Current Opinion in Solid State and Materials Science 7 (2003) 321–330

Supercritical extraction from solid: process design data (2001–2003)

M. Angela A. Meireles *

LASEFI––DEA/FEA, College of Food Engineering, UNICAMP (State University of Campinas), Cx. Postal 6121,
13083-970 Campinas, SP, Brazil
Received 1 August 2003; accepted 31 October 2003

Abstract
Supercritical extraction from solid substrate using carbon dioxide as solvent, with or without the addition of cosolvent, has
proved to be technically feasible. The relatively high investment costs associated with high pressure processes are responsible for the
elimination of this technology at the very early stages of the process design, that is, during the selection of an extraction process. In
order to avoid this, a preliminary analysis of the manufacturing costs must be done with a minimum of experimental information. In
this review a compilation of the process parameters required for the economic analysis is presented.

2003 Elsevier Ltd. All rights reserved.

1. Introduction ings of the sixth International Symposium on Super-

In this review, it will be discussed experimental data
on supercritical fluid extraction (SFE) from solid sub-
stratum applied to natural products, using CO2 as sol-
vent. The period reviewed ranges from January 2001 to
June 2003. SFE from solids, in particular, for obtaining
valuable foods or fine chemistry products, is a growing
area. The precise size of the area is difficult to establish,
but an estimate can be obtained by observing the
numbers returned for a search in ‘‘ScienceDirect.com’’
using the following words: ‘‘supercritical fluids extrac-
tion’’ or ‘‘supercritical fluid extraction’’ or ‘‘compressed
CO2 extraction’’ or ‘‘compressed carbon dioxide
extraction’’ or ‘‘pressurized CO2 extraction’’ or ‘‘pres-
surized carbon dioxide extraction’’. One hundred and
thirty one journal articles were obtained restricting the
search to abstract, keywords and title; including the
article’s full text in the search returned 469 journal
articles. Similar results were obtained in other data-
bases. For example, a search in the ‘‘ISI Web of Sci-
ence’’ and ‘‘Scirus for scientific information only’’
resulted in 514 and 696 journal articles, respectively.
Considering that the journal articles have an average
size of six pages, this means that about 4200 pages were
written on the subject. The recently published proceed-
*
Tel.: +55-19-3788-4033; fax: +55-19-3788-4027.
E-mail address: meireles@fea.unicamp.br (M.A.A. Meireles).
1359-0286/$ - see front matter
2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cossms.2003.10.008
critical Fluids contained 2124 pages, of which 439 dealt
with supercritical fluids applied to natural products [1],
representing about 20% of the total papers presented in
the conference.
From all the reference available, the papers that
provided information on the process parameters, re-
quired for a preliminary estimation of the cost of man-
ufacturing (COM), were selected. This was done because
‘‘how much will it cost’’ is, today, the crucial question to
be answered, to have SFE crossing the line of uncon-
ventional to conventional technique and be considered
one among the various alternative processes to produce
high quality natural extracts.
Papers dealing solely with the development of mass
or thermodynamic models were not included. However,
those that apply simple models based on mass balance
equations to published SFE data were selected. The
experimental data compiled were somewhat arbitrarily
classified in two types, considering the size of the
extractor vessel (VE ); thus, for VE > 50 ml, the SFE units
were classified as process units, and for VE < 50 ml the
units were classified as analytical units. Incidentally,
the experimental data obtained in process units provided
the data required for COM analysis. Phase equilibria or
solubility data are important information for COM
estimation. In spite of that, papers dealing with phase
equilibria were not compiled, but some of the references
that provide experimental solubility or equilibrium data
were listed. Applications using other solvents such as
322 M.A.A. Meireles / Current Opinion in Solid State and Materials Science 7 (2003) 321–330
propane, ethane, or water were included, if the CO2 data
were provided, and the same criterion was applied for
data using cosolvents.
2. What is the best extraction process for. . . ? Or how not
to eliminate SFE
Natural extracts do not compete with synthetic
products with respect to cost. Natural extracts compete
with synthetic products because they were elaborated
using a natural resource, in addition they keep their
original sensory quality. Therefore, it is only meaningful
to compare SFE extracts, which can get very close to the
natural resource they came from, with extracts prepared
by other extractive techniques, such as hydrodistillation
(HD) for volatile oils, or any other low pressure solvent
extraction (LPSE) process, such as enfleurage, leaching,
decoction, elutriation, elution, etc. Nevertheless, HD
and LPSE require a number of associated unit opera-
tions that are not required by SFE, such as decantation,
centrifugation, desolventisation of extract and solid
sludge that may involve distillation and evaporation,
discoloration, etc. Even so, the cost of investment may
not favor SFE, unless the functional properties of the
SFE extracts are confronted with those of the other
extracts. In fact, this is the key information to keep SFE
competitive as an alternative for the extraction step.
Therefore, any SFE study must include a careful deter-
mination of the chemical composition (or the content of
the target compound) of the SFE extract and, if possi-
ble, of one functional property, because this is what can
make the SFE extract more attractive than LPSE or HD
extracts.
Hence, in searching for alternative processes to ob-
tain, for instance, a functional food such as a spice fla-
vor or a natural pigment with a feature of being cancer
preventive, what is the best process? In order to answer
this question, first the desired functional property must
have been confirmed for the SFE extract as was done for
the turmeric SFE extract [2]. Secondly, there must be
prompt answers to the following questions: ‘‘How much
it will cost’’ and ‘‘what is the cost to benefit ratio?’’ This
way, it is possible to make SFE an attractive alternative
among the various extraction processes.
3. Getting process parameters to estimate COM
Experimental SFE data compiled and shown in
Tables 1 and 2 were alphabetically organized by the
substance common name, and the botanic names and
the target compounds were included. The set of infor-
mations required for the preliminary COM analysis was
organized as follows: The geometry of the extractor
vessel was expressed in terms of the extractor’s volume
(VE ), diameter (dB ), and height (HB ). The amount of solid
used (F ), the size of the particles (dp ), the temperature
and the pressure used were also listed. The bed apparent
density (qB ), the solvent flow rate (QCO2 ), and the yield
(Xo ), if not provided, were estimated.
In the past 30 months, experimental data for 43 sys-
tems of the type solid substratum + CO2 were reported
in the literature (Tables 1 and 2). Even considering the
experimental data produced in the past two decades and
data not compiled here, the number of systems studied is
still limited. These experimental data (Tables 1 and 2)
were obtained at temperatures of 10–120 C and pres-
sures of 50–690 bar; the range of CO2 density that was
covered varied from 346 to 924 kg/m3 . For vegetable
raw material, all parts of the plant have been studied,
that is, fruit or seeds, leaves and roots.
For some classes of raw material, like seeds with high
lipid content, a first estimate of the behavior of the
system can be obtained from data measured for a similar
raw material. For aromatic plants, however, it is quite
different. For example, the major compound of clove-
basil (Ocimum gratissimum) is eugenol, while the major
compound of sweet-basil (Ocimum basilicum) is linalool.
This way, the behavior of the system O. gratissimum
+ CO2 can be quite different from the behavior of the
system O. basilicum + CO2 , because, in spite of both
belonging to the same species, different varieties of
aromatic plants can produce entirely diverse extracts
with respect to the chemical composition of the multi-
component mixture. Consequently, experimental data
compiled in Tables 1 and 2 have the indication of the
botanic name as given by the authors.
In order to perform a proper preliminary COM
analysis, there is a minimum of experimental informa-
tions required. They are (i) the bed apparent density
(qB ), (ii) the global (or overall or total) yield (Xo ) per
unit feed material (dry basis) for a given operating
condition, and (iii) the solvent to feed ratio required and
the duration of the SFE cycle, that is, the kinetics of
extraction. Estimating the volume of the extractor vessel
per unit of SFE extract requires the bed apparent den-
sity (qB ) and the global yield (Xo ). It should be consid-
ered that the industrial SFE unit would have two or
extractor vessels [12].
The bed apparent density (qB ) depends on the solid
substrate nature (leaves, roots, seeds, fruits, etc.) and on
the pretreatment used for the raw material, which may
include drying and cutting or milling, and will determine
the particle size. Raw material containing more than 10–
18% (wet basis) of water will require drying (which
should be done at moderate conditions for aromatic
plants), in order to avoid very low process yields. Sun
et al. [4] extracted alkylamides from Echinacea angusti-
folia roots using CO2 and ethanol as cosolvent; they
reported that the yields of the dried roots were about 10
times higher than the yields obtained using fresh roots.
Table 1
Experimental data obtained in process design SFE units (VE > 50 ml) containing overall extraction curves (OEC)
Raw material Botanic name Target VE
106 dB
103 HB
103 F
103 dp
103 qB (kg/m3 ) T (C) P (bar) QCO2
105 Yielda References
(or variety) component (m3 ) (m) (m) (kg) (m) (kg/s) (%)
Anise seedb Pimpinella anisum L. Volatile oil 385 64 130 191 0.355–0.71 30 80–140 1.23–6.12 3.1–10.7 [11]
Black pepper Peper nigrum L. Oleoresin 26.4 10.5 305 29 0.08–0.11 1100 30–40 150–300 0.12–1.05 [14]
Borage seedsc Borago officinalis Borage oil 47 n.a. n.a. 10 n.a. 212.8 40 100–350 1.48 95d [15]
Borage seeds Borago officinalis Borage oil 75 n.a. n.a. 40 0.75 533.3 10–60 50–350 1.48–5.92 29d [16]
Cashew nut Anacardium Extract 500 n.a. n.a. 6–50 n.a. 100 40–60 147–300 1.48 60–65d [17]

M.A.A. Meireles / Current Opinion in Solid State and Materials Science 7 (2003) 321–330
shell occidentale L.
Celery roots Apium graveolens L. Extract 200 n.a. n.a. 50 n.a. 250.0 40 250–350 n.a. 1.70 [18]
Chamomileb Chamomilla recutita Volatile oil 203 39.6 165.5 75.4 0.27–0.54 370 30–40 100–200 3.33–6.66 2.5–4.33 [19]
L. Rauschert oleoresin
Cocoa beanse Theobroma cacao Caffeine 50 n.a. n.a. 3 0.3–2 60.0 70 400 9.5 37.4–66.4d [13]
Theobromine 13.9–29.9
Cocoa butter 27–48
Cocoa beansc Theobroma cacao Methyl- 50 n.a. n.a. 3 0.315–2.00 60.0 50–70 400 9.5 20d [20]
xanthines
Cocoa beanse Theobroma cacao Cocoa butter 300 46 180 115 n.a. 383.3 50 152–248 2.2 4–7d [21]
Dandelionf Taraxacum officinale b-amyrin 5000 n.a. n.a. 1000 0.228 200.0 35–65 150–450 205.56 1.6–4.0 [22]
Weber et Wiggers b-sitosterol
Echinacea Echinacea angustifolia Alkylamides 143 27 250 6 0.150–1.19 41.9 45–60 340–550 5.03 17.5– [4]
driedf 32.5
Echinacea Echinacea angustifolia Alkylamides 143 27 250 25 0.150–1.19 174.7 45–60 340–550 5.03 2.5–7.5 [4]
freshf
Echinaceac Echinacea purpurea Extract 2960 n.a. n.a. 1000 0.650 266.7 40–50 200–300 n.a. 2–3 [23]
Egg yolk – Oil 1200 44 790 250–410 1.2 45 320 200 36–41 [24]
5000 – – 1650 1.2 45 320 620 42
Gingerb; c Zingiber officinale Oleoresin 232 27.6 387 80 0.390 350 25–35 200–250 5.90 1.93–2.65 [5]
Roscoe
Ginger Zingiber officinale Oleoresin 243 28.3 387 80 1.02 339 30–40 150–250 5.2–6.0 2.1–3.0 [6]
Roscoe
Guaran
a n.a. Caffeine 50 n.a. n.a. 3 0.630–1.00 60.0 40–70 100–400 9.50 98d [20]
seedsc
Guaran
a n.a. Caffeine 50 n.a. n.a. 5 0.630–1.00 100.0 40–70 400 15.67 98d [25]
seedsc
Ginkof Ginkgo biloba L. Lactones, 300 n.a. n.a. 90 0.106 300.0 60–120 242–312 8.70 3.6–11.4 [26]
flavonoids
Japape~
no Capsicum annuum L. Oleoresin 50 20 160 20 0.28–0.319 50 40 120–320 4.9–53.9 9–10 [8]
pepper 100 30 140 40 0.28–0.319 100 40 120–320 10.9–120.5
200 55 850 80 0.28–0.319 200 40 120–320 36.8–405.3
Kava root n.a. Extract 2960 n.a. n.a. 1000 0.650 266.7 40–60 200–300 n.a. 3–8 [23]
Lemon balm Melissa officinalis L. Extract 500 48 277 n.a. n.a. n.a. 40 120 23.7 30d [27]
SFE antioxidant
residue
Lippia Lippia sidoides Cham. Volatile oil 220 21.6 600 120 0.334 546 10–25 66.7–78.5 0.62–3.16 1.47–3.11 [28]
sidoidesb
Lovage leaves Levisticum Extract 200 n.a. n.a. 10–50 0.2–1.4 500.0 40 250–350 n.a. 1.56–2.23 [18]

323
officinale Koch.
 324
Table 1 (continued)
Raw material Botanic name Target VE
106 dB
103 HB
103 F
103 dp
103 qB (kg/m3 ) T (C) P (bar) QCO2
105 Yielda References
(or variety) component (m3 ) (m) (m) (kg) (m) (kg/s) (%)
Roots–seeds 200 n.a. n.a. 10–100 n.a. 50–500 40 250–350 n.a.

M.A.A. Meireles / Current Opinion in Solid State and Materials Science 7 (2003) 321–330
Mat
e leaves Ilex paraguariensis Methyl- 50 n.a. n.a. 2 0.315–2.00 40.0 40–70 400 9.5 98d [20]
xanthines
Olive tree n.a. Tocopherol 75 17.5 304.5 15 0.25–1.5 205.3 40 250 1.48 0.015–0.06 [7]
leaves
Oregano Origanum vulgare L. Essential oil 151 45.0 95.0 20 1.550 132.4 40 100 6.94 50–95d [29]
Oregano n.a. volatile oil 151.1 45 95 30 330–700 151.1 27–47 70–200 n.a. 90d [30]
151.1 45 95 15 1550 151.1 27 70 n.a.
Marjoram Majorana hortensis Essential oil 200 n.a. n.a. 25 n.a. 125.0 20–40 100–200 1.67 0.20–1.50 [31]
Moench
Marjoramf Majorana hortensis Pigments 5000 n.a. n.a. 1000 n.a. 200.0 40–60 100–400 n.a. 0.54–3.80 [32]
Moench
Paprikab; g Capsicum annuum L. Oleoresin 590 50.0 300.0 n.a. 0.4–0.6 n.a. 35–55 100–400 2.96 11.5 [33]
Pyrethrum n.a. Extract 200 42 145 50 0.2–1.4 250.0 20–40 70–250 138.9 7.0 [34]
flowers
Pyrethrum n.a. Extract 200 42 145 n.a. – – 40 100 8.3 90d [35]
flowers
Rose hip Rosa canina L. Oil 114 22.0 300.0 n.a. 0.36 n.a. 28–35 100–250 1.33 5.7–6.7 [36]
Saw palmetto n.a. Extract 2960 116 280 1000 0.650 266.7 50–50 250–300 n.a. 11.0 [23]
Spirulina Spirulina maxima Fatty acids & 368.4 50 130 173h 0.30–1.18 940 20–70 150–180 3.33 0.30–0.95 [37]
carotenoids
St. John’s n.a. Extract 2960 116 280 1000 0.650 266.7 22–50 70–300 n.a. 10–12 [23]
wort
Stevia Stevia rebaudiana Volatile oil 232 27.6 387 62 0.83 270 10–30 120–200 5.0–5.6 0.38–1.63 [38]
leavesb ;c Bertoni glycosides
Sunflower n.a. Oil 200 n.a. n.a. 50 0.534 250.0 40–60 250 38.89 90d [39]
seeds
a
Mass of extract/mass of feed.
b
Solubility data reported.
c
Indicates the use of cosolvent.
d
Percentage of the extractable material.
e
Data using ethane is also available.
f
Overall extraction curve is not reported.
g
Data using propane are also available.
h
Plus 0.173 kg of glass beads.
Table 2
Experimental data obtained in screening SFE units (50 ml > VE > 10 ml) with interesting process design information
Raw material Botanic name Target VE
106 dB
103 HB
103 F
103 dp
103 qB T P QCO2
105 Yielda References
(or variety) component (m3 ) (m) (m) (kg) (m) (kg/m3 ) (C) (bar) (kg/s) (%)

M.A.A. Meireles / Current Opinion in Solid State and Materials Science 7 (2003) 321–330
Coriander Coriandrum sativa Extract 16 n.a. n.a. 1.015 n.a. 40 100 2.22 0.3–2.0 [73]
Ginkgo Ginkgo biloba Extract 4 10 50 5 n.a. 1273 60–100 80–300 n.a. 0.8–2.3 [74]
Lemon balm Melissa officinalis Essential oil 10 n.a. n.a. 1 1 n.a. 40–60 138–414 8.70 n.a. [75]
Lemon Monardia citriodora Essential oil 10 n.a. n.a. 1 1 n.a. 40–60 138–414 8.70 n.a. [75]
bergamot
Lemon Eucalyptus citriodora Essential oil 10 n.a. n.a. 1 n.a. n.a. 40–60 138–414 8.70 n.a. [75]
eucalyptus
Lemongrass Cymbopogon citratus Essential oil 10 n.a. n.a. 1 1 n.a. 40–60 138–414 8.70 n.a. [75]
Neem seeds Azadirachta indica Nimbin 10 n.a. n.a. 2 0.6 200 35–55 100–260 0.42–2.16 0.06–0.018 [76]
A. Juss
Rosemary Rosmarinus Extract 5–8 n.a. n.a. 6–9.6 n.a. 120 30–50 200–300 7 3–4.7 [2]
officinalis
Phaffia Phaffia rhodozyma Astaxanthin 10 n.a. n.a. n.a. n.a. n.a. 40–60 100–500 n.a. 85–70d [77]
rhodozymab;c
Savoryc;e; f Satureja hortensis Essential oil 10 n.a. n.a. n.a. n.a. n.a. 50 400 3.48 n.a. [78]
Soybean flour IAC–12 variety Isoflavones 7 n.a. n.a. 1 n.a. 143 40–70 200–360 1.12–2.20 n.a. [79]
Terminalia Terminalia catappa Squalene 10 n.a. n.a. 1 n.a. 100 40–60 136–272 n.a. n.a. [80]
Tomato Pear type All-trans-lyco- 7 n.a. n.a. 0.5 n.a. 71 40 77–281 1.67–6.60 – [81]
pene
b-carotene
a-tocopherol
Tomato n.a. Lycopene 10 n.a. n.a. n.a. n.a. n.a. 32–86 138–483 4.35–27.84 [82]
byproductb
Vernonia Vernonia galamensis Oil 10 n.a. n.a. 2.0 or n.a. n.a. 80–100 520–690 n.a. 5–17 [46]
galamensis 5.0
31 16 155 5 n.a. 160 80–100 520–690 11.84
Wheat germb n.a. Vitamin E 10 n.a. n.a. n.a. 0.13–2.1 n.a. 35–50 138–414 3.48 0.74–1.84 [44]
a
Mass of extract/mass of feed.
b
Overall extraction curve is available.
c
Indicates the use of cosolvent.
d
Percentage of the extractable material.
e
Hot water also used.
f
Thermodynamic and kinetic models discussed.

325
326 M.A.A. Meireles / Current Opinion in Solid State and Materials Science 7 (2003) 321–330
This observation is the fundamental reason to include
drying as a pretreatment step for SFE from ginger [5,6]
and turmeric [2]. In spite of the importance of particle
size on the SFE kinetics, as can be appreciated from
the works of [7,8], and of the variety of sizes employed,
as shown in Table 1, large extraction vessels will not
operate properly with very fine particles. Therefore, little
room is available for optimizing the process with respect
to the particle size diameter, giving us few choices for
this parameter.
The global yield (Xo ) is the amount of soluble mate-
rial that can be extracted from a given vegetable matrix
at a given pressure and temperature, expressed as the
ratio of mass of soluble material to mass of solid sub-
strate. The amount of solute in each raw material is
more or less fixed by nature and the differences in the
edaphoclimate conditions of cultivation, thus, again, is
limited. Nevertheless, the composition of the SFE ex-
tracts can vary dramatically. An aromatic plant such as
clove (Eugenia caryophyllus) has only volatile oil, and so
the solute is just a multicomponent mixture of terpe-
noids (mono-, sesqui- and di-terpenes, various alcohols,
ketone, and aldehydes of terpenoids [9]). If, we now
consider another aromatic plant like fennel (Foeniculum
vulgare) or anise (Pimpinella anisum), then, the SFE
extracts will vary tremendously depending on the pres-
sure and temperature at which the extraction is per-
formed, because fixed oil (mixture of lipids) will also be
present, besides the volatile oil (mixture of terpenoids)
(see for instance the composition of the SFE extract
reported by Sim
andi et al. [10] or the data of Rodrigues
et al. [11] for anise seed oil). This way, the solubility or
the global yield, measured for the system fennel + CO2
or anise seed + CO2 , will represent data for different
mixtures, depending on the operating temperature and
pressure. The opposite happens for clove, because only
volatile oil is present, the global yield will more or less
varies accordingly to the standard variation of the sol-
ubility of a liquid or of a solid in a supercritical fluid.
The global yield can be estimated directly from the
solubility measured for the solid substrate + CO2 , using
the amount of solid used to measure solubility.
Once the bed apparent density and the global yield
are available, the volume of the extractor can be esti-
mated; subsequently, a decision must be made on the
ratio of the bed height (HB ) to the bed diameter (dB ). In
Table 1, the HB =dB ratios for the experimental SFE units
vary from 2 to 29, but to optimize with respect to cost
for the SFE industrial units, the HB =dB ratios should
vary from 5 to 7 [12].
After the size and the geometry of the extractor are
established, the solvent to feed ratio and the mass
transfer rate must be estimated. This can be obtained
from one kinetic experiment that reports the mass of
extract obtained by mass of solvent used (or time of
extraction for a given solvent flow rate). An inspection
of the overall extraction curves (OEC) for the different
types of solid substratum + CO2 systems (independently
of how they are presented), such as seeds, fruit or beans
[8,11,13–16,20,21,25,33,36,39] nuts [17], roots [18,23],
leaves [4,7,18,22,23,26–33,38] rhizomes [5,6], flowers
[19,34,35], egg yolk [24], and algae [37], allows con-
firming that approximately 70–90% (or even more, in
some cases) of the solute is extracted during the constant
extraction rate (CER) period. Thus, in spite of the
advantages for process design simulation of very accu-
rate models, as those described or used in literature
[6,24,30,37,40–43], a simple model that accounts for the
CER period is enough for a preliminary COM analysis
that will or will not keep SFE as a viable process. This
can be obtained by a nonlinear fitting of the OEC to a
spline containing two or three straight lines [19]. The
mass transfer rate for the CER period (MCER ) and the
length of the SFE cycle or the duration of the CER
period (tCER ) are calculated from the slope of the first
line and its intercept with the second line, respectively.
Fig. 1A and B shows OEC obtained for clove
buds + CO2 , at 15 C and 100 and 66.7 bar in two dif-
ferent SFE units (SFE_1 and SFE_2) using the proce-
dure described by Rodrigues et al. [44]. The ratios HB =dB
were 2 and 29, respectively for SFE_1 and SFE_2. A
linear spline was fitted to the OECs obtained at the
highest solvent flow rates, as illustrated in the inset of
Fig. 1A. The mass transfer rates (MCER ) were 7.1 · 107
and 2.7 · 107 kg/s, while the constant extraction periods
were 60 and 61 min for SFE_1 and SFE_2, respectively.
The estimated values of the global yields (Xo ) obtained
as discussed by Zancan et al. [5] were 0.18 and 0.21 kg/
kg, respectively.
From the OEC of the references in Table 1 it is
possible to calculate these parameters, and to obtain a
first preliminary estimate for the COM using the
assumptions of Rosa and Meireles [3]: That the perfor-
mance of the industrial extraction vessel can be con-
sidered similar to that of the experimental apparatus, if
solvent to feed ratio is kept constant. This assumption
would be reasonable if the scale-up would be done
by increasing the vessel diameter and, also, if the CO2
distributor works properly; also, several operating
arrangements could be used, such as counter-current
operation [12]. However, it is mandatory to recognize
that this is an extremely simplified assumption, because
it neglects raw material agglomeration and fluid chan-
nelling, pressure drop increase [12], thus the COM esti-
mated under these conditions is only a preliminary
reference figure; large-scale pilot plant data would de
required for a more realistic COM estimate. Nonethe-
less, this preliminary figure, in spite of its restriction, is,
probably, the only information able to keep SFE as an
alternative for the entrepreneur during the very earlier
stages of process design, when the decision is being made
on what extraction processes will be studied, because of
 M.A.A. Meireles / Current Opinion in Solid State and Materials Science 7 (2003) 321–330 327

20

16

Yield, %
12

4
20 0 20
18 A 0 60 120 18 B
Extractio time/60, s
16 16
14 14
Yield, %

Yield, %
12 12
10 10
8 8 0.75E-5 kg/s
0.60E-5 kg/s 1.11E-5 kg/s
6 0.87E-5 kg/s 6 1.85E-5 kg/s
4 1.67E-5 kg/s 4 2.56E-5 kg/s
2.48E-5 kg/s
2 2
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.5 1.0 1.5 2.0 2.
2.5 3.0
Solvent/Feed, kg/kg Solvent/Feed, kg/kg

Fig. 1. Overall extraction curves for the system clove + CO2 ; experimental data obtained as described by Rodrigues et al. [44]: (A) 100 bar, 15 C
(SFE_1, HB =dB ¼ 2), Inset: QCO2 ¼ 2:48
105 kg/s, MCER ¼ 7:1
107 kg/s and tCER ¼ 60 min. (B) 66.7 bar and 15 C (SFE_2, HB =dB ¼ 28); for
QCO2 ¼ 2:56
105 kg/s, MCER ¼ 2:7
107 kg/s and tCER ¼ 61 min.

the investment cost associated with SFE units. The
behavior of the entrepreneur should not be overlooked,
it is a particularly important issue for the South America
countries, where in spite of the extremely reach flora,
and the large number of natural extract industries SFE
has not find its deserved place.
4. Getting some process parameters from analytical scale
SFE extractors
Two very important informations for process design
can be obtained from analytical scale SFE extractors:
the process temperature and pressure. Consequently, the
SFE extract composition will also be known. Nonethe-
less, any other inference related to kinetics should be
avoided, because they will not be reproducible in larger
vessels. Table 2 shows the compilation of data obtained
in analytical scale SFE units.
The work of Ge et al. [45] is an example of how
process temperature, pressure, and extract composition
can be obtained from such a small apparatus. They have
studied the extraction of vitamin E from wheat germ. A
small extractor vessel (5 ml) was used. The SFE condi-
tions were optimized using the global yield of vitamin E
and its isomers (the target components) as the criteria. A
comparison between the SFE yield (40 C and 272 bar)
and the yields obtained by conventional processes
(hexane and CHCl3 /MeOH) showed that the vitamin E
total yield was comparable for all process, but the a-
tocopherol content was higher in the SFE extracts. Leal
et al. [2] reported isobaric data for the system rosemary
(Rosmarinus officinalis) + CO2 . The results demonstrated
that higher amounts of camphor, verbenone, and trans-
caryophyllene were obtained at 30 C, 200 and 300 bar,
as compared to 50 C. The same behavior was observed
for the antioxidant activities of the SFE. In spite of that,
the global yield was significantly affected by temperature
only at the 200 bar isobar. King et al. [46] studied the
extraction of oil and vernolic acid from V. galamensis,
using high temperatures and pressures to inhibit lypol-
ysis reaction.
Additional experimental data obtained in screening
SFE units are listed in Table 2. The articles report global
yields or solubility data, the effect of pressure and tem-
perature, and, also, the effect of the cosolvent on the
systems studied. Some additional information on pro-
cess conditions can be obtained from the following
articles that used SFE as an analytical tool. Caredda
et al. [47] reported the composition of SFE of bay leaves
(Laurus nobilis) oil as a function of extraction time. Cui
and Ang [48] used SFE as a preparative technique to
extract phloroglucinols from St. John’s wort. SFE was
used to analyze fat in an infant formula powder [49],
semi-volatile compounds from Baltic herring (Clupea
harengus membras) [50], and organochlorines from fish
muscle [51].
5. Phase equilibria data process design
Solubility and phase equilibria data are available for
a several systems. Cristov and Dohrn [52] reviewed the
sources of experimental data measured at high pressure
328 M.A.A. Meireles / Current Opinion in Solid State and Materials Science 7 (2003) 321–330
for a number of interesting systems, and their review
covers the data published from 1994 to 1999. Solubility
data have been reported in literature, including data for
vegetable oils [53], essential oils [11,28,44], and oleore-
sins [8,33].
The global yield can be estimated using the equilibria
data for binary or multicomponent systems taken
without the presence of the solid matrix. In this case,
care must be taken because the presence of the cellulosic
structure will be responsible for a considerable decrease
in solubility, as confirmed by the data of Mohamed et al.
[13]. Solubility and/or phase equilibria data for several
systems have been reported for binary systems [54–57],
ternary systems [58–64], quaternary system [65], vita-
mins [66,67], and systems containing water and ethanol
[68].
6. Conclusions
There are some review papers discussing the appli-
cation of SFE as a preparative tool in specific areas,
such as analytical chemistry [69], aromatherapy [70],
food industry [71] and phytotherapy [72]. Tables 1 and 2
show that data is available only for a limited number of
systems––but because nature works to our favor, it is
possible to start classifying the systems by the nature of
the solid substratum.
Acknowledgements
The author thanks M. Perrut for providing infor-
mation on industrial SFE units. The author is also
grateful to O.J. Catchpole, H.G. Daood, C. Dariva,
R.S. Mohamed, and N.L. Rozzi for providing some
information needed to complete Tables 1 and 2.
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