing both for research and commercialization
purposes.
Signicant progress has been made over the past two decades
in terms of supercritical uid processing of fats and oils, with some
applications reaching commercial level. However, as in any eld,
there are still some challenges ahead and more work is needed
to reach the full potential of possibilities. In 1996, King and List
[3] edited a volume dedicated to lipid chemistry and processing
using supercritical uid technology. The objectives of this concise
review are to reect on the developments and challenges in fats
and oils processing using SC-CO2 over the past two decades both
from fundamentals and process development perspectives and to
provide some insight into future potential.
2. Fundamental aspects
Understanding the fundamentals is critical to any process design
and development. Fundamental aspects involve phase behavior and
solubility as well as density and interfacial tension. In addition,
transport properties, including viscosity, thermal conductivity and
diffusion coefcients are needed for optimal equipment design.
Even though substantial gains have been made in this regard, our
understanding is still limited for the complex multicomponent fats
and oils systems. The amount of fundamental data available is lim-
ited and more work is needed to generate the much needed data.
Measurement of accurate fundamental data is quite challenging
and not many laboratories around the world are equipped for such
measurements under supercritical conditions.
Transport properties of lipid components have been reported to
a limited extent. For example, TaylorAris peak broadening tech-
nique has been used to determine diffusion coefcients of different
lipid components [46]. A high-pressure capillary viscometer was
used to determine the viscosity of fatty acids, their methyl esters
and anhydrous milk fat saturated with SC-CO2 at pressures up to
35 MPa [7]. In terms of thermal conductivity, even though some
attempts have been made using molecular simulation techniques
for other systems, no information is available for SC-CO2 -lipid mix-
tures. For density measurements, magnetic suspension balance [8]
and vibrating tube densimeter [9,10] were used to determine the
densities of corn oil, palm oil, fatty acids and fatty acid esters
saturated with CO2 . More recently, a novel device consisting of
a high-pressure view cell equipped with a spring loaded balance
based on Archimedes principle was developed and the density
of sh oil triglycerides and fatty acid ethyl esters saturated with
high-pressure CO2 was shown to increase with pressure [11].
Interfacial phenomena play an important role in processes
involving supercritical uids with respect to drop formation and
size, mass transfer and mutual solubility. The pendant drop method
is a well-accepted method to determine interfacial tension, which
is correlated with the amount of energy required to increase inter-
facial area. Interfacial tension of vegetable oils [12] and sh oil
triglycerides and fatty acid ethyl esters [13] was determined using
the pendant drop method and it decreased substantially with pres-
sure.
Solubility measurements have to be performed to determine
the optimal conditions for all the processes discussed later and for
the development of thermodynamic models since totally predic-
tive modeling of multicomponent phase behavior in supercritical
uids has not been realized yet. Static, dynamic and recirculation
methods are commonly employed for solubility measurements.
However, a major limitation of the experimental apparatus used
commonly for this purpose is the lack of a visual observation win-
dow on the high-pressure cell. Without a window it is not possible
to observe the phase equilibria, melting behavior of lipids or the
possibility of a density inversion, which may lead to the liquid phase
being pushed out of the cell due to higher density of critical phase
under certain conditions [14]. Solute purity is another critical fac-
tor impacting solubility measurements since the impurities may
enhance or decrease the solubility of a particular solute, depend-
ing on the nature of the solute and impurities as well as the level of
impurities [15,16]. Thus, the solubility information generated may
be limited and in some cases erroneous. Dynamic extraction of a
solute from a plant material [17,18] has also been used to determine
solubility rather than using a pure solute, in part due to the high
cost of pure substrates. In this case, the reported solubility results
may not represent true solubility since interactions of the solute
with the cell matrix of the plant material interfere with the avail-
ability of the solute. In fact, when the solubility of pure -carotene
was compared to the apparent solubility based on extraction from
carrot under similar conditions, not surprisingly, 510 times higher
results were obtained for pure -carotene solubility [19].
Due to the complexities of the multicomponent fat and oil mix-
tures, a systematic approach to understanding solubility behavior
from binary, ternary and quaternary to multicomponent systems of
increasing complexity is extremely valuable. Gcl-stndag and
Temelli [2022] compiled literature data and conducted a critical
evaluation of the solubility behavior of different lipid classes in SC-
CO2 for binary, ternary and higher level systems using Chrastils
equation, which is a simple empirical model correlating solute
solubility with CO2 density. Such a comprehensive analysis also
revealed some discrepancies in the literature data due to the
differences in solute purities and measurement techniques used
as discussed above. As a summary, Fig. 1 shows the solubility
isotherms for representatives of some of the major lipid classes
and minor components of interest, reecting the impact of solute
properties on solubility. Based on the several orders of magni-
tude difference between the solubilities of -carotene and triolein,
Fig. 1. Solubility isotherms of lipid components at 323 K (from Ref. [21]).
 F. Temelli / J. of Supercritical Fluids 47 (2009) 583590
one would expect that it should be a relatively easy separation;
however, in reality that was not the case (unpublished data) since
-carotene is soluble in fats and oils. Such comprehensive anal-
ysis also made it obvious that as one moves from the relatively
simple binary systems to higher level multicomponent systems,
what may be predicted based on binary system behavior was not
valid for the multicomponent systems. Depending on the solute
properties of the lipid mixtures (mono-, di-, triglycerides and fatty
acids and their esters) and the initial feed concentration, both sol-
ubility enhancement and diminution were observed in ternary and
higher systems compared to binary systems, which impacted parti-
tion coefcients and selectivity in multicomponent systems either
positively or negatively [22]. Such behavior has major implications
for separation efciency in a potential fractionation process; thus,
better understanding of the interactions and mixture behavior is
critical for process development.
Use of co-solvents, especially ethanol, has been studied exten-
sively in terms of its impact on the solubility behavior of lipids.
Solubility enhancement is a result of an increase in the density
of the SC-CO2 + co-solvent mixture or intermolecular interactions
between the co-solvent and a particular solute. Co-solvent addition
would be advantageous in a separation process if the selectivity can
be improved due to specic intermolecular interactions between
the co-solvent and specic components of a mixture, since the sol-
ubility of all mixture components is enhanced due to the density
effect. Solubility enhancement as high as 63 was reported for some
fatty acids using ethanol as a co-solvent, mainly due to H-bonding
interactions [23]. When using co-solvents, benets in solubility
enhancement have to be balanced against the negative impact on
process complexity, as discussed later.
In addition to solubility behavior, it is also essential to have a
good understanding of the phase behavior under the supercriti-
cal processing conditions. To achieve a separation of the targeted
lipid components, the operation should be carried out in the two
phase region and the fundamental properties of both phases are
needed. Even though the majority of the studies have focused on
the critical uid phase evaluating the solubility of various compo-
nents in SC-CO2 , understanding the changes in the liquid phase is
just as important. With an increase in pressure, more CO2 is sol-
ubilized in the liquid phase, leading to volume expansion for the
liquid phase. For example, volume expansion was 40% for corn oil
at 60 C and 30 MPa [8] and 25% and 40% for sh oil triglycerides
and fatty acid ethyl esters, respectively, at 40 C and 11.9 MPa [11],
reecting the difference in CO2 solubility in these lipids. With such
a volume expansion, the expectation was that the density of the liq-
uid phase would decrease, but on the contrary as indicated above
density of the liquid phase saturated with CO2 increased with pres-
sure up to the mixture critical point [811]. More work is needed
to fully characterize the fundamental properties of the liquid phase
of fats and oils saturated with high-pressure CO2 and to under-
stand the molecular reasons behind them. Volume expansion of
the liquid phase needs to be taken into account during equipment
design. Needless to say, if the vessel volume is insufcient, the
liquid phase may be overowing the vessel without the desired
separation.
3. Process development
Pioneering work in the early 1980s on fats and oils processing
using SC-CO2 focused mainly on the extraction of oilseeds [2426].
Since then, in addition to building on the know-how of extrac-
tion, processing of fats and oils using SC-CO2 has been expanded
to involve separation and conversion processes for the purposes of
extraction of an oil product, isolation of various fractions enriched
in certain components and conversion of lipids to other high-value
585
ingredients/products through targeted reactions, which may or
may not be catalyzed by lipase enzymes. Comprehensive lists of
references on the application of these unit operations to fats and
oils processing were provided in previous reviews [27,28]. In addi-
tion, recent developments in particle formation processes open up
new avenues for the design of delivery systems for bioactive lipids.
3.1. Separation processes
3.1.1. Extraction
Hexane is the traditional solvent used commercially for the
extraction of oils from various plant materials but hexane use is
under greater scrutiny due to increasing government restrictions
and consumer concerns regarding the safety of the use of organic
solvents in food processing. The use of cold-pressing is expanding
in an effort to claim not processed with organic solvents in the
product label; however, a major drawback of cold-pressing is the
high level of residual oil left in the meal (515%). Thus, SC-CO2 has
become a viable alternative to replace hexane and meet the growing
consumer demand for natural products.
SC-CO2 extraction of oils has been studied extensively since
the early 1980s. Numerous studies have evaluated the impact of
extraction variables on the yield, recovery, and composition of the
extracted oils from various sources. The extraction variables are
temperature, pressure, particle size and moisture content of feed
material, extraction time, CO2 ow rate and solvent-to-feed ratio
and they all need to be optimized for an efcient process. In gen-
eral, extraction yield increases with pressure due to an increase
in lipid solubility in SC-CO2 based on an increase in CO2 density.
The impact of temperature is dependant on competing parame-
ters; the CO2 density decreases with temperature while the vapor
pressure of solutes increases, leading to the well known cross-over
phenomena for solubility isotherms. Thus, the resultant impact of
temperature on solubility is dictated by whichever parameter is
greater at a given pressure. In addition, diffusivity increases with
temperature enhancing mass transfer kinetics during extraction.
As reviewed previously [27,28], unfortunately, some of the extrac-
tion studies evaluated only yield after a few hours of extraction,
rather than the full extraction curve over time, which makes it dif-
cult to interpret the impact of the extraction parameters. In some
cases, there is even confusion over yield vs. recovery in terms of
the numbers reported and care is needed for accurate reporting of
results.
Specialty oils are receiving growing interest due to their
high concentrations of bioactive lipid components, such as
polyunsaturated fatty acids, phytosterols, tocopherols, tocotrienols,
carotenoids and squalene, which have been demonstrated to have
various health benets. Nut oils (almond, hazelnut, peanut, pecan,
pistachio, and walnut), seed oils (apricot, borage, cherry, evening
primrose, ax, grape, hiprose, pumpkin, sea buckthorn, sesame,
etc.), cereal oils (amaranth, oat, rice bran, and wheat germ), and oils
of fruits and vegetables (buriti fruit, carrot, cloudberry, olive husk,
and tomato) are classied under specialty oils [28], which are high
value, small volume oils as opposed to the commodity oils (soy-
bean, canola, corn, sunower, etc.) of low value and high volume.
Specialty oils are also desirable because of their unique aroma and
avor proles, characteristic of the starting material, in comparison
to the bland taste of commodity oils due to the extensive rening
they are subjected to. Preserving the unique avor and aroma pro-
le of specialty oils during SC-CO2 extraction is a major advantage
since volatile aroma compounds are lost during hexane evaporation
in traditional processing. SC-CO2 extraction of specialty oils and the
impact of various extraction parameters as well as the composition
of the different oils obtained were discussed in detail in a recent
review [28].
586 F. Temelli / J. of Supercritical Fluids 47 (2009) 583590
Another important aspect in oil extraction is the use of
co-solvents to increase solvent loading and to recover polar com-
ponents as CO2 is selective for non-polar components. Ethanol has
been the co-solvent of choice for food applications since ethanol
is generally recognized as safe (GRAS). For example, polar phos-
pholipids can be recovered from oilseeds with the introduction of
ethanol, which is not possible with neat SC-CO2 [29]. Even though
ethanol addition may improve the feasibility of a process by increas-
ing solvent loading and/or improving selectivity, this approach
negates the biggest advantage of SC-CO2 in terms of the ease of sol-
vent removal. Ethanol removal from the extract and residual meal
requires evaporation similar to conventional solvent extraction;
however, this aspect has been mostly neglected in the literature
involving the use of ethanol as a co-solvent. Thus, the overall pro-
cess design becomes more complex, which needs to be balanced
against the benets of co-solvent addition. Optimization and fea-
sibility evaluation must be carried out on a case-by-case basis. A
recent approach uses vegetable oils as co-solvent for the recovery
of fat-soluble carotenoids, -carotene [30] and lycopene [31,32].
This approach is promising because the extraction yield of total
carotenoids was substantially higher than that obtained by tra-
ditional solvent and SC-CO2 extraction without or with ethanol
as a co-solvent. Further separation of the co-solvent from the
extract is not necessary since the carotenoid-rich oil can be used
as is without further treatment, while the residual oil in the meal
can be recovered with SC-CO2 alone at the end of the extraction
period.
Mass transfer modeling aspects of lipid extraction from plant
materials have been investigated quite extensively and different
modeling approaches have been critically evaluated [33]. These
models are based on the following mechanism: desorption of oil
from the solid matrix, formation of a shrinking core of condensed
oil in a non-adsorbing porous matrix and diffusion in a homoge-
neous medium [33]. For further improvements in these models, it
was recommended by del Valle and de la Fuente [33] to investigate
the high-pressure sorption isotherms of oil in pretreated substrates
in the presence of CO2 , to develop a correlation of effective diffusiv-
ity values and microstructural features of pretreated seeds and to
assess the effects of pretreatment on the microstructural features
of seeds.
3.1.2. Fractionation
It may be necessary to further fractionate a crude lipid extract for
the purpose of rening or obtaining a fraction enriched in specic
bioactives. In the case of rening, it is well accepted that SC-CO2 -
extracted oils do not require as much rening as hexane-extracted
oils, since many of the components removed during conventional
rening such as phospholipids and chlorophyll are not extracted or
extracted to a very limited extent by SC-CO2 . Moreover, the removal
of bioactives such as phytosterols, tocopherols and tocotrienols
during conventional rening is being questioned. Therefore, the SC-
CO2 -extracted oils can be used as is or with minimal rening, which
may be achieved in a fractionation step following extraction.
Fractionation of lipid mixtures can be achieved using three
different approaches. First, fractional extraction refers to collecting
fractions throughout an extraction period as a function of time
where the extraction temperature and/or pressure may be changed
at certain intervals over time. This allows fractions of differing
compositions to be collected separately. For example, a fraction of
higher free fatty acid content may be collected rst due to their
higher solubility in SC-CO2 (Fig. 1), followed by triglycerides. A
fraction containing some phospholipids may be collected at the
end once triglycerides are depleted. Also, it is possible to add
ethanol as a co-solvent to extract a phospholipid-rich fraction once
triglycerides are depleted by neat SC-CO2 [29].
The second approach to fractionation is fractional separation
where several separators are used in series. In this case, the extrac-
tion temperature and pressure can be set to achieve as high a CO2
density as possible to extract the maximum amount of solutes.
Then, separator conditions would be adjusted for decreasing CO2
density such that fractions of high, medium and low molecular
weight corresponding to low, medium and high volatility com-
pounds, respectively, can be collected in sequence in the separators.
Thirdly, a fractionation column can be used for the separation of
liquid feed mixtures. In general, a packed column has been used for
this purpose with heaters to create a thermal gradient along the col-
umn height, leading to the formation of internal reux to enhance
separation efciency. It is also possible to generate a reux using
an external reux pump. Lab- and pilot-scale columns (14.368 mm
internal diameter and 0.613.6 m high) are operational in research
facilities around the world. These columns have been used for the
fractionation of deodorizer distillates [3438], vegetable and sh
oils [3943], and milk fat [44]. Better understanding of the engi-
neering design aspects of such equipment is needed for optimal
operation of targeted applications.
3.1.3. Coupling with membrane systems
Coupling of supercritical technology with membrane tech-
nology is a novel approach to achieve desired separations.
Development of such a coupled technology was initiated by Sarrade
et al. [45] in the late 1990s and it is currently gaining momentum
in terms of its applications to lipid systems [4648].
Application of membrane technology to different steps (degum-
ming, dewaxing, deacidifying and decolorizing) of edible oil
rening have achieved some commercial success; however, low
permeation rates and low selectivity still remain as challenges for
further improvement [49]. Addition of hexane to dilute the oil
improves the ux but the long-term stability of membranes needs
to be demonstrated [49]. Replacing hexane with SC-CO2 offers
advantages in terms of improving ux, achieving higher diffusivity
and reducing the viscosity of lipid substrates.
From the supercritical uid processing perspective, a major
advantage of coupling cross-ow membrane and SC-CO2 -extra-
ction systems is the recovery of the extract without depressurizing
SC-CO2 , resulting in substantial savings in energy costs associated
with CO2 recompression. In this case, a membrane that would allow
CO2 to permeate while retaining all lipid components is needed.
Alternatively, the membrane module can be another toolbox to
achieve separations that are difcult to perform using CO2 alone.
Thus, those components with similar solubilities in SC-CO2 may
be separated if a membrane module is attached after an extraction
or a fractionation unit. For example, despite the fact that squalene
(C30) is a much larger molecule than oleic acid (C18), squalene and
oleic acid have similar solubilities in SC-CO2 because squalene is
non-polar (Fig. 1). This molecular weight difference can be the driv-
ing force to separate them using a membrane system [48]. Then,
the membrane requirement would be more stringent targeting the
separation of two specic lipid components solubilized in SC-CO2 .
Even though such coupled systems show great promise, some
challenges need to be overcome, including better understanding of
the membrane behavior under supercritical conditions and specic
interactions between the membrane, lipid solutes and CO2 as well
as developing membranes appropriate for such separations and
equipment design for continuous cross-ow tubular membrane
modules.
3.2. Conversion processes
Conducting lipid reactions in SC-CO2 media received much
attention since the rst report by Nakamura et al. [50] in 1986
 F. Temelli / J. of Supercritical Fluids 47 (2009) 583590
on lipase catalyzed reactions in SC-CO2 media. The motivation
for conducting lipid reactions in SC-CO2 media with or with-
out the use of enzymes has been the tunable solvent properties
of supercritical uids by varying temperature and pressure and
the ease of product recovery as well as the fact that increased
reaction rates can be achieved under supercritical conditions com-
pared to conventional media. According to the transition state
theory [51], increasing pressure enhances the reaction rate if
the activation volume is negative. As well, rates of mass trans-
fer limited reactions can be enhanced due to low viscosity,
high diffusivity and very low surface tension of supercritical
uids.
Lipid reactions of importance to the oleochemical industry
include hydrolysis, alcoholysis, glycerolysis, esterication, inter-
esterication and transesterication. Products of these reactions,
including fatty acids, fatty acid esters, mono- and diglycerides, and
structured lipids nd use in a wide variety of applications in food,
pharmaceutical, cosmetic, soap, detergent, biodiesel and bioprod-
uct industries.
Most of these reactions when conducted in the traditional
manner require the use of metal or alkali catalysts and high tem-
peratures (over 200 C). Separation of the catalyst and development
of dark colors and burnt avors are challenges associated with
conventional reactions. Glycerolysis, hydrolysis and esterication
reactions [5254] in SC-CO2 media at 1030 MPa were studied in
a systematic manner and kinetic models were developed. Temper-
ature had to be kept at 250 C, similar to conventional reactions,
since the conversion rate was minimal at lower temperatures.
Even though no catalysts were used, similar conversion rates were
achieved in SC-CO2 media compared to conventional reactions and
light colored products with no off odors were obtained. Kinetic
modeling is an important aspect of understanding and control
of such reactions. However, reaction kinetics aspects need to be
overlaid with mass transfer and phase behavior aspects to have a
better understanding of these complex systems, which is essen-
tial for optimal reactor design and operation. A major challenge
in this regard is the availability of high-pressure equipment with
a window that can withstand temperatures of 250 C to observe
the changes in phase equilibria as the reaction proceeds. Many
of these reactions involve the formation of mono- and diglyc-
erides, which are powerful emulsiers and inuence the phase
behavior as their concentrations change throughout the reaction
period.
To minimize the reaction temperature, lipase enzymes can be
used as a catalyst at a temperature range of 3555 C. The use of
immobilized enzymes offers the advantage of running a continu-
ous ow packed bed reactor, without any concern about catalyst
removal associated with traditional metal catalysts. Furthermore,
higher diffusivity and lower viscosity of SC-CO2 compared to
organic solvents allow faster transport of reactants and products to
and from the active site of the enzyme. Optimization of water lev-
els during enzymatic reactions in SC-CO2 media is essential since
enzymes require a limited amount of water to be present to func-
tion [55]. Presence of excessive amounts of water serves as a barrier
for the transport of lipid components to and from the active site and
leads to a reduction in conversion rate. Immobilized enzymes are
nding increased use at commercial scale in recent years. An impor-
tant consideration is the stability of the enzyme under the specic
reaction conditions and the length of use for each batch of enzyme.
Laudani et al. [56] demonstrated the stability of lipase activity for
over 50 days in a continuous bioreactor producing n-octyl oleate.
Feasibility analysis for high-pressure reactors using SC-CO2 media,
comparing the energy cost of a high temperature (250 C) opera-
tion vs. the cost of immobilized enzymes operating at moderate
temperatures is needed.
587
3.3. Delivery systems
Current developments in particle formation technologies using
SC-CO2 , as summarized in excellent recent reviews [57,58], show
great potential for designing delivery systems for bioactive lipids.
These techniques are already being used for pharmaceutical appli-
cations but not necessarily for bioactive lipids and nutraceutical
ingredients. In general, bioactive ingredients are quite sensitive
to oxygen and heat; therefore, being able to extract and iso-
late such components using SC-CO2 at mild temperatures and
then encapsulate them in a protective coating material while
still under CO2 environment without the use of organic solvents
presents a tremendous advantage. As well, preparation of micro-
and nano-scale materials with functionalities that cannot be met
by traditional techniques is pushing new frontiers and allowing the
design of delivery systems with controlled and targeted release of
bioactive components.
Various particle formation techniques with some variations
have been developed, which can be classied into three major
categories where SC-CO2 can be used as a solvent (rapid expan-
sion of supercritical solutions, RESS), as a gas to saturate a
solution (particles from gas-saturated solutions, PGSS) or as an
anti-solvent (gas anti-solvent, GAS; supercritical uid anti-solvent,
SAS; precipitation with a compressed anti-solvent, PCA; aerosol
solvent extraction system, ASES; solution enhanced dispersion by
supercritical uids, SEDS). Details of these techniques have been
reviewed previously [57,58].
Applications of these techniques to bioactive lipids are quite lim-
ited. Anti-solvent processes have been applied to soy lecithin [59]
and carotenoids [60]. It has been demonstrated that particles of
different morphologies and sizes can be produced by varying pro-
cess parameters. However, more work is needed to understand the
impact of such morphologies, particle size and processing param-
eters on the stability and functionality of these bioactives. These
approaches should also be extended to other lipid bioactives.
4. Commercialization and future outlook
Signicant advances have been made over the past 20 years
towards commercialization of SC-CO2 processing of fats and oils.
For example, extraction of specialty oils [61] and column fractiona-
tion of deodorizer distillate for tocopherol concentration [38] have
reached commercial production.
Over the years, it has been argued that products such as spe-
cialty oils, which are sold at a premium price, can accommodate
the high investment cost of SC-CO2 technology whereas it cannot be
feasible for the processing of larger volume and lower priced com-
modity oils. However, the tide is changing with numerous industry
players looking at this option more seriously. Some major factors
are impacting this change. The industry has been looking for alter-
native solvents as hexane use is facing greater scrutiny. In terms of
process economics, it has been shown that the cost of large capacity
supercritical plants with optimized design and operation is of the
same order of magnitude as that for conventional processes [62].
Elimination of the expensive hexane evaporation and meal desol-
ventization steps from the conventional process and the minimal
rening requirements simplify the overall process in favor of the
SC-CO2 process. Moreover, considering all the latest concerns on
global warming and green house gas emission, another advantage
of potential large scale SC-CO2 processing plants would be captur-
ing and creating new uses for CO2 generated by other industries
rather than releasing it into the atmosphere.
Another aspect in commercialization activities is the consumer
acceptability of new products. An investigation on the sensory qual-
ity and consumer acceptability of SC-CO2 -extracted canola oil that
588 F. Temelli / J. of Supercritical Fluids 47 (2009) 583590
Fig. 2. Potential use of supercritical uid processing in an integrated biorenery.
was not rened to look like the conventional oil revealed that it had
strong avor, which was liked by most panelists [63]. Consumers
were more willing to accept and purchase the product if they were
given nutritional and/or processing information regarding the ben-
ets of SC-CO2 technology, even though initially they responded
negatively to the intense yellow-orange color of the canola oil [63].
Currently, nutraceutical products obtained by SC-CO2 technology
are promoting this aspect on their package label as a marketing
advantage even though this was not the case in the early 1990s.
The potential for novel process development based on SC-CO2
technology by combining various unit operations for high-value
end products is great. For example, extraction can be followed by
conversion, such as feeding SC-CO2 + canola oil from the extractor
to an enzymatic reactor for hydrolysis [64,55] or esterication [65].
At present, hexane-extracted oil is transported from the crushing
plant to other facilities for conversion to various end products in the
oleochemical industry using other solvents and catalysts. An inte-
grated SC-CO2 -based process would consolidate these activities. A
challenge in this approach is the compatibility of the optimal oper-
ating conditions for the extraction and reaction steps. Generally,
higher temperatures and pressures are preferred at the extraction
step to maximize oil solubility in SC-CO2 , whereas the conditions
for the enzymatic reactor are milder. Make-up CO2 may be needed
between the two units to allow independent control of temperature
and pressure in the two units. In addition, changes in the compo-
sition of the extract over time should be taken account to ensure a
consistent feed stream into the reactor.
After two decades of signicant developments, handling of large
volumes of oilseeds is still a major challenge. Even though equip-
ment manufacturers have been working on it for some time, such
a continuous system at commercial scale is not available yet. Com-
mercial plants are still built on a semi-continuous basis, by cycling
through multiple extractor vessels that are lled and emptied
batch-wise [66]. A continuous screw-type system with countercur-
rent movement of solids and CO2 would allow larger throughput
but sealing of inlet and exit ports of such a high-pressure system
is a challenge. The semi-continuous vertical packed bed extractor
(estimated to be 21 m tall) that has been in operation for coffee
decaffeination since the early 1990s in the USA with an estimated
throughput of 22,700 tons/year [14] may be suitable for oilseeds
and other lipid-rich plant materials. Whatever the nal design may
look like, a breakthrough in handling large volumes of oilseeds will
revolutionize fats and oils processing and will lead to new commer-
cial developments globally.
Considering all the developments summarized above and the
latest trends in biorening, a biorenery where the processing of
the lipid fraction is based on supercritical technology is within
reach within the next decade. A biorenery involves the separa-
tion and conversion processing of biomass, including oilseeds and
other lipid-rich plant materials, similar to a petroleum renery,
to produce a variety of ingredients/products for food and non-
food applications. This approach maximizes the utilization and
the value of various crops and biomass. SC-CO2 technology has a
major role to play in future bioreneries. SC-CO2 extraction of lipids
and other minor nutraceutical components leaves behind a meal
enriched mainly in proteins and carbohydrates that can be frac-
tionated and converted as necessary for use in other applications.
Further processing of proteins and carbohydrates may involve the
use of sub- and supercritical water technologies. Combination of
SC-CO2 and high-pressure water technologies will lead to the devel-
opment of truly green bioreneries. Mild conditions of SC-CO2
extraction minimizes the damage to residual proteins, resulting in
better functionality compared to those obtained by traditional sol-
vent extraction [67] and thus the potential for high-value protein
isolates. SC-CO2 extraction of lipids may be followed by different
combinations of fractionation, reaction or particle formation opera-
tions to generate a number of high-value ingredients/products. The
versatility of the SC-CO2 technology allows numerous possibilities
with tremendous potential and one possible approach is depicted
in Fig. 2.
In closing, supercritical uid technology should not be consid-
ered as an alternative to a single extraction step; rather it should
be developed as an integrated process for fats and oils processing,
possibly as part of a larger biorenery. Without such an integrated
approach, the full potential of supercritical technology cannot be
realized. Based on the know-how developed over the past two
decades, we can look forward to bringing some of the novel new
developments to fruition at commercial scale in the next decade.
 F. Temelli / J. of Supercritical Fluids 47 (2009) 583590
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