Supercritical Fluid Extraction and Fractionation of Natural Matter

J.
of Supercritical Fluids 38 (2006) 146–166
Review
Supercritical fluid extraction and fractionation of natural matter

Ernesto Reverchon ∗ , Iolanda De Marco
Università di Salerno, Dipartimento di Ingegneria Chimica ed Alimentare, Via Ponte don Melillo, 84084 Fisciano (SA), Italy
Received 30 June 2005; received in revised form 13 March 2006; accepted 13 March 2006
Abstract
Supercritical extraction and fractionation of natural matter is one of the early and most studied applications in the field of supercritical fluids. In
the last 10 years, studies on the extraction of classical compounds like essential and seed oils from various sources: seeds, fruits, leaves, flowers,
rhizomes, etc., with or without the addition of a co-solvent have been published. Supercritical extraction of antioxidants, pharmaceuticals, colouring
matters, and pesticides has also been studied. The separation of liquid mixtures and the antisolvent extraction are other processes that can perform
very interesting separations. Mathematical modelling has also been developed and refined for some of these processes.
The objective of this review is to critically analyze traditional and new directions in the research on natural matter separation by supercritical
fluids extraction and fractionation.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Supercritical extraction; Liquid fractionation; Purification; Antisolvent extraction; Modelling
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
2. Solids processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
2.1. Selection of the operating parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
2.2. Examples of application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
2.2.1. Essential oils extraction/isolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
2.2.2. Seed oils extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
2.3. High added value compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
2.3.1. Nutraceuticals: Lycopene and Astaxanthin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2.3.2. Pharmaceuticals: Hyperforin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
2.3.3. Pesticides: Pyrethrins and Azadirachtins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
2.4. Mathematical modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
3. Liquid feed processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
3.2.1. Hexane elimination from seed oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
3.2.2. Fried oil fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
4. Antisolvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
4.2.1. Lecithin extraction from soybean oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
∗ Corresponding author. Tel.: +39 089 964116; fax: +39 089 964057.
E-mail address: [email protected] (E. Reverchon).
0896-8446/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2006.03.020
E. Reverchon, I. De Marco / J. of Supercritical Fluids 38 (2006) 146–166 147
4.2.2. Propolis tincture fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159

4.2.3. Proteins extraction from tobacco . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
5. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
1. Introduction ity. In several cases, it is not possible to avoid the co-extraction

of some compound families (with different solubilities, but also
Extraction of compounds from natural sources is the most with different mass transfer resistances in the raw matter). In
widely studied application of supercritical fluids (SCFs) with these cases, it is possible to perform an extraction in successive
several hundreds of published scientific papers. Indeed, super- steps at increasing pressures to obtain the fractional extraction of
critical fluids extraction (SFE) has immediate advantages over the soluble compounds contained in the organic matrix, selected
traditional extraction techniques: it is a flexible process due by decreasing solubilities in the supercritical solvent. Fractional
to the possibility of continuous modulation of the solvent separation allows the fractionation of the SCF extracts, operating
power/selectivity of the SCF, allows the elimination of pollut- the plant with some separators in series at different pressures and
ing organic solvents and of the expensive post-processing of the temperatures. The scope of this operation is to induce the selec-
extracts for solvent elimination. tive precipitation of different compound families as a function
Several compounds have been examined as SFE solvents. of their different saturation conditions in the SCF. For example,
For example, hydrocarbons such as hexane, pentane and butane, this procedure has been applied in the SFE of essential oils
nitrous oxide, sulphur hexafluoride and fluorinated hydrocar- [11–16].
bons [1]. However, carbon dioxide (CO2 ) is the most popular In several cases, the starting material is a liquid mixture. The
SFE solvent because it is safe, readily available and has a low process to be applied is the continuous liquid extraction per-
cost. It allows supercritical operations at relatively low pressures formed in a packed tower. It is worth of note that, while the
and at near-room temperatures. The only serious drawback of extraction from solids is a discontinuous operation, the packed
SFE is the higher investment costs if compared to traditional tower is capable of continuous steady state operation that allows
atmospheric pressure extraction techniques. However, the base the processing of large quantities of liquid mixtures in a rela-
process scheme (extraction plus separation) is relatively cheap tively small apparatus and in a short time.
and very simple to be scaled up to industrial scale. In some other cases, the material to be treated is a liquid mix-
SFE works have been the subject of several reviews [2–10]. ture that contains solid compounds dissolved in it. The extraction
Therefore, we will limit time interval of our analysis to the last of these compounds from the liquid solution cannot be per-
decade (1996 to present time), presenting first a summary of the formed in a packed tower since the solid matter will precipitate
concepts and results that we consider as well established in the on the packings and fixed bed extraction is not possible. In this
literature [2]. case, a supercritical antisolvent extraction (SAE) process has to
Early works on SFE frequently used high pressures be adopted. The pre-conditions to apply antisolvent extraction
(>350 bar) even when relatively supercritical CO2 (SC-CO2 ) are similar to the ones characteristics of supercritical antisolvent
soluble compounds had to be extracted (for example: terpenes, micronization (SAS): the liquid solvent has to be very soluble in
sesquiterpenes, fatty acids, etc.). Operating in this manner, only SC-CO2 , whereas, the solids have to be completely not soluble
the solvent power of the SCF was enhanced. Then, the concept of in the SCF. The scope of the process is not the micronization,
the optimization between solvent power and selectivity has been but the selective extraction of the solid compounds. These condi-
applied and SFE operating conditions have been chosen to obtain tions can be frequently obtained since many organic solvents are
the selective extraction of the compounds of interest, reducing to readily soluble in SC-CO2 even at mild operating conditions and
a minimum the co-extraction of undesired compounds [2]. For many high molecular weight solids show negligible solubilities
successful extraction, not only the solubility of the compounds to in SC-CO2 especially at low CO2 densities.
be extracted and/or of the undesired compounds has to be taken Due to the structural complexity and variability (with the sea-
into account; mass transfer resistances due to the structure of the son, kind, crop, etc.) of the materials to be treated and to the large
raw material and to the specific location of the compounds to be variety of compounds that can be extracted (different molecular
extracted can also play a relevant role. A microscopic analysis weight, polarity, link with the structure, etc.), these processes
of the natural structure can help in understanding where mass are far from to be considered exhaustively studied, though some
transfer resistances are located. Specific experiments performed industrial applications have been already developed. Moreover,
varying particle size and supercritical solvent residence time can an increasing interest has been registered in the extraction of high
also be helpful in this sense. The complex interplay between added value substances, such as antioxidants, pharmaceuticals
thermodynamics (solubility) and kinetics (mass transfer) has to and colouring matters.
be understood to properly perform SFE. Therefore, the scope of this review is to analyze SFE, SAE
Fractional separation of the extracts is another well-known and liquid fractionation studies performed in the last 10 years,
concept that can be useful to improve the SFE process selectiv- considering the evolution of the extraction processes, products
148 E. Reverchon, I. De Marco / J. of Supercritical Fluids 38 (2006) 146–166
and materials treated. A critical analysis will be performed and late continuous solid processing; however, design and operation
the perspectives of the field will be illustrated. of the two extruders is not cheap and simple.
2. Solids processing 2.1. Selection of the operating parameters
It is the most studied SCF application since the most fre- The selection of the operating conditions depends on the spe-
quently required separation process is the extraction/elimination cific compound or compound family to be extracted. Molecular
of one or more compound families from a solid natural matrix. weight and polarity have to be taken into account case by case;
The basic extraction scheme consists of an extraction vessel but some general rules can be applied. First of all, SFE temper-
charged with the raw matter to be extracted. As a rule, the ature for thermolabile compounds has to be fixed between 35
starting material is dried and grinded to favour the extraction and 60 ◦ C; e.g., in the vicinity of the critical point and as low
process. It is loaded in a basket located inside the extractor as possible to avoid degradation. The increase of temperature
that allows fast charge and discharge of the extraction vessel. reduces the density of SC-CO2 (for a fixed pressure) thus reduc-
The SCF at the exit of the extractor flows through a depres- ing the solvent power of the supercritical solvent; but it increases
surization valve to a separator in which, due to the lower pres- the vapor pressure of the compounds to be extracted. Therefore,
sure, the extracts are released from the gaseous medium and the tendency of these compounds to pass in the fluid phase is
collected. increased. However, the most relevant process parameter is the
More sophisticated extraction schemes contain two or more extraction pressure that can be used to tune the selectivity of the
separators. In this case, it is possible to fractionate the extract in SCF. The general rule is: the higher is the pressure, the larger
two or more fractions of different composition by setting oppor- is the solvent power and the smaller is the extraction selectiv-
tune temperatures and pressures in the separators [17–34]. Solids ity. Frequently, the solvent power is described in terms of the
pre-processing is also a parameter that can largely influence SC-CO2 density at the given operating conditions. CO2 density
the separation performance. For example, solid drying, flak- can vary from about 0.15 to 1.0 g/cm3 and is connected to both
ing and particle size optimization have, as a rule, be taken into pressure and temperature. Its variation is strongly non-linear;
account. therefore, the proper selection requires the use of accurate tables
Other possible variations of the SFE processing scheme are: of CO2 properties [77,78].
multistage extraction and co-solvents addition. Multi-step oper- The other crucial parameters in SFE are CO2 flow rate, par-
ation is obtained varying pressure and/or temperature in each ticle size of the matrix and duration of the process (extraction
process step [35,36]. This strategy can be used when it is required time). The proper selection of these parameters has the scope
the extraction of several compound families from the same of producing the complete extraction of the desired compounds
matrix and they show different solubilities in SC-CO2 . It takes in the shorter time. They are connected to the thermodynamics
advantage of the fact that SC-CO2 solvent power can be con- (solubility) and the kinetics of the extraction process in the spe-
tinuously varied with pressure and temperature. For example, cific raw matter (mass transfer resistances). The proper selection
it is possible to perform a first extraction operating at low CO2 depends on the mechanism that controls the process: the slow-
density (e.g., 0.29 g/cm3 , 90 bar, 50 ◦ C) followed by a second est one determines the overall process velocity. CO2 flow rate
extraction step at high CO2 density (e.g., 0.87 g/cm3 , 300 bar, is a relevant parameter if the process is controlled by an exter-
50 ◦ C). The most soluble compounds are extracted during the nal mass transfer resistance or by equilibrium: the amount of
first step (for example, essential oils) and the less soluble in the supercritical solvent feed to the extraction vessel, in this case,
second one (e.g., antioxidants) [37–40]. determines the extraction rate. Particle size plays a determining
A liquid co-solvent can be added to SC-CO2 to increase its role in extraction processes controlled by internal mass transfer
solvent power towards polar molecules. Indeed, SC-CO2 is a resistances, since a smaller mean particle size reduces the length
good solvent for lipophilic (non-polar) compounds, whereas, it of diffusion of the solvent. However, if particles are too small,
has a low affinity with polar compounds. Various authors added they can give problems of channelling inside the extraction bed.
small quantities of liquid solvents (for example, ethyl alcohol) Part of the solvent flows through channels formed inside the
that are readily solubilized by SC-CO2 . When in solution, they extraction bed and does not contact the material to be extracted
modify the solvent power of SC-CO2 [28,32,40–75]. This strat- thus causing a loss of efficiency and yield of the process. As
egy has the drawback that, a larger solvent power could also a rule, particles with mean diameters ranging approximately
mean lower process selectivity and since, as a rule, the co- between 0.25 and 2.0 mm are used. The optimum dimension
solvent is liquid at atmospheric pressure, it will be collected can be chosen case by case considering water content in the
in the separator together with the extracted compounds. Subse- matrix and the quantity of extractable liquid compounds that
quent processing for solvent elimination is required; therefore, can produce phenomena of coalescence among the particles
one of the advantages of the SFE; i.e., solventless operation is thus favouring the irregular extraction along the extraction bed.
lost. Another possible process arrangement is the continuous Moreover, the production of very small particles by grinding
feeding and discharging of the solid to obtain the continuous could produce the loss of volatile compounds. Process duration
processing of the solid matter [76]. This operation is possible is interconnected with CO2 flow rate and particle size and has
adding two solid extruders at the top and at the bottom of the to be properly selected to maximize the yield of the extraction
extractor and can avoid the use of two or more extractors to simu- process.
2.2. Examples of application these process conditions and, therefore, a complex mixture of
essential oil plus these other compounds is obtained.
Some well established industrial processes use SFE to pro- Data on essential oils supercritical extraction is shown in
duce hops extracts, decaffeinated coffee and some food nutri- Table 1 that is alphabetically organized by the common name
tional substances that offer also some aspects of therapeutic (raw material), the botanical name and the target component (the
protection to the human body (nutraceuticals). However, many extract). In Table 1, laboratory, pilot plant and analytical stud-
other applications are possible. ies performed using very small extractors are included. Only in
some of them, the operating conditions have been optimized to
2.2.1. Essential oils extraction/isolation maximize both the total yield and the selectivity of the process;
This process has been widely studied. Essential oils are therefore, yield and the operating conditions can be largely influ-
mainly formed by hydrocarbon and oxygenated terpenes and enced by the final scope of the paper: to selectively obtain the
by hydrocarbon and oxygenated sesquiterpenes. They can be essential oil, or to extrapolate its composition from the unfrac-
extracted from seeds, roots, flowers, herbs and leaves using the tionated extract (“concrete”). An analysis on the influence of
so-called hydrodistillation. This is a very simple process, but some process parameters such as pressure, temperature, extrac-
suffers of many drawbacks: thermal degradation, hydrolysis and tion time, percentage of co-solvents and solvent flow rates is
solubilization in water of some compounds that alter the flavour available in some of the papers considered in Table 1.
and fragrance profile of many essential oils extracted by this
technique. 2.2.2. Seed oils extraction
From the point of view of SFE, essential oils isolation is an Vegetable oil from seeds is traditionally produced by hex-
example of extraction plus fractional separation. Indeed, this ane extraction from ground seeds. The process is very efficient,
process can be optimally performed operating at mild pres- but its major problem is represented by hexane elimination after
sures (from 90 to 100 bar) and temperatures (from 40 to 50 ◦ C) extraction. Three distillation units in series, operated under vac-
since at these process conditions all the essential oil components uum and other ancillary apparatuses (deodorizer, degumming,
are largely soluble in SC-CO2 [79–82]. For example, linalool, etc.), have to be used. The possible thermal degradation of the oil
a typical oxygenated terpene is completely miscible with SC- and the incomplete hexane elimination (from 500 to 1000 ppm
CO2 at pressures larger than about 85 bar when the temperature residue) are the drawbacks of this process. Therefore, several
is set at 40 ◦ C [83]. Essential oils are at least partly located authors have proposed the substitution of the traditional process
inside the vegetable structure; therefore, mass transfer resis- by SC-CO2 extraction of oil from seeds [22,28,41,68,71,85–89]
tances have to be considered too. At the previously discussed (see Table 1). Indeed, triglycerides forming seed oils are read-
operating conditions, essential oil components are extracted ily soluble in SC-CO2 at 40 ◦ C and at pressures larger than
together with cuticular waxes; i.e., paraffinic compounds located about 280 bar. The main parameters to be taken into account
on the surface of vegetable matter with the scope of control- for this process are particle size, pressure and residence time.
ling perspiration. Paraffins exhibit a relatively low solubility at Small particles (1 mm mean diameter or less) and high pressures
these operating conditions [84]; but, of course, if the extrac- (300–500 bar) can strongly reduce the extraction time. After
tion pressure is increased their contribution in the extract will extraction, the SC-CO2 tryglicerides solution is sent to a sep-
be more relevant; other compounds (like fatty acids) could be arator working at subcritical conditions. This operation reduces
also increasingly extracted. Therefore, extraction of waxes is to near zero the solvent power of CO2 and allows the recovery
controlled by their solubility and essential oil extraction is con- of oil. The complete elimination of gaseous CO2 from oil is also
trolled, at least in part, by internal mass transfer resistances in obtained in the separator. The SFE of several seed oils has been
the vegetable structure. As a result of these interactions, the two successfully performed up to the pilot scale.
compound families (essential oil and waxes) are co-extracted at An alternative process has also been proposed, in which the
all operating conditions. To selectively extract the essential oil extraction is performed at a fixed pressure and only tempera-
alone, it is necessary to take advantage of the fact that at low ture variations are used to reduce the oil solubility and obtain its
temperatures (from −5 to +5 ◦ C) waxes are practically insolu- recovery. The advantage of this scheme coupled to heat exchang-
ble in CO2 , whereas, the other compounds maintain very large ers networking is in the reduction of energy consumption in the
solubilities. Therefore, it is possible to fractionate the extract overall extraction process [90].
operating, for example, the extraction at 90 bar, 40 ◦ C and, then,
performing a first separation, for example, at 0 ◦ C, 90 bar, and 2.3. High added value compounds
a second separation at 15 ◦ C and 20 bar. In this manner, in the
first separator the selective precipitation of waxes is obtained The list of high added value compounds (mainly nutraceuti-
and no precipitation of the other extracted compounds occurs, cals and pharmaceuticals) is reported in Table 2. A large spec-
whereas, in the second separator, essential oil is recovered. An trum of compounds can be inserted in these categories, since
industrial plant (V = 1200 dm3 ) that uses this process arrange- food additives with nutritional and pharmaceutical properties
ment has been constructed and successfully operated (Essences, (nutraceuticals) range from tocopherols to carotenoids to alka-
Italy). It is not possible to perform the extraction directly at 0 ◦ C loids to unsatured fatty acids. Pharmaceutical compounds like
and 90 bar, since the vegetable matter contains many other com- Artemisinin (antimalaric drug), to Hyperforin (antidepressant
pound families (antioxidants, colours, etc.) that are soluble at drug), to sterols can be extracted from various matters. Pesticides
Table 1
SFE of oleoresins (OR), essential (EO), volatile (VO) and seed (SO) oils
Raw material Botanical name Extract References
Anise seeds Pimpinella anisum L. EO [91]

Bacuri fruit shells Platonia insignis Mart. EO [92]
Basil leaves Ocimum basilicum EO [69,93]
Borage seeds Borage officinalis L. SO [41,85]
Cashew Anacardium occidentale VO [36,94]
Celery roots Apium graveolens L. SO [28,86]
Chamomile flowers Chamomilla recutita L. R. EO and OR [95]
Clove bud Eugenia caryophyllata EO [19]
Coriander seeds Coriandrum satium L. SO [87]
Eucalyptus leaves Eucalyptus globulus L. EO [17]
Fennel seeds Foeniculum vulgare Mill. SO [22]
Grape seeds Vitis vinifera SO [59]
Hiprose seeds Rosa canina L. SO [68,88,89]
Juniper fruits Juniperus communis L. VO [96]
Laurel leaves Laurus nobilis EO [20]
Lemon balm Melissa officinalis EO [22,27,97]
Lemon bergamot Monarda citriodora EO [97]
Lemon eucalyptus Eucalyptus citriodora EO [97]
Lemongrass leaves Cymbopogon citrates EO [97,98]
Lovage leaves and roots Levisticum officinale Koch. EO [28,69,99,100]
Marjoram leaves Origanum majorana EO [101]
Mint leaves Mentha spicata insularis EO [21,93]
Oregano Origanum vulgare L. EO [67,69,93,102,103]
Palm kernel oil Elaeis guineensis SO [104,105,106]
Pennyroyal Mentha pulegium L. EO [56]
Pepper, black Piper nigrum L. EO [107,108]
Pepper, red Capsicum frutescens L. OR [109]
Rye bran Secale cereale Alkylresorcinols [73]
Sage leaves Salvia desoleana EO [21,69]
Spiked thyme Thymbra spicata EO [110]
Star anise Illicium anisatum EO [19]
Thyme Thyme zygis sylvestris EO [111]
Tuberose concrete Nepeta Tuberosa L. EO [18]
Vernonia seeds Vernonia galamensis SO [71]
or insecticide principles are widely diffused in the vegetable strong obstacle to extraction, since these materials are very fre-
matter and, if extracted by SFE could be used in the biological quently located well inside complex cellular structures and can
agriculture. also be linked to the solid matrix.
Another kind of extraction process is the elimination of pollu- Their extraction by SCFs from various sources has been
tants and pesticides from natural matter in which they obviously studied by several authors [25,32,53,63,64,72,118,136,138–
exert a detrimental effect. These products are outside the scopes 140,150,151,164–169]. Depending on the particular compound
of this work; but, they represent another interesting application studied (molecular weight and number of polar bounds), they
of SFE [65,66,112]. show very low or moderate solubilities in SC-CO2 . Therefore, in
In the following, some relevant cases, that have been recently several cases SC-CO2 added with a co-solvent has been proposed
studied, are discussed in the detail. as the supercritical extraction medium. The most frequently pro-
posed co-solvent is ethyl alcohol since its presence (in traces) in
2.3.1. Nutraceuticals: Lycopene and Astaxanthin the final extracts does not compromise the use in nutraceutical
Carotenoids are a large family of compounds that possess or pharmaceutical applications. However, it is better, when it is
antioxidant and colouring properties and are investigated for possible, to avoid the use of a liquid co-solvent that tends to
food, cosmetic and medical applications. They are contained repropose the problem of solvent elimination from the extracts.
in a large variety of natural sources: vegetables, animals, bac- Most carotenoids are polyunsaturated hydrocarbons contain-
teria, yeasts, microalgae. Traditional carotenoids extraction is ing 40 carbon atoms and two terminal ring systems. Carotenoids
performed by organic solvents with the well-known problems that are composed entirely of carbon and hydrogen are called
of selectivity and organic solvents usage and pollution. Pre- carotenes, whereas, those that also contain oxygen are called
treatments of the starting material play a relevant role in the xanthopylls.
efficiency of the extraction process: crushing, freeze drying, Lycopene is a carotene with relevant antioxidant properties
enzymatic cell degradation have been proposed. The problem and can have a protective effect against various chronic illnesses
is to reduce the internal mass transfer resistance that opposes a (like coronary heart disease and cancer). The major sources of
Table 2
SFE of high added value compounds
Aloe vera leaves Aloe barbadensis Miller ␣-Tocopherol [51]

Animal liver Benzimidazoles [113]
Anise verbena Lippia alba Limonene and carvone [114,115]
Apricot pomace Prunus armeniaca ␤-Carotene [72]
Artemisia Artemisia annua L. Artemisinin [116]
Boldo leaves Peamus boldus M. Boldine [44,117]
Bupleuri radix Bupleurum kaoi Liu Saikosponins [31]
Buriti fruit Mauritia flexuosa Carotenoids and lipids [118]
Cape ash Ekebergia capensis Sparrm. Oleanolic acid and 3-epioleanolic [119]
acid
Chamomile Matricaria recutita Flavonoids and terpenoids [54]
China smilax Smilax china L. Sapogenins [61]
Cocoa beans Theobroma cacao Caffeine, theobromine [120]
Cocoa beans Theobroma cacao Methylxanthines [53]
Cocoa beans Theobroma cacao Cocoa butter [121]
Coffee powder Coffea arabica Coffee aroma [122]
Coneflower Echinacea angustifolia Alkylamides [123]
Coriander seeds Coriandrum sativum Tocopherols, flavonoids and [124]
terpenoids
Crustaceans Astaxanthin [125]
Dandelion leaves Taraxacum officinale ␤-Amyrin and ␤-sitosterol [126]
Dill Anethum graveolens Tocopherol [127]
Espinheira Santa Maytenus ilicifolia Squalene, vitamin E, [128]
Stigmasterol
Eucalyptus leaves Eucalyptus camaldulensis Gallic and ellagic acids [45]
var. brevirostris
Feverfew Tanacetum parthenium Parthenolide [129]
Fresh bay Laurus nobilis Tocopherol [127]
Ginger Zingiber officinale Roscoe Gingerols and shogaols [46,47]
Ginkgo Ginkgo biloba L. Ginkgolides and flavonoids [60,70]
Green tea Cratoxylum prunifolium Catechins [58]
Guaranà seeds Paullinia cupana Caffeine [53,130]
Hawthorn Crataegus sp. Flavonoids and terpenoids [54]
Horsetail Equisetum giganteum L. Oleoresin [131]
Indian almond leaves Terminalia catappa L. Squalene [132,133]
Kava roots and steams Piper methysticum Lactones [62]
Marigold Calendula officinalis Flavonoids and terpenoids [54]
Marjoram Origanum majorana L. Carotenoids and chlorophylls [25]
Marjoram Origanum majorana L. Phenolic and Triterpenoid [134,135]
antioxidants
Matè leaves Ilex paraguariensis Caffeine, Vitamine E, [53,136]
theobromine and stigmasterol
Mexican sunflower Tithonia diversifolia Tagitinin C [137]
Microalgae Botryococcus braunii Alkadienes [138]
Microalgae Chlorella vulgaris Canthaxanthin and Astaxanthin [138]
Microalgae Nannochloropsis gaditana Carotenoids and chlorophyll [139]
Microalgae Spirulina maxima Carotenoids and fatty acids [140]
Microalgae Dunaliella salina ␤-Carotene [138]
Microalgae Arthrospira maxima ␥-Linolenic acid [138]
Microalgae Haematococcus pluvialis Astaxantine and phycocyanine [141]
Milk Thistle Silybum marianum Tocopherol [142]
Moso-Bamboo Phyllostachys heterocycla Ethoxyquin A, sesquiterpene A [52]
and cyclohexanone A
Moutan Paeonia suffruticosa Paeonol [143]
Neem seeds Azadirachta indica A. Juss Nimbin, salannin and [144–147]
azadirachtin
Olive leaves Olea europa Polyphenols [43]
Olive tree leaves Olea europa Tocopherol [148]
Onion Allium cepa L. Onion flavour [24]
Pandanus mealybug Pandanus amaryllifolius 2-Acetyl-1-pyrroline [149]
Roxb.
Paprika Capsicum annuum L. Carotenoids, tocopherols and [150,151]
capsaicinoids
Parsley Petroselinum crispum Tocopherol [127]
Table 2 (Continued )
Poultry feed, eggs and muscle tissue Nicarbazin [152]

Propolis Resina propoli Flavonoids, galangin and caffeic [30]
acid phenethyl ester
Pyrethrum flower Chrysanthemum Pyrethrins [33,34,153]
cinerariifolium
Red grape pomace Vitis vinifera Agiorgitiko Phenolic antioxidants [154]
Red yeast Phaffia rhodozyma Astaxanthin [64]
Rice Tocopherols, tocochromanols and [155]
oryzanols
Rosemary Rosmarinus officinalis L. Rosmanol, carnosic acid and [37–39,42,47,156–159]
carnosol
Sage Salvia officinalis L. Carnosolic acid [29]
Savory Satureja hortensis L. Oil [26]
Saw Palmetto berries Serenoa repens Fatty acids and ␤-sitosterol [62]
Sesame seeds, black Sesamum indicum L. Sesamol, sesaminol and [160,161]
␣-tocopherol
Soybean flour Glycine max Isoflavones [50]
Soybean lecithin Glycine max Phosphatidylcholine [74,75]
Spearmint Mentha spicata Tocopherol [127]
St. John’s Wort Hypericum perforatum L. Hyperforin [162,163]
St. John’s Wort Hypericum perforatum L. Phloroglucinols [57]
St. John’s Wort flowers Hypericum perforatum L. Hyperforin and Adhyperforin [62]
Stevia leaves Stevia rebaudiana Bertoni Glycosides [49]
Stinging nettle Urtica dioica L. Carotenoids and chlorophylls [63]
Sweet grass Hierochloe odorata 5,8-Dihydroxycoumarin and [40]
5-hydroxy-8-O-␤-d-
glucopyranosyl-benzopyranone
Tomato Lycopersicon esculentum Lycopene [32,16,46,162]
Tomato Lycopersicon esculentum Lycopene and ␤-carotene [167–169]
Turmeric Curcuma longa L. Curcumin and curcuminoids [47,48]
Wheat germ Triricum aestivum Vitamin E [170]
Wu-wei-zi Schisandra chinensis Deoxyschisandrin [143]
Lycopene are ripe tomatoes, tomato products and by products Therefore, its extraction can be difficult due to strong inter-
(skins). SFE of Lycopene has been performed using pure SC- nal mass transfer resistances. It is possible that an increase
CO2 [164,167] and with co-solvents [32,166,168,169]. The use of extraction temperature contributes to the degradation of
of appropriate co-solvents (acetone [166], ethanol [169], chlo- chromoplasts.
roform [168], seed oil [32]) increases the extraction rate but has,
as a rule, a negligible influence on the final yield of Lycopene.
Therefore, using pure SC-CO2 at higher pressures can be suf-
ficient to compensate the absence of co-solvent and has the
advantage of producing a solvent free extract.
At pressures lower than about 250 bar, operating at 40 ◦ C,
the extraction of Lycopene is negligible [168]. The yield largely
increases with pressure due to the increase of Lycopene solubil-
ity in the supercritical solvent. From the analysis of the literature,
the parameter that mainly controls Lycopene extraction is the
extraction temperature. Indeed, several authors [32,165–168]
found a very strong increase of Lycopene yield with temper-
ature and decided to operate up to a maximum of 110 ◦ C, as
shown in Fig. 1 [166]. This effect is surprising since they did
not find a similar dependence on temperature for the extraction of
␤-carotene that is also contained in tomato products [167]. The
authors tried to explain this dependence on temperature con-
sidering the increase of SC-CO2 diffusivity with temperature
and an increase of Lycopene vapor pressure; but no explanation
seems completely convincing. Lycopene is contained into veg- Fig. 1. Relative recoveries of Lycopene from tomato skins at different temper-
etable structures called chromoplasts in form of large crystals. atures (adapted from [166]).
Particle size of the ground matter and supercritical solvent compounds co-extracted has not to be underestimated: overall
flow rate are two parameters that can help in understanding extraction yields up to 30% (w/w) of the raw material loaded in
where mass transfer is located (as previously discussed). As a the extractor can be obtained, for example, in the case of yeasts.
rule, the decrease of particle size increases the extraction rate; Therefore, it is worth of note the indication given by Lim et
however, Sabio et al. [167] found a decrease of Lycopene extrac- al. [64] that fractional extraction, performed at two consecutive
tion yield at lower particle size and explained (correctly) this extraction steps at 300 and 500 bar, can increase the Astaxanthin
effect with in-homogeneities along the extraction bed due to concentration in the extracts in the second step up to 10 times;
caking (channelling) of the bed when too small particles were indeed, most of the undesired compounds have been extracted
used. during the first extraction step performed at lower pressure, at
Of course, Lycopene is not the only compound extracted from which Astaxanthin has very low solubility in the supercritical
tomatoes when a SC-CO2 based solvent is used. ␤-Carotene solvent.
and large quantities of lipidic compounds are also co-extracted
[167]. When compared to organic solvent extraction, the various 2.3.2. Pharmaceuticals: Hyperforin
authors found different maximum relative yields in Lycopene, St. John’s wort (Hypericum perforatum) extracts have well
ranging from 53.9% [169] to about 80% [167] to almost 90% known antidepressant properties. Despite the evident clinical
[164] relative yields, the maximum yield being influenced by effects, there is still a controversy regarding the active princi-
the maximum pressure and temperature used. ple of the extracts. Some authors attribute the antidepressant
Astaxanthin is a xanthopyll and its extraction has been pro- activity to Hypericin and its derivatives, whereas, some stud-
posed from various materials as red yeast (Phaffia rhodozyma) ies support the effect of Hyperforin. However, Hypericin is not
[64], microalgae (Chlorella vulgaris [138], Haematococcus plu- extracted by SC-CO2 , even when ethanol is used as co-solvent
vialis [141]), crayfish (crustaceous) [125]. The various authors [62]. Rompp et al. [162] tested the extraction of Hyperforin by
found that pre-treatments oriented at the decrease of particle size SC-CO2 from plant particles in the pressure range 90–160 bar
and/or at the destruction of cell walls are relevant in determin- at 40 and 50 ◦ C, varying CO2 flow rate and operating at vari-
ing the yield and the extraction rate. Particularly, cell walls of ous extraction times. They substantially found that an increase
microalgae have a polymeric structure that strongly obstacles of the extraction pressure leads to a decrease of Hyperforin
the extraction of internal compounds [138]. concentration in the products, due to an increase of undesired
The increase of pressure is also relevant in the extraction compounds co-extraction. Moreover, the variation of solvent
efficiency: operation at pressures larger than 200 bar shows a flow rate showed no significant effect on the extraction yield and
marked increase of extraction rate and yield. Pressures up to Hyperforin content, thus confirming that internal mass transfer
500 bar have been tested, and the maximum yield was identified controls the extraction process.
at this pressure value. Catchpole et al. [62] performed this extraction using liq-
The effect of temperature is relatively less relevant and tem- uid CO2 , SC-CO2 and SC-CO2 plus ethanol as co-solvent (up
perature higher than 50–60 ◦ C are also not indicated to avoid to 10 mass%). Using SC-CO2 plus ethanol they obtained an
extract degradation. Ethanol has been used as co-solvent: it is increase of the total yield with respect to the case of SC-CO2
the only one allowed organic solvent for nutraceutical and phar- alone (at the same extraction conditions: 300 bar, 40 ◦ C) but
maceutical purposes. Valderrama et al. [141], using pressures only a slight increase of Hyperforin extraction was observed.
up to 300 bar, found a strong influence of ethanol addition (up The comparison of the first separator St. John’s Wort oil yield
to 9.4%) on Astaxanthin extraction. The authors that operated in the case of SC-CO2 and liquid CO2 is reported in Fig. 2.
up to 500 bar found, instead, only a marked influence of the co- About the possibility to extract Hypericin, it should be possi-
solvent (percentages up to 15 vol.%) on the extraction rate [64], ble (in principle) to extract this drug using a liquid solvent on the
since the solubility of Astaxanthin in SC-CO2 is larger at higher vegetable matter and, then, to process the obtained solution by
pressures and compensates the absence of co-solvent. Super- antisolvent extraction. In this case, the liquid solvent is extracted
critical solvent flow rate showed only a slight influence on the and insoluble Hypericin is precipitated (see for further details in
extraction yield. the chapter on supercritical antisolvent extraction).
Considering the results in the overall, it is confirmed that
these processes are conditioned by the internal mass transfer, 2.3.3. Pesticides: Pyrethrins and Azadirachtins
as suggested by the strong effect of grinding and of the other Pesticides of biological origin are very effective, non-toxic
pre-treatments and by the negligible influence of supercritical for warm blood animals and have very short degradation times
solvent flow rate. The relatively low solubility of Astaxanthin in the presence of air and light. An example of plant contain-
in SC-CO2 also plays a relevant role: high extraction pres- ing biopesticides is pyrethrum that has a strong action against
sures are required to obtain a good extraction performance and insects and is highly biodegradable. Pyrethrins are the six insec-
the addition of a polar co-solvent increases the extraction rate, ticide components that form the biopesticide: they are readily
since it increases the solubility of Astaxanthin in the solvent soluble in SC-CO2 even at near critical conditions. Therefore, it
mixture. is possible to extract these compounds operating, for example,
Some authors reported a good Astaxanthin extraction yield, at 90 bar, 40 ◦ C [153]. Higher pressures are not required, since
when compared to its initial content in the matrix (up to 97%) they induce the co-extraction of undesidered compounds. This
[141]; however, the problem of the very large quantity of lipidic concept is evident in Fig. 3 where it is reported the overall and
the beads with a film of this material. This process is very

similar to the extraction of volatile oils from flower concretes
[11,16,18]. It allows to work with more concentrated samples
and at controlled conditions inside the extractor. Process condi-
tions are similar to those adopted for the extraction from ground
flowers.
Neem seeds possess a well-known pesticide activity due
to the presence of various active principles collectively called
Azadirachtins that are tetranortriterpenoids formed by a group
of closely related isomers such as Salannin, Gemudin and
Nimbin. Nimbin has also several valuable medicinal proper-
ties [144]. The extraction of these principles using SC-CO2 has
been studied by various authors [144–147]. The first step is, of
course, seeds grinding and pressing to extract the seed oil. Oil
yields between 25 and 30% (w/w) of the starting material have
been reported. In this step, small quantities of Azadirachtins
are also extracted. The second step is SFE that can be per-
formed at 250–300 bar and 40–50 ◦ C. The SFE product can
contain up to 10,000 ppm of Azadirachtins. This process has also
Fig. 2. St. John’s Wort oil yield as a function of CO2 flow rate at two different been proposed on the industrial scale by Essences srl, Salerno,
extraction conditions (adapted from [62]).
Italy.
Tonthubthimthong et al. [144] concentrated their attention
Pyrethrins only extraction yield. When a second extraction step to Nimbin extraction. Concentration of Nimbin in the extracted
at 200 bar and 40 ◦ C is performed, the yield of Pyrethrins has oil was measured by selectively extracting this compound using
no further increase and only undesired compounds are extracted. methanol. Some experiments of active principles extraction have
The fractional separation of the extracts to eliminate co-extracted also been performed adding methanol to SC-CO2 [145,147] in
waxes is, however, required; i.e., the process is very similar to the attempt to obtain more solvent power towards Azadirachtins.
that previously described for essential oils isolation. To eliminate According to Johnson and Morgan [147], 20% methanol is
this problem, Kiriamiti et al. [34] proposed a SC-CO2 washing very effective in this extraction and reduced pressures with
of ungrounded pyrethrum flowers to preliminary extract part of respect to SC-CO2 alone can be used (137 bar). However, Ton-
cuticular waxes. thubthimthong et al. [141] found that methanol is not an effective
A variation of this process has been proposed by Kiriamiti modifier for the selective Nimbin extraction.
et al. [33] that used as the starting material dried crude hexane
extract of pyrethrum flowers that was loaded in the extractor 2.4. Mathematical modelling
mixed with 1 mm glass beads. They obtained the coverage of
Mathematical modelling allows a rational approach to the
extraction problem, giving the opportunity to generalize the
experimental results, and, if successful, to obtain indications
about systems different from those studied (simulation). More-
over, it is useful in the development of scaling-up procedures
from laboratory to pilot and industrial scales. For these reasons
several attempts at mathematical modelling of SFE have been
presented in the literature [2,171,172].
A model should not be a mere mathematical instrument, but
should reflect the physical insight arising from the knowledge of
the solid structure and from experimental observations. Mathe-
matical models, which have no physical correspondence to the
materials and the process studied are of limited validity, although
they can be used to fit some experimental data.
Three different approaches have been proposed for the
mathematical modelling of SFE: (1) empirical [173,174],
(2) based on heat and mass transfer analogy [175,176], and
(3) differential mass balances integration [171,177,178]. The
most proper analysis is obtained from the integration of the
differential mass balances: time dependent concentration
Fig. 3. Overall extraction yield (squares) and Pyrethrins yield (circles) against profiles are obtained for fluid and solid phase. The extraction
the extraction time during a multistep extraction (adapted from [153]). curve is calculated from the fluid phase concentration at the
the grinding process. Their shape can influence the diffusion

of the supercritical solvent [35,171].
From the point of view of the extraction mechanisms, other

considerations are necessary. The equilibrium may exist if:
(a) the material is largely available;

(b) it is distributed on or near the surface;
(c) the kind of equilibrium will depend on the interactions (if
any) with the solid structure.
Mass transfer resistances, in general, may be of two types:

external or internal (and in this case, various possibilities have to
be considered). To take into account mass transfer resistances,
differential mass balances are applied.
Fig. 4. SEM image of a section of sunflower seed. Up to now, mathematical modelling has been mainly applied
to the extraction of seed oils, essential oils or volatile compounds
extractor outlet.In facing mathematical modelling of SFE, and to the adsorption/desorption of terpenic model mixtures
several general aspects have to be taken into account: [181–183], since more data exists in the literature for these pro-
cesses. Materials for which mathematical modelling of SFE has
(a) Solid material structure been attempted are reported in Table 3. We have also indicated if
The knowledge of the botanical aspects and/or optical the model is based on empirical kinetic equations, on the anal-
microscope or scanning electron microscope (SEM) analy- ogy between heat and mass transfer (HMT) or on differential
sis of the material are necessary to visualize its structure. For mass balances integration (DMBI) along the extraction bed or
example, seeds are essentially formed by specialized struc- on a single particle.
tures that operate as small recipient containing the oil. Their Reverchon et al. [179,184,190,192] used scanning electron
shape and structure change seed by seed; but the general microscope to observe broken cells on seed particles surface.
organization is always the same. An example of seed struc- They assumed that broken cells form a single layer, and were
ture observed by SEM is reported in Fig. 4 and evidences able to calculate volumetric broken-to-intact cell ratio and thus
the typical oil bearing structures in the case of sunflower to reduce the number of model parameters to be evaluated from
seed [35,179]. extraction curves. The concept of broken and intact cells was
(b) Location of the compounds to be extracted combined with equilibrium relationship for either free solute
The distribution of the solute within the solid substrate [205,206] or solute interacting with matrix [177,180]. Both types
may be very different. The extractable substances may be of equilibrium were also assumed to occur simultaneously by
free on the surface of the solid material or inside the struc- various authors, the free solute in broken cells and the interact-
ture of the material itself. For example, essential oil can be ing solute in intact cells [179,180,184,190,192]. In one of these
located near the leaf surface in glandular trichomes and/or papers [179], an extensive analysis was performed for six seed
into vacuoles; i.e., intracellular structures located well inside oils extraction using data from literature. The model was first
the leaf [35,180]. validated and then used to simulate several possible cases of
(c) Interactions of solutes with the solid matrix extraction.
Depending on the interactions between the compounds Sovová [172] proposed a general model approach applied to
and the solid structure, different equilibria may be involved. seed oil and essential oil extraction. The model is based on the
Indeed, if the material has no interactions with matrix, equi- division of the process in two extraction periods: the first one
librium solubility has to be taken into account. The material governed by phase equilibrium and the second one by internal
can be adsorbed on the outer surface or inside the solid struc- diffusion in particles, taking into account the concept of broken
ture. In this case, a partitioning equilibrium between solid and intact cells to explain the sudden reduction of the extraction
and fluid phase will occur. rate after the first extraction step. This effect is particularly evi-
(d) Broken-intact cell structures dent in the case of seed oil extraction. The new feature of the
Part of the compounds to be extracted may be near the model is the description of the first extraction period considering
surface of the structure, due to cell breaking during grind- different types of phase equilibria: independent on matrix (sol-
ing. This case is characteristic of grinded seed particles: a ubility equilibrium), adsorbed on the matrix (partition between
non-negligible part of the oil is free on particles surface. the two phases) and different flow patterns, mainly dispersion.
Moreover, membranes modifications may occur due to dry- The model has been verified on data sets from literature, related
ing, freeing part of the soluble material. to seeds (almond) and essential oils (orange peels, pennyroyal).
(e) Shape of particles This model presents a limit in the case of essential oils extrac-
Particles may be spherical, plate-like, etc. as a result of the tion, when the extractable material is located only inside the
original shape of the material (for example, leaves) and of matrix: the concept of broken (in the surface) and intact cells
Table 3
Mathematical modelling of SFE from natural matter
Raw material Extract Type of model References
Almond seeds Seed oil DMBI [179,184]

Atlantlic mackerel Fish oil HMT (single sphere model) [185]
Basil leaves Essential oil DMBI [186]
Blackcurrant seeds Seed oil DMBI [187]
Caraway seeds Essential oil DMBI [186]
Clove bud Essential oil DMBI [188]
Coriander seeds Seed oil DMBI [179]
Cupuacu seeds Fat components DMBI [189]
Fennel seeds Essential oil DMBI [179,190]
Ginger rhizomes Oleoresin DMBI [191]
Grape seeds Seed oil DMBI [179,187]
Hiprose seeds Seed oil DMBI [192]
Jalapeno pepper flakes Oleoresin DMBI [193]
Lavender flower Essential oil DMBI (shrinking-core) [194]
Marigold Oleoresin Various models proposed [195]
Marjoram Essential oil DMBI [186]
Neem seeds Nimbin Empirical models [145]
Olive husk Husk oil Various models proposed [196]
Orange flower concrete Volatile oil DMBI [197]
Oregano bracts Essential oil HMT (single plate model) [35]
Palm oil Carotene and lipids DMBI [198]
Parsley seeds Seed oil DMBI [199]
Peanut Seed oil DMBI [179]
Pennyroyal Essential oil DMBI [180]
Pepper, black Essential oil DMBI [200]
Plane tree leaves Mannitol DMBI [201]
Rosemary leaves Essential oil DMBI [186]
Soybean lecithin mixture Phosphatidylcholine DMBI (shrinking-core) [202]
Sunflower seeds Seed oil DMBI [179,203,204]
Tomato seeds Seed oil DMBI [179]
(inside the particle) is no more applicable and the first part of fractional desorption of bergamot peel oil [181] describing a
extraction controlled by equilibrium does not apply. two steps desorption process with the first step performed at
Gaspar et al. [35] modelled the extraction of oregano essential 40 ◦ C, 75 bar to desorb hydrocarbon terpenes and the second step
oil. The model is based on the prevalent geometry of particles: at 40 ◦ C, 200 bar to desorb the oxygenated compounds. Later,
those obtained from leaves tend to maintain a plate-like geom- Reverchon et al. [183] also modelled the selective adsorption
etry. Mass balances on the particle have been proposed. on silica gel of a complex terpenic mixture formed by 13 com-
Mathematical modelling of SFE has also been proposed ponents. The mixture was divided in four families considered
for some other materials. Wu and Hou [207], for example, as four pseudo-key components. The integration of differential
proposed the extraction of egg yolk oil (cholesterol, glyc- mass balances gave account of the competition among the dif-
erides and moisture) from egg yolk powder with the scope ferent compounds for the occupation of the adsorption sites and
of producing a matrix (solid residue) rich in phospholipids of displacement effects observed at the exit of the adsorption
and proteins. Optimum extraction conditions were found at bed.
55 ◦ C and in the pressure range between 280 and 360 bar. They Flowers concrete is obtained from the dried hexane extract of
applied differential mass balances integration to the egg powder fresh flowers. It is formed by essential oil, colouring matter and
fixed bed. large quantities of cuticular waxes. A fractional extraction pro-
Adsorption–desorption processes can also be treated as cess has been proposed in which the flower concrete is melted
extraction processes: adsorption–desorption isotherms being the and mixed with glass beads, obtaining an inert core (glass)
equilibrium curves due to interactions of the solutes between that supports a given layer of concrete. This process has been
the solid matrix and the fluid phase. Differential mass bal- used successfully for the fractionation of several flower con-
ances also in this case can describe the extraction process. cretes [11,16,18]. Mathematical modelling has been performed
This approach has been used by Reverchon [182] to model the [197,208]. The volatile oil has been considered to be a mixture
selective desorption from silica gel of two key compounds of of four compound families (pseudo-components) extracted from
essential oils: limonene (representative of the hydrocarbon ter- an active layer of concrete on a spherical inert core. Modelling of
penes fraction) and linalool (representative of the oxygenated oxygenated terpenes and oxygenated sesquiterpenes extraction
terpenes fraction). Then, the model has been extended to the was obtained.
3. Liquid feed processing theoretical equilibrium stages required for separation can also
be applied.
The fractionation of liquid mixtures in two or more fractions A possible variation of this processing scheme can consist of
is another relevant process. In a typical apparatus, two pumps the adoption of a temperature profile along the column with the
deliver the liquid solution and SC-CO2 to the packed column. aim of optimising the separation temperature with respect to the
The packing is an inert material characterized by a large spe- composition of the mixtures at different levels inside the column.
cific surface whose scope is to favour the contact between the The extraction of liquid mixtures is controlled by the rela-
liquid and the supercritical fluid. SC-CO2 as a rule flows along tive solubilities in SC-CO2 of the various compounds forming
the column from the bottom to the top, whereas, the liquid solu- the mixture that is the thermodynamic limitation of the process.
tion is usually added to the top. However, it is also possible Mass transfer between the two phases represents the kinetic limi-
to feed the liquid at an intermediate position along the column tation. The distance from the equilibrium condition is the driving
and to add a recycle of part of the fluid phase exiting at the force for the separation along the column.
top.
3.2. Examples of application
3.1. Selection of the operating parameters
The fractionation of liquid mixtures by SFE has been pro-
The process is based on the different solubilities of the liquids posed for various applications, as it can be seen in Table 4.
to be separated in SC-CO2 . The ideal case is obtained when only Two examples will be treated in details in the following:
the compounds to be extracted are soluble in SC-CO2 , whereas, hexane elimination from vegetable oils that represent a new
all the other liquid components are completely insoluble. How- approach to seed oils extraction and fried oil fractionation to
ever, this case is rare and a limited solubility of the other liquid recover reusable compounds.
compounds forming the mixture has to be taken into account.
For this reason, pressure and temperature of the process have to 3.2.1. Hexane elimination from seed oils
be accurately chosen to select the conditions at which there is This process represents a different approach to the supercrit-
the maximum difference in solubility among the compounds to ical extraction of seed oils. Indeed the supercritical extraction
be extracted and all the other compounds in the mixture. Also applied directly to seeds suffers the disadvantage of high costs
in this case, CO2 density is frequently used as a criterion to find due to the use of large pressurised vessels and to the intrinsic dis-
the conditions of maximum selectivity. continuous operation. If the approach is to treat the liquid hexane
The difference in density between the liquid and SC-CO2 is oil mixture after the traditional hexane extraction (composition
another parameter to be taken into account: to allow the counter- 70% hexane–30% oil), it is possible to use smaller apparatuses
current operation, SCF density has to be lower than the one of and a continuous operation that allows the processing of large
the liquid mixture. quantities of the raw mixture.
The traditional operation of packed columns requires that Hexane and triglycerides are both soluble in SC-CO2 , but
liquid flow rate will be larger than the minimum amount that at a temperature of 40 ◦ C, hexane is completely miscible for
assures the complete wetting of the packing. The feed ratio is pressures larger than about 100 bar, whereas, at the same temper-
also selected to avoid the massive entrainment of the liquid in ature, triglycerides show a non-negligible solubility in SC-CO2
the fluid phase (flooding). These conditions have to be respected only for pressures larger than about 250 bar. Therefore, these
also when a supercritical fluid is used as the fluid-processing compounds can be separated, operating in a packed tower at low
medium. The classical calculation in terms of the number of pressures (<200 bar).
Table 4
Fractionation of liquid mixtures by SFE in continuous (C) and semicontinuous (SC) plants
Initial mixture Material to be recovered Process References
Acetic acid + water Acetic acid C [209]

Alcoholic drink Brandy aroma C [210,211]
Citrus peel oil key mixture Limonene and linalool C [212]
Citrus oil Limonene C [213]
Edible oil model mixtures Squalene C [214,215]
Fish oil Vitamin A palmitate C [216,217]
Fried oil Triglycerides C [218]
Glyceride mixtures Lipids SC [219]
Hexane + soybean oil Soybean oil C [220]
Olive leaves + hexane Squalene, ␤-carotene, tocopherol C [221]
Olive oil Squalene C [222]
Olive oil Squalene, tocopherols C [223]
Origanum oil Deterpenation SC [224]
Orange juice Antioxidants C [225,226]
Shark liver oil Squalene C [222,227]
Using these concepts, the fractionation of soybean oil–hexane The supercritical antisolvent extraction (SAE) process is con-
mixtures has been successfully performed using a 1.8 m tall ceptually very similar to supercritical antisolvent micronization
packed tower, charged with stainless steel perforated saddles (SAS); but the scope of the process is the recovery of one or more
with a very large specific surface. The extraction has been per- solid compounds from a liquid mixture. It consists of the contin-
formed at 120 bar, 40 ◦ C using different starting concentration uous flow of SC-CO2 and of the liquid mixture in a pressurized
of soybean oil in hexane. A single passage in the packed tower precipitation vessel. If the process conditions have been prop-
allowed to obtain a bottom product formed by soybean oil con- erly selected, the liquid is rapidly dissolved in the supercritical
taining down to 20 ppm of hexane residue and to recovery pure fluid, whereas, the solid precipitates at the bottom of the pre-
hexane at the top of the column [220]. cipitation vessel. Therefore, in a possible representation of the
process two pumps deliver the liquid solution and the supercriti-
3.2.2. Fried oil fractionation cal fluid, respectively. The precipitation vessel is used to collect
The fractionation process using SC-CO2 can be used to purify the solid and a vessel located downstream the precipitator and
used fried oils. A selective separation of the oil components operated at lower pressure (for example, 30 bar and 25 ◦ C) is
based on their polarity and molecular weight can be attained, used to recover the liquid.
since the degradation compounds are mainly peroxides and poly-
mers of the original tryglicerides mixture. The SC-CO2 purifi- 4.1. Selection of the operating parameters
cation of peanut oil used for frying has been studied using the
continuous fractionation in a packed column. The influence of The first step of this process is the formation of a spray of the
pressure (150–350 bar) and temperature (25–55 ◦ C) on the yield liquid solution. The scope of this operation is to produce a very
and on the composition of top and bottom products was stud- large liquid surface due to the formation of small liquid droplets
ied. Process conditions were selected to separate triglycerides to strongly enhance the rate of solubilization of the liquid phase
from degraded compounds and experimental results indicated in the supercritical medium. For the same reason, the process is
that the operating conditions leading to maximal triglycerides performed at operating conditions at which the liquid solvent is
recovery in the extract were 350 bar, 55 ◦ C, and a solvent-to- completely soluble in SC-CO2 . The knowledge of solubility data
feed ratio of 53. Operating at these conditions, it was possible on the liquid solvents and of the solids in SC-CO2 is mandatory
to recover 97% of the triglycerides feed to the column and for this process for the proper selection of process temperature
approximately 52 wt.% of the used fried oil. The composition and pressure.
of the purified top stream was very similar to that of fresh fried In the case of SAE, the interactions between thermodynamic
oil [218]. constrains and mass transfer mechanisms also control the pro-
cess performance. The enhanced mass transfer that characterizes
3.3. Mathematical modelling SCFs is again a distinctive advantage of their use as extraction
media, together with the fast and complete separation by sim-
Mathematical modelling of counter-current packed column ple depressurisation between the supercritical solvent and the
has been studied only by a few authors [228–232] and only liquid.
in some cases with reference to natural matter fractionation A limitation of this process is the possible formation of a
[228,231]. ternary mixture liquid/solid/SC-CO2 . Indeed, the presence of
The most interesting work is the one proposed by Ruivo et the liquid can induce an increase of the solubility of the solid
al. [228], which performed the dynamic modelling and simula- compounds in SC-CO2 . In this case, the liquid can act as a co-
tion of a packed column. They used the experimental data on solvent from the point of view of the solid solubilization. When
a model binary mixture formed by squalene and methyl oleate, this phenomenon occurs, the part of solid retained in the fluid
fractionated using SC-CO2 . The model was formed by a set of phase obviously does not precipitate and is lost in the liquid
partial differential equations that correspond to the differential recovered in the separation vessel. The limit case is the complete
mass balances on the packed column and algebraic equations solubilization of the solid in the fluid phase that produces the
that describe the mass transfer, the hydrodynamics of the two- process failure.
phase flow through the packings and the ternary thermodynamic
equilibrium for the studied system. The column was considered 4.2. Examples of application
at constant temperature. A fair good agreement was obtained
between measured and predicted composition profiles of the Antisolvent extraction until now has been used in a limited
outlet streams over the time. number of processes (see Table 5) but it has a large potential
for future applications. Some examples will be described in the
4. Antisolvent extraction details: lecithin extraction from soybean oil, propolis tincture
fractionation and tobacco proteins separation.
The recovery of solid compounds from a liquid mixture
requires different process approaches since the fixed bed extrac- 4.2.1. Lecithin extraction from soybean oil
tor is not adapt to process liquid mixtures and the packed tower Crude lecithin, in general, contains a minimum of 35 wt.%
cannot be used in these cases since precipitation of the solid oil, which needs to be reduced to less than 2 wt.% oil before it
compounds will be obtained on the internal packings. can be used as an emulsifier. The crude lecithin is convention-
Table 5 primary product, and an essential oil/ethanol fraction as a sec-

Supercritical antisolvent extraction ondary product. Operating at 300 bar, almost 100% recovery of
Initial mixture Material to recover References flavonoids was obtained. The optimum tincture concentration
Propolis tincture Flavonoids [233]
appeared to be about 10 mass%. The concentration of propolis
Lecithin + triglyceride oil Lecithin [234,235] in the tincture is the parameter that has the greatest effect on the
Essential oil + triglyceride oil Essential oil [234,235] yield and concentration of flavonoids in the product fraction.
Curcuminoid + triglyceride oil Curcuminoid [234,235] The process has been successfully scaled up to a demonstra-
Oat bran + acetone Triacylglycerols [236] tion scale using optimized pressure, temperature, flow ratio and
Lecithin + hexane Lecithin [237]
Tobacco + ethanol Proteins [238]
tincture concentrations obtained from laboratory and pilot scale
trials.
4.2.3. Proteins extraction from tobacco

ally refined for removal of oil by repeated solvent extractions Cigarette manufacturers have devised systems to reduce the
with acetone, as lecithin is ‘acetone insoluble’. Removal of oil nicotine and tar content of the burning tobacco for health reasons.
from crude lecithin by conventional organic solvents has several Most of these systems have resulted in a safer smoking product,
disadvantages, such as, a large amount of solvent is needed, it but they do not remove all of the undesirable constituents in the
is tedious and time-consuming, and a gelatinous lumpy mass tobacco smoke. Proteins in cured tobacco are either precursors
is formed at the final stage, which reduces the mass transfer of undesired compounds in the smoke either a valuable source
efficiency of the process. of useful compounds. Therefore, the supercritical antisolvent
Some authors have proposed to apply the SAE to this process extraction has been used by Scrugli et al. [238] to remove pro-
since seed oils are soluble in SC-CO2 (though at pressures larger tein compounds from cured tobacco by ethanolic extraction and
than about 280 bar, as previously specified) and phospholipids to recover the proteic compounds from the obtained solution.
are completely insoluble in this medium. Thus, the proposed Alkaloids like nicotine are soluble in SC-CO2 especially at high
process consists of operating the antisolvent extraction with SC- densities, cuticular waxes and flavouring compounds can also
CO2 at, for example, 400 bar and 40 ◦ C with a continuous flow been readily extracted. Therefore, a fractionation of the ethanolic
of CO2 and an injection system that sprays in the precipitator extract is possible, if processing conditions are selected to induce
the lecithin containing oil in form of small droplets [239–241]. proteic compounds precipitation and the transfer in the fluid
The oil solubilized in SC-CO2 is extracted and recovered in a phase of the liquid solvent together with nicotine, waxes and
separator operated at low pressure. Lecithin precipitates as a flavouring components. The experiments have been performed
solid powder and is collected time by time when the vessel is at different pressures and solid concentrations. The ethanolic
discharged. extract was efficiently fractionated in all the experiments. The
A further evolution of this process has been proposed by chemical analyzes performed on the fractions recovered shown
Mukhopadhyay and Singh [237]. In this method, crude lecithin that the yield of precipitated material was about 40% (w/w of
is dissolved in hexane and is contacted with dense CO2 . The CO2 extract) in each experiment. Particularly interesting is the total
dissolution in the solution causes a large partial molar volume absence of nicotine in the precipitates, whereas, it is totally
reduction of hexane [242,243]. As a result, there is a reduction of recovered with flavours and pigments, in the ethanolic residues.
its solvent power for lecithin, producing a selective precipitation
of lecithin. 4.3. Mathematical modelling
4.2.2. Propolis tincture fractionation No specific papers dedicated to SAE modelling have until
Propolis contains a high concentration of flavonoids, which now been published. However, due to the similarities of this
are used in a wide range of cosmetic and health food preparations process with SAS, part of the considerations developed for that
for their antimicrobial properties. Propolis is usually dissolved in process [244–248] could be adapted to SAE.
ethanol or ethanol/water mixtures to remove insoluble material Since only precipitation is required in SAE with no speci-
such as waxes. The resultant solution is a propolis tincture. fications on particle size, the spray formation/efficiency is not
A supercritical antisolvent extraction process has been pro- particularly relevant even if a large contact surface favours the
posed for the fractionation of propolis tincture [233] to obtain rate of precipitation.
flavonoids and essential oil fractions by extraction, and to Phase equilibria will play a role even more relevant than in
remove high molecular mass components by antisolvent pre- SAS. Indeed, in SAE we are interested in the separation of the
cipitation. Flavonoids are practically insoluble in pure CO2 , but solid phase and, as a rule, complex mixtures are processed; there-
sufficiently soluble in CO2 + ethanol to enable their separation fore, interactions among the compounds present in the mixture
from high molecular mass and/or more polar components. In are involved and will be very difficult to be predicted.
the first step of the process, supercritical CO2 is used both as an
antisolvent to precipitate high molecular weight components, 5. Conclusions and perspectives
and as a solvent to extract the ethanol and soluble components
of the propolis. This extract is then fractionated in two sepa- SFE and liquids fractionation in the period of time considered
ration steps to create a concentrated flavonoid fraction as the (1996 to present time) have moved along two major direc-
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Supercritical Fluid Extraction and Fractionation of Natural Matter

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of Supercritical Fluids 38 (2006) 146–166

Supercritical fluid extraction and fractionation of natural matter

Keywords: Supercritical extraction; Liquid fractionation; Purification; Antisolvent extraction; Modelling

4.2.2. Propolis tincture fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159

1. Introduction ity. In several cases, it is not possible to avoid the co-extraction

2. Solids processing 2.1. Selection of the operating parameters

Anise seeds Pimpinella anisum L. EO [91]

Aloe vera leaves Aloe barbadensis Miller ␣-Tocopherol [51]

Poultry feed, eggs and muscle tissue Nicarbazin [152]

the beads with a film of this material. This process is very

the grinding process. Their shape can influence the diffusion

From the point of view of the extraction mechanisms, other

(a) the material is largely available;

Mass transfer resistances, in general, may be of two types:

Almond seeds Seed oil DMBI [179,184]

Acetic acid + water Acetic acid C [209]

Table 5 primary product, and an essential oil/ethanol fraction as a sec-

4.2.3. Proteins extraction from tobacco

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