Documente Academic
Documente Profesional
Documente Cultură
Review
a r t i c l e
i n f o
Article history:
Received 20 January 2014
Received in revised form 31 March 2014
Accepted 1 April 2014
Available online 24 April 2014
Keywords:
Supercritical uid extraction
Optimization
Modeling
Scale-up
Economic analysis
Biomass
Trends
a b s t r a c t
Along more than a decade, R&D on supercritical uid extraction (SFE) of vegetable matrices has been
increasingly reported in the literature. Aiming at portraying the current state of this eld and its evolution in terms of raw materials, products, modes of operation, optimization, modeling techniques, and
closeness to industrial application, a large compilation of almost 600 essays from 2000 to 2013 has
been deeply analyzed in order to unveil those indicators and their trends. Furthermore, strengths and
weaknesses are identied, and some remarks that may drive upcoming research are provided.
Globally, more than 300 species are reported in the literature, with prevalence of the extraction of seeds
(28% of works) and leaves (17%). The main families of extracted compounds, cosolvents and operating
conditions adopted are critically examined, being possible to conclude that researchers investigate many
times working regions far from the optimum due to practical limitations or absence of experimental
optimization. Current phenomenological, statistical and semi-empirical approaches are reviewed, along
with scale-up studies, and economic analysis. In the whole, the most comprehensive picture over SFE of
vegetable matrices is provided in this review, highlighting pertinent aspects and opportunities that may
further consolidate the convincing route of this technology for the next years.
2014 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
5.
6.
7.
8.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biomass matrices and naturally occurring molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Focuses of SFE works . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Operating conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Pressure and temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Solvent power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Cosolvent addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4.
Flow rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Subsidiary relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Extraction models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.
Statistical models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Scale-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Economic analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Final remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author. Tel.: +351 234 401549; fax: +351 234 370084.
E-mail address: carlos.manuel@ua.pt (C.M. Silva).
http://dx.doi.org/10.1016/j.supu.2014.04.007
0896-8446/ 2014 Elsevier B.V. All rights reserved.
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116
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142
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144
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157
161
162
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116
1. Introduction
In the last 13 years (20002013), the extracts of more than 300
plant species have been studied using supercritical uid extraction
(SFE) technology. It is worth noting the major share of SFE research
covers vegetable biomass [1,2]. While many extracts and pure components of these species are already in use for human nutrition
and health purposes, others represent potentially new applications
involving plants whose knowledge, in most of the cases, has been
empirically established or still lacks scientic coverage.
The remarkable interest of scientic community on this technology has been driven by the great versatility of carbon dioxide,
the most used solvent in supercritical state, whose properties can
be tuned in order to provide extracts with desirable compositions
(selectivity enhancements), while at the same time it ensures an
innocuous separation process both to human health and to the
environment. Other solvents (e.g. ethane, propane) have also been
object of research but their use is not as widespread as carbon
dioxide, and for this reason the emphasis of this review is on supercritical carbon dioxide (SC-CO2 ).
Among the vast group of species that have been studied under
the scope of SFE, some have appeared in great number in literature since 2000. It is the case of grape (Vitis vinifera L.) [325]
tomato (Solanum lycopersicum L.) [2635], thyme (Thymus vulgaris
L.) [3644], eucalypt (Eucalyptus spp.) [4553], coffee (Coffea spp.)
[5462], sunower (Heliantus annuus L.) [6369], ax (Linum usitatissimum) [7075], rosemary (Rosmarinus ofcinalis L.) [7683],
red pepper (Capsicum anuum L.) [8490], and rice (Oryza variety)
[9197].
In what concerns food related species, the great expansion
of nutraceuticals market in recent years, as an emerging sector
comprising the use of dietary substances for prevention of diseases [98], has been attracting the attention of researchers and
food industry. In this context, SFE is advantageously positioned
as a sustainable and safe extraction option for the preparation
of plant extracts for supplements and nutrient enriched products
in which, as Perrut anticipated in 2000 [99], the natural character of the preparation mode has a high marketing value. Besides
those requisites, when SFE is applied to eatable raw materials
as a pretreatment for removal of compounds (e.g. cleaning of
rice), other advantages are also observed, such as the enhancement of product shelf life and, eventually, the shortening of the
cooking time [1]. In addition, research on this eld has also
explored the valorization of residues from main stream processes
[100,101].
As a result, a substantial number of dairy plant products has been
object of SFE technology, such as, among others, apricot (Prunus
armeniaca L.) [102106], carrot (Daucus carota L.) [107110],
cashew (Anacardium occidentale L.) [111114], cocoa (Theobroma
cacao) [115117], garlic (Allium sativum L.) [118121], ginger
(Zingiber ofcinale) [122126], ginseng (Panax spp.) [127130],
laurel (Laurus nobilis L.) [131135], orange (Citrus sinensis L.)
[136140], oregano (Origanum spp.) [141145], pumpkin (Cucurbita spp.) [146150], soybean [151156], turmeric (Curcuma longa
L.) [157161], and wheat germ (Triticum spp.) [162167].
Following a major trend of western pharmaceutical industry
of integrating oriental folk medicine species that have been used
for centuries in natural formulations for a myriad of health problems, extracts of a signicant number of species used in those
contexts have been prepared using SFE. Although many species
are still to be recognized for their health/nutrition benets by
health authorities such as World Health Organization, others have
seen their bioactivity conrmed, such as on the cases of Acorus
calamus [168], Andrographis paniculata [169], Azadirachta indica
[170173], Curcuma longa [157161], Cyperus rotundus [174], Ocimum gratissimum [175,178,179], Panax ginseng [127,129], Taxus
baccata L. [180]. Its application has been directed by the interest to isolate and quantify phytopharmaceuticals existing in those
extracts so that further pharmacological studies can then be carried
out in order to conrm the respective bioactivities. An elucidating perspective on this research path was recently published for
the case of triterpenoid compounds, either with respect to their
extraction with SC-CO2 [181], either in terms of the corresponding bioactivity studies that support their therapeutic potential
[182].
This review intends to document and systematize the progresses of supercritical CO2 extraction research upon natural
extracts, with emphasis on raw materials, products, modes of
operation, optimization, modeling techniques, and closeness to
industrial application. A large compilation of almost 600 essays
from 2000 to 2013 has been deeply analyzed in order to unveil
indicators and trends. It is expected that this compilation and discussion provide hints and suggestions to researchers with respect
to the different aspects that contribute to the nal viability of SFE
technologies and, thus, to its widespread implementation at commercial level.
The review is structured in the following way: Section 2 is
devoted to the presentation of biomass matrices and naturally
occurring molecules, followed, in Section 3, by the focuses of SFE
research. In Section 4, aspects related to the operation of SFE units,
the impact and optimization of process variables are covered. Modeling is introduced in Section 5, and discussed in terms of empirical,
simplied, comprehensive and statistical approaches. The next two
sections highlight the scale-up (Section 6) and economic analysis
(Section 7). Final remarks conclude the review in Section 8.
2. Biomass matrices and naturally occurring molecules
When overviewing the eld of vegetable matrices extracts for a
period larger than a decade, a vast group of species arises as issue of
SFE research, hence revealing the strong interest and attention that
supercritical uids have conquered. A wide-ranging compilation
of works in this eld is presented in Table 1, sorted by the scientic names of plant species substrates. Information regarding the
vegetable species, target molecules and operating conditions (pressure, temperature, solvent ow rate, and cosolvent content) are
provided for each SFE publication, as well as the respective analytical techniques employed and complementary features about each
work.
Considering the representative number of works covered in this
review, it is possible to depict some structural tendencies regarding the directions research has followed in this eld, such as the
characteristics of the biomass matrices that have been most studied. Accordingly, Fig. 1 presents a statistical distribution of the
vegetables matrices types mostly found on SFE publications. It
becomes clear that supercritical uids have been mainly applied
to the extraction of seeds and leaves. Together, they represent 45%
of the plant fractions of all the works considered, being seeds the
biggest fraction (28%), and leaves (17%). They are followed by fruits
(10%), roots (7%), owers (5%), rhizomes (3%) and bark (2%). On the
other hand, parts such as stems, branches, and woods seem not
to justify individual studies of SFE, being instead included only in
cases where matrices comprise mixtures of components, such as
aerial parts, which account for 9% of the researched matrices. In
addition, processed vegetables like pomace or husks represent 5%
of the 544 SFE publications considered.
In view of the vast diversity of molecules found in natural
matrices, vegetables are typically matter of research for more
than one application. Depending on the species and plant component studied, SFE processes can be devoted to many naturally
occurring compounds. Furthermore, SFE extracts obtained from
vegetable matrices are typically mixtures of the following family
Table 1
Publications comprising SFE vegetable raw materials from 2000 to 2013, and their respective features.
Plant part
Target
Extraction
yield (wt%)
P (bar)
T ( C)
Berries
Fruit
Phenolic
1.45.20
80300
60
Tea
Seed
730
300400
6080
Cuphea
Seed
28.1
270
Abutilon hybridum
Malvaviscus drummondii,
Pavonia hastata,
Pavonia. lasiopetala
Sida spinoza
Hibiscus
Seed
11.4
Achyrocline satureioides
Macela
Flower
Acori graminei
Rhizome
Agrimonia eupatoria
Agrimonia procera
Leaf
Alkanna tinctoria
Allium cepa L.
Onion
Bulb
Allium cepa L.
Onion
Allium cepa L.
Onion
-Asarone
Analytical technique
Other Features
Ref.
EtOH
GCMS
Antioxidant activity
[242]
Gravimetric
Soxhlet extraction
Sonication
ANOVA
[243]
50
GC
Acid value
Gardner color
FAME
[244]
534
80
FAME
GC-FID
Soxhlet extraction
[245]
8796
200300
3035
Modeling
[246]
80140
3555
GCMS
Hydrodistillation
[247]
04.3
150350
3542
GCMS
2.53.0
kg1
Alkannin
50300
3080
30 kgCO2
0.62.5
100300
4565
Bulb
0.0050.025
103287
30950
Bulb
0.2954.68
160240
3545
Sulphur
Allium sativum L.
Garlic
Bulb
3-Vinyl-4H-1,2-dithiin
0.81
100
4555
Allium sativum L.
Garlic
Flake
Allicin
0.42.3
150450
3565
Allium sativum L.
Garlic
Flake
0.61.0
140400
3560
Allium sativum L.
Alnus glutinosa (L.) Gaertn
Garlic
Clove
Bark
1.53.8
240
300450
35
4060
Aloe vera
Leaf
0.131.5
350450
3250
Alpinia oxyphylla
Seed
Amaranthus caudatus
Amaranth
Seed
Amaranthus caudatus
Amaranth
Seed
Amaranthus caudatus
Amaranth
Seed
Amaranthus cruentus
Amaranthus
Bract
Amaranthus paniculatus
Amaranth
Seed
Ammi majus
Seed
Anacardium occidentale L.
Cashew
Anacardium occidentale L.
Cashew
Fruit
Anacardium occidentale L.
Cashew
Fruit
Allicin
Betulin,
betulinic acid,
lupeol
3 LCO2
kg1
sample
sample
1.362.80
2040
4565
3.48.3
200400
40
46
200400
40
06
150250
4070
0.54.8
100300
4070
Squalene
110280
60100
Furocoumarins
250550
4080
300
4060
225300
50
200300
4060
Squalene
Anacardic acid
060
Cardanol
123
10% EtOH
20160 kgCO2 kg1 sample
845 kgCO2 kg1 sample
HPLC
[248]
HPLC
RSM
DoE
[249]
GCMS
Pilot scale
Two-step decompression
system
Steam distillation
Soxhlet extraction
[250]
Gravimetric Analysis
GCMS
Adsorbent bed
[251]
GCMS
RSM
DoE
[252]
GC
GCMS
DoE
RSM
[119]
HPLC
Modeling
[121]
HPLC
HPLC
TLC
GCMS
LCMS
RP-HPLC
Gravimetric analysis
[120]
Soxhlet extraction
[118]
[253]
DoE
Antioxidant activity
RSM
DoE
[254]
HPLC
GC
GCMS
Ultrasound extractions
[222]
[255]
HPLC
GC-FID
[256]
HPLC
[198]
Gravimetric analysis
Soxhlet extraction
Solubility
Flow rate effect
Modeling
[257]
HPTLC
Modeling
DoE
[199]
1 H NMR
SC chromatography
[232]
HPLC
Modeling
[111]
GCMS
Cost optimization
[113]
GCMS
Modeling
Flow rates effect
Thermal method comparison
[112]
Common name
Scientic name
117
118
Table 1 (Continued)
Common name
Plant part
Anacardium occidentale L.
Cashew
Shell
Andrographis paniculata
Hempedu bumi
Leaf
Andrographolide
Andrographis paniculata
Hempedu Bumi
Leaf
Andrographolide
Anemopsis californica
Yerba mansa
Leaf
Angelica archangelica L.
Angelica
Root
Scientic name
Angelica dahurica
Angelica gigas Nakai
Angelica sinensis
Angelica acutiloba
Target
T ( C)
1.14.0
147294
4060
80240
4070
100
40
355
100
90120
4060
24
Rhizome
Ferulic acid
Herb
Phytosterols
-Sitosterol, stigmasterol
Apium graveolens L.
Celery
Seed
Arbutus unedo L.
Strawberry
Fruit
250350
0.84.0
300500
4565
250
45
45
4080
150300
Arrabidaea chica (Humb.
Bonpl.)
Leaf
Artemisia absinthium L.
Wormwood
Leaf + ower
Artemisia annua L.
Wormwood
Leaf
Anthocyanins
Artemisinin
Artemisia arborescens L.
Helichrysum splendidum
(Thunb.) Less
Artemisia capillaris T.
Whole plant
Capillarisin
Artemisia sieberi
Wormwood
Aerial parts
Camphor
Leaf
kg1
(75% EtOH/25% H2 O)
60 LCO2 kg1 sample
80
100200
296
023
015% EtOH
015% H2 O
015% Acetic acid
4450
0.48
Phenols
Analytical technique
sample
300
40
0.753.66
90180
4050
07
75400
3050
020% EtOH
0140 kgCO2 kg1 sample
88447 kgCO2 kg1 sample
EtOH
0400 kgCO2 kg1 sample
0.10.4
90
50
173
50
101304
3565
1.714.9
Atractylode lancea
Root
2.310.3
150250
4060
Atractylodis macrocephalae
Baizhu
Rhizome
3.676.76
150450
4060
Neem
Seed
585
100260
3055
Neem
Seed
570
100260
Neem
Seed
085
100260
kg1
Ref.
Gravimetric analysis
Fractionation
[114]
X-ray diffraction
HPLC
Purication objective
SEM
[169]
HPLC
TLC
Modeling
Particle sizes effect
[258]
GCMS
Steam distillation
[259]
GCMS
Hydrodistillation
[260]
GCMS
DoE
[261]
GCMS
Solid-phase microextraction
[262]
HPLC
[263]
HPLC
APCI
MS
Soxhlet extraction
DoE
[221]
Modeling
[264]
RSM
DoE
Antioxidant activity
Fractionation
Organic solvent extraction
[265]
03.6
Other Features
HPLC
[266]
[267]
GC-FID
DoE
Hydrodistillation
Soxhlet extraction
Modeling
[196]
GCMS
Hydrodistillation
[268]
Bioactivity test
DoE
RSM
[269]
GC
GCMS
Hydrodistillation
DoE
[211]
GCMS
DoE
[270]
HPLC
dp , Q effects
[171]
3560
2262 LCO2
sample
54 LCO2 kg1 sample
4.726 LCO2 kg1 sample
010% MeOH
02.7 LCO2 kg1 sample
Gravimetric
dp effect
Modeling
Q effects
[173]
3560
Gravimetric analysis
Modeling
Effect of particle size
[172]
kg1
Neem
Seed
Nimbin
00.02
100260
3560
Baccharis dracunculifolia
Baccharis
Leaf
2.44.7
200400
4060
1253 kgCO2
sample
85 kgCO2 kg1 sample
Baccharis dracunculifolia,
Baccharis
(E)-nerolidol; spathulenol
0.38
90120
4060
Baccharis trimera
Baccharis
1.72.3
90
4070
Baccharis trimera
Baccharis
0.32.0
100300
3040
Birch
Leaf
Amino acids
100400
35100
Bixa orelana L.
Annatto
Seed
Carotenoid bixin
145
200300
5060
Bixa orelana L.
Annatto
Seed
Bixin
100350
3050
Bixa orelana L.
Annatto
Seed
Bixin
1.43.5
200400
4060
MeOHH2 Oacetonitrile
100 kgCO2 kg1 sample
5% EtOH
[271]
HPLC
[170]
HPLC
Soxhlet extraction
[272]
GC
GCMS
[273]
GC
GCMS
GCMS
Modeling
[274]
Modeling
Solvent extraction
Soxhlet extraction
[275]
[277]
GC-FID
Modeling
Flow rates effect
Particle sizes effect
Modeling
UVvis
spectrophotometer
HPLC
Economic analysis
Scale-up
Modeling
[279]
HPLC-FLD
Gravimetric analysis
[276]
[278]
Root
Anoectochilus roxburghii
P (bar)
56
Angelica
Extraction
yield (wt%)
Borage ofcinalis L.
Borage
Seed
-Linolenic acid
00.18
0350
3060
Borage ofcinalis L.
Borage
Seed
Fatty acids
030
200300
4060
kg1
Borage
Seed
0.124.3
100350
40
Borago ofcinalis L.
Borage
Seed
030
200300
55
Borago ofcinalis L.
Borage
Seed
957
150250
3060
Brassica napus L.
Rapeseed
Seed
512
300
40
Brassica napus L.
Rapeseed
Seed
7.728.1
200300
4060
Brassica napus L.
Rapeseed
Seed
Brassica napus L.
Canola
Press cake
sample
1847
517
100
Phenolics
2.110.3
300500
4060
10% EtOH
61 kgCO2 kg1 sample
100250
5080
200
45
Brassica oleracea
Broccoli
Leaf
Amino acids
Black cumim
Medlar
Seed
Seed
Benzaldehyde
-Terpinene
kg1
Root
Saikosaponins
918
300400
4050
2400 LCO2
Cajanus cajan
Pigeonpea
Leaf
Cajaninstilbene acid
pinostrobin
0.21.3
200400
4070
9% (v/v) EtOH
EtOH
Calendula ofcinalis L.
Marigold
Flower
Faradiol
500
50
Calendula ofcinalis L.
Marigold
Flower
02.6
120200
2040
Calendula ofcinalis L.
Matricaria recutita
Marigold
Chamomile
Flower
01.8
90100
4050
Calendula ofcinalis L.
Marigold
Flower
3.8
100200
2040
Marigold
Hawthorn
Chamomile
Flower
Camellia sinensis L.
Tea (green)
Seed
Camellia sinensis L.
Tea (green)
Leaf
Camellia sinensis L.
Tea (green)
Leaf
Phenolic
sample
kg1
016 LCO2
sample
0.520% (v/v) EtOH
Soxhlet extraction
[282]
Gravimetric analysis
Modeling
[283]
GCMS
RSM
Modeling
Soxhlet extraction
Solvent extraction
Vortex extraction
[284]
HPLC
[156]
[285]
GCMS
Solvent extraction
[286]
GCMS
Hydrodistillation
[287]
HPLC
DoE
[288]
HPLC
Antioxidant activity
DoE
SEM
RSM
[289]
LPLC
HPLC
Preparative HPLC
[290]
Gravimetric analysis
Modeling
[291]
Soxhlet extraction
Hydrodistillation
Modeling
SEM
Particle sizes effect
[292]
Modeling
Solvent extraction
[293]
GC
GCMS
3545
HPLC
RSM
DoE
Antioxidant activity
[295]
Caffeine
150300
4560
HPLC
Ultrasonic assisted
Moisture effect
DoE
[296]
Epigallocatechin gallate
100300
4060
HPLC
Modeling
Soxhlet extraction
[297]
GCMS
Soxhlet
[298]
GC-FID
RSM
DoE
Particle sizes effect
[299]
Microencapsulation
[86]
Fractionation
[88]
Soxhlet extraction
Particle sizes study
Modeling
[85]
kg1
17.322.1
300400
4080
Seed
1021
250350
4060
3060 kgCO2
sample
19 kgCO2 kg1 sample
Capsicum annuum L.
Red pepper
200300
45100
300500
6080
450
50
Fruit
HPLC
GCMS
5090
Seed
Fruit
[691]
14.829%
Hemp
Paprika
50
Hemp
Paprika
[281]
GC
300689
Cannabis sativa L.
Capsicum annuum L.
[185]
0.55.5
Cannabis sativa L.
Capsicum annuum L.
[280]
Modeling
Soxhlet extraction
Gravimetric analysis
Bupleurum falcatum
Calendulae os
Crataegus ssp.
Matricaria recutita L.
Soxhlet extraction
Vitamin A and E
Carotenoid
8185
[294]
HPLC
HPLC-PAD-MS
GC
Spectrophotometry
Borago ofcinalis L.
GC
GC
119
120
Table 1 (Continued)
Extraction
yield (wt%)
P (bar)
T ( C)
Seed
010
200400
40
Flake
00.11
120320
40
Flake
155
320540
40
Scientic name
Common name
Plant part
Capsicum annuum L.
Paprika
Capsicum annuum L.
Jalapeno
Capsicum annuum L.
Red pepper
Target
Analytical technique
Other Features
Ref.
GCMS
HPLC
HPLC
Solvent extraction
Soxhlet extraction
Modeling
[89]
HPLC
Soxhlet extraction
Micrograph
Fractal analysis
Pelletization
Modeling
[87]
GCMS
GC-FID
Gravimetric analysis
SEM
Use of biotic elicitor
DoE
RSM
Rancimat test
DSC
Velocity effect
[90]
[84]
Capsicum annuum L.
Red pepper
Fruit
0.72.2
100500
4060
Capsicum frutescens L.
Red pepper
Fruit
16
162230
40
Capsicum frutescens L.
Red pepper
Seed
Capsaicinoids
1590
162218
40
HPLC
Soxhlet extraction
DoE
RSM
[301]
Capsicum spp.
Piper nigrum
Zingiber ofcinale
Chili
Black Pepper
Ginger
Piperine
4.112.0
300
40
1 H NMR spectroscopy
Soxhlet extraction
[124]
Carthamus tinctorius
Safower
Seed
1040
220280
3540
GC-FID
[302]
Carum carvi L.
Caraway
Fruit
Limonene
carvone
19
70400
80
Carum carvi L.
Caraway
Seed
Carvone
limonene
5080
2860
[303]
Carum carvi L.
Caraway
Seed
90
50
FT-IR
GC-FID
GCMS
Hydrodistillation
[304]
Carum copticum
Carum
Seed
1.05.8
101304
3555
Hydrodistillation
ANOVA
[305]
Cassia tora
Juemingzi
Seed
0.27
250
45
GC
GCMS
GC-FID
GCMS
HPLC
DoE
Soxhlet extraction
Ultrasonic solidliquid
extraction
Water extraction
Antioxidant activity
DoE
[307]
GCMS
GC
Modeling
[309]
HPLC
GC
In-line inclusion
[310]
GC-DIC
GCMS
GCMS
Soxhlet extraction
Hydrodistillation
Soxhlet extraction
Hydrodistillation
[311]
Two-step decompression
system
[216]
Ceratonia siliqua L.
Carob tree
Chamomilla recutita L.
Chamomile
Leaf
00.45 (%)
Flower
0.54.3
Chamomilla recutita L.
Rauschert
Chamomile
Flower
Chrysobalanus icaco
Abajeru
Leaf
Lupenol
Cinnamomum zeylanicum
Cinnamon
Bark
Tyrosinase
melanin
Cistus ladanifer L.
Roc Rose
Leaf
Labdanum
0.10.5
Citrullus lanatus
Watermelon
Fruit
Lycopene
0.0010.004
Citrullus lanatus
Hibiscus sabdarriffa Lin
Kalahari melon
Roselle
Seed
Tocopherols
Citrullus lanatus
Kalahari melon
Seed
Phytosterol
200400
4080
150220
4160
100200
3040
0.30.9 LCO2
kg1
sample
MeOH 2.26.6% v/v
GCMS
GC-FID
HPLC
HPLC
3 kgCO2
kg1
sample
kg1
1.9
90
40
92 kgCO2
0.95
105200
4080
90120
4050
80100
3070
GC
207414
7090
HPLC
200400
4080
200400
4080
59.578.5
sample
[207]
[306]
[308]
[312]
[205]
HPLC
RSM
DoE
[224]
GC-FID
RSM
DoE
[313]
Catharanthus roseus
03% MeOH
03% EtOH
03% Acetone
03% Acetonitrile
03% Hexane
03% Dichloromethane
03% Chloroform
03% Toluene
[300]
Citrus depressa
Fruit
Nobiletin, tangeretin
0.41.6
200400
4080
Pomelo
Fruit
Flavonoids
1.72.4
280420
6080
Citrus junos
Yuzu
Seed
1028
200500
4070
Citrus latifolia
Tanaka
Lime
Fruit
1.63.6
90110
4060
276345
4050
HPLC
78108
4095
515% EtOH
HPLC
1030% EtOH
8.6 LCO2 kg1 sample
HPLC
Limonene
Peel
Citrus plants
Peel
Naringin
Grapefruit
Seed
Limonoids
naringin
0.10.6
345483
4060
Citrus sinensis
Korean orange
Peel
Perillyl alcohol
00.9
150200
3060
Citrus sinensis
Korean orange
Peel
Perillyl alcohol
04.4
200
50
Citrus sinensis
Orange
Fruit
613
200
40
Citrus sinensis,
C.limon
C. reticulata
Cytrus
Seed
02.41
85490
40
Orange
Pomace
0.853
100300
4050
Citrus unshiu
Press cake
L-limonene
palmitic and oleic acids
n-Butyl benzenesulfonamide
-sitosterol
[314]
Gravimetric Analysis
Antioxidant activity
RSM
DoE
Conventional solvent
extraction
Soxhlet extraction
[241]
Hydrodistillation
[316]
GC-FID
GC
GCMS
172448
70
020% EtOH
Cocos nucifera L.
Coconut
Kernel
9.864.7
517
120
Coffea arabica
Coffee
Husk/spent
0.59.7
100300
4060
Coffee
Residue
Coffea arabica
Coffea robusta
Coffee
Residue
Kahweol
cafestol
16-O-methylcafestol
Coffea arabica
Coffee
Bean
Cafestol, kahweol
Coffea arabica
Coffee
Bean
Caffeine
Coffea arabica
Coffee
Bean
Coffee
Bean
Robusta coffee
Husks
[136]
Modeling
Diatomaceous earth
Scale-up
Organic solvent extraction
Extractors effect
Fractionation
[138]
Antioxidant capacity
Ultrasound
Soxhlet extraction
[139]
GCMS
Coffea spp.
Coffee
Coix lachrymal-jobi
Adlay
Adlay
RSM
DoE
[320]
Soxhlet extraction
Diatomaceous earth
[321]
HPLC
Modeling
Soxhlet extraction
Antioxidant activity
[54]
Commiphora myrrha
Acorus calamus
Coptis chinensis
Commiphora
Acorus
Coptis chinensis
140190
4070
GC-FID
DoE
RSM
Soxhlet extraction
[62]
15
190
4055
Gravimetric analysis
Economic analysis
Tryacylglicerides prole
[61]
HPLC
Soxhlet extraction
DoE
[55]
017
6090
62.5 LCO2
152352
5070
250300
5090
5060
200300
60100
Seed
4.219.4
150350
Seed
8097
100300
11.682.6
Seed
Colchicine
Exudates
rhizomes
Rhizome
Furanogermacranes
Berberine
kg1
235380
152352
Seed
[140]
012
2459
Caffeine
[137]
Gravimetric analysis
[319]
Pilot plant
GC-FID
GC-EM
0340 kgCO2 kg1 sample
[318]
GC
Carotenoids
[317]
Maceration extraction
Reux extraction
DoE
RSM
Multistep extraction
GC
84 kgCO2 kg1 sample
20100 kgCO2 kg1 sample
[315]
sample
HPLC
[58]
RSM
DoE
HPLC
[59]
HPLC
4060
HRGC
Soxhlet extraction
Modeling
[57]
3055
Gravimetric analysis
[322]
GCMS
[323]
kg1
100250
3550
180 LCO2
247
2540
07% MeOH
HPLC
3.23.5
90
4550
0.157.53
200600
60
EtOH
MeOH
1,2-Propanediol
HPLC
sample
GCMS
HPLC
[56]
[60]
[324]
[168]
[325]
121
122
Table 1 (Continued)
Scientic name
Common name
Plant part
Target
Extraction
yield (wt%)
P (bar)
T ( C)
Analytical technique
Other Features
Ref.
Leaf
-Caryophyllene
34
80300
60
GCMS
Fractionation
Soxhlet extraction
Hydrodistillation
Modeling
[326]
100300
3050
Coriandrum sativum L.
Coriander
Seed
0.82.0
116280
3858
Coriandrum sativum L.
Coriander
Seed
0.050.6
90150
4050
Leaf
[327]
Hydrodistillation
[328]
GC
GCMS
[329]
GC
[330]
Gravimetric analysis
Modeling
[331]
Rancimat method
HPLC
GC
Solvent extraction
DoE
RSM
[332]
Coriandrum sativum L.
Coriander
Seed
016.4
200300
35
Corylus avellana L.
Juglans regia
Corylus avellana L.
Hazel
Walnut
Hazel
Fruit
0.050.6
180234
3548
Fruit
6080
180234
3548
Corylus avellana L.
Hazel
Fruit
150600
4060
GC
Solubility measurements
Modeling
[333]
Corylus avellana L.
Hazel
Fruit
300450
4060
Gravimetric Analysis
RSM
DoE
[334]
Leaf
Leaf
Cucumis melo
Cantalupensis
Cucumis melo var.
reticulatus
Cucurbita cifolia
Cucurbita cifolia
Cantaloupe
Seed
Seed
Seed
117
Catechins
Linoleic acid
125250
4080
00.9
6779
1028
22.730.4
600
40
4043
8693
180200
180200
3545
3545
Cucurbita maxima
Pumpkin
Seed
630
151344
3575
Cucurbita moschata
Cucurbita cifolia
Pumpkin
Seed
1098
250300
55
Cucurbita moschata
Pumpkin
Fruit
-Carotene,
-carotene
lutein ester
Pumpkin
Seed
Spinasterol
7,22,25-stigmastatrienol
Cuminum cyminum L.
Cumin
Seed
Cuminaldehyde
Curcuma longa L.
Turmeric
Rhizome
Curcuma longa L.
Turmeric
Rhizome
Curcuma longa L.
Turmeric
Rhizome
Turmerone
ar-turmerone
kg1
4.8 LCO2
sample
3 kgCO2 kg1 sample
270 kgCO2 kg1 sample
3001500 LCO2
kg1
sample
HPLC
DoE
[335]
GC
Modeling
[336]
GC
Antioxidant activity
Soxhlet
[337]
GC
Modeling
Soxhlet extraction
[338]
[146]
GC
DoE
RSM
Solvent extraction
Flow rates efffect
[148]
HPLC
Solvent extraction
DoE
RSM
[149]
GCMS
Solvent extraction
[147]
GCMS
kg1
250371
4076
150 LCO2
36.1
400
40
1.73.5
550
100
57
125325
3555
sample
25
200400
4060
6130 kgCO2
07
300
30
sample
GC-FID
Turmeric
Rhizome
Curcuminoids
4.56.5
250300
45105
Curcuma longa L.
Turmeric
Rhizome
Curcuminoids
4.522.6
250300
45
EtOH
Quince
Seed
100345
3065
RSM
DoE
[161]
GCMS
Steam distillation
[157]
GC-FID
[160]
GCMS
DoE
RSM
Ultrasound assisted
extraction
[340]
GC-FID
Solvent extraction
Steam distillation
Accelerated solvent
extraction
[341]
Spectrophotometry
Spectrophotometry
HPLC
GC
Cymbopogon citratus
Lemongrass
80
50
[339]
GCMS
6.916.1% EtOH/Isopropyl
Curcuma longa L.
[150]
[159]
[158]
Antitumor activity
Spectrophotometry
Cymbopogon citratus
Lemongrass
Cynara cardunculus L.
Leaf
Root
Cynanchum paniculatum
(Bge.) Kitag
Cardoon
Cyperus rotundus
Paenol
Seed
Rhizome
-Cyperone
0.41.7
80120
2350
0.16.0
100200
4555
4.724
150300
3555
2.6
200
40
kg1
Carrot
Root
Carotenes
0.25
330
40
24 kgCO2
EtOH
Daucus carota L.
Carrot
Root
Carotenoids
1.52.5
276551
4070
Carrot
Umbels
90
40
Carrot
Root
Carotol
Persimmon
Fruit
Carotenoids
Dillapiole
limonene
-calacorene
Herb
Geraniol
1.3
450
40
Plant
Plumbagin
Diplotaenia cachrydifolia
Aerial parts
Diplotaenia cachrydifolia
Aerial parts
Dracocephalum moldavica L.
Moldavian dragonhead
Drosera intermedia
Echinacea purpurea
sample
90100
4050
016 kgCO2
36
300
4080
520% EtOH
280000 LCO2 kg1 sample
0.32.5
101304
3575
0.02.4
101304
3575
0.6
200
40
Kava
Aerial parts
23
250300
4060
Saw Palmetto
St. Johns wort
212
1012
38
80
405
207483
80
4080
09.26
275413
4070
sample
[108]
[107]
Antimicrobial activity
Hydrodistillation
Particle size study
[109]
GC-FID
GCMS
[110]
[344]
HPLC
GCMS
Hydrodistillation
Soxhlet extraction
Solvent extraction
Two-step decompression
system
[193]
Palm
Fruit
Oil
77.8
140300
4080
Elaes guineensis
Palm
Fiber
Fatty acids
Carotene, Lipids
2.95.3
200300
4555
Elettaria cardamomum L.
Elettaria
Seed
25
90110
4050
Cardamom
Seed
100300
3555
Aerial parts
136340
4080
010% H2 O
010% MeOH
3040
Pilot scale
[346]
Elaeis guineensis
120300
NMR
HPLC
GC
HPLC
Kernel cake
00.9
[174]
[345]
Palm
Aerial parts
Purication
RSM
DoE
Elaeis guineensis
Horsetail
[183]
Palm
Equisetum giganteum L.
Soxhlet extraction
Biodiesel production
GCMS
Ekebergia capensis
Elaeis guineensis
Ephedra sinica
TLC
GC
HPLC
HPLC
MS
GC
GCMS
Fruit
Flower/stem
Root
Wood
Kernel
Triglycerides
[343]
GCMS
kg1
[342]
Particle size efffect
DoE
Ultrasonic extraction
Steam distillation
Soxhlet extraction
Microwave-assisted
extraction
2% (mol) H2 0
HPLCDAD
[347]
HPLC
[348]
NMR
GC
Uterotonic activity
Fractionation
Solubility analysis
Micrograph
[349]
[350]
[351]
GC-FID
Spectrophotometry
Modeling
[187]
GCMS
Hydrodistillation
Particle size effect
Subcritical propane extraction
Solvent extraction
Organic solvent extraction
[353]
[356]
053 kgCO2
kg1
HPLC
GCMS
GC
sample
GC
GCMS
Daucus carota L.
GCMS
HPLC-PDA
HSCCC
[352]
[354]
[355]
123
124
Table 1 (Continued)
Scientic name
Extraction
yield (wt%)
P (bar)
T ( C)
150250
40100
1,8-Cineole
1.42.0
80250
4060
Gallic acid
12.016.6
400
70
138414
4060
15% EtOH
200 LCO2 kg1 sample
100240 LCO2 kg1 sample
0.01.3
100200
4060
0.280.51
300
5070
Common name
Plant part
Target
Coca
Leaf
Cocaine
Eucalyptus camaldulensis
Eucalypt
Leaf
Eucalyptus camaldulensis
var.brevirostris
Eucalypt
Leaf
Eucalyptus citriodora
Melissa ofcinalis
Monarda citriodora
Cymbopogon citratus
Lemon eucalypt
Lemon balm
Leaf
Eucalyptus globulus
Eucalypt
Bark
Betulinic acid
betulonic acid
oleanolic acid
ursolic acid
3-acetyloleanolic acid
3-acetylursolic acid
-sitosterol
Eucalyptus globulus
Eucalypt
Bark
Phenolic
Eucalypt
Bark
120200
Betulinic acid
betulonic,acid
oleanolic acid
ursolic acid
3-acetyloleanolic acid
3-acetylursolic acid
-sitosterol
4060
Eucalypt
Bark
Betulinic acid
betulonic,acid
oleanolic acid
ursolic acid
3-acetyloleanolic acid
3-acetylursolic acid
-sitosterol
0.51.7
100200
40
Eucalyptus globulus
Eucalypt
Bark
Betulinic acid
betulonic,acid
oleanolic acid
ursolic acid
3-acetyloleanolic acid
3-acetylursolic acid
-sitosterol
0.041.2
100200
4060
Eucalypt
Eucalyptus
Leaf
Eucalyptus tereticornis
Eucalyptus
Clove
Ginger
Bud
leaf
rhizome
Seed
Bark
GC-FID
GCMS
DoE
RSM
[357]
GCMS
Hidrodistillation
[51]
RP-HPLC
Antioxidant activity
Hydrodistillation
[50]
GC
GCMS
Hydrodistillation
MANOVA
[358]
GCMS
Soxhlet extraction
Kinetic and equilibrium
properties calculation
[46]
HPLC-UV
ESI-MS
Antioxidant activity
DoE
RSM
[53]
GCMS
Modeling
[47]
GCMS
Soxhlet extraction
Fractionation
[49]
GCMS
DoE
[48]
Soxhlet extraction
[52]
Methyl morolate
Aucubin
Ref.
Eucalyptus globulus
Eucalyptus grandis
Eucalyptus globulus
Eucalyptus spathulata
Eucalyptus microtheca
Other Features
200
60
100300
4555
MeOH
GCMS
NMR
GC-FID
Hydrodistillation
[45]
0.811
67250
1540
GCMS
Modeling
Solubility measurement
Flow rate study
[359]
0.62.0
180300
45330
HPLC
Soxhlet extraction
[360]
Gravimetric analysis
Modeling
Scale-up
[361]
Gravimetric
Modeling
Extractor geometry study
Flow rates effect
Scale-up
SFC
[362]
Hidrodistillation
Soxhlet extraction
Particle sizes effect
DoE
[364]
Clove
Clove
Vetiver
Clove
Bud
66150
Bud
root
1550
5.813.3
100200
3540
Bud
Eugenol
17.1
300
50
Bud
Eugenol
1823
100300
3050
436 kgCO2
kg1
sample
HPLC
16,000 LCO2 kg1 sample
GC
GCMS
[363]
Eucalyptus globulus
Analytical technique
Eugenia uniora L
Brazilian cherry
Fruit
Sesquiterpenes
ketones
0.420.56%
150250
4060
Euphorbia rigida
Euphorbia
Leaf + stalk
Hydrocarbons
8.6
400
50
Fruit
Evodiamine
rutaecarpine
0.66.5
200400
5070
0.85.5
101303
4565
0.050.82
90190
120
3555
40
200350
4555
100300
3040
Evodia rutaecarpa
Ferula assa-foetida
Ferulago Angulata
Foeniculum vulgare
Thymus vulgaris
Fennel
Thyme
Aerial parts
Seed
leaf
Foeniculum vulgare
Fennel
Seed
Foeniculum vulgare
Fennel
Seed
(E)-anethol
213
Fennel
Fruit
098
90100
4050
35106 kgCO2
Fennel
Seed
1.55.5
80150
4057
sample
kg1
ANOVA
PCA
FDA
[365]
GC-FID
GCMS
Soxhlet extraction
[366]
HPLC
Soxhlet extraction
[367]
GC
GCMS
Hydrodistillation
[368]
GCMS
GC-O
Coupled distillation
[369]
[37]
GCMS
Hydrodistillation
[370]
GC
TLC
Hydrodistillation
Modeling
[371]
GC
GCMS
Gravimetric analysis
Two-step decompression
Hydrodistillation
[372]
GC
GCMS
Hydrodistillation
[373]
HPLC
RSM
DoE
Antioxidant activity
Antioxidant activity
[374]
Garcinia mangostana L.
Mangosteen
Fruit
Xanthones
0.236.5
200300
4060
100300 kgCO2
Garcinia mangostana L.
Mangosteen
Fruit
Xanthones
5.3715.14
180380
4060
Ginkgo biloba
Ginkgo biloba
Leaf
Flavonoids
00.24
100300
3565
UVvis
spectrophotometry
SEM
[239]
Ginko biloba
Ginko biloba
Leaf
0.02.3
100300
5080
HPLC
Ginko biloba
Leaf
4.511.4
242312
60120
HPLC
DoE
EtOH preextraction
Soxhlet extraction
[376]
Ginko biloba
Ginko biloba
Ginko biloba
Leaf
204340
4080
HPLCESI-MS
[378]
Glycine variety
Soybean
Distillate
Flavonoids
terpenoids
Terpene lactone
avonoids
Bilobalide
ginkolides
Fatty acids, tocopherols,
sterols, squalene
241310
5090
3265
Glycine variety
Soybean
Flakes
Lecithin
655
80
Glycine variety
Soybean
Distillate
Tocopherols
110318
5060
Glycine variety
Soybean
Bean
219
300500
Glycine variety
Soybean
Bean
07
100300
Glycyrrhiza
Root
Gossypium spp.
Cotton
Seed
Guaicum Bulnesia
Wood
Guilielma speciosa
Pupunha
Fruit
Helianthus annuus L.
Sunower
Seed
Helianthus annuus L.
Sunower
Distillate
Helianthus annuus L.
Sunower
Helianthus annuus L.
Helianthus annuus L.
Triglycerides
Gossypol
Fatty acids
carotenes
sample
RP-HPLC
kg1
6.7 LCO2
15% EtOH
sample
4060
4050
1.22.8
150350
4060
2.143.1
350550
6080
0.7
120
80
13
250300
5045
HPLCESI/MS
614 kgCO2
kg1
sample
12003600 LCO2 kg1 sample
6593 kgCO2 kg1 sample
kg1
090
250
40
0650 kgCO2
Polyphenol
20100
200700
4080
Distillate
Tocopherols
phytosterols
20100
150230
65
Sunower
Leaf
Allelopathic compounds
02
100500
3550
Sunower
Leaf
Allelopathic compounds
0.21.6
380
50
sample
[377]
[152]
HPLC
SCF
Fractionation
[155]
GC
ODS traps
[151]
Gravimetric analysis
[153]
HPLC
RSM
DoE
[154]
GCMS
Antibacterial activity
[379]
[380]
GCMS
RSM
DoE
Hydrostillation
GC
Modeling
[189]
HPLC
Modeling
Two-step decompression
system
[67]
Gravimetric analysis
[63]
DoE
Cluster Analysis
[66]
Pilot scale
Flow rates effect
Cluster Analysis
Biological activity
[64]
HPLCUV/Vis
HPLC-ELSD
GC
5% MeOH
5% DSMO
5% H2 O
[375]
Foeniculum vulgare
GCMS
[381]
[69]
125
126
Table 1 (Continued)
Scientic name
Common name
Plant part
Target
Extraction
yield (wt%)
P (bar)
T ( C)
Analytical technique
Other Features
Ref.
Helianthus annuus L.
Sunower
Leaf
Allelopathic compounds
0.11.2
300500
50
Gravimetric analysis
Cluster Analysis
Pilot scale
[65]
Helianthus annuus L.
Sunower
Seed
095
200600
4080
Gravimetric analysis
Modeling
Flow rates study
Particle sizes effect
[68]
Flower
04.5
100200
4060
4.868.12
300600
5095
Helichrysum italicum
Hemerocallis disticha
Daylily owers
Flower
Hibiscus cannabinus L.
Kenaf
Seed
Hibiscus cannabinus L
Kenaf
Seed
Lutein
zeaxanthin
0.520
Seabuckthorn
Fruit
Tocopherol
carotene
Hippophae rhamnoides L.
Sea buckthorn
Fruit
-Sitosterol
9.910.9
200600
4080
038 kgCO2
400600
4080
150350
3555
150600
4080
Hippophae rhamnoides L.
Sea buckthorn
Seed
0.12.9
150300
3045
Hippophae rhamnoides L.
Sea buckthorn
Seed
16
200300
3540
Hippophae rhamnoides L.
Sea buckthorn
Fruit
Hippophae rhamnoides L.
Seabuckthorn
Seed
Hippophae rhamnoides L.
Sea buckthorn
Fruit
Hordeum vulgare L.
Zea mays
Malt
Corn
Seed
Barley
Hordeum vulgare L.
Hylocereus undatus
White pitaya
Hypericum carinatum:
-Sitosterol
kg1
2.4 kgCO2
sample
030% (v/w) mEtOH
030% (v/w) EtOH
030% (v/w) 2-Propanol
0137 kgCO2 kg1 sample
267 LCO2
kg1
sample
kg1
150600
4080
2.489.28
7.609.68
100400
4575
81
138276
4065
1.11.4
650
60100
Tocochromanols
4.04.7
200450
40
Tocopherol
0.21.7
100350
4080
5.54
250
40
1.053.04
90/120/150/200
(sequence)
80
350
4060
Aliphatic hydrocarbons
Phloroglucinol,
benzophenone derivatives
Hyperforin, dhyperforin
bilobalide, ginkgolide A, B, Q
0140 kgCO2
sample
24 kgCO2 kg1 sample
Hypericum perforatum L.
14
100350
40
Hypericum perforatum L.
04.8
100200
4050
Hyssopus ofcinalis
Hyssop
Leaf + ower
Hyssopus ofcinalis
Hyssop
Root
Ilex paraguariensis
Illicium verum
Yerba mate
Chinese star anise
Leaf
Seed
Methylxantines caffeine
Fatty acids
Leaf
Jatropha curcas L.
Seed
Sesquiterpene
lactones, sesquiterpene acids
and avonoids
Triglycerides
Juglans regia L.
Walnut
Juglans regia L.
Walnut
Fruit
Terpinen-4-ol
1,8-cineol
30
100
[383]
Soxhlet extraction
Ultra-sonic assisted solvent
extraction
[384]
GCMS
HPLC
DoE
Soxhlet extraction
Antioxidant activity
RSM
[202]
HPLC
Solvent extraction
Soxhlet extraction
[226]
Gravimetric Analysis
2-Step decompression
Particle size effect
Particle size effect
Organic solvent extraction
[386]
HPLC
Modeling
[227]
HPLC
DoE
RSM
Antioxidant activity
Micrograph
ANOVA
Sensory evaluations
Soxhlet extraction
[388]
TLC
HPLC
Fractionation
Soxhlet extraction
Folch method
[390]
HPLC
Economic analysis
[391]
GCMS
Soxhlet extraction
Microwave-assistant
extraction
Aqueous enzymatic
extraction
[392]
HPLC
ANOVA
[393]
GCMS
Steam distillation
Particle size effect
[395]
Modeling
Optimization
[246]
Hydrodistillation
Modeling
SEM
DoE
Hydrodistiilation
[396]
Gravimetric
Antioxidant activity
[385]
Hypericum perforatum L.
Ginkgo biloba
Leaf
Gravimetric analysis
GC
111
Seed
Flower
sample
[382]
kg1
1.02.3
90100
4050
0.28 kgCO2
0.12.9
100350
4575
03.79
6.8023.72
120200
100300
4070
3050
0.65
90
50
14.448.9
250350
4060
sample
095
180234
3548
0550 kgCO2
68.2
689
85
sample
[527]
[389]
[394]
GC-FID
GC
GCMS
HPLC
HPLC
GCMS
kg1
[387]
RSM
DoE
Hydrodistillation
2-step decompression
[397]
[398]
[186]
[399]
GC
RSM
Soxhlet extraction
[184]
HPLC
Soxhlet extraction
Rancimat method
[400]
Gravimetric
[401]
Hippophae rhamnoides L
kg1
GCMS
GC-FID
HPLC
Juniperus communis L.
Juniper
Fruit
0.20.4
90200
40
Juniperus communis L.
Juniper
Fruit
4.512.5
90125
4050
618 kgCO2
Juniperus communis L.
Juniper
Fruit
0.14
80100
40
90200
40
30 kgCO2
kg1
200350
4555
05% MeOH
Juniperus communis L.
Juniper
Fruit
Juniperus communis L.
Juniper
Leaf
Juniperus oxycedrus L.
Juniper
Leaf + fruit
015
80100
50
Juniperus virginiana L.
Cedarwood
Wood
4.510.4
103689
40100
Juniperus Virginiana L.
Cedarwood
Wood
0.20.5
Cedrol
cedrene
Lavender
Flower
Laurus nobilis
Bay
Basil
Coriander
Dill
Spearmint
Marjoram
Peppermint
Oregano
Parsley
Rosemary
Sage
Thyme
Leaf
Tocopherol
Laurus nobilis L.
Laurel
Leaf
Monoterpenes, oxygenated
derivates
Laurus nobilis L.
Laurel
Leaf
1,8-Cineole
Laurus nobilis L.
Daphne
Laurus nobilis L.
1.2
414
100
1.37
100
40
0.82
90
50
340
3575
90250
40
Lavandula angustifolia
Lavender
Flower
Lavandula hybrida
Lavandin
Flower
Flower
Aerial parts
Lepidium apetalum
5.59.8
73207
4653
Linalyl acetate
7795
80120
4555
Linalool
linalyl acetate
camphor
1,8-cineole
79.499.0
10130
3595
015 LCO2
kg1
112 LCO2
kg1
sample
sample
sample
[402]
GC
GCMS
Hydrodistillation
[403]
GCMS
GC-FID
Steam distillation
[404]
GC-FID
GCMS
GCMS
GC-FID
GCMS
Hydrodistillation
Particle sizes effect
Hydrodistillation
[405]
2-Step decompression
Hydrodistillation
Antiviral activity test
[407]
GC
Steam distillation
[408]
GC
Water extraction
[409]
GC
Modeling
[410]
HPLC
Algae extraction
[135]
GC-FID
GC-M
GCMS
[132]
Hydrodistillation
2-step decompression system
HPLC
[133]
[134]
HPLC
Hydrodistillation
[131]
GCMS
RSM
DoE
Antioxidant activity
DoE
Periodic static-dynamic
procedure
[411]
RSM
DoE
Soxhlet extraction
[413]
RSM
DoE
Solvent extraction
Hydrodistillation
Fractionation
Antioxidant activity
[414]
GC-FID
[406]
GC-FID
120180
40
Seed
11.7935.56
200300
5070
GCMS
DoE
RSM
Antioxidant activity
[415]
1.62.2
200350
40
GCMS
[416]
Lovage
Celery
Seed
leaf
root
Ligusticum chuanxiong
Ligusticum
Root
Lingusticum chuanxiong
Linum usitatissimum L.
Flax
Waste
Linum usitatissimum L.
Flax
Seed
Ligustilide
butylidenephalide
Policosanols
05
200350
5570
03.85
350
70
7.4
552
60
35.741.0
413620
100
GCFID
GCITMS
[412]
12.212.7
Camphor
sample
40
0.9
1040 kgCO2
kg1
3550
028
Flower
9097273 LCO2
kg1
101405
Fruit
Lavender
80140
Seed
Lavandula angustifolia
sample
Hydrodistillation
GCMS
2.53.9
sample
GC-FID
GCMS
[212]
[417]
GCMS (SIM)
[418]
GCMS
[74]
GC-FID
RSM
Soxhlet extraction
Particle sizes effect
[73]
127
128
Table 1 (Continued)
Scientic name
Common name
Plant part
Target
Extraction
yield (wt%)
P (bar)
T ( C)
Analytical technique
Other Features
Ref.
Linum usitatissimum L.
Flax
Seed
2125
210550
5070
10210 kgCO2
HPLC
GC-FID
Soxhlet extraction
[71]
Linum usitatissimum L.
Flax
Seed
Lignans
1.42.7
350450
4060
HPLC
[72]
Linum usitatissimum L.
Flax
Straw
Wax
0.521.23
200400
4070
RSM
DoE
RSM
DoE
Linum usitatissimum L.
Flax
Seed
1040
300500
5070
Gravimetric analysis
[75]
Linum usitatissimum L.
Linseed
Seed
8.628.8
250
50
Linum usitatissimum
Brassica rapa
Brassica napus
Brassica juncea
Sinapis alba
Flax
solin
canola
mustard
Seed
2149
517
100
GC
[420]
Lippia
Leaf
Limonene
carvone
0.25.7
80120
4050
GC
[210]
Leaf/stem
Carvone
Hydrodistillation
Solvent extraction
Soxhlet extraction
SEM
Hydrodistillation
Simultaneous distillation
Microwave-assisted
Hydrodistillation
Antioxidant activity
GCMS,
LCMS
HPLC
Hydrodistillation
[422]
[419]
[421]
100140
4550
Thymol
1.21.8
6779
1025
GCMS
Steam distillation
Solvent extraction
Modeling
[423]
Lycopene
72.580.0
400
60
HPLC
[203]
Fruit
00.65
100180
4080
Leaf
1.4
200
50
100400
3575
0.84.7
50200
3565
0.74.7
50200
3565
24
100250
3040
240
250450
40
4060
1.06.6
101
50
1.64.2
100250
83197
2040
4486
100300
4080
230
100180
3540
1098
100
50
Lippia
Leaf + ower
Lippia sidoides
Lippia
Leaf
Lycopersicum esculentum
Corylus avellana
Tomato
Hazelnut
Pulp/fruit
Macadamia integrifolia
Macadamia
Marjoram
Mangifera indica L.
Mango
Leaf
Mangiferin
quercetin
Marchantia convoluta
Whole plant
Matricaria chamomilla
Chamomile
Flower
Matricaria recutita
Maydis stigma
Chamomile
Flower
Flower
Leaf
Maytenus ilicifolia
Melaleuca cajuputi
Leaf
Leaf
Melissa ofcinalis L.
GCMS
[70]
1.63.2
Marchantia convoluta
GCMS
Lemon balm
Aerial parts
Melissa ofcinalis, L.
Lemon balm
Leaf
Mentha pulegium L.
Pennyroyal
Leaf + lower
Mentha pulegium L.
Pennyroyal
Aerial parts
Mentha spicata
Salvia desoleana
Mint
Sage
Leaf
Matricine
chamazulene
-bisabolol
Flavonoids
Sesquiterpenes,
oxygenated derivatives
Gallic acid, protocatechuic
acid,
p-hydroxybenzoic acid
vanillic acid, syringic acid
Phenols
Pulegone
menthone
100200
3555
90
50
GC
Modeling
[424]
GCMS
Hydrodistillation
[209]
HPLC
Antioxidant activity
Hydrodistillation
[425]
GCMS
[426]
GCMS
GCMS
HPLC
EtOH
4000 LCO2 kg1 sample
020% (v/v) pentane
010% (v/v) EtOH
010% (v/v) MeOH
GCMS
UVVis
Spectrophotometry
HRGCFID
[427]
Soxhlet extraction
Steam distillation
Scale-up
Fractionation
Modeling
DoE
[428]
Soxhlet extraction
Maceration/Sonication
extraction
Particle sizes study
Organic solvent extraction
ANOVA
Soxhlet extraction
Organic solvent extraction
[430]
[429]
[237]
MeOH
GCMS
GC-FID
GC-MS
HPLC
Rancimat method
[434]
Gravimetric
Steam distillation
Modeling
[435]
GCMS
Hydrodistillation
[436]
GCMS
Fractionation
Hydrodistillation
[437]
kg1
15 kgCO2
053% MEtOH
sample
[431]
[432]
[433]
sample
Mentha spicata L.
Spearmint
Leaf
Mentha spicata L.
Spearmint
Mentha spicata L.
Spearmint
Mentha spicata L.
Spearmint
Microula sikkimensis
Mikania glomerata Spreng
00.32
69103
3949
Flake
1.32.9
100300
4050
Leaves
0.251.82
90170
3555
Leaves
Carvone
limonene
Catechin, epicatechin,
rutin, luteolin, myricetin,
apigenin and naringenin
Seed
Guaco
Momordica charantia L.
4060
30 kgCO2
2735
210270
3555
100
70
Fruit
Flavonoids
1.21.5
250350
3050
Leaf + stem
Kernel
Phenolic compounds
0.22.0
6.7136.13
103241
150300
2550
3560
-Sitosterol
0.32.0
200450
40
Myristica fragrans
Nutmeg
Seed
Terpenes
24
150200
4050
Myristica fragrans
Nutmeg
Fruit
2-Alkylcyclobutanones
151253
80
Leaf
Catnip
0.56.3
100350
Nepetalactone
4.65.7
413
40
Aerial parts
Nepetalactone
0.228.9
100355
3575
sample
Nicotiana spp
Nicotiana tabacum L.
Nigella damascena
Tobacco
Tobacco
Nigella
Leaf
Leaf
Seed
Solanesol
Nicotine, neophytadiene
Nigella sativa L.
Black Cumin
Seed
Thymoquinone
Nigella sativa L.
Black Cumin
Seed
Nigella sativa L.
Black Cumin
Seed
Nigella sativa L.
Black Cumin
Seed
0.41.0
10.650.0
80250
100300
150350
2560
40
40
0.20.3
150200
3545
1428
200500
40
0.831.7
Thymoquinone
200300
4070
150350
4050
[438]
GCMS
Hydrodistillation
Soxhlet extraction
Antioxidant activity
DoE
Particle size effect
[439]
HPLC
RSM
DoE
[441]
GC
DoE
[442]
HPLCUV
Maceration
Ultrasound
Infusion
[443]
DoE
RSM
Antioxidant activity
Antioxidant activity
RSM
DoE
[238]
[225]
0.24 LCO2
MeOH
Modeling
GCFID
GCMS
GCMS
GCMS
GC-HRMS
RSM
DoE
Anova
GC-FID
GCMS
Steam distillation
DoE
sample
90120 kgCO2 kg1 sample
0.3 LEtOH kg1 CO2
0.30.5 kgCO2 kg1 sample
120% H2 O
36 kgCO2 kg1 sample
UVVis
spectrophotometry
HPLC
[444]
[445]
[446]
[447]
GCMS
GC-FID
HPLC
TLC
GCMS
GCMS
GC
GCMS
GC
HPLC
01% EtOH
60 LCO2
Gravimetric Analysis
GC
[440]
[448]
[449]
Soxhlet extraction
2-step decompression system
DoE
Neural networks
Modeling
[450]
[451]
[452]
[453]
[234]
Antioxidant activity
[454]
Soxhlet extraction
[455]
Antioxidant
DoE
[235]
GCMS
ESI-MS
Economic analysis
[177]
Ocimum basilicum
Basil
Seedling
523
100300
3050
Ocimum basilicum
Basil
Seed
1.081.95
99243.7
2550
GCMS
Oil characterization
[176]
Ocimum gratissimum L.
Clove basil
Leaf
0.911.79
100300
40
GC-FID
[178]
Ocimum gratissimum L.
Ocimum micranthum Willd
Ocimum selloi Benth
Ocimum
Leaf
Eugenol
0.12.1
70
33
GCMS
Oenothera biennis L.
Primrose
Seed
Fatty acids
21
200300
4060
GC
Soxhlet extraction
Modeling
[185]
Olea europaea L.
Olive
Husk
475
100300
4060
Gravimetric Analysis
Soxhlet extraction
RSM
DoE
[230]
Olea europaea L.
Olive
Husk
6480
75350
4060
HPLC
RSM
DoE
Fractionation
[456]
Olea europaea L.
Olive
Leaf
Tocopherol
438
250450
4060
HPLC
Soxhlet extraction
[457]
Olea europaea L.
Olive
Pomace
Tocopherols
350
50
SFC
GCMS
Fractionation
[229]
GC-FID
DoE
RSM
Solubility
[200]
Olea europaea L.
Olive
Pomace
Squalene
03
75125
3343
517 kgCO2
kg1
sample
Coumarin
Mulberry
Nepeta persica
sample
Leaf
Morus alba
Gravimetric Analysis
Gravimetric analysis
kg1
100300
Noni
Nepatia cataria
3.06.9
Morinda citrifolia
Moringa oleifera
Myrtus communis L.
[175]
129
130
Table 1 (Continued)
Scientic name
Common name
Plant part
Target
Olea europaea L.
Olive
Leaf
Oleuropein
Ophiopogon japonicus
Root
6-Aldehydo-isoophiopogono
A,
6-formylisoophiopogonanone
A
Extraction
yield (wt%)
P (bar)
T ( C)
100300
50100
0.10.3
150350
5565
Analytical technique
Pear bush
Seed
4.26.0
250400
6550
Origanum majorana
Marjoram
020
100400
4060
Origanum majorana
Marjoram
Aerial parts
3.8
450
50
Origanum virens L.
Oregano
Flower
595
50300
2747
Origanum virens L.
Oregano
Bract
5080
70200
2747
Origanum vulgare L.
Thymus zygis L.
Salvia ofcinalis
Rosmarinus ofcinalis L.
Origanum vulgare L.
Oregano
Thyme
Sage
Rosemary
Oregano
Leaf
0.93.2
300
40
Leaf
0.115.3
150300
4060
07% EtOH
Origanum vulgare L.
Oregano
150
40
Oriza spp.
Rice
Bran
205320
4580
Oriza spp.
Rice
Bran
Oriza spp.
Rice
Bran
Oriza spp.
Rice
Bran
-Oryzanols
Oryza sativa L.
Rice
Bran
Aroma
Oryza sativa L.
Rice
Bran
Oryza sativa L.
Rice
Bran
Panax ginseng
Ginseng
Panax ginseng
Ginseng
Lipids, -oryzanol
Niosomes
[145]
HPLC
GCMS
Pilot scale
Two-step decompression
[142]
Pilot scale
[141]
7% EtOH
LCMS
LC-DAD
GCMS
Pilot scale
Antimicrobial activity
[143]
HPLC
Fractionation
Deacidication
LikensNickerson extraction
[97]
120
50
020
100400
5060
11.2
200
40
Solvent extraction
[96]
Soxhlet extraction
Solubility analysis
[94]
GC
Soxhlet extraction
[95]
GCMS
Cooking stage
[91]
GC-FID
Deacidication
Pilot scale
Particle size effect
Economic study
Soxhlet extraction
Modeling
Biological activity
[92]
HPLC
TPC
[93]
3560
HPLC
Soxhlet extraction
Ultrasonic extraction
[129]
240
45
Gravimetric
[130]
300
50
bis(2-ethylhexyl) sodium
sulfosuccinate/EtOH
3% (v/v) EtOH
HPLC
[127]
SEM
[214]
GCMS
[215]
HPTLC
GC
HPLC
ICP-MS
Soxhlet extraction
Three-step decompression
[463]
Ginsenosides
2040
207483
110
Pandan
Leaf
2-Acetyl-1-pyrroline
01
200
50
6250 LCO2
06% EtOH
kg1
HPLC
Gravimetric
HPLC
104312
Root
2-Acetyl-1-pyrroline
[144]
40
Ginseng
Bran
[461]
Modeling
Effect of particle size
SEM
300
Panax quinquefolius
Leaf
[460]
HPLC
Antioxidant activity
DoE
RSM
Organic solvent extraction
Rancimat method
DoE
RSM
Gravimetric analysis
18.1
Ginsenoside
Millet
GCMS
[462]
4080
Root
Pandanus
[459]
Hydrodistillation
3075
American ginseng
DoE
Soxhlet extraction
Antimicrobial tests
680
Panax quinquefolium
HPLC
ESI-MS
NMR
GC
GCMS
345689
Ginsenosides
[458]
HPLC
LC-ESI
GC
025
1.110.7
Root
Ref.
sample
120455
4080
2040 LCO2
300500
4060
sample
HPLC
LCMS
GCMS
GC-FID
[128]
Opuntia dillenii
Other Features
Papaver Somniferum L.
Poppy
Seed
15.838.7
210550
5070
0.32.0
150350
4565
Paullinia cupana
Guaran
Seed
Caffeine
04
100400
4070
Pelargonium graveolens
Geranium
Root
Geraniol
0.23.8
100300
4070
Pelargonium graveolens
Geranium
Root
Citronellol
80160
40100
Perovskia
Aerial parts
100300
4565
Persea americana
Avocado
Fruit
59.5662.87
420450
4045
0.41.13
100200
4050
Persea indica
Branch
Ryanodanes
05% MEtOH
05% EtOH
05% Dicloromethane
05% n-hexane
78 102 LCO2 kg1 sample
Parsley
Seed
131
100150
3545
Peumus boldus M.
Boldo
Oregano
Leaf
branch
0.43.1
100
40
Peumus boldus M.
Boldo
Bark
1.62.9
400600
4060
Peumus boldus M.
Boldo
Leaf
0.52.9
60450
3060
Pfafa glomerata
Brazilian Ginseng
Root
-Ecdysone
0.180.56
100300
3050
Phyllanthus emblica
Emblica
Fruit
Phenolic compounds
1.12.5
150250
555
Physalis peruviana
Physalis
Leaf
Flavonoids
phenols
3.615.5
400
60
05% EtOH
Picea abies
Spruce
Bark
2.53.3
260
70
Pimpinella anisum L
Aniseed
Seed
3.110.7
80180
30
Pimpinella anisum L
Pinus brutia
Aniseed
Pine
Seed
Bark
Pinus pinaster
Pinus sylvestris L.
Pine
Wood
Sawdust
Piper amalago
Boldine
Catechins
epicatechin
Phenolics
Fatty and resin acids
0.32.1
0.11.6
kg1
GCMS
[464]
DoE
HPLC
[465]
[466]
GCMS
Steam distillation
[194]
GCMS
[195]
GC
GCMS
[208]
[467]
HPLC
GCMS
Modeling
Organic solvent extraction
[468]
GC
Hydrodistillation
Modeling
[469]
Matrix pretreatment
[470]
HPLC
Antioxidant activity
Solvent extraction
[471]
HPLC
GC-FID
GCMS
[472]
TLC
HPLC
GCMS
Antioxidant activity
[473]
[474]
NMR
HPLC-DAD-MS/MS
Solvent extraction
[475]
GCMS
TLC
Modeling
[476]
Neural networks
Pilot scale
Sonication
[477]
[478]
[240]
80180
200800
30
2780
0.22.9 kgCO2
03% (w/w) EtOH
Gravimetric Analysis
HPLC
100250
74250
3050
4060
GC-FID
GCMS
Soxhlet extractions
[479]
[188]
HPLC
[480]
Gravimetric analysis
[481]
Root
125250
4060
Piper nigrum
Pepper
Seed
160260
3550
Piper nigrum L.
Black pepper
Fruit
90150
4050
GCMS
Modeling
[482]
Pistachia vera
Pistachio
Seed
100350
4565
015% MeOH
Gravimetric Analysis
[483]
Pistacia lentiscus L.
Pistachio
Berry + leaf
90200
50
Pistacia vera L.
Pistachio
Seed
10150
4080
Plukenetia volubilis
Sacha inchi
Seed
41.950.1
300400
4060
GC
Modeling
Particle size effect
Soxhlet extraction
Cold Pressing
[486]
Prunus amygdalus
Almond
Seed + kernel
1565
330
50
HPLC
Multifactor analysis of
variance
Micrograph
[487]
Prunus armeniaca L
Apricot
Bagasse
36
304507
4060
Spectrophotometry
Modeling
[106]
012
Phenolic
0.45
Omega-3
-Carotene
GCMS
EtOH
n-hexane
GC-FID
GC
[484]
[485]
131
132
Table 1 (Continued)
Scientic name
Common name
Plant part
Apricot
Pomace
Prunus armeniaca L.
Apricot
Kernel
Prunus armeniaca L.
Apricot
Kernel
Prunus armeniaca L.
Apricot
Pomace
Prunus avium L.
Cherry
Pomace
Prunus avium L.
Cherry
Fruit
Prunus avium L.
Cherry
Seed
Prunus persica
Peach
Prunus persica
Peach
-Carotene
Extraction
yield (wt%)
P (bar)
T ( C)
Other Features
Ref.
Spectrophotometry
HPLC
Solvent extraction
Particle size effect
Flow rate effect
[102]
SEM
Gravimetric Analysis
[104]
GC
RSM
[103]
HPLC
RSM
Static extraction
[105]
Antioxidant activity
RSM
DoE
Solvent extraction
Fractionation
Solvent extraction
Hexane extraction
RSM
[488]
18
304507
4060
542
300600
4070
422
300450
4060
39
133473
4377
50200
2060
0.5
250
50
28
180220
4060
Kernel
118
150250
40
Gravimetric Analysis
Modeling
Particle size effect
Scale-up
[491]
Seed
030
150198
4051
GCMS
[492]
HPLC
[494]
Ultrasound assisted
[495]
TLC
GCMS
Modeling
Soxhlet extraction
Ultrassound extraction
Hydrodistillation
[496]
HPLC
DoE
Particle sizes effect
[497]
HPLC
Pilot scale
[498]
Gravimetric Analysis
RSM
DoE
[499]
-Carotene
5150 LCO2
Analytical technique
sample
TLC
HPLC
GC
Prunus persica
Peach
Kernel
3.824
100300
5070
Prunus spp.
Almond
Seed
298
350550
3550
Prunus spp.
Almond
Seed
017
200320
4060
Psidium guajava
Guava
Leaf
1.33.9
100300
8654
Psoralea corylitolia L.
Fructus Psoraleae
Seed
Psoralen
isopsoralen
5.09.8
260340
4060
Pteris semipinnata L.
Aerial parts
Ent-11a-hydroxy-15-oxokaur-16-en-19-oic-acid
0.000.05
300
55
Pueraria lobata
Root
Puerarin
daidzein
rutin
0.22.0
150250
4060
Pueraria lobata
Root
Puerarin
0.40.6
100300
4060
HPLC
132468
3370
HPLC
180
40
0.712.8
Punica granatum
Pomegranate
Seed
Quercus urfassea L.
Quercus suber L.
Oak
Fruit
Quercus suber L.
Oak
Cork
Triterpenes
200250
50
Herb
Rosavin
1821
200
7080
Rhodiola rosea
[493]
FAME
HPLC
TLC
13 C NMR
[500]
RSM
DoE
Flow rates effect
Soxhlet extraction
Soxhlet extraction
[501]
[503]
HPLC
[502]
[504]
Soxhlet extraction
RSM
DoE
[505]
Gravimetric
Micrograph
[506]
Gravimetric
Modeling
[507]
Gravimetric
Soxhlet extraction
Ultrasound water bath
Microwave extraction
Subcritical uid extraction
ANOVA
[508]
[509]
Gravimetric
SEM
Modeling
[510]
Seed
4.77.1
300500
4060
Rose hip
Seed
00.35
300
40
Rosehip
Seed
07.5
300400
4050
Rosa canina L.
Rose hip
Seed
5.72
250
30
Rose hip
Seed
300700
60
Rosa spp.
Hiprose
Seed
103689
4070
07.4
[490]
Spectrophotometry
Gravimetric
Rose hip
[489]
Prunus armeniaca L.
Target
Rosemary
Leaf
Rosmarinus ofcinalis L.
Rosemary
Leaf
Rosmarinus ofcinalis L.
Rosemary
Leaf
Rosmarinus ofcinalis L.
Foeniculum vulgare
Pimpinella anisum
Rosemary
fennel
anise
Leaf
seed
leaf
Rosmarinus ofcinalis L.
Rosemary
Leaf
Rosmarinus ofcinalis L.
Rosemary
Leaf
Rosmarinus ofcinalis L.
Rosemary
Leaf
Rosmarinus ofcinalis L.
Rosemary
Leaf
Salvia lavandulifolia
Spanish sage
Leaf/ower
Salvia miltiorrhiza
Danshen
Root
Salvia ofcinalis L.
Sage
Salvia offcinalis L.
Ocimum basilicum
Origanum vulgare
Levisticum offcinale
Sage
Basil
Oregano
Lovage
90400
4060
100300
3040
100180
4060
0.13.5
100350
3040
0.53.1
100400
40
100205
4055
300350
4060
02% EtOH
1,8-Cineole
250
60
1.21.8
90100
4050
05
200400
4060
1246
250350
40
Leaf + ower
0.21.5
172255
55
Santalum album
Boswellia carterii
Wood (resin)
1.36.5
90120
4560
Santolina chamaecyparissus
Flower
0.11.4
8090
4050
Santolina insularis
Aerial parts
80120
4570
Terpinene
thymol
carvacrol
5.98.7
303405
5575
Carnosol
carnosic acid
rosmarinic acid
0.876.42
300450
40
0.91.4
90250
0.91.6
Satureja hortensis L.
Savory
Satureja hortensis L.
Savory
Satureja montana
Savory
Aerial parts
Satureja montana
Savory
Herb
Aerial parts
15
Phenols
Tanshinones
Thymoquinone
SFC-FID
GC
Spectrophotometry
TLC
Gravimetric Analysis
[77]
UPLCMS
Antioxidant activity
[78]
GCMS
Antioxidant activity
Three steps sequential
Two-step decompression
[79]
GC-FID
GCMS
[80]
GCMS
Hydrodistillation
Modeling
Flow rate effect
Particle size effect
[511]
HPLC
DoE
[512]
Gravimetric Analysis
3-Step decompression
Antioxidant activity test
Antimicrobial activity
Hydrodistillation
[513]
GCMS
Hydrodistillation
[514]
GC
GCMS
Hydrodistillation
SEM
Particle size effect
Flow rate effect
2-Step decompression
Hidrodistillation
Cytotoxic and antimicrobial
activity
Two steps of DoE
RSM
Hydrodistillation
[515]
Gravimetric Analysis
RP-HPLC
GC
GCMS
[82]
Hydrodistillation
Solvent extraction
Modeling
Particle size effect
Flow rate effect
2-stage separation
Modeling
Steam distillation
Economic analysis
GCMS
GC-FID
[76]
[81]
[83]
[179]
[516]
[517]
GC-FID
HPLC
Antioxidant activity
Organic solvent extraction
[518]
40
GC
Hydrodistillation
Soxhlet extraction
Antioxidant activity
[519]
90100
4050
GC
GCMS
Hydrodistillation
SEM
Particle size effect
Flow rate effect
Hydrodistillation
Steam distillation
2-step decompression
[236]
Schinus molle L.
Leaf
0.40.7
90
50
Schisandra chinensis
Fruit
18.5
250
50
GCMS
Steam distillation
Soxhlet extraction
Ultrasonic extraction
[521]
Schisandra chinensis
Stem + leaf
0.21.3
200270
4060
RP-HPLC
Modeling
[233]
Lignan
cinnamic acid
GCMS
Rosmarinus ofcinalis L.
[520]
133
134
Table 1 (Continued)
Scientic name
Common name
Scutellaria baicalensis
Plant part
Target
Extraction
yield (wt%)
P (bar)
T ( C)
Root
Baicalin
0.18.3
200400
4060
Analytical technique
Other Features
Ref.
HPLC
DoE
Soxhlet extraction
[522]
Spectrophotometry
Solvent extraction
[523]
GCMS
Hydrodistillation
[524]
Sesamum indicum L.
Black Sesame
Seed
4152
200400
3585
Leaf
0.130.60
90
50
Silybum marianum
Silybum
Seed
525
100300
580
HPLC
Soxhlet extraction
Acid value test
Modeling
[525]
Simmondsia chinensis
Jojoba
Seed
1052
300600
7090
Gravimetric Analysis
Solvent extraction
Flow rate effect
Particle size effect
[526]
0.010.70
200600
4060
Vitamin E
Stem
Sinomenine
Lycopene
4570
250350
4575
0.0010.002
250450
4070
200400
40100
00.03
300
4080
0.0010.004
300460
4080
Lycopene
200500
40100
Lipids
Lycopene
-carotene
250300
6080
Pomace
Lycopene
365533
4763
Tomato
Fruit
Lycopene
-carotene
400
4070
Tomato
Lycopene
200400
7090
05% (w/w)EtOH
05% (w/w) Canola oil
7180 LCO2 kg1 sample
Root
Quinolizidine alkaloids
oxymatrine
matrine
Spilanthol
0.30.5
200300
4555
1.24.8
250
50
150350
4080
020% EtOHH2 O
200250
30
90120
50
175325
4555
Tomato
Skin
Solanum lycopersicum L.
Tomato
Fruit
Solanum lycopersicum L.
Tomato
Fruit
Lycopene
Solanum lycopersicum L.
Tomato
Fruit
Lycopene
Solanum lycopersicum L.
Tomato
Waste
Trans-Lycopene
Solanum lycopersicum L.
Tomato
Waste
Lycopene
Solanum lycopersicum L.
Tomato
Fruit
Solanum lycopersicum L.
Tomato
Waste
Solanum lycopersicum L.
Tomato
Solanum lycopersicum L.
Solanum lycopersicum L.
Sophora avescens
Jamb
Stevia rebaudiana
Flower
leaf
stem
Leaf
Stevia
Leaf
Syzygium aromaticum L.
Clove
Bud
Tagetes erecta
Marigold
Flower
Stevioside
rebaudioside A
01.2
Lutein esters
0.40.7
HPLC
HPLC
Spectrophotometry
[27]
HPLC
Cluster analysis
[30]
HPLC
DoE
RSM
DoE
ANOVA
RSM
[35]
[33]
HPLC
UVVis
Gravimetric
HPLC
[32]
HPLC
Antioxidant activity
RSM
DoE
Soxhlet extraction
Pretreatment effect
Soxhlet extraction
[204]
GCMS
GC-FID
HPLC
HPLC
TLC
Modeling
[34]
Scale-up
DoE
[529]
GC
Hydrodistillation
Organic Solvent extraction
Antioxidant activity
Anti-inammatory activity
Solvent extraction
RSM
DoE
[530]
Modeling
[532]
Modeling
[533]
Ultrasound assisted
Modeling
Particle size effect
[534]
HPLC
HPLC
HPLC
[528]
HPLC
HPLCUV
GC-FID
GCMS
TLC
HPLC
Spectrophotometry
[26]
[28]
[29]
[31]
[531]
335450
0.030.07
Solanum lycopersicum L.
Tanacetum cinerariifolium
(Trevir) Sch. Bip.
Glebionis coronaria (L.)
Spach
Glebionis segetum (L.) Fourr
Plagius osculosus (L.) Alavi
and Heywood
Chrysanthemums
Flower
Pyrethrins
Tanacetum parthenium
Feverfew
Flower
Parthenolide
Tanacetum parthenium
Feverfew
Seed
Parthenolide
Dandelian
Leaf
-Amyrin
-sitosterol
Taxus baccata
Yew
Needle
10-Deacetylbaccatin III
Squalene
Terminalia catappa
Theobroma cacao
Cocoa
Seed
Cocoa
Bean
Theobroma cacao
Cocoa
Bean
4050
200800
4080
1.54
3565
100400
6575
718
138275
40
5292
350
60
25% EtOH
152248
50
200400
50
3553 kgCO2
kg1
150450
313
423 kgCO2
sample
kg1
sample
0750 kgCO2 kg1 sample
Cupuacu
Seed
560
248352
5070
Thymbra spicata
Thymbra
0.67
80120
4060
Thymus vulgaris L.
Thyme
Flower + leaf
0.71.9
200
40
Thymus vulgaris L.
Thyme
550
100
40
Thyme
Flower
Thymus vulgaris L.
Thyme
Leaf
Thymus vulgaris L.
Thyme
Thymus vulgaris L.
Thyme
Leaf
Thymus vulgaris L.
Thymus zygis L.
Thyme
Thyme
Leaf
Leaf
Thyme
Aerial parts
Torresea cearensis
Emburana
Seed
Coumarin
Fruit
Diosgenin
Leaf
Root
Seed
Isoavones
Tribulus terrestris L.
Trifolium pratense L.
Trifolium pretense L.
Trigonella foenum-graecum L.
Red clover
Red clover
P-Cymene
y-terpinene
linalool
thymoquinone
Phenolic
Thymol
0140 kgCO2
kg1
Theobroma grandiorum
Thymus vulgaris L.
Hydrodistillation
Cytotoxic activity
Antiviral activity
[535]
HPLC
Pilot scale
2-step decompression
[197]
HPLC
SFC
Caffeine
theobromine
Thymol, carvacrol
GCMS
sample
Densitometry
DoE
RSM
Organic solvent extraction
[537]
HPLC
Soxhlet extraction
[180]
GCMS
HPLC
HPLC
Gravimetric Analysis
Antioxidant activity
[201]
[117]
GC
Supercritical ethane
[115]
HPLC
Ethane extraction
[116]
HPLC
Supercritical ethane
extraction
Modeling
RSM
DoE
Steam distillation
[538]
Gravimetric Analysis
Modeling
[36]
HPLC
GCMS
Steam distillation
Modeling
[540]
GC
Hydrodistillation
Soxhlet extraction
Antioxidant activity
[39]
Modeling
Conventional solvent
extraction
Ultrassound assisted
extraction
Soxhlet extraction
Pilot scale
[42]
Steam distillation
Soxhlet extraction
Pilot scale
Soxhlet extraction
[44]
GCMS
kg1
112
90100
40
2852 kgCO2
1.15
100
40
0.64.0
80400
40
4.9
400
60
3.34.7
1.2
150400
100150
40
40
011
80214
3057
85240
3550
17.4
100300
3555
2.334.08
100400
137
200300
3575
80
4550
sample
GCMS
HPLC
GCMS
GC
GCMS
Hydrodistillation
Sensorial analysis
[539]
[43]
[38]
[40]
GC
GCMS
RSM
DoE
Steam distillation
[41]
HPLC
[541]
HPLC
Gravimetric Analysis
5% (v/v) (14:1) MeOH/H2 O
n-Hexane
[536]
HPLC/MS
GCMS
HPLC-FLD-MS
Antioxidant activity
RSM
DoE
Soxhlet extraction
Theobroma cacao
29
90300
[542]
[543]
[544]
[545]
135
136
Table 1 (Continued)
Scientic name
Common name
Tripterygium wilfordii
Plant part
Target
Extraction
yield (wt%)
P (bar)
T ( C)
Root
Tripterine
0.37
100300
4070
Analytical technique
Other Features
Ref.
Acetone
EtOH
Ethyl acetate
n-butanol
019% EtOH
HPLC
Soxhlet extraction
[546]
TLC
Soxhlet extraction
Butt extraction
Soxhlet extraction
Physicochemical
characterization
[165]
Gravimetric Analysis
HPLC
Soxhlet extraction
[167]
GC
HPLC
[162]
HPLC
DoE
RSM
Antioxidant activity
Antioxidant activity
Conventional solvent
extraction
[163]
Soxhlet extraction
[547]
Triticum spp.
Wheat
Flour
Lipids
0.61.4
172517
60100
Triticum spp.
Wheat
Germ
Tocopherols
7.38.0
50300
1060
Triticum spp.
Wheat
Germ
5092
250380
55
Triticum spp.
Wheat
Germ
1421
400550
4080
Wheat
Germ
Triticum spp.
Wheat
Undaria pinnatida
Tocopherol
148602
4060
Bran
100300
4060
Seaweed
Aerial parts
230
100
Valeriana ofcinalis L.
Valerian
Root
Valeriana ofcinalis L.
Valerian
Root
Valeriana ofcinalis L.
Valerian
Root
Valerian
Root
Vernonia galamensis L.
Iron weed
Seed
Vernolic acid
Vetiver
Root
Khusimol,
zizanoic acid
Vetiveria zizanioides L.
Vetiver
Root
Valerenic acid
Valerenic acids
0.59.5
1060 kgCO2
kg1
sample
0.22.0
100200
4070
0.12.5
100200
4050
1.84.9
152228
3761
0.81.9
250400
3565
2040
138690
4080
3.2
200
40
3.904.35
300
40
GC-FID
[164]
[166]
[548]
HPLC
GC-FID
GCMS
Modeling
SEM analysis
[549]
GC
GCMS
GCMS
Mixture design
[550]
Hydrodistillation
[551]
Gravimetric Analysis
GC-FID
Deacidication
[552]
GC
GCMS
GC-FID
Hydrodistillation
Sensory evaluation
[553]
HPLC
Pilot plant
Antioxidant activity
[554]
GCMS
RSM
DoE
Hydrodistillation
Soxhlet extraction
[555]
GC-FID
[556]
GS-MS
RSM
DoE
[554]
TLC
GC
Hydrodistillation
Kinetics study
[557]
TLC
TLC-densitometry
GC
HPLC
Soxhlet extraction
DoE
RSM
[558]
Vetiveria zizanioides L.
Vetiver
Root
0.461.38
100220
4063
240 kgCO2
Vetiveria zizanioides L.
Vetiver
Root
2.03.5
200
40
Vetiveria zizanioides L.
Vetiver
Grass
06
100190
4050
Vetiveria zizanioides L.
Vetiver
Root
3.44.7
100300
40
Chaste tree
Fruit
6.4
100450
4060
Vitis vinifera L.
Grape
Seed
11.5
180220
4050
Antioxidant activity
[21]
Grape
Seed
016
160200
40
GC-FID
Vitis vinifera L.
GC-FID
[20]
Vitis labrusca B.
Grape
Seed
5.712.3
137167
6776
58% EtOH
HPLC
Matrix enzymatic
pretreatment
RSM
DoE
Antiradical activity
Vitis spp.
Grape
Pomace
0.021.2
150300
40
2866% EtOH
HPLC
Vitis spp.
Grape
Seed
012
280550
40
Vitis vinifera L.
Grape
Seed
816
250
80
Vitis vinifera L.
Grape
Fruit
4060
520% MeOH
Tryacylglicerides
Gallic acid
protocatechuic acid
phydroxybenzoic
acid
Anthocyanins
Glycosides
sample
GCMS
HPLC
GC
[15]
Fractionation
[24]
[13]
[3]
DoE
Sand bed
Diatomaceous earth
[19]
Triticum spp.
-Tocopherol
GC
HPLC
Grape
Marc
Polyphenols
270350
4050
Vitis vinifera L.
Vitis vinifera L.
Grape
Grape
Skin
Marc
Resveratrol
Polyphenols
80150
40
50
Vitis vinifera L.
Grape
Marc
Polyphenols
350
50
Vitis vinifera L.
Grape
Pomace
Phenolics
150
40
Vitis vinifera L.
Grape
Seed
250
40
Vitis vinifera L.
Grape
Seed
0.17.9
60254
3060
Vitis vinifera L.
Vitis vinifera L.
Grape
Grape
Pomace
Seed
2.828.9
0.000.15
80350
200300
9850
40
Vitis vinifera L.
Grape
Seed
2.56.2
300400
3540
Vitis vinifera L.
Grape
Seed
9.110
655
80
Vitis vinifera L.
Grape
Pomace
Phytosterols
6.611.2
370
65
Vitis vinifera L.
Grape
Fruit/seed
Polyphenols
0.010.03
200500
45
Vitis vinifera L.
Grape
Skin
(+)-Catechin,
()-epicatechin,
quercetin,
rutin
100300
60
Vitis vinifera L.
Grape
Seed
350
40
Vitis vinifera L.
Grape
Seed
250300
3050
Yellow Horn
Seed
165334
2862
Zanthoxylum bungeanum
Phenol
Phenolic
13.42
4061
Seed
Zataria
Zea mays
Corn
Germ
Zea mays
Corn
Bran
2.34.1
Rhizome
Zingiber ofcinale
Zingiber ofcinale
Ginger
Ginger
Rhyzome
Rhizome
Gingerols
Gingerol
Zingiber ofcinale
Ginger
Rhizome
Gingerol
Ginger
Rhizome
Zingiber ocinale
Ginger
Rhyzome
[559]
[560]
[18]
Electrophoresis
GCMS
Biological activity
Diatomaceous earth
Antioxidant activity
Soxhlet extraction
5080
015% EtOH
3555
210525
4086
96
345690
4080
2.89.1
20150
3060
160
160
40
40
1.92.7
200250
2535
090
150250
2040
[17]
[10]
[9]
GC-FID
GC
Propane extraction
[11]
HPLC
HPLCMS
Solidliquid extraction
Solubility tests
[22]
[16]
HPLCELSD
DoE
Scale-up
[7]
HPLCUV
SFC-UV
HPLCMS
Fractionation
[5]
GCMS
GC-FID
HPLC
Solvent extraction
[6]
UVvis
spectrophotometer
[14]
HPLC
[8]
Scale-up
Economic analysis
HPLC
200400
40
Diatomaceous earth
HPLC
Amperometric
Detection
101304
Thymol; l-terpinene;
r-cymene
Phytosterols
HPLC
GCMS
[23]
[25]
DoE
Particle sizes effect
Soxhlet extraction
Flow rate effect
Antioxidant activity
RSM
RSM
Antioxidant activity
[561]
HPLC
GC
GCMS
Steam distillation
[563]
HPLC
GC-FID
Modeling
[564]
HPLC-FLD-MS
[223]
SFC
GCMS
[562]
Vitis vinifera L.
Steam distillation
DoE
Ultrassound assisted
Ultrasound
Particle size effect
FE-SEM
[565]
GCMS
GC-FID
DoE
Modeling
[122]
GCMS
Modeling
[123]
GCMS
Drying effect
[125]
[126]
[126]
137
138
Fig. 1. Type of the biomass matrices used in SFE works along 20002013, for a total of 544 publications considered.
and growth mechanisms [192]. Terpenoids comprise chemical entities that have one or more isoprene units (IU) linked together and
repositioned through cyclization, functionalization and arrangement. The extraction of these compounds has been one of the
dominant objectives driving SFE research. Due to their diversity,
it is common to classify these molecules according to the number
IU, giving rise to different subgroups:
- monoterpenoids, with two IU, such as geraniol [193,194] or citronellol [195];
- sesquiterpenoids, three IU, like artemisin [196] or parthenolide
[197];
- diterpenoids, with four IU, like cafestol [55,62] and kahweol
[55,62].
- triterpernoids, with six IU, such as ursolic acid [4749,52] or squalene [152,198201];
with
eight
IU,
like
-carotene
- tetraterpenoids,
[31,32,102,105,106,108,149,187,189,202]
or
lycopene
[2629,3133,35,203206];
When considered from an end-user point of view, terpenoids
affect the organoleptic perception of natural products, as they can
have fragrant and colorant features. For instance, tetraterpenoids
are typically responsible for the colors that many fruits and vegetables exhibit within red, brown and yellow tones. Nevertheless it is
at avor and fragrance levels that these compounds are more frequently investigated in view of food and cosmetic applications. For
instance, terpenoids such as limonene, camphor, geraniol, 2-acetyl1-pyrroline or labdanum are known for their scent and avoring
properties, and have been reported in SFE extracts [194,207216].
On the other hand, advantages may be taken from the protection functions played by these compounds when applied to human
health. Several terpenoids have seen their bioactivity proved for
many functions. For instance, triterpenic acids like ursolic, oleanolic, betulinic and betulonic acids exhibit a wide range of biological
activities being recognized as promising compounds for the development of new multi-targeting bioactive agents [217220].
Within the group of triterpenoids, phytosterols are a particular
class of compounds that assume a special importance for human
health purpose in view of reducing cholesterol intestinal absorption. The most representative phytosterols occurring in vegetable
139
Fig. 2. Main families of compounds found in the extracts obtained by SFE of vegetable biomass, and examples from each one.
140
4. Operating conditions
While the previous section addressed specic trends regarding
the vegetable biomass, which can be of a diverse chemical composition, involve very distinct physical structures, and raise different
process strategies, SFE research will now be systematized in terms
of the solvent phase characteristics, particularly the operating conditions that most inuence the performance of such processes.
141
Fig. 3. Most common operating conditions for the SC-CO2 extraction of vegetable matrices, for a total of 543 publications considered (Table 1). Darker clouds represent
regions of higher CO2 densities in each work, and lighter circles delimit the regions of lower CO2 densities. Superimposed are lines of constant CO2 density and Hildebrand
solubility parameter.
Another fundamental variable is the selectivity of SC-CO2 to distinct target molecules, which combines all previous dependences in
a very competitive way. Taking into account that temperature inuences similarly the vapor pressure of all extractable compounds,
their distinct solubilization in the supercritical solvent becomes a
matter of both temperature and pressure. Moreover, as the intermolecular interactions are the key factor of the separation, the role
played by cosolvents is of great importance (topic discussed below).
Finally, the so-called tunable properties of supercritical solvents
that contribute to the attractiveness of this technology, comprise,
among other possibilities, the chance to play with temperature at
near constant density regions (high pressure), but our compilation
of works show that it is not being very explored by researchers in
higher pressure experiments. Researchers exhibit a preference to
approach density variations through pressure manipulation rather
than temperature.
1/2
= 1.25Pc
r
r,eb
1/2
= 1.25Pc
(P, T )
eb (P, Teb )
(1)
This is a very simple expression that may help drawing conclusions, at least as a rst approximation. Aiming at a convenient
analysis of CO2 solvent power, lines of its Hildebrand solubility
parameter are also plotted in Fig. 3 for values where they equal
the solubility parameter of some typical organic solvents (at 25 C),
namely isopentane, n-pentane, n-hexane, cyclohexane and toluene.
As can be noticed, SC-CO2 only reaches a solvent power comparable to typical organic solvents when its density is higher than
800 kg m3 . This observation implies that the experimental conditions that have been mostly chosen in the soft (P,T) region of SFE
works lie below the zone where the solvent power of SC-CO2 is
comparable to organic solvents. On the other hand, with respect
to higher pressure conditions region, the solubility parameter of
SC-CO2 is somewhere between those of cyclohexane and toluene.
These comparative considerations become relevant in view of the
fact that it is common practice to compare SFE results with Soxhlet
or distillation yields involving organic solvents, and for this reason
it is pertinent to take into account a priori that the selected (P,T)
conditions of SC-CO2 may not provide equivalent solvent powers
per se.
142
Fig. 4. Inuence of pressure and temperature upon (A) ursolic acid diffusivity in CO2 , (B) ursolid acid solubility in CO2 , and (C) SC-CO2 density. Data calculated from
Wilke-Chang [570], PengRobinson [571], and Pitzer and Schreiber [572] equations.
Fig. 5. Most employed cosolvents in SFE of vegetables matrices, based on 166 SFE
publications of database.
cosolvent @ 25 C
(Mpa0.5 )
Extraction yield
(wt.%)
Carvone conc.
c (wt.%)
n-Hexane
Toluene
Chloroform
Acetone
Dichloromethane
Acetonitrile
Ethanol
Methanol
3.6
4.4
4.5
4.6
4.9
5.8
6.3
7.1
3.23
3.25
3.44
3.30
3.24
2.91
2.85
2.95
57.53
57.22
58.11
57.89
57.16
57.11
57.89
57.77
Pure CO2
3.5
2.43
R2 ( vs.
) = 80%
57.97
R2 ( vs. c) = 18%
143
the extraction time, which in case of being too high can lead to a
period of preferential solute extraction followed by the undistinguished uptake of other compounds. In such situations extraction
curves can provide richer information about cases of apparent lack
of selectivity.
Another noteworthy aspect from Table 2 emerges from the comparison between the results achieved with pure SC-CO2 ( = 3.5) and
its modication with n-hexane ( = 3.6). Despite the close Hildebrand parameters values of the two molecules, results evidence
that the modication leads to a global yield 1.33 times greater than
when only CO2 is employed. This example clearly expresses how
supercritical uidsolid systems that involve modied SC-CO2 (for
which there is a lack of equilibrium data and properties) and natural matrices (which typically comprise a mixture of solutes) are
challenging media to be studied.
As far as water is concerned, the circumstances of working with
this cosolvent are special given that most vegetable matrices typically exhibit natural moisture. This is the reason for the common
preliminary drying stage before SFE takes place. However moisture content is typically reduced to a minimum level rather than
completely removed from the matrix.
In cases where water can be technically employed with success
as cosolvent, the drying stage can then be softer and optimized,
leading to energy and utility savings. Besides these savings, water is
obviously an inexpensive cosolvent to include in a SC-CO2 process,
being this a motive that fosters even more its potential inclusion
in commercial SFE units. Nonetheless the economic advantages are
only attractive if such SC-CO2 modication leads to an enhancement that justies this option. There are examples in literature
attesting an effective enhancement brought about by water addition. It is the case of SFE of andrographolide from Andrographis
paniculata Nees leaves [169] (see Fig. 6) whose results reveal
that water is able to increment the concentration of the target
compound in supercritical extracts in a comparable degree of
ethanol. According to this investigation, 15% of water (the percentage basis is not mentioned) increases the concentration of
andrographolide in extract from 61.6% to 84.3%. In a different
application, it has been demonstrated that water favors a selective removal of caffeine from green tea in relation to the use
of ethanol [575]. In the same study, the selectivity of water as
cosolvent for caffeine extraction (in relation to epigallocatechin
gallate) was shown to be 3.6 times greater than when ethanol was
employed.
4.4. Flow rate
While P and T affect the thermodynamic (density and solutes
solubility) and transport properties (viscosity and diffusivity), solvent velocity is an independent variable that inuences directly
the axial dispersion, the convective mass transfer coefcient, and
the accumulation in the bulk (i.e. supercritical phase). Therefore,
it may be rationally incremented to enhance the extraction rate
upon the reduction of the lm resistance to mass transfer and bulk
concentration. As the external lm diffusion (kf ) and the global
driving force are increased, a positive effect on extraction yield is
achieved.
When analyzing SFE results from the perspective of ow rate,
the chief variable is the surface velocity or, equivalently, the interstitial velocity through the bed. A systematization of SFE works in
terms of interstitial velocities is not feasible in this review due to
lack of information about extractors and beds, but an illustrative
picture can be provided based on the values of SC-CO2 ow rate
per mass of bed reported in the compilation of Table 1. Considering that the nal goal of scientic research on SFE is its commercial
implementation, it would be positive if upcoming works on the eld
could provide more information regarding extractors and beds.
144
Fig. 6. Andrographolide concentration enhancement in SC-CO2 extracts of Andrographis paniculata Nees leaves upon addition of three different modiers (water, ethanol
and acetic acid) at 240 bar and 70 C. Data taken from reference [169].
5. Modeling
In this section an overview of SFE modeling is provided, yet specic works on this subject were published by Oliveira et al. [576],
Sovov et al. [577] and del Valle et al. [578]. It begins with some
considerations regarding subsidiary thermodynamic and kinetic
relations usually required by models (Section 5.1), followed by the
presentation of models based on their distinct complexity levels
(Section 5.2). The last part is devoted to statistical modeling (Section 5.3).
In general, SFE modeling typically involves the analysis of
extraction curves from where kinetic and thermodynamic aspects
of the SFE processes are related quantitatively with great advantage
for further upscaling and optimization studies as well as for economic assessments. Also in the scope of modeling subject, design
of experiments and the response surface methodology have been
adopted by SFE researchers as statistical methods that allow the
disclosure of operating conditions impact on results and also comprise a way of describing experimental results when fundamental
data is scarce or does not exist.
5.1. Subsidiary relations
Density () SC-CO2 density is perhaps the most important
variable of the process from which experimental results are interpreted on rst level, but also when more demanding calculations
have to be performed. It can be obtained from thermodynamic
tables [579], or from an equation of state (EoS) such as the
one from Pitzer and Schreiber [572]. When dealing with cosolvents such as ethanol, estimations can be achieved with resort
to PengRobinson or other EoS plus mixing rules with adequate
interaction parameters. Details are discussed by Pilavtepe and
Yesil-Celiktas [580].
Viscosity () The viscosities of supercritical uids are necessary
for the prediction of diffusivities and mass transfer coefcients, and
also for hydrodynamic studies. Predictive and correlation methods
for dense uids are listed by Reid et al. [570], Stephan and Lucas
[582], Silva et al. [583], Monnery et al. [584], and Sovov and Prochazka [585]. Examples of such methods are Jossi, Stiel and Thodos
[570], Altunin and Sakhabetdinov [586], and Vesovic and Wakeham
[587].
Diffusivities (D12 ) The calculation of diffusivities is of major
importance as this property is required to estimate: (i) effective diffusivities (Deff ), and linear driving force coefcients (kLDF );
145
Fig. 7. Maximum amounts of SC-CO2 used in the SFE of vegetables matrices for a total of 231 publications considered.
Fig. 8. Cumulative curves of total extraction yield of E. globulus bark at different CO2 ow rates. Fixed conditions: 200 bar, 40 C, 5 (wt.%) ethanol. Data taken from [47].
146
a
T
+b
(2)
c
T2
a
+b
T
(3)
yi = f
exp
a
T
+b
(4)
k
yi = fk ycosolv
exp
a
T
+b
(5)
= exp
1
T
(a + b)f + cycosolv + dT
(6)
yi = yi,CO
+ a(yi,CO
)b (ycosolv )c
2
(7)
yi =
Pisat
exp
SCF
Pi
Visolid (P Pisat )
RT
(8)
Ref
Expression
Eq.
Subra et al.
[633]
(9)
Naik et al.
[635]
= x0 (1 eKt )
where, is the extraction yield, t is time, x0 is
the concentration of the target species in the
raw material expressed in the same units of ,
and K is the model parameters related to the
rate of extraction.
t
= x0
b+t
(10)
147
the extraction curve exhibits more than one period, the complete
solution is the combination of expressions upon the denition of
characteristic times that delimit the transitions between such periods [639].
As an alternative approach, the previous specication of different extraction stages and further application of simplied
expressions linked with the mass transfer mechanisms that prevail in each of them can be advantageous. Povh et al. [309] dened
extraction regions in accordance with the model of Sovov [640]
i.e. constant extraction rate (CER) and falling extraction rate (FER)
periods and applied then straight lines in order to obtain the
kinetic parameters related to that phenomenological model. The
parameters were successfully conrmed by the corresponding values of Sovov.
Comprehensive phenomenological models Despite the usefulness of simplied models for the collection of phenomenological
insights about SFE processes, only far-reaching theoretical
approaches allow the study of broader aspects that inuence the
separation performance. In this respect, topics like ow pattern,
solutematrix interactions, accumulation in the bed, axial dispersion, mass transfer resistances in series and/or in parallel may be
mentioned.
The broken plus intact cells model (BICM) proposed by Sovov
[608,641], the shrinking core model (SCM) from Goto et al. [642] or
the combination of the latter two (SCM-BIC) as proposed by Fiori
et al. [643] are perhaps the sound examples of SFE comprehensive modeling. The differences between those models rely on the
conception of how extraction takes place in the solid phase. These
models are summarized in Table 5.
BICM has been the most adopted approach in SFE modeling and
is devoted to matrices submitted to milling in which two distinct
structures are left to be extracted: cells with broken walls and
intact cells. Accordingly, it considers that solutes removal can be
driven by convection from broken (external) cells to the supercritical phase, and/or by diffusion from inner intact cells to the outer
broken cells. According to this model, the extraction curves are
divided in three regions, each one characterized by the dominance
of specic or combined mass transfer mechanisms. In this sense,
the initial period is named constant extraction rate (CER), where
the prevailing resistance is the external lm diffusion and affects
mostly accessible solutes on particles surface. The second period
is called falling extraction rate (FER) and combines the vanishing
contribution of the convective term of CER with the increasingly
important intraparticle diffusion of solutes from inner intact cells.
Being an intermediate region, the noticeable outcome of this period
is a progressive decrease of the oil ux as the accessible solute from
broken cells reaches depletion and the internal diffusion from intact
cells denotes an increasing relevance for the course of the whole
process. The nal period is the one with the slowest rate because
the extraction is uniquely based on the transport of solutes from
intact cells through diffusion. This period is known as DC, which
stands for diffusion controlled. A summary of the mathematical formulation of BICM is presented in Table 6. Detailed reviews
covering this issue, including all assumptions and examples of
application, are provided by Oliveira et al. [576] and Huang et al.
[644].
In a complementary study, Silva et al. [645] provided a comparison between numerical simulations of supercritical uid extraction
for two distinct cases: the original concept of broken plus intact
cells where the internal mass transfer occurs in parallel or in series.
The calculated results were compared with experimental data and
showed similar performance. Later, Passos et al. [568] modeled the
SFE of untreated and enzymatically pre-treated grape seeds, being
able to demonstrate that the tted BICM parameters do reect
the internal structure changes due to hydrolysis and grinding efciency.
148
Table 4
Simplied models for SFE processes.
Name
Ref
Logistic model
[123]
Desorption model
[636]
[145]
Expression
Eq.
x0
1 + exp(btm )
1
=
exp(btm ) 1 + exp [b (tm t)]
where, is the extraction yield, t is time, x0 is the concentration of the target species in the raw material, and
b and tm are the two parameters of the model.
A
=
[1 exp(kd B)] [exp(kd t) 1]
kd
QCO2 (1 b )x0 s
A=
wb b f
b Lb Sf
B=
QCO2
where QCO2 is the CO2 mass ow rate, b is the bed porosity, Lb is the length of the bed, S is the extractor
cross-sectional area, wb is the mass of raw material in the extractor, s and f are the biomass and solvent
densities,
respectively.
= x0
0.8
(2n + 1)
exp
Deff (2n + 1) 2 t
l2
(11)
(12)
(13)
(14)
(15)
n=0
where D
[637]
= x0
6
2
n2
exp
Dm n2 2 t
Rp2
(16)
n=1
[638]
Brunner
where Rp is particle
radius.
y QCO2
kf a0 w
t 1 exp
=
w
QCO2 (1 b )s
where a0 is the specic external surface area (m2 m3 ).
(17)
Table 5
Comprehensive phenomenological models for SFE processes: BICM = broken plus intact cells model, SCM = shrinking core model, SC-BICM = bridged model comprising
shrinking core and broken plus intact cells concepts.
Model
BICM
SCM
SC-BICM
Ref.
[608,641]
[642]
[643]
Expression
Eq.
y
y
SC phase : f
= jf
+U
t
h
x1
Broken cells : gf (1 )
= js jf
t
x2
Intact cells : (1 g)s (1 )
= js
t
where y is the solute uid phase concentration, x1 and x2 are the solute concentration in the broken and intact cells,
respectively, g is the grinding efciency, js is the ux from intact cells to broken cells, jf is the ux from broken cells to SC
solvent, U is the interstitial velocity, f is the solvent density and s is the solid density and is the bed porosity, t is time and
h is the axial coordinate.
y
y
SC phase : f
=j
+U
t h
ypores
Deff
2
Solid phase :
r
=0
r
r 2 r
and
j = kf ap (ypores y)
where kf is the convective mass transfer coefcient, ap is the particle specic surface area, ypores is the solute concentration in
diffusion coefcient and r is the radial coordinate in the particle.
the pore network,Deff is the effective
y
y
+U
SC phase : f
=j
t
h
Vex
k y y
= 3f
Solid phase : j =
Rp x0
t
k = f (exhaustion model chosen)
where Vex is the volumetric exhaustion degree of the particle, x0 is the concentration of the solute in the raw material, k is the
overall mass transfer coefcient (varies along r), Rp is the particle radius, j is the ux from particles to solvent.
(18)
(19)
(20)
(21)
(22)
(23)
(24)
(25)
(26)
149
Table 6
Integrated form of BICM.
Model equations
t[1 exp(Z)]
woil = QCO2 yoil
y
t[t tCERexp(Zm(t)
woil = QCO
2 oil
Z)] WQ
y
Wx0
CO2
1 exp
(tCER t)
woil = w x0 oil ln 1 + exp
W
yoil
w
Eq.
for 0 t tCER
for tCER t tFER
(27)
(28)
for ttFER
(29)
Complementary equations:
WQ
Zyoil
1
CO2
ln
exp
(tCER t) g
Zm(t) =
Ww
w
1g
kf a0 w f
Z=
QCO2 b
w ks a0
W=
QCO2 (1 )
(1 g)w x0
tCER =
QCO2 yoil
Z
w
Wx0
tFER = tCER +
ln g + (1 g) exp
yoil
WQCO2
(30)
(31)
(32)
(33)
(34)
where w is the solid mass in oil-free basis, b is the bed density, kf a0 is the
solvent phase volumetric mass transfer coefcient, and ks a0 is the solid
phase volumetric mass transfer coefcient.
et al. [77] were able to infer how bed geometry inuences relevant
parameters like the period of constant extraction rate (tCER ) and
global mass transfer coefcient. Yield results exhibit a noticeable
enhancement when beds have larger length to diameter values, e.g.
beds that favor length in comparison to diameter.
The compilation of SFE publications covered by this review
found many examples of modeling. Table 7 provides a classication
of papers with emphasis on modeling results. The type of approach
employed is highlighted (whether empirical, simplied or comprehensive) as well as the designation of models employed. From
Table 7 one can disclose that solubility modeling has been marginal
in comparison to extraction curves studies, and also that BICM is
by far the most chosen to t and interpret experimental results.
5.3. Statistical models
Design of experiments (DoE) As mentioned above, the accurate phenomenological modeling of processes involving natural
biomass is complex and many times impossible to achieve because
of the lack of necessary subsidiary data. A trend has been identied
since 2000, involving the greater presence of statistical modeling
such as design of experiments in published articles. The DoE refers
to statistical strategies that allow more precise data and more complete information to be obtained from an experimentally studied
phenomenon with minimal number of assays and lowest material
costs [666]. It is thus an efcient method that provides instructive
data with minimum resources as counterpart.
A clear-cut picture regarding the use of DoE in SFE works is
shown in Fig. 10. Roughly one in ve works from our database
comprise design of experiments and two thirds of these involve
response surface methodology. In terms of experimental designs
types, there is a balance between BoxBehnken (BBD), Central Composite (CCD), Full Factorial and Fractional Factorial Designs, with
a slight dominance of BoxBehnken and Central Composite, with
28% and 26%, respectively. Concerning the variables to be studied
150
Table 7
SFE publications that comprise modeling studies. Sol = solubility, Ext = extraction.
Matrix
Scope
Type of Model
Model
Ref.
Amaranth
Sol
Sol
Ext
Ext
Ext
Sol
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Sol
Sol
Sol
Sol
Ext
Ext
Sol
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Sol
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Sol
Ext
Ext
Ext
Ext
Ext
Empirical
Empirical
Simplied
Comprehensive
Comprehensive
Empirical
Comprehensive
Comprehensive
Simplied
Empirical
Comprehensive
Comprehensive
Simplied
Simplied
Comprehensive
Empirical
Statistical
Comprehensive
Comprehensive
Simplied
Simplied
Chrastil [609]
Del-Valle and Aguilera Chrastil modication [612]
Reverchon and Osseo [650]
Sovov [641]
Sovov [641]
Splines
Sovov [641]
Sovov [641]
Martnez et al. [123]
Esquvel et al. [634]
Reverchon [651]
Sovov [641]
Tan and Liou [636]
Brunner [638]
Sovov [641]
Esquvel [634]
Neural networks + Goto et al. [642]
Sovov [641]
Skerget
and Knez [652]
Hong [653]
Brunner [638]
BET
Henry
Freundlich
PengRobinson of state
Mukhopadhyay [655]
Goto et al. [642]
Chrastil [609]
Subra et al. [633]
Naik et al. [633]
Reverchon and Osseo [650]
Sovov [641]
Sovov [641]
Adaptation of Goto et al. [656]
Sovov [641]
Martnez et al. [123]
Araus [657]
Sovov [641]
Martnez et al. [123]
Crank [637]
Crank [637]
Naik et al. [633]
Tan and Liou [636]
Goto et al. [656]
Sovov [641]
Sovov [641]
Sovov [641]
Goto et al. [656]
Tan and Liou [636]
Sovov [641]
Sovov [641]
Sovov [641]
Martnez et al. [123]
[257]
Aniseed
Annatto
Annatto
Apricot
Artemisia annua L.
Baccharis trimera
Baccharis trimera
Blac cumin
Black pepper
Borage, Primrose
Canola, Sesame
Cashew
Cashew
Celery
Chamomile
Clove
Coffee
Coffee
Cupuacu
Fennel
Hyssop
Jalapeno
Lavender
Marigold
Marigold
Marigold
Neem
Neem
Nutmeg
Orange
EoS
Comprehensive
Comprehensive
Empirical
Empirical
Empirical
Simplied
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Simplied
Comprehensive
Simplied
Simplied
Simplied
Empirical
Simplied
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Simplied
Comprehensive
Comprehensive
Comprehensive
Approximate
Comprehensive
Comprehensive
Empirical
Simplied
Comprehensive
Simplied
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Simplied
Simplied
Simplied
Empirical
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Chrastil [609]
Andrich et al. [63]
Sovov [641]
Tan and Liou [636]
Reverchon [651]
Sovov [641]
Sovov [608]
Sovov [641]
Akgun [659]
Sovov [641]
Sovov [641]
Martnez et al. [123]
Tan and Liou [636]
Gaspar et al. [145]
Reverchon [660]
Chrastil [609]
Goto et al. [656]
Goto et al. [642]
Sovov [641]
Goto et al. [642]
Sovov [641]
[476]
[277]
[279]
[104]
[196]
[274]
[275]
[234]
[482]
[185]
[654]
[111]
[112]
[264]
[309]
[361]
[57]
[54]
[326]
[538]
[371]
[338]
[122]
[123]
[568]
[645]
[333]
[331]
[658]
[396]
[84]
[410]
[534]
[291]
[293]
[172]
[173]
[446]
[138]
151
Table 7 (Continued)
Matrix
Scope
Type of Model
Model
Ref.
Oregano
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Sol
Ext
Simplied
Simplied
Statistical/Empirical
Comprehensive
Comprehensive
Simplied
Empirical
Comprehensive
Comprehensive
Comprehensive
Simplied
Simplied
Simplied
Simplied
Simplied
Comprehensive
[145]
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Ext
Sol
Sol
Sol
Ext
Ext
Ext
Ext
Ext
Ext
Sol
Ext
Ext
Sol
Comprehensive
Simplied
Simplied
Simplied
Comprehensive
Empirical
Comprehensive
Comprehensive
Comprehensive
Approximate
Empirical
Empirical
Empirical
Comprehensive
Comprehensive
Comprehensive
Comprehensive
Simplied
Simplied
Empirical
Simplied
Comprehensive
EoS
Oregano
Palm
Paprika
Parsley
Peach
Pupunha
Rapeseed
Red pepper
Rice
Rosemary
Rosemary
Sacha inchi
Safower
Schisandra chinensis
Shiitake mushroom
Spanish sage
Spearmint
Stevia
Sunower
Sunower
Sunower
Thyme
Thyme
Tomato
Tomato
Turmeric
Valerian
Vetiver
Simplied
Simplied
Comprehensive
Comprehensive
Empirical
Simplied
Simplied
Comprehensive
Empirical
Comprehensive
Sovov [641]
Andrich et al. [63]
Chrastil [609]
del Valle and Aguilera [612]
Yu et al. [617]
Sovov [641]
Catchpole [664]
Goto et al. [656]
Reverchon et al. [665]
Brunner [638]
Chrastil [609]
Tan and Liou [636]
PengRobinson
[569]
[187]
[85]
[469]
[491]
[189]
[283]
[87]
[92]
[77]
[76]
[486]
[302]
[233]
[662]
[511]
[438]
[532]
[63]
[67]
[68]
[36]
[540]
[28]
[29]
[159]
[549]
[556]
152
Table 8
Compilation of SFE publications employing design of experiments (DoE) or response surface methodology (RSM) in the period 20002013.
Matrix
Variables
Alkanna tinctoria
Allium cepa L.
Allium sativum L.
P
P
t
T
T
T
Aloe vera
Alpinia oxyphylla
Amaranthus paniculatus
Angelica dahurica
Anoectochilus roxburghii
Arbutus unedo
Artemisia annua L.
Artemisia capillaris T.
Artemisia sieberi
Atractylode lancea
Brassica napus
Bupleurum falcatum
Cajanus cajan
Camellia sinensis L.
Camellia sinensis L.
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
T
T
T
T
T
T
T
Modier Conc.
T
T
T
T
T
T
T
Q
t
Solvent to
sample ratio
cmodier
t
t
Q
cmodier
cmodier
Q
t
t
t
t
t
t
t
Factors
Cannabis sativa L.
Capsicum frutescens
P
P
T
usupercial
dp
Capsicum frutescens
Catharanthus roseus
Ceratonia siliqua
Citrullus lanatus
Citrus grandis L. Osbeck
Citrus paradisi Macf.
Citrus unshiu
Coffea arabica
Coffea spp.
Corylus avellana L.
Corylus avellana L.
Cratoxylum prunifolium Dyer
Cucurbita maxima
Curcuma longa L.
Cucurbita moschata
Cydonia oblonga Miller.
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
usupercial
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
t
cmodier
Q
t
t
cmodier
cmodier
Q
usupercial
cmodier
t
Q
Dynamic t
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
t
cmodier
t
cmodier
cmodier
cmodier
dp
dp
t
cmodier
t
t
Dryness
t
t
Dynamic t
cmodier
Modier/solid
t
t
t
t
Q
cmodier
Q
cmodier
dp
Q
t
t
dp
cmodier
Extractions
number
Q
dp , w
cmodier
cmodier
Q
cmodier
cmodier ,
Ultrasonic
Power
cmodier
dp
Static t,
Modier Conc.
dp
Modiers Ratio
Static t
Q
Q
Runs
Features
Ref.
3
3
4
Levels
3
3
3
15
17
27
RSM, BoxBehnken
RSM, BoxBehnken
RSM, BoxBehnken
[249]
[252]
[119]
4
3
5
4
3
3
3
2
4
3
3
4
3
3
5
3
3
2
3
3
3
2
3
3
4
3
3
5
3
4
9
15
67
8
9
17
8
13
9
9
17
9
20
20
16
Orthogonal array
RSM, BoxBehnken
Full Factorial
Orthogonal array
Orthogonal array
RSM, BoxBehnken
Full Factorial
RSM, Central composite
Orthogonal array
Orthogonal array
RSM, BoxBehnken
Orthogonal array
RSM, Central composite
RSM, Central composite
Orthogonal array
[254]
[255]
[199]
[261]
[221]
[265]
[196]
[269]
[211]
[270]
[284]
[288]
[289]
[295]
[296]
3
2
3
3
15
12
[299]
[301]
2
4
4
3
3
3
3
2
3
3
3
3
3
3
2
5
5
2
3
3
3
3
3
4
3
3
3
3
5
3
3
3
11
19
18
20
17
15
15
16
15
15
13
9
16
13
9
35
RSM, BoxBehnken
Central composite
RSM, Central composite
RSM, Central composite
RSM, Fractional Factorial
RSM, Central composite
RSM, Central composite
RSM, BoxBehnken
RSM, BoxBehnken
RSM, BoxBehnken
Full Factorial
RSM, BoxBehnken
RSM, BoxBehnken
RSM, Fractional Factorial
Orthogonal array
RSM, Central composite
RSM, BoxBehnken
RSM, Central composite
RSM, Central composite
3
3
3
4
3
3
3
3
3
3
3
3
2
3
3
4
3
3
3
3
4
4
3
3
3
3
5
3
4
3
3
3
4
3
3
3
2
3
3
3
3
2
3
3
3
3
3
4
3
1/3
3
2
3
34
3
3
5
3
4
3
3
3
3
3
9
15
20
33
11
27
9
9
15
4
17
15
8
17
17
25
17
8
15
18
31
30
15
17
18
17
16
20
9
15
20
16
Orthogonal array
RSM, BoxBehnken
RSM, Central composite
RSM, Central composite
RSM, Full factorial
RSM, Full factorial
Orthogonal array
Orthogonal array
RSM, BoxBehnken
Orthogonal array
RSM, BoxBehnken
RSM, Central composite
Full Factorial
RSM, BoxBehnken
RSM, BoxBehnken
Orthogonal array
RSM, BoxBehnken
RSM, Fractional Factorial
RSM, BoxBehnken
RSM, Central composite
RSM, Central composite
RSM, Central composite
RSM, BoxBehnken
RSM, BoxBehnken
RSM, Central composite
RSM, BoxBehnken
Taguchi method
RSM, Central composite
Orthogonal array
RSM, BoxBehnken
RSM, Central composite
RSM, Central composite
[343]
[345]
[567]
[357]
[53]
[48]
[364]
[497]
[375]
[376]
[154]
[380]
[66]
[202]
[388]
[397]
[186]
[184]
[412]
[411]
[413]
[415]
[75]
[72]
[70]
[237]
[440]
[441]
[442]
[238]
[445]
[448]
[300]
[307]
[308]
[313]
[241]
[319]
[320]
[55]
[62]
[334]
[332]
[335]
[148]
[161]
[149]
[340]
153
Table 8 (Continued)
Matrix
Variables
Factors
Nepeta persica
Nigella sativa L.
P
P
T
T
Dynamic t
t
Nigella sativa L.
Olea europaea L.
Olea europaea L.
Olea europaea L.
Ophiopogon japonicus
Opuntia dillenii
Origanum majorana
Origanum munituorum
P
P
P
P
P
P
P
P
T
T
T
T
T
T
T
T col
t
t
t
Q
t
t
Tcol
P
P
P
P
P
P
P
T
T
Packing
T
T
T
T
t
t
cmodier
Q
cmodier
usupercial
t
Pueraria lobata
Punica granatum
Rosa aff. Rubiginosa
Salvia miltiorrhiza
Satureja hortensis L.
Satureja hortensis L.
Scutellaria baicalensis
Solanum lycopersicum L.
Solanum lycopersicum L.
Solanum lycopersicum L.
Solanum lycopersicum L.
Sophora avescens
Stevia rebaudiana
Taraxacum ofcinale Weber et Wiggers
Thymbra spicata
Thymus zygis L. subsp. Sylvestris
Tribulus terrestris
Trigonella foenum-graecum L.
Triticum spp.
Vetiveria zizanioides L.
Vetiveria zizanioides L.
Vitex agnus castus
Vitis labrusca B.
Vitis vinifera L.
Vitis vinifera L.
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
cmodier
Q
t
t
t
cmodier
t
Q
cmodier
t
Q
Modier
t
t
t
t
t
t
cmodier
cmodier
dp
Dynamic t
P
P
P
T
T
T
t
t
Modier
bot
top
Static t
dp Q, matrix
dryness, ow
direction
dp
dp
cmodier
Packing,
cmodier
cmodier
cmodier
cmodier
Solid/Solvent
ratio
Q
cmodier
Modier
cmodier
Static t
Q
Modier
cmodier ,
Trestrictor
Ttrap
Solvent in trap
Vrap
Packing
cmodier
Levels
Runs
Features
Ref.
4
7
5
2
25
16
Taguchi method
Fractional Factorial
[450]
[234]
3
4
4
3
4
3
2
5
3
3
2
3
3
4
3
2
27
26
18
15
9
16
11
8
Full factorial
Orthogonal array
RSM, Full Factorial
BoxBehnken
RSM, Orthogonal array
RSM, Orthogonal array
RSM, Full Factorial
RSM, Fractional Factorial
[235]
[457]
[456]
[200]
[459]
[460]
[461]
[569]
3
4
3
4
3
3
4
4
3
2/4
3
5
3
3
9
9
26
27
20
13
27
Orthogonal array
Orthogonal array
RSM, Fractional Factorial
RSM, BoxBehnken
Fractional Factorial
RSM, Fractional Factorial
RSM, BoxBehnken
[465]
[474]
[485]
[103]
[105]
[490]
[488]
3
3
3
4
4
3
4
3
3
2
2
4
3
2
3
3
4
3
3
3
3
2
3
3
12
3
5
3
3
3
3
3
3
5
3
3
3
3
3
3
3
5
5
5
5
3
3
4
2/3
2
17
17
13
9
10
15
9
17
19
9
17
9
15
11
15
13
31
20
23
19
17
11
16
9
32
RSM, BoxBehnken
RSM, Central composite
RSM, Fractional Factorial
Orthogonal array
Fractional factorial
RSM, BoxBehnken
Orthogonal array
RSM, BoxBehnken
Central composite
RSM, Full Factorial
RSM, Central composite
Orthogonal array
RSM, BoxBehnken
RSM, Full Factorial
RSM, BoxBehnken
RSM, Fractional Factorial
RSM, Central composite
RSM, Central composite
RSM, Central composite
RSM, Central composite
RSM, Central composite
Full Factorial
Orthogonal array
Orthogonal array
Fractional factorial
[499]
[501]
[505]
[512]
[517]
[517]
[522]
[26]
[35]
[28]
[204]
[529]
[531]
[537]
[539]
[41]
[542]
[545]
[163]
[555]
[554]
[558]
[15]
[7]
[19]
2
4
3
3
4
2/3
20
16
12
[561]
[565]
[122]
154
Fig. 9. Experimental and tted extraction curves of rosemary leaves (Rosmarinus ofcinalis L.). Experiments performed at 300 bar, and 40 C and different ow rates: (, ,
, ) 8.33 105 kg s1 , () 5.25105 kg s1 . Lb is for bed length and Db bed diameter.
Adapted from Carvalho et al. [77].
155
Fig. 10. Trends on the use of DoE and RSM in SFE articles within 20002013, for a total of 547 publications considered.
Q2
=
Q1
W 2
b2
Wb1
Lb1
D
b1
Lb2
Db2
(35)
and
Q2
=
Q1
W 2
b2
Wb1
Lb1
Lb2
D 3
b1
Db2
(36)
where Eq. (35) is specially devoted to cases where the total amount
of extractable solute (x0 ) is determined from experiments using
different SFE units, and Eq. (36) allows one to calculate a ow rate
that ensures the same kinetic behavior between two SFE units.
In a very instructive study, del Valle et al. [507] evaluated the
inuence of scale on the SFE of rosehip seeds, in which 1 L and
2.6 L capacity units were used to undertake the experiments. They
started by tting a two-period model (based on solubility dominance at the onset and intraparticle diffusion limitations at the
end of extraction) to the 1 L assays, which was considered to represent data adequately. However, for the runs carried out in the
2.6 L extractor the model failed to describe the proles, particularly
along the curvature branches. Several possibilities were raised to
explain the lack of t of the model, namely: (i) transport of solute
156
Fig. 11. Examples of RSM for the SFE yields of different species. A avonoid from SFE of Pueraria lobata [499]; B cajaninstilbene acid from pigeonpea (Cajanus cajan) [289];
C oil from axseed (Linum usitatissimum) [75]; D essential oil from vetiver (Vetiveria zizanioides L.) [555].
Fig. 12. Experimental and modeled extraction curves of different scale-up criteria
SFE experiments and their respective small scale curves from peach (Prunus persica)
almond. Plot retrieved from [491].
through CO2 recycling stream; (ii) axial dispersion in the supercritical phase; and (iii) ow heterogeneity in the bed. The authors
performed then a sensitivity analysis through model simulations,
by varying the inlet oil concentration, axial dispersion coefcient,
and solvent interstitial velocity (solid lines in Fig. 13). It is noticeable
that the three variables inuence the process toward the experimental data. In addition, the occurrence of a heterogeneous ow
inside the extractor was undoubtedly the factor that most efciently improved the representation of the measured data. Despite
the usefulness of the model to disclose the physical phenomena
guiding the SFE, only new experiments could allow, in their case,
the elucidation of whether the discrepancies between model and
data in the 2.6 L extractor were due to only one of the factors or to
their conjugation.
Other scale-up works are listed in Table 9, such as the one of
Kotnik et al. [428] who worked with a 60 mL and 4 L vessels for the
extraction of chamomile (Matricaria chamomilla) owers, that of Lu
et al. [498] who reported the SFE of Pteris semipinnata L. in a 20 L
pilot scale extractor, or that of Rannali et al. who performed SC-CO2
extractions of carrot (Daucus carota L.) root oil in 5 L pilot extractor. Special attention should be paid to the work of Han et al. [302],
who successfully attempted the upscaling of the SFE of safower
seed with a jump from a 0.5 to 260 L extractor using QCO2 wb1 as
scale-up criterion. Alternatively, Fullana et al. [234] presented an
alternative approach to scale-up based on the use of neural networks, which allows addressing upscaling within few requirements
regarding kinetics information.
In general, scale-up that targets big jumps in extractor dimensions embody the last step of a research path that began with an
initial exploratory lab experiment and which reaches scale studies
after being matter of working conditions optimization and modeling. A signicant volume of resources (time, material, human) is
required to accomplish such research path, reason why preliminary economic assessments are sometimes carried out to foresee
the gross viability of the process. When process remains promising and scale-up stage is overcome with success, the process has
nally reached the point of being studied under deeper economic
assessments.
157
Table 9
Higher scale and scale-up studies on SFE.
Matrix
Scales
Unit capacity
Allium cepa L.
Bixa orellana L.
Intermediate
Lab
Lab
Lab
Pilot
Lab
Intermediate
Intermediate
Lab
Lab
Lab
Lab
Intermediate
Intermediate
Intermediate
Lab
Intermediate
Lab
Intermediate
Intermediate
Intermediate
Intermediate
Intermediate
Lab
Intermediate
Intermediate
Lab
Lab
Lab
Intermediate
Intermediate
Intermediate
Lab
Intermediate
Lab
Intermediate
Lab
Intermediate
5L
0.007 L
0.029 L
0.5 L
260 L
0.5 L
5L
5L
0.006 L
0.280 L
0.280 L
0.2 L
5L
5L
2L
0.01 L
1.2 L
0.060 L
5L
2L
2L
2L
2L
0.3 L
6.5 L
20 L
0.01 L
1L
0.06
4L
10.3 L
5L
0.01 L
4L
0.01 L
2L
0.3 L
5.1 L
Carthamus tinctorius
Citrus sinensis
Daucus carota L.
Eugenia caryophillus
Glycine variety
Helianthus annuus L.
Helianthus annuus L.
Matricaria chamomilla
Origanum vulgare L.
Thymus zygis L.
Salvia ofcinalis L.
Rosmarinus ofcinalis L.
Pinus brutia
Pteris semipinnata L.
Sophora avescens
Tanacetum parthenium
Thymus vulgaris L.
Thymus vulgaris L.
Triticum spp.
Vitis vinifera L.
Vitis vinifera L.
7. Economic analysis
General considerations Despite its ultimate position within
the necessary research background that conrms the technical
potential of a specic SFE process and encourages further advances
toward commercial application, economic assessment results provide valuable insights even at earlier stages of research, when
decisions regarding operating conditions, matrix pretreatments
and/or cosolvent addition can be pondered and dealt in time.
However, owing to the fact that economic assessments easily
reect inaccuracies of previous optimization, modeling and scaleup, one should aim to have a reliable knowledge of the process
when performing this type of studies. For instance, the capital cost of a SFE process is not linear with pressure, as some
equipment components are available in discrete steps [674], and
for this reason wrong conclusions upon economic viability can
be taken. In addition, from the point of view of incomes, the
scale of production can inuence the market prices from the side
of an excessive offer leading to saturation and decline of profits.
With regard to the types of operation scheme, it has been
shown that continuous operation is the one that generally minimizes the total costs, but the difference to batch extraction is not
signicant enough to justify the continuous approach, at least for
large-scale operation [1]. The main reason is the larger amount of
energy needed to introduce and remove the biomass at separate
locations necessary in continuous operation, in comparison to the
time-sequenced operation steps in a conventional batch system
[1]. For this reason most of the commercial units that inspire new
Scale-up criteria
Ref.
[250]
[279]
wCO2 wb1
[302]
QCO2 wb1
[138]
wCO2 wb1 and QCO2 wb1
[108]
[361]
vsupercial
tresidence , CO2
[153]
Lb /Db
QCO2 wb1
[64]
[65]
Lb /Db
[428]
[142]
[478]
QCO2 wb1
[498]
[529]
[197]
[42]
[43]
[162]
wCO2 wb1
[7]
[23]
wCO2 wb1
158
Fig. 13. Sensitivity analysis of the simulated extraction yield of roll milled rosehip
seeds (0.1 mm size) as a function of specic solvent mass in 2.6 L plant experiments
with 200 g min1 of CO2 at 40 C and 300 bar: (A) effect of the oil concentration at
the extractor inlet; (B) effect of the axial dispersion coefcient inside the bed; and
(C) effect of the non-uniformity of solvent ow (i.e. the presence of an outer annular
region of high interstitial velocity, and an inner circular region of lower interstitial
velocity). Symbols represent experimental data.
Figure retrieved from [507].
properly scoring of the added-value provided by the SFE technology in relation to bulk essential oils, because the economics of the
process should reect two specicities of this technology: (1) lower
extraction yields may exhibit interesting selectivity gains as counterpart; (2) both composition and extraction yield vary with time
and upon modications in other operating conditions. As a result,
economic viability can be seen as an optimized trade-off between
the concomitant variations of yield and concentration, from the
income side, and the investment and operation expenditures, from
the xed and variable costs, respectively.
In order to emphasize the signicant differences of approaching
SFE to maximize extraction yields or to produce extracts enriched in
159
Fig. 14. Commercial quotations (for small scale purchasing) of some essential oils. Data were taken from one European supplier [676], with exception of coffee oil [677].
the extraction cycles are, the greater the human handling needs
become. In addition, the duration of extraction cycles has a chief
inuence on productivity and therefore on economic viability, since
it is advisable to work during the constant extraction rate (CER)
period (see gure of Table 6), which implies to replace the (almost)
exhausted biomass inside extractor by a virgin one in spite of
keeping the process running on the falling extraction rate (FER
see Table 6) period. These considerations require semi-continuous
operation involving arrangements of several beds in series or in
parallel [23,61,81,279,678,679].
At industrial level, the time needed to unload, reload and pressurize an extractor may not be negligible if dealing with processes
involving low extraction times. Melo et al. [61] addressed this
issue in detail, by performing an economic study of SFE of spent
coffee (Coffea spp.) grounds. This is a key factor that shall be
correctly tackled to boost the productivity and protability of
SFE units.
With respect to the SC-CO2 modication with organic solvents,
it is frequently exploited without the full acknowledgment of the
economic impact this option may represents. The inclusion of cosolvents may inuence licensing, since then SFE plants lose their
innocuous character upon explosion, re and pollution hazards that
pure CO2 ensures. On the other hand, the employment of cosolvents
brings an additional source of raw material costs, and requires extra
equipment to be purchased, such as a liquid pumps, independent
tubing lines, and units for their subsequent recovery/purication.
In view of the semi-continuous nature of SFE processes, the choice
of plant layouts is also a relevant matter. Assessments typically
consider layouts with 23 bed in parallel or series. The nal
decision should reect a deal between investment costs, cycle duration, labor costs and protability [23,61,81,279,678,679]. Economic
analyses provide key answers to this issue.
(37)
(38)
160
Fig. 15. Commercial quotations (for small scale purchasing) of some of SFE target compounds. Data were taken from one European supplier [680] and are presented in
logarithmic scale.
(39)
Table 10
List of assumptions necessary for an economic assessment of a SFE process.
General
FCI
COL
CUT
CWT
CRM
w 0.6
2
(40)
w1
V
extractor1 Q2
Vextractor2 Q1
0.24
(41)
161
Fig. 17. Cost of manufacturing (COM) deviation as function of the separator pressure
(reference = 45 bar). Data for SFE of spent coffee grounds at 300 bar, 50 C, t = 0.7 h,
1
= 30 kgCO2 kgSCG 1 h1 [61].
QCO2 wsample
8. Final remarks
Fig. 16. Comparison of COM values for the extraction of rosemary, fennel, and anise
extracts. Bars represent extract and essential oil obtained by SFE, and essential oil
obtained by steam distillation [81].
162
a way that allows the design of a pathway from feedstock to products. In this sense, improvements are expected in upcoming years
in order to enhance the quality of the research in the eld on a
cradle-to-gate perspective.
From
a
comprehensive
observation,
thermodynamic/equilibrium is still a eld where further research is
recommended, namely on the fundamental modeling of solutes in
SC-CO2 , modied or not with cosolvents. While this observation
embodies an effective opportunity for further consolidation of SFE
research, scale-up is perhaps the second area where there is a
substantial margin for deeper experimental work. Many authors
limit the scale-up to slight volume or capacity jumps, placing
their studies closer to lab scale than to a real commercial scale. As
long as research comprises lab and real pilot units, together with
reliable modeling and scale-up criteria, the uncertainty associated
with natural biomass may be left behind, and the supercritical
technology may reach an effective consolidation for industry.
In addition, the combination of more comprehensive scale-up
works with economic assessment studies would foster a clearer
perception of the techno-economic appeal of SFE.
Beyond the aforementioned items, that can attenuate current
sources of uncertainty for the SFE processes themselves, the knowledge of extracts price is frequently a source of uncertainty that can
hinder their correct economic assessments. Taking into account the
novelty of some active principles or their relatively niche dimension market, the establishment of a price for an extract can be so
inuential that a whole SFE process viability can be strongly penalized or unrealistically overestimated per se, independently of other
aspects. Given that SFE many times allows the enhancement of
target species concentration in extracts, SFE selectivity advantages
for the quality of a nal extract can only be fully disclosed upon a
proper estimation of the extracts market price for different compositions. As long as extract prices for distinct solutes concentration
are known, the SFE can be matched with purication techniques
giving rise to the possibility that economic viability is only set
upon coupling extraction and additional downstream separation
steps. In the whole, this argument highlights combined and hybrid
processes embodying SFE to provide extracts with higher quality
(higher market values).
To conclude, the extensive compilation and critical systematization of works provided by this review document the substantial
advances that SFE eld has been achieving as a result of the intense,
progressive and multidisciplinary research. Since 2000 the eld has
burst in terms of new biomass species, investigation of extracts
enrichment and molecules isolation, and in the required tools and
background knowledge necessary to reach a nal degree where the
feasibility of SFE implementation is expected. Through research,
SFE has reached new industrial sectors into which there used to
be weak ties. It is the case of pulp and paper industry and the
recent election of supercritical CO2 as a breakthrough technology
for the 2050 world, attributed by the Confederation of European
Paper Industries (CEPI) [690].
Considering all these remarks, we do believe that SFE has overcome the foreseen promising character, being presently an effective
alternative that, in a question of time, will nd its widespread echo
on the side of industrial partners.
Nomenclature
1H
NMR
a0
APCI
BBD
BICM
c
CCD
central composite design
CER
constant extraction rate
CZE-HPLC capillary electrophoresis with high-performance liquid
chromatography
bed diameter
Db
DC
diffusion controlled
tracer diffusion coefcient
D12
Deff
effective diffusion coefcient
Dax
axial dispersion
DSC
Differential scanning calorimetry
particle diameter
dp
DoE
design of experiments
DSMO dimethyl sulfoxide
equation of state
EoS
ESIMS electrospray ionizationmass spectrometry
EtOH
ethanol
FAME
fatty acid methyl esters analysis
FDA
factorial discriminant analysis
falling extraction rate
FER
FE-SEM eld emission scanning electron microscopy
grinding efciency
g
GCDIC gas chromatographyionization detection
GCMS gas chromatographymass spectrometry
GC-FID gas chromatography-ame ionization detector
gas chromatography-olfactometry
GC-O
GC-HRMS gas chromatography coupled with high resolution mass
spectrometry
h
axial coordinate
high-performance liquid chromatography
HPLC
HPLC-DAD high performance liquid chromatography with diode
array detection
HPLC-ELSD high-performance liquid chromatography with evaporative light scattering detector
HPLCESI-MS high-performance liquid chromatography with
electrospray ionization and mass spectrometry
HPLC-FLD high performance liquid chromatography with postcolumn uorescence derivatization
HPTLC high-performance liquid layer chromatography
HPLCPAD-MS high-performance liquid chromatography with
pulsed amperometric detector and mass spectrometry
high resolution gas chromatography
HRGC
HSCCC high-speed counter-current chromatography
ICP-MS inductively coupled plasma mass spectrometry
IU
isoprene units
j
mass ux
k
convective mass transfer coefcient
desorption constant
kd
Lb
length of the bed
LC-ESI liquid chromatography with electrospray ionization
LC-DAD liquid chromatography with diode array detection
LCMS liquid chromatographymass spectrometry
LPLC
low pressure liquid chromatography
plate thickness
l
NMR
nuclear magnetic resonance
MeOH methanol
OT
orthogonal test
pressure
P
PCA
principal component analysis
PR
Peng Robinson
Q
mass ow rate
r
radial coordinate
R
gas constant
Rp
particle radius
RP-HPLC reversed phase high-performance liquid chromatography
RSM
response surface methodology
Re
Reynolds number
S
bed cross-sectional area
SEM
scanning electron microscopy
Schmidt number
Sc
SC-CO2 supercritical carbon dioxide
SCM
shrinking core model
SC-BICM model bridging SCM and BICM
SFC
supercritical uid chromatography
SFE
supercritical uid extraction
Sh
Sherwood number
time
t
T
temperature
Tcolbot
temperature at the bottom of the column
temperature at the top of the column
Tcoltop
TT
triterpenic
TLC
thin layer chromatography
TPC
thermo-chromatographic pulse
U
intersticial velocity
UPLCMS ultra-performance liquid chromatographymass spectrometry
V
molar volume
Vex
volumetric exhaustion degree
v
volume
x
solid phase concentration
gas or supercritical phase concentration
y
w
mass
w
mass in a oil free basis
Greek letters
density
porosity
viscosity
163
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