Anda di halaman 1dari 62

J.

of Supercritical Fluids 92 (2014) 115176

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids


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

Review

Supercritical uid extraction of vegetable matrices: Applications,


trends and future perspectives of a convincing green technology
M.M.R. de Melo, A.J.D. Silvestre, C.M. Silva
CICECO, Department of Chemistry, University of Aveiro, Aveiro 3810-193, Portugal

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.

116
116
139
140
140
141
142
143
144
144
147
149
154
157
161
162
163
163

116

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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)

CO2 & co-solvent

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]

1020 LCO2 kg1 sample


015% EtOH

Gravimetric

Soxhlet extraction
Sonication
ANOVA

[243]

50

15 kgCO2 kg1 sample

GC

Acid value
Gardner color
FAME

[244]

534

80

20 LCO2 kg1 sample

FAME
GC-FID

Soxhlet extraction

[245]

8796

200300

3035

Modeling

[246]

80140

3555

GCMS

Hydrodistillation

[247]

04.3

150350

3542

416 kgCO2 kg1 sample


960 LCO2 kg1 sample
1% EtOH

GCMS

2.53.0

kg1

Alkannin

50300

3080

30 kgCO2

0.62.5

100300

4565

2941 kgCO2 kg1 sample

Bulb

0.0050.025

103287

30950

200800 LCO2 kg1 sample

Bulb

0.2954.68

160240

3545

66220 LCO2 kg1 sample

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 barbadensis Miller

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

97 kgCO2 kg1 sample


1.8 kgCO2 kg1 sample
010% EtOH
545 kgCO2 kg1 sample

020% (v/w) MeOH

1.362.80

2040

4565

3.48.3

200400

40

5600 LCO2 kg1 sample

46

200400

40

5.6 LCO2 kg1 sample

06

150250

4070

0.54.8

100300

4070

4000 LCO2 kg1 sample


100 kgCO2 kg1 sample

Squalene

110280

60100

1200600 LCO2 kg1 sample

Furocoumarins

250550

4080

300

4060

225300

50

200300

4060

Tocopherols, fatty acids,


sterols

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

Organic solvent extraction


Ultrasound extraction

[256]

HPLC

Particle size effect

[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]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

Angelica sinensis (Oliv.) Diels


(Umbelliferae)

T ( C)

CO2 & co-solvent

1.14.0

147294

4060

411 LCO2 kg1 sample

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

28 LCO2 kg1 sample


21,81843,636 LCO2

296

023

015% EtOH
015% H2 O
015% Acetic acid

4450

0.48

Phenols

Analytical technique

sample

040 kgCO2 kg1 sample


EtOH
50 LCO2 kg1 sample
H2 O

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

14 kgCO2 kg1 sample

173

50

7.5 (wt)% ethyl-acetate

101304

3565

1.84.2 LCO2 kg1 sample

1.714.9

Atractylode lancea

Root

2.310.3

150250

4060

Atractylodis macrocephalae

Baizhu

Rhizome

3.676.76

150450

4060

Azadirachta indica A. Juss

Neem

Seed

585

100260

3055

Azadirachta indica A. Juss

Neem

Seed

570

100260

Azadirachta indica A. Juss

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

Particle sizes effect

[263]

HPLC
APCI
MS

Soxhlet extraction
DoE

[221]

Modeling

[264]

RSM
DoE
Antioxidant activity
Fractionation
Organic solvent extraction

[265]

10150 kgCO2 kg1 sample


30 kgCO2 kg1 sample
020% (w/w) EtOH

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

2186 LCO2 kg1 sample

Gravimetric analysis

Modeling
Effect of particle size

[172]

kg1

Azadirachta indica A. Juss

Neem

Seed

Nimbin

00.02

100260

3560

Baccharis dracunculifolia

Baccharis

Leaf

DHCA, PHCA, p-coumaric


acid, kaempferide

2.44.7

200400

4060

1253 kgCO2
sample
85 kgCO2 kg1 sample

Baccharis dracunculifolia,

Baccharis

Branch and leaf

(E)-nerolidol; spathulenol

0.38

90120

4060

340 LCO2 kg1 sample

Baccharis trimera

Baccharis

Branch and leaf

1.72.3

90

4070

80 LCO2 kg1 sample

Baccharis trimera

Baccharis

Stem and leaf

0.32.0

100300

3040

Betula pendula Roth

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

35482 kgCO2 kg1 sample

[271]

HPLC

[170]

HPLC

Soxhlet extraction

[272]

GC
GCMS

ODS trap (n-hexane)


Hydrodistillation

[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]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

Caprylic acid methyl ester

375015,000 LCO2 kg1 sample


0130 kgCO2 kg1 sample
120 kgCO2
02% EtOH

kg1

Borage

Seed

0.124.3

100350

40

Borago ofcinalis L.

Borage

Seed

030

200300

55

060 kgCO2 kg1 sample

Borago ofcinalis L.

Borage

Seed

957

150250

3060

1000 LCO2 kg1 sample

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

10130 kgCO2 kg1 sample


626 kgCO2 kg1 sample

1847

517

100

Phenolics

2.110.3

300500

4060

10% EtOH
61 kgCO2 kg1 sample

100250

5080

200

45

2035% (v/v) MeOH


2 LCO2 kg1 sample

Brassica oleracea

Broccoli

Leaf

Amino acids

Bunium persicum Boiss.


Mespilus germanica L.

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

105 kgCO2 kg1 sample

Calendula ofcinalis L.

Marigold

Flower

02.6

120200

2040

Calendula ofcinalis L.
Matricaria recutita

Marigold
Chamomile

Flower

01.8

90100

4050

030 kgCO2 kg1 sample


035 kgCO2 kg1 sample

Calendula ofcinalis L.

Marigold

Flower

3.8

100200

2040

50 kgCO2 kg1 sample

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

4001800 LCO2 kg1 sample

HPLC

RSM
DoE
Antioxidant activity

[295]

Caffeine

150300

4560

62.5625 LCO2 kg1 sample

HPLC

Ultrasonic assisted
Moisture effect
DoE

[296]

Epigallocatechin gallate

100300

4060

30240 LCO2 kg1 sample

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

Seed, fruit, stem

200300

45100

100133 LCO2 kg1 sample

300500

6080

450

50

EtOH (13% v/v)


270 kgCO2 kg1 sample
1547 kgCO2 kg1 sample

Fruit

HPLC
GCMS

5090

Seed

Fruit

[691]

14.829%

Hemp

Paprika

Bed length effect


Flow rate effect
SEM

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

0160 kgCO2 kg1 sample

0370 kgCO2 kg1 sample

Scientic name

Common name

Plant part

Capsicum annuum L.

Paprika

Capsicum annuum L.

Jalapeno

Capsicum annuum L.

Red pepper

Target

CO2 & co-solvent

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

7168 kgCO2 kg1 sample

HPLC

Soxhlet extraction
DoE
RSM

[301]

Capsicum spp.
Piper nigrum
Zingiber ofcinale

Chili
Black Pepper
Ginger

Piperine

4.112.0

300

40

030 kgCO2 kg1 sample

1 H NMR spectroscopy

Soxhlet extraction

[124]

Carthamus tinctorius

Safower

Seed

1040

220280

3540

7243 kgCO2 kg1 sample

GC-FID

[302]

Carum carvi L.

Caraway

Fruit

Limonene
carvone

19

70400

80

Particle size effect


Modeling
Pilot scale
Harvest time effect
Particle sizes effect

Carum carvi L.

Caraway

Seed

Carvone
limonene

5080

2860

Analytical technique study

[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

Terpenoid indole alkaloids


(Vindoline, catharanthine)

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

13.5 LCO2 kg1 sample

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

58148 LCO2 kg1 sample

90120

4050

80100

3070

28 kgCO2 kg1 sample

GC

207414

7090

90 LCO2 kg1 sample


1015% EtOH

HPLC

200400

4080

200400

4080

59.578.5

sample

72 LCO2 kg1 sample

[207]

[306]

[308]

[312]

[205]

HPLC

RSM
DoE

[224]

GC-FID

RSM
DoE

[313]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Catharanthus roseus

03% MeOH
03% EtOH
03% Acetone
03% Acetonitrile
03% Hexane
03% Dichloromethane
03% Chloroform
03% Toluene

[300]

Citrus depressa

32 LCO2 kg1 sample


EtOH
515 LCO2 kg1 sample

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

60320 LCO2 kg1 sample

276345

4050

3600 LCO2 kg1 sample

HPLC

78108

4095

515% EtOH

HPLC

1030% EtOH
8.6 LCO2 kg1 sample

HPLC

Citrus grandis L. Osbeck

Citrus maxima Merr

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

Citrus sinensis. L. Osbeck

Orange

Pomace

0.853

100300

4050

Citrus unshiu

Press cake

L-limonene
palmitic and oleic acids
n-Butyl benzenesulfonamide
-sitosterol

Particle size effect

[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

410 LCO2 kg1 sample

Coffea arabica

Coffee

Husk/spent

0.59.7

100300

4060

101189 kgCO2 kg1 sample

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

Coffea arabica variety Mundo


Novo

Coffee

Bean

Coffea canephora var. Robusta

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

Coix lachrymal-jobi L. var.


Adlay
Colchicum autumnale L.

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

91 kgCO2 kg1 sample

GC-FID

DoE
RSM
Soxhlet extraction

[62]

15

190

4055

85 kgCO2 kg1 sample

Gravimetric analysis

Economic analysis
Tryacylglicerides prole

[61]

HPLC

Soxhlet extraction
DoE

[55]

017

6090

62.5 LCO2

152352

5070

0200 kgCO2 kg1 sample

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

415% (wt.) EtOH


Coffea arabica
Coffea robusta

[319]

Pilot plant

GC-FID
GC-EM
0340 kgCO2 kg1 sample

[318]

GC

28% (wt.) EtOH

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

05% (wt.) EtOH


05% (wt.) isopropyl alcohol
35197 kgCO2 kg1 sample
90 kgCO2 kg1 sample

HRGC

Soxhlet extraction
Modeling

[57]

3055

7.5200 LCO2 kg1 sample

Gravimetric analysis

Ultrasound assisted SFE


Flow rate effect

[322]

GCMS

Ultrassound assisted SFE


Particle size effect
Organic solvent extraction
Soxhlet extraction
Sonication
Hydrodistillation
Steam distillation
Soxhlet

[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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Citrus paradisi L. (variety Ruby


Red)
Citrus paradisi Macf.

HPLC

[56]
[60]

[324]

[168]
[325]

121

122

Table 1 (Continued)
Scientic name

Common name

Cordia verbenacea D.C.

Cordia verbenacea D.C.

Plant part

Target

Extraction
yield (wt%)

P (bar)

T ( C)

CO2 & co-solvent

Analytical technique

Other Features

Ref.

Leaf

-Caryophyllene

34

80300

60

177 kgCO2 kg1 sample

GCMS

Fractionation
Soxhlet extraction
Hydrodistillation
Modeling

[326]

20100 kgCO2 kg1 sample

100300

3050

Coriandrum sativum L.

Coriander

Seed

0.82.0

116280

3858

Coriandrum sativum L.

Coriander

Seed

0.050.6

90150

4050

Leaf

47 kgCO2 kg1 sample


040 kgCO2 kg1 sample
501500 kgCO2 kg1 sample

[327]

Hydrodistillation

[328]

GC
GCMS

Particle size effect


Hydrodistillation
SEM

[329]

GC

Organic solvent extraction

[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

0127 kgCO2 kg1 sample

GC

Solubility measurements
Modeling

[333]

Corylus avellana L.

Hazel

Fruit

300450

4060

218 kgCO2 kg1 sample

Gravimetric Analysis

RSM
DoE

[334]

Cratoxylum prunifolium Dyer

Leaf

Croton zehntneri Pax et Hoff

Leaf

Cucumis melo
Cantalupensis
Cucumis melo var.
reticulatus
Cucurbita cifolia
Cucurbita cifolia

Cantaloupe

Seed

Fig leaf gourd


Pumpkin

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

Cucurbita pepo convar.


citrullina

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

30 kgCO2 kg1 sample

1.73.5

550

100

57

125325

3555

sample

513 kgCO2 kg1 sample


1.76.7 LCO2 kg1 sample
kg1

25

200400

4060

6130 kgCO2

07

300

30

01 kgCO2 kg1 sample

sample

GC-FID

Turmeric

Rhizome

Curcuminoids

4.56.5

250300

45105

Curcuma longa L.

Turmeric

Rhizome

Curcuminoids

4.522.6

250300

45

EtOH

Cydonia oblonga Miller

Quince

Seed

100345

3065

24 LCO2 kg1 sample

RSM
DoE

[161]

GCMS

Steam distillation

[157]

GC-FID

Organic solvent extraction


Soxhlet extraction
Hydrodistillation
Modeling
Pilot plant
Drying pretreatment
Soxhlet extraction
Modeling
Drying pretreatment

[160]

GCMS

DoE
RSM
Ultrasound assisted
extraction

[340]

GC-FID

Solvent extraction
Steam distillation
Accelerated solvent
extraction

[341]

Spectrophotometry

Spectrophotometry
HPLC
GC

0.81.1% (v/v) MEtOH

Cymbopogon citratus

Lemongrass

80

50

19144 LCO2 kg1 sample


030% Hexane
030% Dichloromethane

[339]

GCMS

6.916.1% EtOH/Isopropyl
Curcuma longa L.

[150]

[159]

[158]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

2.83.7 kgCO2 kg1 sample


02000 LCO2 kg1 sample

4.724

150300

3555

180 kgCO2 kg1 sample

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

2.55.0% (w/w) Canola oil

Daucus carota L. subsp. carota

Carrot

Umbels

90

40

Daucus carrota L., cultivar


Chanteney

Carrot

Root

Carotol

Diospyros kaki Thunb.

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]

Particle sizes effect


Solvent extraction
ANOVA
Antifungal activity
Hydrodistillation

[107]

Antimicrobial activity
Hydrodistillation
Particle size study

[109]

GC-FID
GCMS

[110]

[344]

HPLC

518 kgCO2 kg1 sample

GCMS

Hydrodistillation
Soxhlet extraction
Solvent extraction
Two-step decompression
system

[193]

87 kgCO2 kg1 sample


020 kgCO2 kg1 sample

Palm

Fruit

Oil

77.8

140300

4080

Elaes guineensis

Palm

Fiber

Fatty acids
Carotene, Lipids

2.95.3

200300

4555

317 kgCO2 kg1 sample

Elettaria cardamomum L.

Elettaria

Seed

25

90110

4050

218 kgCO2 kg1 sample

Elettaria cardamomum Maton

Cardamom

Seed

100300

3555

25% (w/w) EtOH

Aerial parts

136340

4080

010% H2 O
010% MeOH

3040

Pilot scale

[346]

Elaeis guineensis

120300

NMR
HPLC
GC
HPLC

03.8% (v/v) MeOH

Kernel cake

00.9

[174]

[345]

Palm

Aerial parts

Purication

RSM
DoE

Elaeis guineensis

Horsetail

[183]

Articial neural network

Palm

Equisetum giganteum L.

Soxhlet extraction
Biodiesel production

GCMS

Ekebergia capensis
Elaeis guineensis

Ephedra sinica

TLC
GC
HPLC
HPLC
MS

GC
GCMS

315 LCO2 kg1 sample

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

Particle sized effect


ANOVA
Soxhlet extraction

Spectrophotometry

Modeling

[187]

GCMS

Hydrodistillation
Particle size effect
Subcritical propane extraction
Solvent extraction
Organic solvent extraction

[353]

Organic solvent extraction

[356]

6.6610 LCO2 kg1 sample

053 kgCO2

kg1

HPLC
GCMS
GC
sample

GC
GCMS

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Daucus carota L.

GCMS
HPLC-PDA
HSCCC

[352]

[354]
[355]

123

124

Table 1 (Continued)
Scientic name

Extraction
yield (wt%)

P (bar)

T ( C)

CO2 & co-solvent

150250

40100

515% (v/v) MeOH/H2 O (29:71)

1,8-Cineole

1.42.0

80250

4060

2500 LCO2 kg1 sample

Gallic acid

12.016.6

400

70

138414

4060

15% EtOH
200 LCO2 kg1 sample
100240 LCO2 kg1 sample

0.01.3

100200

4060

80 kgCO2 kg1 sample

0.280.51

300

5070

45 LCO2 kg1 sample

Common name

Plant part

Target

Erythroxylum coca var. coca

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

Zingiber ofcinale Roscoe


Eucommia ulmoides

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]

EtOH (1520% w/w)


551 kgCO2 kg1 sample

GCMS

Modeling

[47]

GCMS

Soxhlet extraction
Fractionation

[49]

GCMS

DoE

[48]

Soxhlet extraction

[52]

8110 kgCO2 kg1 sample


08% (wt.) EtOH

31 kgCO2 kg1 sample


05% (wt.) EtOH

Methyl morolate

Aucubin

Ref.

05% (wt.) EtOH

Eucalyptus globulus

Eucalyptus grandis
Eucalyptus globulus
Eucalyptus spathulata
Eucalyptus microtheca

Other Features

200

60

551 kgCO2 kg1 sample

100300

4555

MeOH

GCMS
NMR
GC-FID

Hydrodistillation

[45]

0.811

67250

1540

2.5 kgCO2 kg1 sample

GCMS

Modeling
Solubility measurement
Flow rate study

[359]

0.62.0

180300

45330

400 LCO2 kg1 sample

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]

03% (v/v) H2 OEtOH


03% (v/v) H2 O
03% (v/v) MeOH
03% (v/v) EtOH
03% (v/v) H2 OMeOH
03% (v/v) H2 OEtOH
Eugenia caryophillus
Eugenia caryophillus
Vetiveria zizanioides (L.)
Nash ex Small

Clove
Clove
Vetiver

Eugenia caryophyllata Thunb.


Eugenia caryophyllata Thunb.

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]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

36 kgCO2 kg1 sample


0.6 kgCO2 kg1 sample
010% MEtOH
180,000 LCO2 kg1 sample
16% (v/v) MeOH
1.54.7 LCO2 kg1 sample
4.8% (v/v) MeOH

3.65.4 LCO2 kg1 sample


05% MEtOH
0449 kgCO2 kg1 sample
kg1

Fennel

Fruit

098

90100

4050

35106 kgCO2

Foeniculum vulgare Mill

Fennel

Seed

1.55.5

80150

4057

36285 kgCO2 kg1 sample

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

524% (mol) EtOH

HPLC

DoE
EtOH preextraction
Soxhlet extraction

[376]

Ginko biloba
Ginko biloba

Ginko biloba

Leaf

204340

4080

520% (v/v) MeOH


16/4% (v/v) MeOH/H2 O

HPLCESI-MS

Organic solvent extraction

[378]

Glycine variety

Soybean

Distillate

Flavonoids
terpenoids
Terpene lactone
avonoids
Bilobalide
ginkolides
Fatty acids, tocopherols,
sterols, squalene

EtOH (5% w/w)


616 LCO2 kg1 sample
60% (v/w) EtOH
110% EtOH

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 uralensis Fisch

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

(14.7) 104 LCO2 L1 sample


1820 kgCO2 kg1 sample

4050

814.5 LCO2 kg1 sample

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

6119 kgCO2 kg1 sample

Distillate

Tocopherols
phytosterols

20100

150230

65

Sunower

Leaf

Allelopathic compounds

02

100500

3550

Sunower

Leaf

Allelopathic compounds

0.21.6

380

50

sample

42126 kgCO2 kg1 sample


3.84.7% H2 O

[377]

[152]

HPLC

SCF
Fractionation

[155]

GC

ODS traps

[151]

Gravimetric analysis

Particle sizes effect


Modeling
Scale-up

[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

Three-step SFE extraction


Soxhlet extraction
Modeling
Pilot-scale

[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]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Foeniculum vulgare

GCMS

[381]

[69]

125

126

Table 1 (Continued)
Scientic name

Common name

Plant part

Target

Extraction
yield (wt%)

P (bar)

T ( C)

CO2 & co-solvent

Analytical technique

Other Features

Ref.

Helianthus annuus L.

Sunower

Leaf

Allelopathic compounds

0.11.2

300500

50

2126 kgCO2 kg1 sample

Gravimetric analysis

Cluster Analysis
Pilot scale

[65]

Helianthus annuus L.

Sunower

Seed

095

200600

4080

425 kgCO2 kg1 sample

Gravimetric analysis

Modeling
Flow rates study
Particle sizes effect

[68]

Flower

04.5

100200

4060

36 kgCO2 kg1 sample

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

38 kgCO2 kg1 sample

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

Hordeum vulgare L. var. Robur

Barley

Hordeum vulgare L.

Brewers Spent Grain

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

30 LCO2 kg1 sample

Tocopherol

0.21.7

100350

4080

66400 LCO2 kg1 sample

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

St. Johns wort


Ginko biloba

Hypericum perforatum L.

St. Johns Wort

14

100350

40

2675 LCO2 kg1 sample

Hypericum perforatum L.

St. Johns Wort

04.8

100200

4050

45 kgCO2 kg1 sample

Hyssopus ofcinalis

Hyssop

Leaf + ower

Hyssopus ofcinalis

Hyssop

Root

Ilex paraguariensis
Illicium verum

Yerba mate
Chinese star anise

Leaf
Seed

Methylxantines caffeine
Fatty acids

Inula viscosa (L.) Aiton


Inula graveolens (L.) Desf

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

76 kgCO2 kg1 sample

Antioxidant activity

[385]

EtOH, MeOH, 2-propanol

Hypericum perforatum L.
Ginkgo biloba

Leaf

Gravimetric analysis

GC

111

Seed

Flower

sample

[382]

EtOH/acetic acid (9:1)

kg1

1.02.3

90100

4050

0.28 kgCO2

0.12.9

100350

4575

0.06.0% (v/v) MeOH

03.79
6.8023.72

120200
100300

4070
3050

(015%) (v/v) EtOH

0.65

90

50

14.448.9

250350

4060

sample

095

180234

3548

0550 kgCO2

68.2

689

85

70 LCO2 kg1 sample

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

Subcritical solvent extractions

[401]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Hippophae rhamnoides L

kg1

GCMS
GC-FID
HPLC

Juniperus communis L.

Juniper

Fruit

0.20.4

90200

40

30 kgCO2 kg1 sample


kg1

Juniperus communis L.

Juniper

Fruit

4.512.5

90125

4050

618 kgCO2

Juniperus communis L.

Juniper

Fruit

0.14

80100

40

180 kgCO2 kg1 sample

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

17 kgCO2 kg1 sample

0.82

90

50

21 kgCO2 kg1 sample

340

3575

90250

40

Lavandula angustifolia

Lavender

Flower

Lavandula hybrida

Lavandin

Flower

Lavandula stoechas L. ssp.


cariensis (Boiss.) Rozeira

Flower

Lavandula viridis LHr

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

0.10.93 LCO2 kg1 sample

[406]

GC-FID

120180

40

Seed

11.7935.56

200300

5070

375 LCO2 kg1 sample

GCMS

DoE
RSM
Antioxidant activity

[415]

1.62.2

200350

40

100200 kgCO2 kg1 sample

GCMS

Extractor size study

[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

Levisticum ofcinale Koch.


Apium graveolens L.

Camphor

sample

40

0.9

1040 kgCO2

kg1

3550

028

Flower

9097273 LCO2

kg1

101405

Fruit
Lavender

20.8 LCO2 kg1 sample

80140

Seed

Lavandula angustifolia

sample

Hydrodistillation

880 LCO2 kg1 sample


16 LCO2 kg1 sample
110% (v/v) EtOH
60 LCO2 kg1 sample
(0.61.2) 105 LCO2 kg1 sample
01 LEtOH kg1 sample

GCMS

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

L. Stoechas subspecies C. Boiss

2.53.9

sample

GC-FID
GCMS

[212]

[417]

GCMS (SIM)

[418]

GCMS

Organic solvent extraction

[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)

CO2 & co-solvent


kg1

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

163 kgCO2 kg1 sample

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

272 kgCO2 kg1 sample

Gravimetric analysis

[75]

Linum usitatissimum L.

Linseed

Seed

8.628.8

250

50

05% (v/v) EtOH

Particle size effect


Flow rate effect
RSM
DoE
Economic analysis
Modeling

Linum usitatissimum
Brassica rapa
Brassica napus
Brassica juncea
Sinapis alba

Flax
solin
canola
mustard

Seed

2149

517

100

7.5132 LCO2 kg1 sample


015% EtOH

GC

Reference method extraction

[420]

Lippia alba Mill.

Lippia

Leaf

Limonene
carvone

0.25.7

80120

4050

51654 kgCO2 kg1 sample

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

23 kgCO2 kg1 sample

Thymol

1.21.8

6779

1025

2 kgCO2 kg1 sample

GCMS

Steam distillation
Solvent extraction
Modeling

[423]

Lycopene

72.580.0

400

60

2151 kgCO2 kg1 sample

HPLC

Mixture of raw materials

[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

Majorana hortensis Moench

Marjoram

Mangifera indica L.

Mango

Leaf

Mangiferin
quercetin

Marchantia convoluta
Whole plant

Matricaria chamomilla

Chamomile

Flower

Matricaria recutita
Maydis stigma

Chamomile

Flower
Flower

Maytenus aquifolium Martius


(Celastraceae)

Leaf

Maytenus ilicifolia
Melaleuca cajuputi

Leaf
Leaf

Melissa ofcinalis L.

GCMS

[70]

1.63.2

Lippia dulcis Trev.

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

53 LCO2 kg1 sample


80 LCO2 kg1 sample
240 kgCO2 kg1 sample
020% EtOH
020% MEtOH
1.85.3 LCO2 kg1 sample
6 LCO2 kg1 sample
MeOH

GC

Modeling

[424]

GCMS

Hydrodistillation

[209]

HPLC

Antioxidant activity
Hydrodistillation

[425]

GCMS

Organic solvent extraction

[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]

50100 kgCO2 kg1 sample

Gravimetric

Steam distillation
Modeling

[435]

GCMS

Hydrodistillation

[436]

GCMS

Fractionation
Hydrodistillation

[437]

kg1

15 kgCO2
053% MEtOH

sample

[431]
[432]
[433]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Lippia alba Mill.

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

6.818.4 LCO2 kg1 sample

100

70

Fruit

Flavonoids

1.21.5

250350

3050

Leaf + stem
Kernel

Phenolic compounds

0.22.0
6.7136.13

103241
150300

2550
3560

015% (w/w) EtOH


060 kgCO2 kg1 sample

Leaf and bark

-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

80 LCO2 kg1 sample


kg1

sample

12 LCO2 kg1 sample


06% (v/v) MeOH

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]

Organic Solvent Extraction


Soxhlet extraction
Modeling
Particle size effect

[225]

5551000 LCO2 kg1 sample


EtOH

0.24 LCO2
MeOH

Leaf, stem, bud

Modeling

GCFID
GCMS
GCMS
GCMS
GC-HRMS

68 LCO2 kg1 sample


kg1

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

Fertilizer dosage effect


Harvesting time effect
Hydrodistillation
Steam distillation

Oenothera biennis L.

Primrose

Seed

Fatty acids

21

200300

4060

155 kgCO2 kg1 sample

GC

Soxhlet extraction
Modeling

[185]

Olea europaea L.

Olive

Husk

475

100300

4060

60009000 LCO2 kg1 sample

Gravimetric Analysis

Soxhlet extraction
RSM
DoE

[230]

Olea europaea L.

Olive

Husk

6480

75350

4060

840036,000 LCO2 kg1 sample


01% EtOH

HPLC

RSM
DoE
Fractionation

[456]

Olea europaea L.

Olive

Leaf

Tocopherol

438

250450

4060

200600 LCO2 kg1 sample

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Coumarin

Mulberry

Nepeta persica

sample

Leaf

Morus alba

Gravimetric Analysis

Gravimetric analysis
kg1

100300

Noni

Nepatia cataria

1520% (w/w) EtOH


60 kgCO2 kg1 sample

3.06.9

Morinda citrifolia
Moringa oleifera

Myrtus communis L.

2288 kgCO2 kg1 sample

[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)

CO2 & co-solvent

100300

50100

72,000 LCO2 kg1 sample

0.10.3

150350

5565

Analytical technique

020% (v/v) EtOH


020% MeOH
020% H2 O
50 LCO2 kg1 sample
MeOH

13133 kgCO2 kg1 sample

Pear bush

Seed

4.26.0

250400

6550

Origanum majorana

Marjoram

Leaf and top

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

055 kgCO2 kg1 sample


33100 kgCO2 kg1 sample

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

20 kgCO2 kg1 sample

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]

7854 LCO2 kg1 sample

HPLC

Fractionation
Deacidication
LikensNickerson extraction

[97]

2941 kgCO2 kg1 sample


018 kgCO2 kg1 sample

120

50

020

100400

5060

78 kgCO2 kg1 sample


2040 LCO2 kg1 sample
379 kgCO2 kg1 sample

11.2

200

40

1035% (w/v) EtOH

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

1080 LCO2 kg1 sample

Gravimetric

[130]

300

50

bis(2-ethylhexyl) sodium
sulfosuccinate/EtOH
3% (v/v) EtOH

Ultra-sound assisted SFE


Reverse microemulsion

HPLC

Ultra High pressure extraction


Soxhlet extraction
Ultrasound-assisted
extraction
Microwave-assisted
extraction
Soxhlet extraction

[127]

SEM

[214]

GCMS

Organic solvent extraction


Steam distillation

[215]

HPTLC
GC
HPLC
ICP-MS

Soxhlet extraction
Three-step decompression

[463]

Ginsenosides

2040

207483

110

Pandanus amaryllifolius Roxb.

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

Panicum miliaceum (L.)

DoE

Soxhlet extraction
Antimicrobial tests

680

Panax quinquefolium

Pandanus amaryllifolius Roxb.

HPLC
ESI-MS
NMR

GC
GCMS

345689

Ginsenosides

[458]

HPLC
LC-ESI

GC

025

1.110.7

Root

29 kgCO2 kg1 sample

Ref.

sample

1131% (mol) MetOH


DMSO
7200 LCO2 kg1 sample
kg1

120455

4080

2040 LCO2

300500

4060

444 kgCO2 kg1 sample

sample

HPLC
LCMS
GCMS
GC-FID

[128]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Opuntia dillenii

Other Features

Papaver Somniferum L.

Poppy

Seed

Patrinia villosa Juss

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 atriplicifolia Benth.

Perovskia

Aerial parts

100300

4565

Persea americana

Avocado

Fruit

59.5662.87

420450

4045

0.41.13

100200

4050

Persea indica

Branch

Ryanodanes

5105 kgCO2 kg1 sample


MEtOH 1020% v/v
0400 kgCO2 kg1 sample
35 kgCO2 kg1 sample
140 kgCO2 kg1 sample

05% MEtOH
05% EtOH
05% Dicloromethane
05% n-hexane
78 102 LCO2 kg1 sample

Parsley

Seed

131

100150

3545

1300 kgCO2 kg1 sample

Peumus boldus M.

Boldo
Oregano

Leaf
branch

0.43.1

100

40

6 kgCO2 kg1 sample

Peumus boldus M.

Boldo

Bark

1.62.9

400600

4060

113 kgCO2 kg1 sample

Peumus boldus M.

Boldo

Leaf

0.52.9

60450

3060

15634 kgCO2 kg1 sample


010% EtOH

Pfafa glomerata

Brazilian Ginseng

Root

-Ecdysone

0.180.56

100300

3050

Phyllanthus emblica

Emblica

Fruit

Phenolic compounds

1.12.5

150250

555

19 kgCO2 kg1 sample


EtOH
211% (v/v)MeOH

Physalis peruviana

Physalis

Leaf

Flavonoids
phenols

3.615.5

400

60

05% EtOH

Picea abies

Spruce

Bark

2.53.3

260

70

16 kgCO2 kg1 sample

Pimpinella anisum L

Aniseed

Seed

3.110.7

80180

30

0.00.4 kgCO2 kg1 sample

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

Particle sizes effect


Hydrodistillation
Solvent Extraction
Steam distillation

[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

Hot pressurized water


extraction
Soxhlet extraction

[472]

TLC
HPLC
GCMS

Antioxidant activity

[473]

Organic solvent extraction


DoE
Antimicrobial activity
Antioxidant activity
Hydrodistillation
Solvent extraction

[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

020% (wt.) EtOH


010% (w/w) EtOH
2300 LCO2 kg1 sample

GC-FID
GCMS

Soxhlet extractions

[479]
[188]

HPLC

Compressed gas extraction

[480]

Gravimetric analysis

Particle sizes effect


Flow rates effect

[481]

Root

125250

4060

Piper nigrum

Pepper

Seed

160260

3550

Piper nigrum L.

Black pepper

Fruit

90150

4050

0340 kgCO2 kg1 sample

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

Organic solvent extraction


Ultrasonic aided extraction
Antioxidant activity
Hydrodistillation
Two-step decompression
system
DoE
RSM
Soxhlet extraction
Solvent extraction

Plukenetia volubilis

Sacha inchi

Seed

41.950.1

300400

4060

130 kgCO2 kg1 sample

GC

Modeling
Particle size effect
Soxhlet extraction
Cold Pressing

[486]

Prunus amygdalus

Almond

Seed + kernel

1565

330

50

1573 kgCO2 kg1 sample

HPLC

Multifactor analysis of
variance
Micrograph

[487]

Prunus armeniaca L

Apricot

Bagasse

36

304507

4060

887 LCO2 kg1 sample

Spectrophotometry

Modeling

[106]

012
Phenolic

0.45

Omega-3

-Carotene

GCMS

EtOH
n-hexane

GC-FID

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Petroselinum sativum Hoffm.

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)

CO2 & co-solvent


kg1

Other Features

Ref.

Spectrophotometry
HPLC

Solvent extraction
Particle size effect
Flow rate effect

[102]

SEM
Gravimetric Analysis

Particle size effect


Modeling

[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

123386 kgCO2 kg1 sample

Gravimetric Analysis

Modeling
Particle size effect
Scale-up

[491]

Seed

030

150198

4051

0140 kgCO2 kg1 sample

GCMS

Flow rate effect


Extractor geometry effect

[492]

2.55.0% (mol/mol) EtOH


25% (w/w) EtOH
1060 kgCO2 kg1 sample

HPLC

Particle size effect


Solvent extraction
Three-step decompression
system

[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

050 kgCO2 kg1 sample


03% EtOH
612 kgCO2 kg1 sample
03% EtOH
1090 LCO2 kg1 sample
228% EtOH
2040 LCO2 kg1 sample
020% (wt.) EtOH

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

2335 kgCO2 kg1 sample


06 kgCO2 kg1 sample

Psoralea corylitolia L.

Fructus Psoraleae

Seed

Psoralen
isopsoralen

5.09.8

260340

4060

1200 LCO2 kg1 sample

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

12.3 kgCO2 kg1 sample

HPLC

132468

3370

4663 (w/w) EtOH


80192 LCO2 kg1 sample

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

53266 kgCO2 kg1 sample


015% EtOH
750 LCO2 kg1 sample
0.30.6% (v/v) EtOH

96 kgCO2 kg1 sample


324540 kgCO2 kg1 sample
10% H2 O
3 kgCO2 kg1 sample

[493]

FAME
HPLC
TLC
13 C NMR

[500]
RSM
DoE
Flow rates effect
Soxhlet extraction
Soxhlet extraction

[501]

Organic solvent extraction

[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]

2754 kgCO2 kg1 sample

Matrix pretreatment effect

[509]

220 kgCO2 kg1 sample

Gravimetric

SEM
Modeling

[510]

Seed

4.77.1

300500

4060

Rosa aff. Rubiginosa

Rose hip

Seed

00.35

300

40

Rosa aff. Rubiginosa

Rosehip

Seed

07.5

300400

4050

Rosa canina L.

Rose hip

Seed

5.72

250

30

060 kgCO2 kg1 sample


9.283 kgCO2 kg1 sample
0.41.6 kgCO2 kg1 sample

Rosa mosqueta; Rosa aff.


Rubiginosa

Rose hip

Seed

300700

60

Rosa spp.

Hiprose

Seed

103689

4070

07.4

[490]

Spectrophotometry
Gravimetric

Rose hip

Rosa aff. Rubiginosa

[489]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

2.5 LCO2 kg1 sample


245 kgCO2 kg1 sample

90400

4060

100300

3040

100180

4060

0.13.5

100350

3040

0.53.1

100400

40

100205

4055

36 kgCO2 kg1 sample


07% EtOH
05% EtOH

Carnosic acid, rosmanol,


carnosol

300350

4060

02% EtOH

1,8-Cineole

250

60

3 LCO2 kg1 sample

1.21.8

90100

4050

4165 kgCO2 kg1 sample

05

200400

4060

1246

250350

40

Leaf + ower

0.21.5

172255

55

1375 LCO2 kg1 sample


20 kgCO2 kg1 sample
02% EtOH
07.5% EtOH

Santalum album
Boswellia carterii

Wood (resin)

1.36.5

90120

4560

120 kgCO2 kg1 sample

Santolina chamaecyparissus

Flower

0.11.4

8090

4050

21 kgCO2 kg1 sample

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

03% (wt.) EtOH


025 kgCO2 kg1 sample

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

Organic solvent extraction


Microwave assisted
Hydrodistillation

[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

510% (v/v) EtOH

[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]

7 kgCO2 kg1 sample


515% (w/w) EtOH

GC-FID
HPLC

Antioxidant activity
Organic solvent extraction

[518]

40

40 kgCO2 kg1 sample

GC

Hydrodistillation
Soxhlet extraction
Antioxidant activity

[519]

90100

4050

44 kgCO2 kg1 sample

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

250 LCO2 kg1 sample

GCMS

Steam distillation
Soxhlet extraction
Ultrasonic extraction

[521]

Schisandra chinensis

Stem + leaf

0.21.3

200270

4060

1074 kgCO2 kg1 sample

RP-HPLC

Modeling

[233]

Lignan
cinnamic acid

GCMS

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

CO2 & co-solvent

Analytical technique

Other Features

Ref.

0.4% (v/v) MeOH


0.4% (v/v)EtOH
0.4% (v/v)
1,2-Propanediol

HPLC

DoE
Soxhlet extraction

[522]

Spectrophotometry

Solvent extraction

[523]

GCMS

Hydrodistillation

[524]

225300 LCO2 kg1 sample

Sesamum indicum L.

Black Sesame

Seed

4152

200400

3585

Seseli bocconi Guss

Seseli bocconi Guss

Leaf

0.130.60

90

50

Silybum marianum

Silybum

Seed

525

100300

580

6582 kgCO2 kg1 sample

HPLC

Soxhlet extraction
Acid value test
Modeling

[525]

Simmondsia chinensis

Jojoba

Seed

1052

300600

7090

249 kgCO2 kg1 sample


010% Hexane

Gravimetric Analysis

Solvent extraction
Flow rate effect
Particle size effect

[526]

0.010.70

200600

4060

Sinomenium acutum (Thunb.)


Rehd et Wils

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

130 kgCO2 kg1 sample

Pomace

Lycopene

365533

4763

71773 LCO2 kg1 sample

Tomato

Fruit

Lycopene
-carotene

400

4070

Tomato

Fruit and seed

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

24% (3/4 EtOH + H2 O)

1.24.8

250

50

150350

4080

020% EtOHH2 O

200250

30

35 kgCO2 kg1 sample

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 rebaudiana Bertoni

Stevia

Leaf

Syzygium aromaticum L.

Clove

Bud

Tagetes erecta

Marigold

Flower

Stevioside
rebaudioside A
01.2

Lutein esters

0.40.7

HPLC
HPLC
Spectrophotometry

Particle size effect

[27]

HPLC

Cluster analysis

[30]

HPLC

DoE
RSM
DoE
ANOVA
RSM

[35]

[33]

HPLC
UVVis

Particle size study


Flow rate study
Solvent Extraction
RSM
DoE
Modeling
Modeling
Soxhlet extraction

Gravimetric
HPLC

Particle size effect


Solvent extraction

[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

220 kgCO2 kg1 sample

HPLC
HPLC

842 kgCO2 kg1 sample


150300 kgCO2 kg1 sample

[528]

HPLC

HPLCUV

GC-FID
GCMS
TLC
HPLC
Spectrophotometry

[26]

[28]

[29]

[31]

[531]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

335450
0.030.07

Solanum lycopersicum L.

Spilanthes acmella var.


oleracea

15,000 LCO2 kg1 sample


MeOH
340 kgCO2 kg1 sample
020% Hazelnut oil
515% EtOH/H2 O/Canola Oil
21 LCO2 kg1 sample

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

Taraxacum ofcinale Weber et


Wiggers

Dandelian

Leaf

-Amyrin
-sitosterol

Taxus baccata

Yew

Needle

10-Deacetylbaccatin III

Leaf and seed

Squalene

Terminalia catappa
Theobroma cacao

Cocoa

Seed

Cocoa

Bean

Theobroma cacao

Cocoa

Bean

4050

200800

4080

1933 kgCO2 kg1 sample

1.54

3565

100400

6575

718

138275

40

850 LCO2 kg1 sample


10% MeOH
45 LCO2 kg1 sample

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

Leaf and branch

0.67

80120

4060

Thymus vulgaris L.

Thyme

Flower + leaf

0.71.9

200

40

830 LCO2 kg1 sample

Thymus vulgaris L.

Thyme

550

100

40

514 kgCO2 kg1 sample

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

Thymus zygis L. subsp.


Sylvestris

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]

Fermentation level effect


Roasting time effect

[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

94 kgCO2 kg1 sample

0.64.0

80400

40

4886 LCO2 kg1 sample

4.9

400

60

3.34.7
1.2

150400
100150

40
40

011

80214

3057

2118 kgCO2 kg1 sample

85240

3550

021 kgCO2 kg1 sample

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

Flow rate effect


Particle size effect
RSM
DoE
Soxhlet extraction

[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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

CO2 & co-solvent

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

Organic solvent extraction


Pilot Scale

[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

369 LCO2 kg1 sample

Triticum spp.

Wheat

Germ

1421

400550

4080

2080 kgCO2 kg1 sample

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

Valeriana ofcinalis var.


latifolia

Valerian

Root

Vernonia galamensis L.

Iron weed

Seed

Vernolic acid

Vetiveria zizanioides (L.) Nash


ex Small

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

16.7 LCO2 kg1 sample


MeOH
05% EtOH
05% MeOH
132 kgCO2 kg1 sample

1.84.9

152228

3761

412 LCO2 kg1 sample

0.81.9

250400

3565

2040

138690

4080

3.2

200

40

20,00050,000 LCO2 kg1 sample


015% EtOH
8 kgCO2 kg1 sample

3.904.35

300

40

733 kgCO2 kg1 sample


kg1

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

Phase equilibrium study


Modeling
Economic analysis

[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

162 kgCO2 kg1 sample

Vetiveria zizanioides L.

Vetiver

Grass

06

100190

4050

Vetiveria zizanioides L.

Vetiver

Root

3.44.7

100300

40

Vitex agnus castus

Chaste tree

Fruit

6.4

100450

4060

Vitis vinifera L.

Grape

Seed

11.5

180220

4050

Antioxidant activity

[21]

Grape

Seed

016

160200

40

90 kgCO2 kg1 sample


010 kgCO2 kg1 sample

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

024 kgCO2 kg1 sample

Vitis vinifera L.

Grape

Seed

816

250

80

41 kgCO2 kg1 sample

Vitis vinifera L.

Grape

Fruit

4060

520% MeOH

Tryacylglicerides

Gallic acid
protocatechuic acid
phydroxybenzoic
acid
Anthocyanins

Glycosides

sample

40 LCO2 kg1 sample


515% (v/v) EtOH
010% (v/v) EtOH
81108 kgCO2 kg1 sample
2239 kgCO2 kg1 sample

GCMS
HPLC
GC

[15]

Fractionation

[24]

Extractor volume study


Modeling
Solubility

[13]

Species varieties comparison

[3]

DoE
Sand bed
Diatomaceous earth

[19]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Triticum spp.

-Tocopherol

GC
HPLC

150200 LCO2 kg1 sample


025% MeOH
515% EtOH
10% H2 O

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

Xanthoceras sorbifolia Bunge

Yellow Horn

Seed

165334

2862

20100 kgCO2 kg1 sample

Zanthoxylum bungeanum

Phenol
Phenolic

13.42

4061

Seed

Zataria multiora Boiss

Zataria

Zea mays

Corn

Germ

Zea mays

Corn

Bran

Zingiber corallinum Hance

2.34.1

Rhizome

Zingiber ofcinale
Zingiber ofcinale

Ginger
Ginger

Rhyzome
Rhizome

Gingerols
Gingerol

Zingiber ofcinale

Ginger

Rhizome

Gingerol

Zingiber ofcinale Rosco

Ginger

Rhizome

Zingiber ocinale

Ginger

Rhyzome

2.0123 kgCO2 kg1 sample


767 kgCO2 kg1 sample
4% (wt.) EtOH
1050 LCO2 kg1 sample
525% (v/v) EtOH

[559]

Species variety effect

[560]
[18]

Electrophoresis
GCMS

Biological activity
Diatomaceous earth
Antioxidant activity
Soxhlet extraction

5080

015% EtOH

3555

15 LCO2 kg1 sample


MeOH

210525

4086

100300 kgCO2 kg1 sample

96

345690

4080

2.89.1

20150

3060

160
160

40
40

1.92.7

200250

2535

090

150250

2040

60120 LCO2 kg1 sample


015% EtOH
58 LCO2 kg1 sample

158 kgCO2 kg1 sample


01.2%EtOH
01.2% Isopropyl Alcohol
010 kgCO2 kg1 sample
30 LCO2 kg1 sample

[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

13 kgCO2 kg1 sample

101304

Thymol; l-terpinene;
r-cymene

Phytosterols

45180 LCO2 kg1 sample


07% MeOH
1020% (wt.) EtOH
4 kgCO2 kg1 sample
0130 kgCO2 kg1 sample
010% (wt.) EtOH
40 LCO2 kg1 sample
08% EtOH
015% EtOH
015% MetOH
6 LCO2 kg1 sample
010% EtOH
24 LCO2 kg1 sample
040% MetOH

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]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Fig. 1. Type of the biomass matrices used in SFE works along 20002013, for a total of 544 publications considered.

of compounds: triglycerides, fatty acids, fatty alcohols, terpenoids,


phytosterols, tocopherols, tocotrienols, and phenolics. Examples
from each family are presented in Fig. 2.
Triglycerides constitute the lion share of edible oils extracts.
They are neutral lipids with a triesters structure of glycerol and
fatty acids. Besides their important application for cooking purposes, it is known that their abundance in extracts lead to high
quality biodiesel. Notwithstanding some examples of biodiesel production research from SFE extracts, namely from cardoon (Cynara
cardunculus L.) [183] and Jatropha curcas L. [184], the number of
publications covering this application was found to be very low.
The classication of triacylglycerides is usually achieved attending to the respective esteried fatty acids, but the free fatty acids
are also a specic family of compounds that occur independently
in SFE extracts. Moreover, in some cases, free fatty acids have been
studied as target compounds for extraction, such as in SFE of borage
(Borage ofcinalis L.) [185], primrose (Oenothera biennis L.) [185],
chinese star anise (Illicium verum) [186], palm (Elaes guineensis)
[187], pine (Pinus sylvestris L.) [188], pupunha (Guilielma speciosa)
[189] and soybean (Glycine variety) [152]. These compounds are
keystones for soaps, oleochemical esters, oils and lubricants [190]
and in some cases their concentration may be helpful to control the
quality of oils [186]. Since fatty acids oxidation can lead to aldehydes formation, and consequently odor problems, they can have a
negative impact on products [188]. Therefore, depending on the
studied case, fatty acids removal can be advantageous.
Regarding fatty alcohols it is known that they play an important industrial role as oleochemical solvents, plasticizers, and as
surfactants in detergent formulations [190]. However due to the
easiness they can be produced from fatty acids and from ethylene
or other olens, specic SFE approaches aiming at the extraction
of these molecules tend not to be explored. These compounds
are frequently found in leaves and seeds, and most frequently are
waxy at room temperature [191]. For this reason extracts containing fatty alcohols may exhibit oil turbidity, a visual effect that can
be considered inconvenient depending on the nal application of
the extract. No work specically addressing SFE of fatty alcohols as
target molecules is reported in Table 1.
A wide range of naturally occurring chemicals found in
vegetable matrices belong to the terpenoids group, secondary
metabolites whose role in plants is related to protection, pollination

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

139

Fig. 2. Main families of compounds found in the extracts obtained by SFE of vegetable biomass, and examples from each one.

species are -sitosterol, campesterol and stigmasterol, and many


SFE publications have targeted them. These compounds have been
found in extracts of Anoectochilus roxburghii [221], amaranth (Amaranthus spp.) [222], corn (Zea mays) [223], eucalypt (Eucalyptus
globulus) [4649,52], grape (Vitis vinifera L.) [6], Kalahari melon
(Citrullus lanatus) [224], mulberry (Morus alba) [225], orange (Citrus sinensis) [139], pumpkin (Curcurbita spp.) [147], sea buckthorn
(Hippophae rhamnoides L.) [226,227], soybean (Glycine spp.) [152],
and sunower (Helianthus annuus L.) [69].
Tocopherols and tocotrienols are specic families of compounds
also found in many plant extracts. One of the most important
molecules of this group is vitamin E (-tocopherol), a powerful
antioxidant whose decient concentration in human organisms
lead to chronic diseases [228]. The structural differences between
the -pherol and -trienol derivatives are in the aliphatic side chains.
While tocotrienols occurrence is restricted to fewer species, tocopherols are produced by all photosynthetic vegetables as part of
their antioxidative system to cope with environmental stresses
such as intende se light, UV radiation and low temperatures
[228]. The presence of these compounds in SFE papers has been
reported in works with olive (Olea europaea L.) [229,230], sea
buckthorn (Hippophae rhamnoides L.) [202], soybean (Glycine spp.)
[151,152], sunower (Helianthus annuus L.) [69], wheat (Triticum
spp.) [162164].
Phenolic compounds embody a vast group of compounds related
to plants growth, development and defense. These compounds
commonly exhibit an active organolepsy due to their contribution to color and taste of vegetable products. From a structural

point of view, phenolics comprise an aromatic ring with one of


more hydroxyl substituents, being the number and arrangement of
the hydroxyl groups attached to the ring criteria of classication.
Besides the most simpler phenolic structures (e.g. catechol, benzoic acid or gallic acid), high-molecular weight insoluble molecules
are formed between phenolics and compounds of different nature,
such as carbohydrates, proteins [231]. Depending on the vegetable
species, extracts obtained by SFE can comprise substances from
several phenolic groups like coumarins [232], cinnamic acids [233],
quinones [39,234236], avonoids [237241], lignans [72,233].
3. Focuses of SFE works
Considering the abundance of compounds that are prone to be
found in supercritical extracts, it becomes pertinent to expose different possible focuses of SFE researchers for the vegetables under
investigation. For this, it is convenient to divide biomass species
based on usual extract classications, namely edible oils (higher
volume, lower value) and essential oils (higher value, lower volume).
The most abundant extracts from vegetable matrices are the
edible oils, which are mostly constituted by mixtures of triacylglycerides obtained with high extraction yields from the following
typical sources: palm, soybean, sunower, rapeseed, peanut, cottonseed, coconut, olive, corn, and sesame species. An edible oil, like
palm oil, may reach triacylglycerides concentrations around 95%
[566], and the use of SFE is many times devoted to other purposes
than their bulk extraction. Instead, it is more commonly linked

140

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

to attempts to enhance the concentration of valuable compounds


existing in minor concentrations. In the whole, SFE works regarding
these edible oils have focused in the following goals:
(i) tentative replacement of organic solvents like n-hexane as
extraction agents, avoiding thus the consequent environmental and human health hazards;
(ii) enrichment of main stream oils with bioactive or other distinctive minor constituents. In this respect, one may mention
several SFE works on palm [187,352,567], where -carotene,
squalene, -tocopherol contents were evaluated;
(iii) valorization of vegetable residues or by-products from main
extraction processes in order to uptake available bioactive
molecules. Several works on sunower distillate [63,69], soybean distillate [151,152], olive pomace [200,229], and olive
husk [456,457] are examples of this approach.
(iv) valorization of non-explored vegetable parts that do not belong
to the prime oil extraction process, such in the cases of SFE of
sunower leaves [6466] and of olive leaves [230].
Essential oil is the general classication used for volatile oils
that can be obtained by steam distillation of plants. This category
of extracts has been the core area of the research on SFE of natural matrixes since 2000 because it includes valuable specialty oils.
Although the extraction yields obtained through the employment
of SC-CO2 are quite exible, it is common to establish essential oils
as a group of natural extracts comprising up to 5% of vegetal dry
matter.
The presence of bioactive compounds makes essential oils interesting for numerous applications. With respect to their commercial
relevance, they are widely applied in segments such as avors,
fragrances, food ingredients, nutraceuticals, phytopharmaceuticals
and cosmetics. In this context, the research on SFE has mainly
aimed at technical validation, in order to support its feasibility as an
alternative process for applications where the desired green and/or
healthy characters are required. Different approaches can be found
in the literature regarding the SFE of essential oils:
(i) for new or unusual plant species, SFE is sometimes used simply as an exploratory method that provides new extracts to be
further characterized, puried or tested regarding their bioactivity or other distinctive features. Works involving Ligusticum
chuanxiong [418], Cyperus rotundus [174], Cassia tora [306] may
consulted in this respect.
(ii) for species whose extracts and bioactive compounds are
known, SFE advantages as an alternative technology are
assessed in comparison to other methods, usually organic
solvent extraction or steam distillation. Examples of this
approach are found in the publications regarding yerba mansa
(Anemopsis californica) [259], Catharanthus roseus [307], Zataria
multiora Boiss [563], thyme (Thymus vulgaris L.) [44].
(iii) concentration enhancement of bioactive or organolepsy
related compounds in extracts by means of supercritical fractionation, multistage decompression, or combination of SFE
with matrix pretreatments. Matrix pretreatment examples
may be consulted in SFE works of grape (Vitis vinifera L.)
seed [20,568], and turmeric (Curcuma longa L) [158], while
fractionation examples may be consulted for SFE of cashew
(Anacardium occidentale L.) [114], origanum (Origanum vulgare
L.) [569] and chamomile (Matricaria chamomilla) [428]. Multistage decompression can be found in the following 8urfa:
SFE of laurel (Laurus nobilis) [133], sea buckthorn (Hippophae
rhamnoides L.) [386] and rosemary (Rosmarinus ofcinalis L.)
[83].

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.

4.1. Pressure and temperature


SFE is traditionally dened as a high pressure (P) technology
and this variable is in fact of supreme importance for many technical and economic aspects of this process. The most direct property
prone to be affected by pressure variations is density (), which
can be used to perceive how close SC-CO2 reaches a liquid-like
solvent power. When studying the inuence of density on SFE
behavior (intimately related to solvent power), pressure is a much
preferable variable to tune its values as it offers considerably wider
manipulation margins than temperature. In fact, while pressure
usually ranges up to 8 or 10 times the usual minimum values investigated in experiments (ca. 100 bar), temperature is many times
restricted to a narrower window, i.e. up to 3 times the common
low 40 C.
Fig. 3 presents a distribution of SFE operating conditions mostly
found in literature (543 publications). For each work, the maximum
and minimum densities studied were plotted in PT coordinates,
being possible to observe that essays typically focus on pressures
from 100 to 400 bar. Within this interval, and taking into account
the temperature window considered, densities can range from 200
to 900 kg m3 , as revealed by the density lines superimposed in
Fig. 3. The interdependence between pressure and density can be
fully disclosed in this graph: for instance, a sensitive interrelation
is visibile at low pressures (e.g. 100 bar), where densities can oscillate up to 70% from 40 C to 100 C, while at higher pressures (e.g.
400 bar) the corresponding oscillation only reaches a maximum of
20%.
It is noticeable in Fig. 3 that most works concentrate in temperature values within 4060 C, yet this accumulation is greater
around the lower value. This trend reveals that researchers have
been eager to explore the pressure impact on results at lower temperatures, probably due to the higher degree of density variation
on this region but also owing to concerns regarding thermal degradation of extractable labile compounds, equipment limitations and
costs policy.
The predilection to work at 40 C implies that the opportunity to
assess the impact of temperature on SFE processes at higher pressures (e.g., higher than 300 bar) is being much less considered. Since
density suffers a lower degree of variation at higher pressures and
kinetic variables exhibit weaker dependences on pressure in comparison to temperature, the interesting opportunity to study the
inuence of temperature via vapor pressure (solubility) and transport properties is being discarded. In this respect, Fig. 4 presents,
without loss of generality, the PT dependence of ursolic acid diffusivity (D12 ) and solubility (y*) in SC-CO2 , and also of CO2 density.
Along the displayed ranges one can depict that diffusivity becomes
favorable when approaching 200 bar and 100 C while solubility
exhibits a distinct trend, being its best pole around 500 bar and
100 C. In fact, y*, D12 and density exhibit their maxima at distinct
PT values. Considering that density is many times used as general (though simplistic) criterion to choose operating conditions or
to support the discussion of experimental results, the elucidating
example from Fig. 4 stresses that the optimum PT conditions of a
SFE process are those that best suit the trade-off between kinetics
and equilibrium behaviors.

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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.

4.2. Solvent power


SC-CO2 density and solvent power may be related through
Hildebrand solubility parameter () which enables the establishment of a preliminary comparison of many solvents as long as the
solute remains the same. Although this parameter is majorly used
for non-supercritical solvents, a supercritical state version for the
CO2 was early proposed by Giddings and coworkers [573,574] with

the following dependence on the critical pressure, Pc , and reduced


density at temperature T and at the normal boiling point, Teb :

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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.

The effect of pressure and temperature upon solubility can be


briey described in this way: (i) concerning pressure, it increases
the supercritical uid density, thus increasing its solvent power;
(ii) with respect to temperature, it inuences the solvent properties, namely density, and also the solute properties, mostly vapor
pressure. Increasing temperature, density decreases (lower solubility) and vapor pressure increases (higher solubility). Attending
to this double inuence upon solubility, the proper selection of
temperature requires a trade-off of these two opposing effects.

4.3. Cosolvent addition


With regard to the use of modiers, Fig. 5 shows a statistic of
the most employed cosolvents. The chief reason for adding a second
solvent to the supercritical phase relies on the tunable afnity to
polar solutes that modied SC-CO2 allows. This is the prime reason
why 38% of 441 publications reviewed in this work (that contain
the necessary information) include at least one experimental assay
with modied CO2 .
The application of cosolvents in SFE works has been unsurprisingly dominated by ethanol, which was selected in 53% of the
works involving entrainers (see Fig. 5). Ethanol is an innocuous
solvent both at human health and environmental levels (like
SC-CO2 ) and this is a strong advantage comparing to n-hexane
or even methanol, particularly when SFE is devoted to applications in food, cosmetic or pharmaceutical industries. Besides the

Fig. 5. Most employed cosolvents in SFE of vegetables matrices, based on 166 SFE
publications of database.

referred advantages, ethanol is substantially polar (1.69 d [570])


which means that the addition of small amounts may increase
expressively the polarity of the supercritical solvent.
In addition, methanol comes second with a share of 21%, and is
followed by water and dichloromethane, with 5% and 3%, respectively. Despite being more polar than ethanol, methanol raises
hazard concerns to human health, a fact that discourages an

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176


Table 2
SFE results of caraway (Carum carvi L.) seeds using eight different CO2 modiers at
400 bar and 80 C. Data taken from [207]. Correlation between extraction yield ( )
or carvone concentration I in extracts and the Hildebrand solubility parameter ()
of cosolvent.
Modier
10% (v/v)

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%

extended use of it. In fact it is being progressively abandoned nowadays.


A noteworthy aspect of SFE works with modied CO2 is that they
are implemented in two distinct ways: the more conventional procedure involves the mixing of the SC-CO2 with the cosolvent in a
xed proportion along time, which requires a pump and independent feed line for each uid, while the alternative is through the
impregnation of the matrix with the cosolvent at the onset of the
experiment, followed by the extraction with pure SC-CO2 . While
the former approach is commonly characterized in terms of the
modier content in the supercritical mixture, the latter is usually
described in term of the total quantity of cosolvent impregnated. To
the best of our knowledge there are no works targeting a comparative study of the two techniques, reason why carefulness should
be given when comparing works that employ distinct cosolvent
addition procedures. Additionally, more accuracy is recommended
when referring the concentration of cosolvent, particularly regarding whether mass, volume or molar basis is used to describe the
addition percentages.
With respect to the impact of cosolvents on results, the typical
approach involves the comparison between the modied SC-CO2
and the pure SC-CO2 results. This provides experimental arguments
to check if the inclusion of a cosolvent in the process is worthwhile from the point of view of yields or extract concentrations
enhancement. A less explored approach is the comparison of the
impact of different cosolvents on results. In this respect, Table 2
presents experimental measurements concerning SFE of caraway
(Carum carvi L.) seeds using 8 different CO2 modiers under identical operating conditions [207]. The Hildebrand solubilities for
each cosolvent (at 25 C) are also given in Table 2 to highlight
their different polarity. One of the objectives of the authors was
to assess if modied SC-CO2 could maximize the carvone concentration in caraway seed oil, which enhances the nal quality of
the product. The results from Table 2 reveal two important facts:
modiers failed to enhance carvone content in the oil as desired,
but they did affect the extraction yields obtained. Despite the fact
that the various supercritical mixtures provide higher extraction
yields ( , %) in comparison to pure SC-CO2 , a negative correlation
of 80% was found between and . Being negative, it means that
from an extraction yield perspective the option toward the most
polar cosolvent (methanol) is the less preferable (it only enhances
yield results by 21%). Less polar cosolvents such as chloroform or
toluene increase the extraction yield in greater extents, 41% and
33%, respectively.
The very weak correlation (18%) between modier Hildebrand
parameter and carvone concentration is a straightforward indicator of null selectivity provided by the different co-solvents in
this case. However, one should bear in mind that the unexpected
lack of selectivity observed in many systems may also be due to

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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].

In this sense, both academic and industry readers would benet


from richer data regarding bed length (Lb ), bed diameter (Db ), bed
porosity (b ) and particle size (dp ). This would allow a better disclosure and assessment of the hydrodynamics impact on experimental
results. In addition, these data are also very useful to interpret
scale-up experiments and approach industrial reality.
Fig. 7 presents an analysis of 231 SFE works, where individual ow rates were combined with extraction time and graphed
in kgCO2 kg1 sample units in abscissa. This study points out that
40% of the works comprised a CO2 usage ranging from 0 to
40 kgCO2 kg1 sample , and that the other 40% are between 40 and
140 kgCO2 kg1 sample . Even though this information cannot be taken
as a correct measurement of the extraction efciency, it at least provides worthwhile hints of typical energy and utilities costs from
pumps, heating and cooling steps that SFE processes always imply.
Some of the data of Fig. 7 were taken from works where extraction curves were measured, leading to yields and concentration
proles along time or spent CO2 . Extraction curves are vital for
the correct assessment of kinetic aspects as they allow the visualization of distinct extraction regimes (characterized by distinct
extraction rates) and the inspection of the mechanisms that govern
the separation in different moments.
If a low interstitial velocity (low ow rate) is chosen, the lm
resistance and/or the accumulation in the bulk may prevail over
intraparticular diffusion and solubility issues, thus diminishing the
rate of extraction by itself. On the other hand, if the extractor is
being run under very high interstitial velocity, the most representative sources of limitation may be therefore attributed to solubility
and/or to intraparticle diffusion. Nonetheless, high velocities may
also lead to a misuse of SC-CO2 that will then be spent in excess at
the expenses of non-optimized utility and energy costs. This aspect
is important to increase the economic viability of a SFE unit.
Fig. 8 illustrates an optimization of ow rate by graphing cumulative curves of total extraction yield of E. globulus bark measured
at 200 bar, 40 C, with 5 (wt.%) of ethanol, for different CO2 ow
rates [47]: 6, 12 and 14 g min1 . When QCO2 is doubled from 6
to 12 g min1 a relevant enhancement of the extraction rate is
observed. An additional increase to 14 g min1 shows no further
signicant yield enhancement. As a result, it was considered that
12 g min1 is an optimized value for SFE ow rate since it originates an interstitial velocity that maximizes the rate of extraction
while simultaneously minimizes utilities and energy costs. This
is an elucidative example of a rational selection of a ow rate
value.

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 );

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

145

Fig. 7. Maximum amounts of SC-CO2 used in the SFE of vegetables matrices for a total of 231 publications considered.

(ii) convective mass transfer coefcients (kf ), via Sherwood (Sh),


Reynolds (Re) and Schmidt (Sc) numbers; and (iii) axial dispersion
coefcients (Dax ), via Peclet (Pe), Reynolds and Schmidt numbers.
Several models can be found in the literature for D12 calculation:
the predictive expressions of Lai and Tan [588], Magalhes et al.
[589], Vaz et al. [590592], Wilke-Chang [570], Zhu et al. [593], and
the correlations of Dymond [594], Funazukuri and Wakao [595],
Liu et al. [596] and Magalhes and coworkers [597603]. A worth
noting feature concerning the application of various models of Magalhes et al. is the fact that these authors provide spreadsheets for
the estimation of D12 , which may be consulted in the supplementary material of the original papers [592,597,598,601].
Convective mass transfer coefcients (kf ) Empirical relations of
the type Sh = Re Sc are generally employed and may be consulted in Oliveira et al. [576] and Sovov et al. [577]. Del Valle and
de la Fuente [604] presented a comparison between experimental
values of kf in the SFE of oil seeds where an overestimation tendency
of these methods at certain conditions is revealed.
Axial dispersion (Dax ) Axial dispersion coefcients in supercritical uids can be estimated by nondimensional correlations listed

in the review of Oliveira et al. [576]. The simplest correlations set


axial dispersion as function of Re, Sc, bed porosity (b ) and D12 , as it
is the case of Wakao and Funazkri [605], Catchpole et al. [606] and
Yu et al. [607]. In general, the axial dispersion is neglected when the
rule of thumb Lb > 50 dp is obeyed, where Lb is the length of the bed
and dp is the average diameter of biomass particles. However, even
in such cases the axial dispersion term should not be eliminated
from material balances in order to facilitate the numerical solution
of the model.
Solubility (yi * ) Due to the fact that natural matrices contain several compounds from different chemical families, solubility
predictions are many times hindered by the complexity of raw
materials and the uncertainty of interactions between existing
molecules. It is common practice to simplify the calculation
approach either by considering the oil as a single entity or by considering one specic solute as the unique compound to be dissolved
in SC-CO2 . In addition, solubility of edible oils is many times approximated using data from the rst period of extraction of cumulative
curves, more specically using their slope for very low ow rates. It
is worth noting this is only legitimate when SC-CO2 gets saturated

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

along bed. Reference and application of this procedure can be found


in the work of Sovov [608].
The correlation model (Eq. (2)) early proposed by Chrastil [609]
for binary systems found great acceptance among researchers to
estimate solubilities in SC-CO2 . It was conceived from the principle
that solvation complexes solutesolvent exist under equilibrium,
so that the solubility (yi * ) is a function of solvent density (f ) and
temperature:
yi = fk1 exp

a
T

+b

(2)

where k1 is a parameter representing the average number of


CO2 molecules in the complex (also called association number),
a depends on vaporization and solvation enthalpies of the solute,
and b is dependent on the solute molecular weight. To mention
one example of application of this expression, Gcl-stndag and
Temelli [610] used it to correlate the solubilities of several minor
lipid components such as -carotene, -tocopherol, stigmasterol
and squalene.
Two important empirical modications of the seminal expression of Chrastil are worth noting, one from Adachi and Lu [611] and
the other from Del Valle and Aguilera [612]. Del Valle and Aguilera
introduced a temperature dependence on the heat of vaporization
of solute, leading to a new expression that exhibits a quadratic
temperature term:
yi = fk1 exp

c

T2

a
+b
T

(3)

This expression was correlated by the authors with solubility


data of vegetable oils comprising triacylglycerides with 18 carbon
atoms by treating the oil as a single entity. The proposed parameters are k1 = 10.724, a = 18,708, b = 40.361 and c = 2,186,840, for
T given in K, and yi and f given in kg m3 .
In a different approach, Adachi and Lu [611] assumed that the
association number depends upon density rather than being a constant value. Hence, Eq. (2) gives rise to:
(c+df +e2 )

yi = f

exp

a
T

+b

(4)

Several other expressions, from which some are improvements


of the aforementioned ones, have been published in the literature. One may cite Mendez-Santiago and Teja [613], Sung and Shim
[614], Bartle et al. [615], Kumar and Johnston [616], Yu et al. [617]
and Gordillo et al. [618] and Garlapati and Madras [619] as examples.
With regard to ternary systems, i.e. involving cosolvents,
Gonzlez et al. [620] proposed a modication to the Chrastil equation so that the inuence of cosolvent is included in the calculations
through a dependence on its mass concentration (ycosolv ), and by
setting an association number also for the cosolvent (k ):


k
yi = fk ycosolv
exp

a
T

+b

(5)

In addition, Mendez-Santiago and Teja [621] proposed an new


semiempirical density-based model for ternary cosolvent systems
which adds a cosolvent term to their original binary expression.
The model was subjected to modication by Sauceau et al. [581]
who incorporated a ClausiusClapeyron relation for the sublimation pressure and gave rise to a T-dependent term:
yi P
P std

= exp

1
T

(a + b)f + cycosolv + dT

(6)

where d is a constant that in case of being null restitutes the


Mendez-Santiago and Teja [621] expression for ternary systems;
Pstd is a constant value for pressure under standard conditions,
1 bar. Another modication to the Mendez-Santiago and Teja for
ternary systems was published by Thakur and Teja [622]. Still for

ternary (cosolvent) systems, Sovov [623] proposed an empirical


equation where solubility in a mixture of SC-CO2 and cosolvent is
given by a power function that relates the solubility in pure CO2
(yi , CO2 ) with the cosolvent mass fraction (ycosolv ) as follow:

yi = yi,CO
+ a(yi,CO
)b (ycosolv )c
2

(7)

where a, b and c are model constants to be tted to experimental


data.
The rigorous thermodynamic approach to predict solubilities of
pure solids or liquids in a supercritical uid (SCF) comprises the
classical isofugacity condition that results in a well-known equilibrium relation, reliant on Poynting factor, solute vapor pressure
(Pisat ), fugacity coefcient of the solute in supercritical phase (iSCF ),
and molar volume of the pure solid or liquid (Visolid ):

yi =

Pisat

exp
SCF

Pi

Visolid (P Pisat )
RT


(8)

where R is the universal gas constant. Considerations regarding


the properties embodied in Eq. (8) are expressed in the following
paragraphs.
With respect to Pisat , two strategies may be adopted for its calculation, which mostly depend on the available knowledge about
the system under study:
(i) For known systems, Pisat can be calculated by the Clapeyron
equation, for which fusion properties of the solute and an adequate
saturation curve are necessary. A more detailed description of this
approach is given by Garnier et al. [624], who also provide a list of
useful properties related the application of the PengRobinson (PR)
EoS to solubility calculations for several solutes in SC-CO2 .
(ii) For less known systems, Pisat may be obtained through an
integrated form of the ClausiusClapeyron equation [625], which
demands solute boiling and melting temperatures, entropies and
heat capacity changes, as well as the respective critical properties. For these, group contribution methods may be employed with
advantage. An example of this type of calculation is provided in the
work of de Melo et al. [46] for binary systems involving SC-CO2 and
triterpenic acids.
Concerning iSCF , it is computed by means of an equation of
state such as PR-EoS or RedlichSoaveKwong EoS, among many
other possibilities. Further aspects regarding the application of the
PR-EoS may be found in both works of Garnier et al. [624] and
de Melo et al. [46]. A full compilation of works that employ EoS
to model phase equilibria of solutes in supercritical media is pro
vided by Skerget
et al. [626] or Daz-Reinoso et al. [627], including
examples employing less common EoS options, such as the group
contribution EoS, UNIFAC, the perturbed hard sphere chain EoS,
the quasi-chemical nonrandom lattice uid, regular solution model
with a FloryHuggins term, and the multiuid nonrandom lattice
uid.
As far as Visolid is concerned, values may be obtained from available compilations of this property for several molecules [628,629],
or, alternatively, from available databases such as RCS ChemSpider [630] that promptly provide predictions for a wide variety of
chemical compounds.
Other works have been published with alternative thermodynamic emphasis. For instance, Su [631] recently proposed an
approach to solubility modeling through a two-parameter expression developed from the regular solution model coupled with the
FloryHuggins equation. The correlative results from this equation
are comparable to those obtained with three parameters semiempirical equations. In addition a semiempirical correlation based
on regular solution theory that employs the van der Walls EoS was
early published by Ziger and Eckert [632].

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176


Table 3
Empirical models for SFE processes.
Name

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)

5.2. Extraction models


Empirical models When results are to be described by simple mathematical expressions, empirical models provide easy and
prompt solutions. Expressions can be found in the literature that
easily describe the shape of SFE curves such as Subra et al. [633] and
Naik et al. [635] (see Table 3). These models are usually built in relation to the initial solute concentration in the matrix (x0 ) and involve
an adjustable parameter that may not allow any physical interpretation. Despite being able to provide reliable ttings, empirical
models do not allow mass transfer coefcients to be determined
and thus are of little aid for a deep understanding of the process,
namely when scale-up objectives are targeted.
Simplied models The derivation of phenomenological models for SFE processes includes rate equations and mass balances to
both supercritical uid and solid phases, and require kinetic and
equilibrium data, and possibly some features of the physical structure of the matrix. Owing to the usual lack of information at both
kinetics and equilibrium levels, and also to the implied complexity of natural matrixes, simplied models providing approximate
solutions have been published and adopted by research community. The application of simplied models to SFE results can provide
useful hints regarding the limitations that prevail in a SFE process, which enable phenomena with insignicant importance to
be discarded from future rigorous modeling.
Examples of simplied models have been proposed by Martnez
et al. [123], Tan and Liou [636], and Gaspar [145] and Crank
[637], among others (see Table 4). Their adequacy may be tested
case-by-case upon tting the proposed equations to experimental
extraction curves. They normally embody one or two adjustable
parameters (time or mass transfer related constants) and typically
need at least the initial solute concentration in the biomass to be
known.
The Logistic model (Eq. (11)), proposed by Martnez et al. [123],
neglects axial dispersion and the accumulation in the bed, and
assumes that the interfacial mass transfer only depends on the
composition of the extract along the process. A logistic equation,
usually applied to model population growth, is adopted to describe
the variation of the extract composition along time. The Desorption model (Eqs. (12)(14)) of Tan and Liou [636] assumes no
accumulation in the bed and that the interfacial mass transfer of
the extraction is well described by a rst-order kinetic expression
whose parameter kd is the desorption constant. The Simple Single Plate model (Eq. (15)) (slab geometry) and the Diffusion model
(Eq. (16)) (sphere particles) presented by Gaspar et al. [145] and
Crank [637], respectively, assume also there is no accumulation in
the bed nor lm resistance to mass transfer, and that the process is
governed by intraparticle diffusion.
Some simplied models have been derived for specic extraction periods, as is the case of Brunner [638] model (Table 4, Eq.
(17)), which relates the outlet oil concentration with the solubility
in SC-CO2 during the rst extraction period, when oil is essentially
removed from the surface layers of the particles. This model is
appropriate to constant rate extraction (CER) stages. In cases where

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

Table 4
Simplied models for SFE processes.
Name

Ref

Logistic model

[123]

Desorption model

[636]

Simple Single Plate model

[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

eff is the effective diffusivity, and l the


plate thickness.
Diffusion model

[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.

Following a different approach, the SCM assumes that there is a


sharp dynamic boundary between the extracted and non-extracted
regions of the particles, which moves toward the center as the
extraction proceeds. The axial dispersion effect can be considered
while radial dispersion is many times neglected if the extractor
is of small diameter. Instead of relying on the concept of broken
and intact cells, SCM simply assumes that the cells of the matrix
have identical conditions in terms of structures and solutes concentration, and that solutes suffer an irreversible desorption from
the matrix. As for BICM, the full list of assumptions and examples
of application of SCM can be consulted in the reviews of Oliveira
et al. [576] and Huang et al. [644].
The premise of considering a uniform structure for the matrix is
a delicate one, as natural biomass can easily evidence variations on
its microstructure due to being composed of different tissues/cells,

(18)
(19)
(20)

(21)
(22)
(23)

(24)
(25)
(26)

but also owing to drying and pretreatment processes. It is known


that attempts to enhance extraction yield through acoustic waves
[646] or enzymatic hydrolysis [20] pretreatments can substantially modify the raw material, leading to fractions of cells with
eased access to solutes in comparison to intact cells. Adding to this
remark, both SCM and BICM assume that all cells of the matrix, at
initial conditions, contain solute. In fact, inert or already depleted
cells can be present and in these cases the extractable part of the
matrix represents a fraction of the whole biomass. The chance that
part of the matrix does not contribute for the extraction is not
enclosed in any of the two phenomenological models and could be
a valuable enhancement for an improved interpretation of the SFE.
Finally, Fiori et al. [647] conceived a model that conjugates
features of BICM and SCM (SC-BICM), and their combination
of concepts provides novel representation possibilities for the

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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.

particles exhaustion over time, enumerated by the authors as


discrete, continuous and semi-continuous models for solid phase.
These cases combine dynamic concentration boundary with the
distinct extraction mechanisms due to matrix cells nonuniformities described by broken or intact cells approach. The basic
mathematical formulation of the SC-BICM models is given in
Table 5. Broader considerations can be found in the original paper
[647] and on subsequent reviews [576,644].
In view of being the most employed model, the presentation of an integrated form of BICM is pertinent. In this sense,
Table 6 illustrates the various extraction periods and corresponding algebraic equations to model SFE. Nimet et al. [648] applied
this model to ten extraction curves of sunower seeds, where
,t
Z, W, r, yoil
CER , tFER , ks a and kf a are adjustable parameters. Working with palm oil, Jesus et al. [649] applied this integrated form
of BICM to palm oil extraction curves, and set only ks a and kf a as
adjustable parameters
An example of extraction curves modeling is given in Fig. 9 for
the case SFE rosemary leaves (Rosmarinus ofcinalis L.). In this work,
Carvalho et al. [77] present a study where three models from those
mentioned above (Esquvel et al., SCM and BICM) are tested against
ow rate and bed geometry variations. From the goodness of the
t achieved, better results are given by Esquvel et al. equation, followed by BICM whose representation was slightly better than SCM.
Despite their results suggest the empirical model of Esquvel et al.
to be preferable, the nature of information that can be obtained by
the two phenomenological models is of superior interest. In fact,
they allow predictions for distinct operating conditions, being precious for ultimate scale-up studies where accurate simulations are
fundamental. The extraction curves presented in Fig. 9 provide also
interesting information regarding the signicant impact of ow
rates on SFE results, as discussed in previous section, and raise
geometric aspects into analysis.
By applying physical models to experimental data measured
in beds with different height to diameter (Lb /Db ) ratios, Carvalho

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

Cordia verbenacea D.C.

Cupuacu
Fennel

Fig leaf gourd


Ginger
Ginger
Grape
Grape
Hazelnut
Hazelnut, Walnut
Hypericum caprifoliatum

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]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

Adaptation from Bartle et al. [661]


Gaspar et al. [145]
Stepwise regression
Sovov [641]
Sovov [641]
Reverchon and Osseo [650]
Naik et al. [633]
Sovov [641]
Adaptation from Sovov [641]
Sovov [641]
Martnez et al. [123]
Crank [637]
Campos et al. [291]
Kitzberger et al. [662]
Tan and Liou [636]
Goto et al. [642]
Peker et al. [663]
Brunner [638]
Crank [637]
Sovov [641]
Goto et al. [656]
Esquvel et al. [634]
Tan and Liou [636]
Martnez et al. [123]
Sovov [641]
Chrastil [609]
Sovov [641]
Straight lines
Sovov [641]
Martnez et al. [123]
Tan and Liou [636]
Crank [637]
Goto et al. [656]
Esquvel et al. [634]
Sovov [608]

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

by these techniques, it was with no surprise that results showed


pressure and temperature to have been chosen in 94% and 92% of
the works, respectively. The third most chosen factor is time, which
was present in 42% of the works. Modier concentration (cmodier ),
particle diameter (dp ) and ow rate (Q) follow the latter with 20%,
15% and 13%, respectively.
In Table 8 a selection of SFE works in which DoE was employed is
listed. Notwithstanding the general use of six variables mentioned
above, works typically comprise designs with 3 factors having pressure and temperature as the commonest variables. Concerning the
levels of variation, the majority of works applied 3 degrees of variation for factors, though 2 and 4 levels were also found. The number
of factors and levels has a direct implication in the number of experiments and at the end plays a role in the DoE typology adopted.
With respect to DoE typologies, orthogonal tests (OT) enable
factors assessment to be dealt independently despite having a common (dependent) test of signicance [667]. They were initially
developed to make DoE more applicable by reducing the number
of experiments that full factorial designs requires [668]. OT designs
are prone to be saturated since the degrees of freedom for all effects

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]

are typically equal or close to the number of unique factor-level


combinations included in the experiments [669]. In this sense, it
allows the maximum number of factor-levels to be tested within
the smallest setting of experiments. Application of orthogonal tests
may be found in the works of Liu et al. with emblica [474], Xie et al.
with Patrinia Villosa [465], and Cao and Ito with grape seed [7],
among others that are also listed in Table 8.
Central composite designs require at least ve levels for each
factor, which may be useful to conrm quadratic inuences on
the response, nevertheless they imply more trials to be carried out
[670]. One strong advantage of CCD option is ensuring uniformity
of precision within the experimental space, rather than in the central region of the response. This feature ensures protection against
bias [671]. Examples of CCD employment in SFE works are provided
by Danh et al. with vetiver (Vetiveria zizanioides L.) [555], Kassama
et al. with tomato skin (Solanum lycopersicum L.) [35], and Mitra
et al. with pumpkin seed (Cucurbita maxima) [148].
BoxBehnken may be preferable to CCD for two reasons: factors need only be varied over three levels and fewer runs are
required [670]. The drawbacks of this design are essentially two:

152

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

Cynanchum paniculatum (Bge.) Kitag


Diplotaenia cachrydifolia
Elaes guineensis
Erythroxylum coca var. coca
Eucalyptus globulus
Eucalyptus globulus
Eugenia caryophyllata Thunb.
Fructus psoralea
Garcinia mangostana L.
Ginkgo biloba
Glycine variety
Gossypium variety
Helianthus annuus L.
Hippophae rhamnoides L.
Hippophae rhamnoides L.
Hyssopus ofcinalis
Illicium verum
Jatropha curcas L.
Lavandula angustifolia
Lavandula angustifolia
Lavandula hybrida
Lepidium apetalum
Linum usitatissimum L.
Linum usitatissimum L.
Linum usitatissimum L.
Maydis stigma
Mentha spicata L.
Mentha spicata L.
Microula sikkimensis
Momordica charantia L.
Moringa oleifera
Myrtus communis 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
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]

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

Patrinia villosa Juss


Phyllanthus emblica
Pistacia vera L.
Prunus armeniaca L.
Prunus armeniaca L.
Prunus avium L.
Prunus cerasus

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

Xanthoceras sorbifolia Bunge.


Zingiber corallinum Hance
Zingiber ofcinale

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

quadratic inuences adequacy are not checked, and the variance


of the response is assumed to be the same as center points variance [670], which is a pertinent issue when the conclusions focus
on peripheral areas of experimental space rather than on middle.
Table 8 presents several works using BBD, as the cases of SFE of
axseed (Linum usitatissimum) from zkal [75], olive (Olea europaea
L.) pomace from Stavroulias and Panayiotou [200], spent coffee
grounds from Barbosa et al. [62] or Thymbra spicata carried out by
Sonsuzer et al. [539].
Response surface methodology (RSM) DoE arises frequently as
part of Response Surface Methodology, since the latter comprises
a package of statistical design and analysis tools implemented to
determine how a response is affected by a set of quantitative variables in a specied region [670]. RSM typically involves the tting
of polynomial functions with linear and quadratic terms that have

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

RSM, Central composite


Orthogonal array
Fractional Factorial

[561]
[565]
[122]

resemblance with the effects and interactions given by the DoE.


The difference is that while DoE provides insights on positive and
negative inuence of each effect or interaction under study, RSM
combines all effects according to their statistical signicance and
provide models (based only on the signicant terms) that represent the experimental results within the experimental conditions
ranges covered by the regression. In addition, this method provides
useful 2D and 3D graphical means to visualize the behavior of the
responses and to easily interpret the results.
The aforesaid methods are worthwhile to optimize the operating conditions of processes toward the identication of maxima
and minima in responses [671]. Being an experimental optimization technique, RSM sometimes allow a maximum or a minimum
to be found in the margins of the variable values boundaries. In
these cases further studies are required to optimize the response.

154

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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].

Examples of this happening may be consulted in the works of de


Lucas et al. with olive (Olea europaea L.) husk oil [456] or zkal
et al. with axseed (Linum usitatissimum) oil [75]. Nonetheless one
should remember that apparatus limitations many times delimit
the range of study for the chosen factors, specically in the case
of pressure. From the matrices point of view, temperature variations are many times hindered in the upper values in order to avoid
the undesired thermal degradation of solutes. Fig. 11 presents two
cases where RSM results identied an inner set of optimized conditions (2A and 2B) and two cases where further optimization would
be necessary to reach and conrm an optimum zone (2C and 2D).
Other works comprising RSM are compiled in Table 8.
To conclude this section, one may recall the extensive review of
Franceschini and Macchietto on the state of the art of model-based
design of experiments [672], where the authors stressed the importance of scientic community to keep fostering the use of DoE so it
becomes a standard tool for experimentalists and industrial applications. While this message applies naturally to SFE, the thirteen
years from 2000 year plainly conrm advances on this trend.
6. Scale-up
As an alternative technology competing with the conventional
solvent extraction that has a long history of application in industry,
some promising SFE works have been matter of upscaling studies.
This section covers this issue by presenting a compilation of papers
on scale-up studies and discussing some of them.
For a process to reach an adequate scale-up level, it is expected
that it has been previously assessed upon optimization of operating conditions, selection of preferable extraction times from yield
vs. time curves, and modeling of the same curves in order to disclose extraction mechanisms that characterize the rate by which
solutes are removed from biomass. When SFE research approaches
exploitation scenarios, it is highly recommendable that the process variables have been previously analyzed with attention at lab
scale. Nonetheless, it is common practice to nd empirical scale-up
studies and units working under conditions optimized for distinct
biomass species and molecules. Such procedure can lead to erroneously scaled-up units.
With respect to scale-up criteria, SFE upscaling should obey
rules regarding geometric, physical and chemical relationships,

which are to be kept unchanged intentionally according to the


mechanism that drives the process. Such carefulness ensures more
accuracy when comparing results obtained at different scales, and
also assures that these results are phenomenologically consistent.
In this sense, there is a different adequate relationship for each type
of limitation governing the SFE process. Four criteria may be listed:
i. When solubility limits the process, the mass of spent SC solvent
per mass of bed raw material (wCO2 wb1 ) should be kept constant
[99];
ii. When diffusion is the major limitation, the ratio of SC solvent
ow rate to mass of bed raw material (QCO2 wb1 ) should be kept
constant [99];
iii. When both limitations are relevant, wCO2 wb1 and QCO2 wb1 values should be held constant [99];
iv. An alternative approach is to x both wCO2 wb1 , QCO2 wb1 and x
also a dimensionless number such as Re. This may imply changing particle size of the raw material, since variables like P and T
cannot be changed [491];
A fth criterion should also be mentioned which rather than
being based in mass transfer or equilibrium arguments, it concerns
geometric similarity issues. In this respect, the option to x the
ratio of bed length and bed diameter (Lb /Db ) can also be found in
literature for upscaling SFE processes [65,153].
It is worth noting that besides the choice of proper upscaling criteria results may still not be conrmed at higher scales
as a consequence of irrelevant phenomena at smaller scales that
become non-negligible at higher scales [138,507]. The aggregation
of biomass and channeling are two illustrative examples that must
be cited in this respect. For this reason, checking of modeling results
at two scales is essential to conrm the reliability of the obtained
results [673].
Fig. 12 presents an example of scale-up studies performed following two of the aforementioned relationships for SFE of peach
almond (Prunus persica) oil [491] and results are also tted with
BICM. In the reported case, distinct agreement observations arose
from the application of criteria (ii) and (iv). In fact, the scale-up
experiment performed under a x ratio of ow rate and mass of
raw material (ii) led to good results, while the establishment of
Re number and the two ratios proposed in (iv) exhibited higher

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

155

Fig. 10. Trends on the use of DoE and RSM in SFE articles within 20002013, for a total of 547 publications considered.

deviations. Despite this dissonance, such results can be useful for


the SFE process by taking the visible deviations as opportunities
to check the scale-up assumptions and to reinterpret extraction
phenomena mechanisms. Nevertheless, such approach is only recommended when scale-up experiments are not too costly, or when
the upscaling is performed in smaller units, closer to lab scale than
to industrial reality.
As aforediscussed (Section 5.3, Fig. 9) bed geometry may inuence SFE processes, a statement that is particularly prone to concern
when SFE studies involve different extractors at different scales.
Taking this into account, Carvalho et al. [77] devised two expressions that relate working conditions (SC-CO2 ow rate, Q, and bed
weight, wb ) at different bed geometries (diameter, Db , and length
Lb ):

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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.

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

economic studies comprise semi-continuous operation, reliant on


a succession of batches.
A very pertinent question for a proper economic evaluation
relies on the main objective of the SFE process, namely if it is of
low volume/high value type or high volume/low value scenario.
This issue is connected to the aspects discussed in section 3. In fact,
the motivation of the work should be clear at economic level, so
that the real product can be undoubtedly identied: whether valuable compounds diluted/mixed in oils/extracts, or ordinary bulk
extracts/oils with no other features than the fact of being natural
mixtures obtained by a green separation technology. In the rst
case, the solutes concentration may be the key variable to the viability of the process while, in the second, the success may be reliant
on the capacity to obtain high extraction yields in short times.
Most of the economic assessment studies on SFE addresses
cases where bulk extracts/oils are the goal of the process. In this
sense, low attention has been paid to the impact of the concentrations/purities of the nal extracts. Such fact is somehow misleading
because much of the research of last years has been centered on the
enhancement of specic bioactive molecules in SC-CO2 extracts.
For instance, the enrichment of extracts/oils is the most invoked
reason to justify the frequent usage of cosolvents, as reported in
Section 4.3. The inclusion of modiers can only be judged if, at the
end of the process, the nal product is priced taking into account
its eventual enriched composition. The purpose of the SFE technology is not merely to make possible more productive separations
in comparison to other reference methods, but also to produce
extracts/oils with precious enrichments on fractions comprising
interesting compounds. In this sense, the eld demands a more

158

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

target molecules, the following gures should be analyzed: Fig. 14


shows market quotations of essential oils (obtained by steam distillation), and Fig. 15 illustrates the market prices of target molecules
of some SFE works from Table 1, when sold with high purities
(>70%). It is worth noting that these prices were not obtained for
bulky purchasing and certainly exhibit deviations from industrial
trade reality. Nevertheless, the reported data were obtained from
few suppliers, which means that all values are on the same comparison basis, namely European market.
As can be observed, the majority of the essential oils reported in
14 have quotations between 25 and 150 D kg1 . The most expensive examples were found for chamomile, vetiver and black peper,
with prices varying from 288 to 454 D kg1 . These values arise from
an already existing market whose oils are produced by technologies
like steam distillation or hydrodistillation. The green label of both
SFE and water-based separations suggests that these quotations are
also suitable for economic analysis of SFE processes. Nonetheless
this equivalence neglects the real value of the enriched extracts
that supercritical solvents may obtain. For this reason, one could
expect a worthier quotation for the SFE oils when they exhibit
enhanced concentrations of target compounds. For instance, in a
recent work on SFE of spent coffee grounds [62], it is shown that the
content of anticarcinogenic diterpenoids (cafestol, kawheol, and
16-O-methylcafestol) in the oil obtained by SC-CO2 extraction of
spent coffee grounds more than trebles that of the oil produced
by solidliquid extraction using dichloromethane. Such selectivity
gain should be taken into account so that the SFE is fairly pondered
at economic level.
Another clearcut example of the necessity to bring reasonable
prices to the economic assessment of supercritical separations is
provided by eucalypt, in the sense it has the lowest prices among
those reported in Fig. 14 (23 D kg1 ). However, from the outer bark
of eucalypt, one can obtain extracts with concentrations of ursolic
and betulinic acids as high as 27 (wt.%) [4648,675]. Upon checking
the valuable prices of both molecules in high purity supply contexts
(values higher than 6 105 D kg1 see Fig. 15), a more consistent price should be associated to such product. These remarks on
extracts/oils prices are of vital importance for the viability of SFE
projects, and though literature has no other solution than to adopt
essential oil quotations, these simplistic comparisons are many
times misleading in view of the superior quality of some products
achieved with supercritical solvents.
With respect to the industrial context by which SFE is cogitated, when the overall purpose of a SFE process is to enhance
the protability of an already existing process by means of using
raw material spare parts or by including a SFE step to concentrate
in the nal product (or remove from it) a minor constituent, the
process economics may benet from the availability of raw materials, utilities and labor resources. Such context can be sufcient to
ensure viability, as raw material purchasing and transport costs can
be eliminated from the calculations. For instance, Leal et al. [177]
concluded that the cost of raw material of the SFE of sweet basil
(Ocimum basilicum) represented 80% of the process costs, prevailing over energy or utility costs. One example of a SFE research that
has been studied in complementation to a main industrial process
is the extraction of Eucalyptus globulus bark, which is the dominant
species in Portuguese pulp and paper industry. In this context, the
SFE of triterpenic acids from E. globulus bark can take advantage
from the readiness of raw material and the existence of utilities
in the mill, two important synergies to enhance the process economics.
When considering xed costs, labor parcel is a non-negligible
variable due to the semi-continuous character of SFE processes
and the resulting need to periodically handle raw-material at the
onset and end of each extraction cycle. This variable communicates intimately with the duration of extraction, since the shorter

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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.

Economic assessment methods Most research found in literature


regarding the economics of SFE process rely on the methodology of
Turton et al. [681] which sets the cost of manufacturing (COM) as
a function of investment cost (FCI), labor cost (COL), utility cost
(CUT), waste treatment cost (CWT) and raw material cost (CRM),
using the following relation:
COM = 0.304FCI + 2.73COL + 1.23(CUT + CWT + CRM)

(37)

Since total investment is usually expressed upon an annual


depreciation rate (e.g. 10% per year), FCI is time-dependent and
demands an analogous correspondence on the other terms of Eq.
(19). In this way, the resulting COM value will then represent the
sum of xed and variable costs on a yearly basis.
Once COM value itself has no connection with production, reason why many times it is combined with annual production to
determine the specic production cost (US$ per mass of product). By stipulating a market value for the supercritical extract,
net income calculations can be accomplished and lead to a fuller
disclosure regarding the economy of the process:
Annual Net Income = Annual Revenue COM

(38)

To determination of both annual revenue and COM terms


require that a simulation of the production is performed with all the
optimized operating conditions (P, T, t, Q) and other variables, some
of them established by the researcher. In Table 10 these variables
are listed for analysis.
A key variable is the price of the SFE unit, whose impact on the
process economics is substantial. Some useful rules and information can be used, such as the formula proposed by Lack et al. [682],

160

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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.

for units comprising three extractors operating up to 550 bar, that


sets FCI as function of extractors volume (Vextractor ):
FCI = 1.0162 ln(Vextractor ) 4.9147

(39)

Table 10
List of assumptions necessary for an economic assessment of a SFE process.
General

1. Unit working period (h per day and h per year);


2. Number of workers per extractor;
3. Scale-up criterion;
4. Minimum pressure in the separator (extract collection vessel);
5. Required time to unload, load and pressurize one extractor;
6. Denition whether CO2 is lost in each full decompression or not;
7.Bed density;
8. Bed porosity;
9. Market price of SFE extract;
10. Matrix initial moisture;
11. Dried matrix heat capacity;

FCI

12. Annual depreciation rate;


13. SFE unit price;

COL

14. Labor cost;

CUT

15. Electricity cost;


16. Steam cost;

CWT

17. Waste treatment cost;

CRM

18. Matrix drying cost;


19. Matrix milling cost;
20. Other matrix pretreatment cost;
21. Make-up CO2 purchasing price.

In alternative, the expression from Peters and Timmerhaus [683]


allows FCI to be estimated from the already known cost of another
unit, as long as annual process raw material (w) is compensated:
FCI2 = FCI1

 w 0.6
2

(40)

w1

A similar but more accurate expression was proposed by Perrut


[99], who replaced w by the pair Vextractor and Q, and corrected the
exponent:
FCI2 = FCI1

V

extractor1 Q2

Vextractor2 Q1

0.24
(41)

Attending to recent literature works, prices of SFE units have


been estimated as 1.22 M$ (US) for 2 0.5 m3 extractors [684] or
2 M$ (US) for units comprising 2 0.4 m3 extractors and also a ash
tank, CO2 reservoir, condenser, one pump, and a heat exchanger
[23].
In what concerns CUT, CWT and CRM it is necessary to perform
simulations to solve mass and energy balances for the operating
conditions of the SFE unit under analysis. The choices of SuperPro
Design [23,685,686] and Aspen Plus [61,687] may be cited as the
most popular simulators that can be adopted for this purpose.
Economic assessment examples Studies on the economics of SFE
processes have been addressed in literature by several authors in
the last years. Some examples are presented in the following for
illustration.

Working on SFE of sweet basil (Ocimum basilicum), Leal et al.


[177] used COM methodology to cross the concomitant impact of
different pressures and cosolvent (water) contents on the costs of
manufacturing. They showed the minimum costs to be nearly 48
US$ kg1 product for operation at 300 bar and 20% water addition,
and that the highest COM values to be for 300 bar operation and 1%
water addition, 1049 US$ kg1 product .

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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].

Danielski et al. [92] carried out an economic analysis on their SFE


work with rice (Oryza sativa L.) bran (by-product of rice processing)
followed by a stage of oil deacidication. They showed the production costs of the combined unit were competitive when contrasted
with the commercial prices of rice bran oil.
Pereira and Meireles [81] performed an economic analysis on
their SFE work with rosemary (Rosmarinus ofcinalis L.), fennel
(Foeniculum vulgare) and anise (Pimpinella anisum) essential oils.
They adopted COM methodology and focused specically cost estimation rather than protability. Fig. 16 presents the main results of
their essay. Applying the COM approach to the extraction of essential oils by steam distillation from the same matrices, Pereira and
Meireles proved SFE to lead to COM values 1.82.5 times inferior.
de Melo et al. [61] applied net income and COM calculations
to the SFE of spent coffee grounds, and concluded the process is
protable even for non-optimized extraction times, independently
of the chosen layout and capacity, due to the high market price
of coffee oil. Upon a sensitivity analysis, they showed the minimum pressure in the separator (extract collection vessel) has a
substantial impact on results. Fig. 17 was retrieved from their work
and illustrates the variation of COM values against separator pressure: above 45 bar (reference value), COM increased substantially. If
65 bar is chosen as minimum pressure instead of 45 bar, COM value
directly increases 18%. Such behavior stresses how this variable is
quite inuential on the nal costs of the process. In addition, this
example points out that recompression costs can be less important
than the costs of losing CO2 in each full decompression, particularly
when the process viability favors short extraction times, i.e. higher
number of cycles.

Last decades progress From an academic point of view, research


on SFE has evolved and diversied since the early works on 1970
and 1980 decades, when this technology appeared vigorously as
a promising bet for the upcoming years. Up to now, despite all
progress achieved, wide implementation SFE technology is still to
emerge, though the massive contribute of many researchers along
years toward its consolidation.
The signicant progress on this eld is better disclosed if the
yearly expectations of Rizvi at al. [688] are revisited. They stressed
in 1986 that SFE was suffering technical restrictions imposed by the
lack of knowledge concerning the complexity of natural substrates,
which could be overcome with the development of reliable predictive models. Thirteen years later Smith et al. [689] still presented
SFE as an immature technology still lacking robustness, as operational problems were prone to arise as consequence of the results
being too matrix dependent.
Based on this review, one can assure that last decades have
seen great advances for which full characterization and quantication of supercritical extracts, assessment of kinetic and equilibrium
aspects, phenomenological modeling and optimization of operating conditions using statistical tools like DOE and RSM are
elucidating examples. Nonetheless, an important weakness is
still found regarding fundamental research on the SFE of natural biomass so that the solutesmatrix interactions can be better
understood and correctly taken into account by reliable predictive
models.
Despite many SFE works lead to no further contribution than
extracts production and their subsequent characterization, this
review emphasizes that SFE eld has been fed with intermediate
research (e.g., optimization of operating conditions or modeling)
and by scale-up and economic studies that place investigation very
close to industrial partners. From industry side, there is still some
hesitancy on a widespread implementation of supercritical technology both to new raw materials and well known ones, despite
the number of patents lled every year in this area. In this respect,
Machado et al. [2] published recently some data concerning patents
from 1974 to 2012, where a substantial raise is observed since 2000,
being the maximum in 2012, with 61 documents deposited. In addition food and agricultural sector represents one third of the SFE
patent applications reviewed by these authors.
Opportunities for the upcoming years The cumulative knowledge achieved in the area provided substantial progress on
analytical, engineering, scale-up and economic issues regarding
implementation of SFE processes at industrial level. Nevertheless,
as Brunner [1] noted, much of the SFE research is not structured in

162

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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

proton nuclear magnetic resonance


specic external surface area
atmospheric pressure chemical ionization
BoxBehnken design
broken and intact cells model
concentration

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

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

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


Hildebrand solubility parameter



fugacity coefcient
yield
Subscript
b
bed
critical
c
cosolv relative to cosolvent
eb
at normal boiling point
f
uid
relative to species i
i
LDF
linear driving force
melting
m
Pi
at pressure i
r
reduced
s
solid
at standard conditions
std
0
initial moment
Superscript
*
equilibrium
f
uid phase
mix
mixture
saturation
sat
std
standard
SCF
supercritical uid phase
solid phase
solid
Acknowledgements
Authors acknowledge the 7th Framework Programme FP7/2007
2013 for funding project AFORE: Forest Bioreneries: Addedvalue from chemicals and polymers by new integrated separation,

163

fractionation and upgrading technologies (CP-IP 228589-2) and to


Associate Laboratory CICECO (Pest-C/CTM/LA0011/2013).

References
[1] G. Brunner, Applications of supercritical uids, Annual Review of Chemical
and Biomolecular Engineering 1 (2010) 321342.
[2] B.A. Souza Machado, C.G. Pereira, S.B. Nunes, F.F. Padilha, M.A. Umsza-Guez,
Supercritical uid extraction using CO2 : main applications and future perspectives, Separation Science and Technology 48 (2013) 27412760.
[3] F. Agostini, R.A. Bertussi, G. Agostini, A.C.A. dos Santos, M. Rossato, R. Vanderlinde, Supercritical extraction from vinication residues: fatty acids,
-tocopherol, and phenolic compounds in the oil seeds from different varieties of grape, Scientic World Journal (2012) 19.
[4] L. Arce, A.G. Lista, A. Ros, M. Valcrcel, Screening of polyphenols in grape
marc by on-line supercritical uid extraction-ow through sensor, Analytical
Letters 34 (2001) 14611476.
[5] M. Ashraf-Khorassani, L.T. Taylor, Sequential fractionation of grape seeds into
oils, polyphenols, and procyanidins via a single system employing CO2 -based
uids, Journal of Agricultural and Food Chemistry 52 (2004) 24402444.
[6] T.H.J. Beveridge, B. Girard, T. Kopp, J.C.G. Drover, Yield and composition of
grape seed oils extracted by supercritical carbon dioxide and petroleum
ether: varietal effects, Journal of Agricultural and Food Chemistry 53 (2005)
17991804.
[7] X.L. Cao, Y.C. Ito, Supercritical uid extraction of grape seed oil and subsequent
separation of free fatty acids by high-speed counter-current chromatography,
Journal of Chromatography A 1021 (2003) 117124.
[8] A. Chafer, M.C. Pascual-Mart, A. Salvador, A. Berna, Supercritical uid extraction and HPLC determination of relevant polyphenolic compounds in grape
skin, Journal of Separation Science 28 (2005) 20502056.
[9] T.L. Da Silva, E.C. Bernardo, B. Nobre, R.L. Mendes, A. Reis, Extraction of victoria
and red globe grape seed oils using supercritical carbon dioxide with and
without ethanol, Journal of Food Lipids 15 (2008) 356369.
[10] L.M.A.S. de Campos, F.V. Leimann, R.C. Pedrosa, S.R.S. Ferreira, Free radical scavenging of grape pomace extracts from cabernet sauvingnon (Vitis
vinifera), Bioresource Technology 99 (2008) 84138420.
[11] L. Dos Santos Freitas, J.V. de Oliveira, C. Dariva, R.A. Jacques, E.B. Caramao,
Extraction of grape seed oil using compressed carbon dioxide and propane:
extraction yields and characterization of free glycerol compounds, Journal of
Agricultural and Food Chemistry 56 (2008) 25582564.
[12] L. Dos Santos Freitas, R.A. Jacques, M.F. Richter, A.L.d. Silva, E.B. Caramao, Pressurized liquid extraction of vitamin E from Brazilian grape seed oil, Journal of
Chromatography A 1200 (2008) 8083.
[13] L. Fiori, Grape seed oil supercritical extraction kinetic and solubility data: critical approach and modeling, Journal of Supercritical Fluids 43 (2007) 4354.
[14] L. Fiori, D. de Faveri, A.A. Casazza, P. Perego, Grape by-products: extraction of
polyphenolic compounds using supercritical CO2 and liquid organic solvent
a preliminary investigation, Cyta-Journal of Food 7 (2009) 163171.
[15] K. Ghafoor, F.Y. AL-Juhaimi, Y.H. Choi, Supercritical uid extraction of phenolic
compounds and antioxidants from grape (Vitis labrusca B.) seeds, Plant Foods
for Human Nutrition 67 (2012) 407414.
[16] R. Murga, R. Ruiz, S. Beltran, J.L. Cabezas, Extraction of natural complex phenols and tannins from grape seeds by using supercritical mixtures of carbon
dioxide and alcohol, Journal of Agricultural and Food Chemistry 48 (2000)
34083412.
[17] B. Palenzuela, L. Arce, A. Macho, E. Munoz, A. Rios, M. Valcarcel, Bioguided extraction of polyphenols from grape marc by using an alternative
supercritical-uid extraction method based on a liquid solvent trap, Analytical and Bioanalytical Chemistry 378 (2004) 20212027.
[18] B. Palenzuela, R. Rodriguez-Amaro, A. Rios, M. Valcarcel, Screening of polyphenols in grape marc by online supercritical uid extraction amperometric
detection with a PVC-graphite composite electrode, Electroanalysis 14 (2002)
14271432.
[19] M. Palma, L.T. Taylor, B.W. Zoecklein, L.S. Douglas, Supercritical uid extraction of grape glycosides, Journal of Agricultural and Food Chemistry 48 (2000)
775779.
[20] C.P. Passos, R.M. Silva, F.A. Da Silva, M.A. Coimbra, C.M. Silva, Enhancement
of the supercritical uid extraction of grape seed oil by using enzymatically
pre-treated seed, Journal of Supercritical Fluids 48 (2009) 225229.
[21] C.P. Passos, R.M. Silva, F.A. Da Silva, M.A. Coimbra, C.M. Silva, Supercritical uid
extraction of grape seed (Vitis vinifera L.) oil. Effect of the operating conditions
upon oil composition and antioxidant capacity, Chemical Engineering Journal
160 (2010) 634640.
[22] M. Pinelo, A. Ruiz-Rodriguez, J. Sineiro, F.J. Senorans, G. Reglero, M.J. Nunez,
Supercritical uid and solidliquid extraction of phenolic antioxidants from
grape pomace: a comparative study, European Food Research and Technology
226 (2007) 199205.
[23] J.M. Prado, I. Dalmolin, N.D.D. Carareto, R.C. Basso, A.J.A. Meirelles, J.V. Oliveira,
E.A.C. Batista, M.A.A. Meireles, Supercritical uid extraction of grape seed:
process scale-up, extract chemical composition and economic evaluation,
Journal of Food Engineering 109 (2012) 249257.

[24] T. Vatai, M. Skerget,


Z. Knez, Extraction of phenolic compounds from elder
berry and different grape marc varieties using organic solvents and/or supercritical carbon dioxide, Journal of Food Engineering 90 (2009) 246254.

164

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

[25] E.E. Yilmaz, E.B. Ozvural, H. Vural, Extraction and identication of proanthocyanidins from grape seed (Vitis vinifera) using supercritical carbon dioxide,
Journal of Supercritical Fluids 55 (2011) 924928.
[26] C. Yi, J. Shi, S.J. Xue, Y.M. Jiang, D. Li, Effects of supercritical uid extraction
parameters on lycopene yield and antioxidant activity, Food Chemistry 113
(2009) 10881094.
[27] G. Vasapollo, L. Longo, L. Rescio, L. Ciurlia, Innovative supercritical CO2 extraction of lycopene from tomato in the presence of vegetable oil as co-solvent,
Journal of Supercritical Fluids 29 (2004) 8796.
[28] E. Vgi, B. Simndi, K.P. Vsrhelyin, H. Daood, . Kry, F. Doleschall, B. Nagy,
Supercritical carbon dioxide extraction of carotenoids, tocopherols and sitosterols from industrial tomato by-products, Journal of Supercritical Fluids 40
(2007) 218226.
[29] U. Topal, M. Sasaki, M. Goto, K. Hayakawa, Extraction of lycopene from tomato
skin with supercritical carbon dioxide: effect of operating conditions and
solubility analysis, Journal of Agricultural and Food Chemistry 54 (2006)
56045610.
[30] J. Shi, C. Yi, S.J. Xue, Y.M. Jiang, Y. Ma, D. Li, Effects of modiers on the prole
of lycopene extracted from tomato skins by supercritical CO2 , Journal of Food
Engineering 93 (2009) 431436.
F. Temelli, S.E. Guigard, B. Tomberli, C.G. Gray, Apparent sol[31] M.D.A. Saldana,
ubility of lycopene and -carotene in supercritical CO2 , CO2 + ethanol and
CO2 + canola oil using dynamic extraction of tomatoes, Journal of Food Engineering 99 (2010) 18.
[32] E. Sabio, M. Lozano, V. Montero de Espinosa, R.L. Mendes, A.P. Pereira, A.F.
Palavra, J.A. Coelho, Lycopene and -carotene extraction from tomato processing waste using supercritical CO2 , Industrial & Engineering Chemistry
Research 42 (2003) 66416646.
[33] B.P. Nobre, A.F. Palavra, F.L.P. Pessoa, R.L. Mendes, Supercritical CO2 extraction
of trans-lycopene from Portuguese tomato industrial waste, Food Chemistry
116 (2009) 680685.
[34] S. Machmudah, S. Zakaria, M. Winardi, M. Sasaki, N. Goto, K. Kusumoto,
Hayakawa, Lycopene extraction from tomato peel by-product containing
tomato seed using supercritical carbon dioxide, Journal of Food Engineering
108 (2012) 290296.
[35] L.S. Kassama, J. Shi, G.S. Mittal, Optimization of supercritical uid extraction
of lycopene from tomato skin with central composite rotatable design model,
Separation and Purication Technology 60 (2008) 278284.
[36] S.A.B.V. de Melo, G.M.N. Costa, R. Garau, A. Casula, B. Pittau, Supercritical CO2
extraction of essential oils from Thymus vulgaris, Brazilian Journal of Chemical
Engineering 17 (2000) 367371.
[37] M.C. Daz-Maroto, I.J. Daz-Maroto, E. Sanchez-Palomo, M.S. Perez-Coello,
Volatile components and key odorants of fennel (Foeniculum vulgare Mill.) and
thyme (Thymus vulgaris L.) oil extracts obtained by simultaneous distillationextraction and supercritical uid extraction, Journal of Agricultural and Food
Chemistry 53 (2005) 53855389.
[38] M.R. Garca-Risco, G. Vicente, G. Reglero, T. Fornari, Fractionation of thyme
(Thymus vulgaris L.) by supercritical uid extraction and chromatography,
Journal of Supercritical Fluids 55 (2011) 949954.
[39] C. Grosso, A.C. Figueiredo, J. Burillo, A.M. Mainar, J.S. Urieta, J.G. Barroso,
J.A. Coelho, A.M.F. Palavra, Composition and antioxidant activity of Thymus vulgaris volatiles: comparison between supercritical uid extraction and
hydrodistillation, Journal of Separation Science 33 (2010) 22112218.
[40] M. Moldo-Martins, M.G. Bernardo-Gil, M.L.B. da Costa, Sensory and chemical evaluation of Thymus zygis L. essential oil and compressed CO2 extracts,
European Food Research and Technology 214 (2002) 207211.
[41] M. Moldo-Martins, A. Palavra, M.L.B. da Costa, M.G. Bernardo-Gil, Supercritical CO2 extraction of Thymus zygis L. subsp sylvestris aroma, Journal of
Supercritical Fluids 18 (2000) 2534.
[42] S.S. Petrovic, J. Ivanovic, S. Milovanovic, I. Zizovic, Comparative analyses of the
diffusion coefcients from thyme for different extraction processes, Journal
of the Serbian Chemical Society 77 (2012) 799813.
[43] B. Simandi, V. Hajdu, K. Peredi, B. Czukor, A. Nobik-Kovacs, A. Kery, Antioxidant activity of pilot-plant alcoholic and supercritical carbon dioxide extracts
of thyme, European Journal of Lipid Science and Technology 103 (2001)
355358.
[44] Z. Zekovic, Z. Lepojevic, D. Vujic, Supercritical extraction of thyme (Thymus
vulgaris L.), Chromatographia 51 (2000) 175179.
[45] F. Ashtiani, F. Sedkon, Y. Yamini, K. Khajeh, Supercritical carbon dioxide
extraction of volatile components from two eucalyptus species (E. spathulata
and E. microtheca), Journal of Essential Oil Bearing Plants 10 (2007) 198208.
[46] M.M.R. de Melo, E.L.G. Oliveira, A.J.D. Silvestre, C.M. Silva, Supercritical uid
extraction of triterpenic acids from Eucalyptus globulus bark, Journal of Supercritical Fluids 70 (2012) 137145.
[47] R.M.A. Domingues, M.M.R. de Melo, C.P. Neto, A.J.D. Silvestre, C.M. Silva, Measurement and modeling of supercritical uid extraction curves of Eucalyptus
globulus bark: inuence of the operating conditions upon yields and extract
composition, Journal of Supercritical Fluids 72 (2012) 176185.
[48] R.M.A. Domingues, M.M.R. de Melo, E.L.G. Oliveira, C.P. Neto, A.J.D. Silvestre,
C.M. Silva, Optimization of the supercritical uid extraction of triterpenic
acids from Eucalyptus globulus bark using experimental design, Journal of
Supercritical Fluids 74 (2013) 105114.
[49] R.M.A. Domingues, E.L.G. Oliveira, C.S.R. Freire, R.M. Couto, P.C. Simes, C.P.
Neto, A.J.D. Silvestre, C.M. Silva, Supercritical uid extraction of Eucalyptus
globulus Barka promising approach for triterpenoid production, International Journal of Molecular Sciences 13 (2012) 76487662.

[50] A.H. El-Ghorab, K.F. El-Massry, F. Marx, H.M. Fadel, Antioxidant activity of
Egyptian Eucalyptus camaldulensis var. brevirostris leaf extracts, NahrungFood 47 (2003) 4145.
[51] J.D. Francisco, E.P. Jarvenpaa, R. Huopalahti, B. Sivik, Comparison of Eucalyptus
camaldulensis Dehn. oils from Mozambique as obtained by hydrodistillation
and supercritical carbon dioxide extraction, Journal of Agricultural and Food
Chemistry 49 (2001) 23392342.
[52] D.J.S. Patinha, R.M.A. Domingues, J.J. Villaverde, A.M.S. Silva, C.M. Silva, C.S.R.
Freire, C. Pascoal Neto, A.J.D. Silvestre, Lipophilic extractives from the bark
of Eucalyptus grandis x globulus, a rich source of methyl morolate: selective
extraction with supercritical CO2 , Industrial Crops and Products 43 (2013)
340348.
[53] S.A.O. Santos, J.J. Villaverde, C.M. Silva, C.P. Neto, A.J.D. Silvestre, Supercritical
uid extraction of phenolic compounds from Eucalyptus globulus labill bark,
Journal of Supercritical Fluids 71 (2012) 7179.
[54] K.S. Andrade, R.T. Goncalvez, M. Maraschin, R.M. Ribeiro-do-Valle, J. Martnez,
S.R.S. Ferreira, Supercritical uid extraction from spent coffee grounds and
coffee husks: antioxidant activity and effect of operational variables on
extract composition, Talanta 88 (2012) 544552.
[55] J.M.A. Arajo, D. Sandi, Extraction of coffee diterpenes and coffee oil using
supercritical carbon dioxide, Food Chemistry 101 (2006) 10871094.
[56] .B.A. de Azevedo, T.G. Kieckbusch, A.K. Tashima, R.S. Mohamed, P. Mazzafera,
S.A.B.V. de Melo, Supercritical CO2 recovery of caffeine from green coffee
oil: new experimental solubility data and modeling, Qumica Nova 31 (2008)
13191323.
[57] R.M. Couto, J. Fernandes, M.D.R.G. da Silva, P.C. Simes, Supercritical uid
extraction of lipids from spent coffee grounds, Journal of Supercritical Fluids
51 (2009) 159166.
[58] A.B.A. de Azevedo, P. Mazzafera, R.S. Mohamed, S. de Melo, T.G. Kieckbusch,
Extraction of caffeine, chlorogenic acids and lipids from green coffee beans
using supercritical carbon dioxide and co-solvents, Brazilian Journal of Chemical Engineering 25 (2008) 543552.
[59] A.L. Oliveira, S.S. Silva, M.A.P. Da Silva, M.N. Eberlin, F.A. Cabral, Sensory
and yield response surface analysis of supercritical CO2 extracted aromatic
oil from roasted coffee, Journal of Food Science and Technology-Mysore 38
(2001) 3842.
[60] J. Tello, M. Viguera, L. Calvo, Extraction of caffeine from Robusta coffee (Coffea
canephora var. Robusta) husks using supercritical carbon dioxide, Journal of
Supercritical Fluids 59 (2011) 5360.
[61] M.M.R. de Melo, H.M.A. Barbosa, C.P. Passos, C.M. Silva, Supercritical uid
extraction of spent coffee grounds: measurement of extraction curves, oil
characterization and economic analysis, Journal of Supercritical Fluids 86
(2014) 150159.
[62] H.M.A. Barbosa, M.M.R. de Melo, M.A. Coimbra, C.P. Passos, C.M.
Silva, Optimization of the supercritical uid coextraction of oil and
diterpenes from spent coffee grounds using experimental design and
response surface methodology, Journal of Supercritical Fluids 85 (2014)
165172.
[63] G. Andrich, S. Balzini, A. Zinnai, V. De Vitis, S. Silvestri, F. Venturi, R. Fiorentini,
Supercritical uid extraction in sunower seed technology, European Journal
of Lipid Science and Technology 103 (2001) 151157.
[64] L. Casas, C. Mantell, M. Rodriguez, A. Torres, F.A. Macias, E.J.M. de la Ossa,
Supercritical uid extraction of bioactive compounds from sunower leaves
with carbon dioxide and water on a pilot plant scale, Journal of Supercritical
Fluids 45 (2008) 3742.
[65] L. Casas, C. Mantell, M. Rodriguez, A. Torres, F.A. Macias, E.J.M. de La Ossa,
SFE kinetics of bioactive compounds from Helianthus annuus L, Journal of
Separation Science 32 (2009) 14451453.
[66] L. Casas, C. Mantell, M. Rodriguez, A. Torres, F.A. Macias, E.M. de la Ossa, Effect
of the addition of cosolvent on the supercritical uid extraction of bioactive
compounds from Helianthus annuus L, Journal of Supercritical Fluids 41 (2007)
4349.
[67] H.K. Kiriamiti, E. Rascol, A. Marty, J.S. Condoret, Extraction rates of oil from
high oleic sunower seeds with supercritical carbon dioxide, Chemical Engineering and Processing 41 (2002) 711718.
[68] U. Salgin, O. Doker, A. Calimli, Extraction of sunower oil with supercritical CO2 : experiments and modeling, Journal of Supercritical Fluids 38 (2006)
326331.
[69] L. Vazquez, C.F. Torres, T. Fornari, N. Grigelmo, F.J. Senorans, G. Reglero,
Supercritical uid extract ion of minor lipids from pretreated sunower oil
deodorizer distillates, European Journal of Lipid Science and Technology 108
(2006) 659665.
[70] Y. Athukorala, G. Mazza, Optimization of extraction of wax from ax straw by
supercritical carbon dioxide, Separation Science and Technology 46 (2011)
247253.
[71] B. Bozan, F. Temelli, Supercritical CO2 extraction of axseed, Journal of the
American Oil Chemists Society 79 (2002) 231235.

[72] L.M. Comin, F. Temelli, M.A. Saldana,


Supercritical CO2 extraction of
ax lignans, Journal of the American Oil Chemists Society 88 (2011)
707715.
[73] D.S. Ivanov, R.R. Colovic, J.D. Levic, S.A. Sredanovic, Optimization of supercritical uid extraction of linseed oil using RSM, European Journal of Lipid Science
and Technology 114 (2012) 807815.
[74] W.H. Morrison, R. Holser, D.E. Akin, Cuticular wax from ax processing waste
with hexane and super critical carbon dioxide extractions, Industrial Crops
and Products 24 (2006) 119122.

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176


[75] S.G. Ozkal, Response surface analysis and modeling of axseed oil yield in
supercritical carbon dioxide, Journal of the American Oil Chemists Society 86
(2009) 11291135.
[76] O. Bensebia, D. Barth, B. Bensebia, A. Dahmani, Supercritical CO2 extraction
of rosemary: effect of extraction parameters and modelling, Journal of Supercritical Fluids 49 (2009) 161166.
[77] R.N. Carvalho, L.S. Moura, P.T.V. Rosa, M.A.A. Meireles, Supercritical uid
extraction from rosemary (Rosmarinus ofcinalis): kinetic data, extracts
global yield, composition, and antioxidant activity, Journal of Supercritical
Fluids 35 (2005) 197204.

[78] M. Herrero, M. Plaza, A. Cifuentes, E. Ibnez,


Green processes for the extraction
of bioactives from rosemary: chemical and functional characterization via
ultra-performance liquid chromatographytandem mass spectrometry and
in-vitro assays, Journal of Chromatography A 1217 (2010) 25122520.
[79] S. Irmak, K. Solakyildirim, A. Hesenov, O. Erbatur, Study on the stability of
supercritical uid extracted rosemary (Rosmarinus offcinalis L.) essential oil,
Journal of Analytical Chemistry 65 (2010) 899906.
[80] M. Lo Presti, S. Ragusa, A. Trozzi, P. Dugo, F. Visinoni, A. Fazio, G. Dugo, L.
Mondello, A comparison between different techniques for the isolation of
rosemary essential oil, Journal of Separation Science 28 (2005) 273280.
[81] C.G. Pereira, M.A.A. Meireles, Economic analysis of rosemary, fennel and anise
essential oils obtained by supercritical uid extraction, Flavour and Fragrance
Journal 22 (2007) 407413.

[82] P. Ramirez, F.J. Senorans, E. Ibnez,


G. Reglero, Separation of rosemary antioxidant compounds by supercritical uid chromatography on coated packed
capillary columns, Journal of Chromatography A 1057 (2004) 241245.

[83] F.J. Senorans, E. Ibnez,


S. Cavero, J. Tabera, G. Reglero, Liquid
chromatographic-mass spectrometric analysis of supercritical-uid extracts
of rosemary plants, Journal of Chromatography A 870 (2000) 491499.
[84] J.M. del Valle, M. Jimenez, J.C. de la Fuente, Extraction kinetics of pre-pelletized
peppers with supercritical CO2 , Journal of Supercritical Fluids 25
Jalapeno
(2003) 3344.
[85] B. Nagy, B. Simandi, Effects of particle size distribution, moisture content, and
initial oil content on the supercritical uid extraction of paprika, Journal of
Supercritical Fluids 46 (2008) 293298.
[86] A. Romo-Hualde, A.I. Yetano-Cunchillos, C. Gonzalez-Ferrero, M.J. Saiz-Abajo,
C.J. Gonzalez-Navarro, Supercritical uid extraction and microencapsulation
of bioactive compounds from red pepper (Capsicum annum L.) by-products,
Food Chemistry 133 (2012) 10451049.
[87] E. Uquiche, J.M. del Valle, J. Ortiz, Supercritical carbon dioxide extraction of
red pepper (Capsicum annuum L.) oleoresin, Journal of Food Engineering 65
(2004) 5566.
[88] A. Ambrogi, D.A. Cardarelli, R. Eggers, Fractional extraction of paprika using
supercritical carbon dioxide and on-line determination of carotenoids, Journal of Food Science 67 (2002) 32363241.
[89] A. Tepic, Z. Zekovic, S. Kravic, A. Mandic, Pigment content and fatty acid composition of paprika oleoresins obtained by conventional and supercritical
carbon dioxide extraction, Cyta-Journal of Food 7 (2009) 95102.
[90] U. Salgin, A.S. Ustun, U. Mehmetoglu, A. Calimli, Supercritical CO2 extraction
of accumulated capsidiol from biotic elicitor-activated Capsicum annuum L
fruit tissues, Journal of Chemical Technology and Biotechnology 80 (2005)
124132.
[91] P. Bhattacharjee, T.V. Ranganathan, R.S. Singhal, P.R. Kulkarni, Comparative aroma proles using supercritical carbon dioxide and LikensNickerson
extraction from a commercial brand of Basmati rice, Journal of the Science of
Food and Agriculture 83 (2003) 880883.
[92] L. Danielski, C. Zetzl, H. Hense, G. Brunner, A process line for the production
of rafnated rice oil from rice bran, Journal of Supercritical Fluids 34 (2005)
133141.
[93] A. Manosroi, W. Ruksiriwanich, M. Abe, H. Sakai, W. Manosroi, J. Manosroi,
Biological activities of the rice bran extract and physical characteristics of
its entrapment in niosomes by supercritical carbon dioxide uid, Journal of
Supercritical Fluids 54 (2010) 137144.
[94] G. Perretti, E. Miniati, L. Montanari, P. Fantozzi, Improving the value of rice
by-products by SFE, Journal of Supercritical Fluids 26 (2003) 6371.
[95] C.H. Wang, C.R. Chen, J.J. Wu, L.Y. Wang, C.M.J. Chang, W.J. Ho, Designing
supercritical carbon dioxide extraction of rice bran oil that contain oryzanols
using response surface methodology, Journal of Separation Science 31 (2008)
13991407.
[96] Z.M. Xu, J.S. Godber, Comparison of supercritical uid and solvent extraction
methods in extracting -oryzanol from rice bran, Journal of the American Oil
Chemists Society 77 (2000) 547551.
[97] N.T. Dunford, J.W. King, Phytosterol enrichment of rice bran oil by a supercritical carbon dioxide fractionation technique, Journal of Food Science 65 (2000)
13951399.
[98] R.R. Chaudhury, U.M. Rafei, Traditional Medicine in Asia, World Health Organization, New Delhi, 2002.
[99] M. Perrut, Supercritical uid applications: industrial developments and
economic issues, Industrial & Engineering Chemistry Research 39 (2000)
45314535.
[100] M.M.R. de Melo, C.M. Silva, Supercritical uid extraction of oil and bioactive compounds from grape residues: experimental optimization, modeling
and economic evaluation, in: J.S. Cmara (Ed.), Grapes: Production, Phenolic
Composition and Potential Biomedical Effects, Nova Publisher.
[101] M.M.R. de Melo, A.J.D. Silvestre, C.M. Silva, Enhanced technologies for the
valorization of waste and side vegetable products using supercritical uids,

[102]

[103]

[104]

[105]

[106]

[107]

[108]

[109]

[110]

[111]

[112]

[113]

[114]

[115]

[116]

[117]

[118]

[119]

[120]

[121]

[122]

[123]

[124]

[125]

165

in: S. Pandalai (Ed.), Recent Research Developments in Chemical Engineering,


Transworld Research Network.
I.S. Sanal, A. Guvenc, U. Salgin, U. Mehmetoglu, A. Calimli, Recycling of apricot pomace by supercritical CO2 extraction, Journal of Supercritical Fluids 32
(2004) 221230.
S.G. Ozkal, M.E. Yener, L. Bayindirli, Response surfaces of apricot kernel oil
yield in supercritical carbon dioxide, Lwt-Food Science and Technology 38
(2005) 611616.
S.G. Ozkal, M.E. Yener, L. Bayindirli, Mass transfer modeling of apricot kernel
oil extraction with supercritical carbon dioxide, Journal of Supercritical Fluids
35 (2005) 119127.
I.S. Sanal, E. Bayraktar, U.U. Mehmetoglu, A. Calimli, Determination of optimum conditions for SC-(CO2 plus ethanol) extraction of -carotene from
apricot pomace using response surface methodology, Journal of Supercritical
Fluids 34 (2005) 331338.
O. Doker, U. Salgin, I. Sanal, U. Mehmetoglu, A. Calimli, Modeling of extraction
of -carotene from apricot bagasse using supercritical CO2 in packed bed
extractor, Journal of Supercritical Fluids 28 (2004) 1119.
M. Sun, F. Temelli, Supercritical carbon dioxide extraction of carotenoids from
carrot using canola oil as a continuous co-solvent, Journal of Supercritical
Fluids 37 (2006) 397408.
A. Ranalli, S. Contento, L. Lucera, G. Pavone, G. Di Giacomo, L. Aloisio, C. Di
Gregorio, A. Mucci, I. Kourtikakis, Characterization of carrot root oil arising
from supercritical uid carbon dioxide extraction, Journal of Agricultural and
Food Chemistry 52 (2004) 47954801.
S.B. Glisic, D.R. Misic, M.D. Stamenic, I.T. Zizovic, R.M. Asanin, D.U. Skala,
Supercritical carbon dioxide extraction of carrot fruit essential oil: chemical composition and antimicrobial activity, Food Chemistry 105 (2007)
346352.
A. Maxia, B. Marongiu, A. Piras, S. Porcedda, E. Tuveri, M.J. Goncalves, C.
Cavaleiro, L. Salgueiro, Chemical characterization and biological activity of
essential oils from Daucus carota L. subsp carota growing wild on the Mediterranean coast and on the Atlantic coast, Fitoterapia 80 (2009) 5761.
W.B. Setianto, S. Yoshikawa, R.L. Smith, H. Inomata, L.J. Florusse, C.J. Peters,
Pressure prole separation of phenolic liquid compounds from cashew (Anacardium occidentale) shell with supercritical carbon dioxide and aspects of its
phase equilibria, Journal of Supercritical Fluids 48 (2009) 203210.
R.N. Patel, S. Bandyopadhyay, A. Ganesh, Extraction of cashew (Anacardium
occidentale) nut shell liquid using supercritical carbon dioxide, Bioresource
Technology 97 (2006) 847853.
R.N. Patel, S. Bandyopadhyay, A. Ganesh, Economic appraisal of supercritical
uid extraction of rened cashew nut shell liquid, Journal of Chromatography
A 1124 (2006) 130138.
R.L. Smith, R.M. Malaluan, W.B. Setianto, H. Inomata, K. Arai, Separation of
cashew (Anacardium occidentale L.) nut shell liquid with supercritical carbon
dioxide, Bioresource Technology 88 (2003) 17.
R.S. Mohamed, P. Mazzafera, Extraction of cocoa butter from
M.D.A. Saldana,
Brazilian cocoa beans using supercritical CO2 and ethane, Fluid Phase Equilibria 194 (2002) 885894.
P. Mazzafera, C. Zetzl, G. Brunner, Extraction
R.S. Mohamed, M.D.A. Saldana,
of caffeine, theobromine, and cocoa butter from Brazilian cocoa beans using
supercritical CO2 and ethane, Industrial & Engineering Chemistry Research
41 (2002) 67516758.
E.K. Asep, S. Jinap, T.J. Tan, A.R. Russly, S. Harcharan, S.A.H. Nazimah, The
effects of particle size, fermentation and roasting of cocoa nibs on supercritical uid extraction of cocoa butter, Journal of Food Engineering 85 (2008)
450458.
M.E. Rybak, E.M. Calvey, J.M. Harnly, Quantitative determination of allicin in
garlic: supercritical uid extraction and standard addition of alliin, Journal of
Agricultural and Food Chemistry 52 (2004) 682687.
R. Li, W.-c. Chen, W.-p. Wang, W.-y. Tian, X.-g. Zhang, Extraction of essential
oils from garlic (Allium sativum) using ligarine as solvent and its immunity activity in gastric cancer rat, Medicinal Chemistry Research 19 (2010)
10921105.
J.M. del Valle, C. Mena, M. Budinich, Extraction of garlic with supercritical CO2
and conventional organic solvents, Brazilian Journal of Chemical Engineering
25 (2008) 535542.
J.M. del Valle, V. Glatzel, J.L. Martnez, Supercritical CO2 extraction of allicin
from garlic akes: screening and kinetic studies, Food Research International
45 (2012) 216224.
K.C. Zancan, M.O.M. Marques, A.J. Petenate, M.A.M. Meireles, Extraction of
ginger (Zingiber ofcinale Roscoe) oleoresin with CO2 and co-solvents: a study
of the antioxidant action of the extracts, Journal of Supercritical Fluids 24
(2002) 5776.
J. Martnez, A.R. Monteiro, P.T.V. Rosa, M.O.M. Marques, M.A.A. Meireles,
Multicomponent model to describe extraction of ginger oleoresin with supercritical carbon dioxide, Industrial & Engineering Chemistry Research 42
(2003) 10571063.
O.J. Catchpole, J.B. Grey, N.B. Perry, E.J. Burgess, W.A. Redmond, N.G. Porter,
Extraction of chilly, black pepper, and ginger with near-critical CO2 , propane,
and dimethyl ether: analysis of the extracts by quantitative nuclear magnetic resonance, Journal of Agricultural and Food Chemistry 51 (2003)
48534860.
J.P. Bartley, A.L. Jacobs, Effects of drying on avour compounds in Australiangrown ginger (Zingiber ofcinale), Journal of the Science of Food and
Agriculture 80 (2000) 209215.

166

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

[126] S. Balachandran, S.E. Kentish, R. Mawson, M. Ashokkumar, Ultrasonic


enhancement of the supercritical extraction from ginger, Ultrasonics Sonochemistry 13 (2006) 471479.
[127] S.Q. Zhang, R.Z. Chen, H. Wu, C.Z. Wang, Ginsenoside extraction from Panax
quinquefolium L. (American ginseng) root by using ultrahigh pressure, Journal
of Pharmaceutical and Biomedical Analysis 41 (2006) 5763.
[128] J.A. Wood, M.A. Bernards, W.K. Wan, P.A. Charpentier, Extraction of ginsenosides from North American ginseng using modied supercritical carbon
dioxide, Journal of Supercritical Fluids 39 (2006) 4047.
[129] H.C. Wang, C.R. Chen, C.M.J. Chang, Carbon dioxide extraction of ginseng root
hair oil and ginsenosides, Food Chemistry 72 (2001) 505509.
[130] D.L. Luo, T.Q. Qiu, Q. Lu, Ultrasound-assisted extraction of ginsenosides in
supercritical CO2 reverse microemulsions, Journal of the Science of Food and
Agriculture 87 (2007) 431436.
[131] H. Marzouki, A. Piras, B. Marongiu, A. Rosa, M.A. Dessi, Extraction and separation of volatile and xed oils from berries of Laurus nobilis L. by supercritical
CO2 , Molecules 13 (2008) 17021711.
[132] J. Ivanovic, D. Misic, M. Ristic, O. Pesic, I. Zizovic, Supercritical CO2 extract and
essential oil of bay (Laurus nobilis L.) chemical composition and antibacterial
activity, Journal of the Serbian Chemical Society 75 (2010) 395404.
[133] A. Caredda, B. Marongiu, S. Porcedda, C. Soro, Supercritical carbon dioxide
extraction and characterization of Laurus nobilis essential oil, Journal of Agricultural and Food Chemistry 50 (2002) 14921496.
[134] S. Beis, N. Dunford, Supercritical uid extraction of daphne (Laurus nobilis L.)
seed oil, Journal of the American Oil Chemists Society 83 (2006) 953957.

[135] D.J.M. Gmez-Coronado, E. Ibanez,


F.J. Ruprez, C. Barbas, Tocopherol measurement in edible products of vegetable origin, Journal of Chromatography
A 1054 (2004) 227233.
[136] Y.W. Lee, C.H. Lee, J.D. Kim, Y.Y. Lee, K.H. Row, Extraction of perillyl alcohol in
Korean orange peel by supercritical CO2 , Separation Science and Technology
35 (2000) 10691076.
[137] C.H. Lee, K.H. Row, Y.W. Lee, J.D. Kim, Y.Y. Lee, Supercritical uid extraction
of perillyl alcohol in Korean orange peel, Journal of Liquid Chromatography
& Related Technologies 24 (2001) 19871996.
[138] A. Berna, A. Tarrega, M. Blasco, S. Subirats, Supercritical CO2 extraction of
essential oil from orange peel; effect of the height of the bed, Journal of
Supercritical Fluids 18 (2000) 227237.
[139] P. Benelli, C.A.S. Riehl, A. Smania, E.F.A. Smania, S.R.S. Ferreira, Bioactive
extracts of orange (Citrus sinensis L. Osbeck) pomace obtained by SFE and
low pressure techniques: mathematical modeling and extract composition,
Journal of Supercritical Fluids 55 (2010) 132141.
[140] J.B. Fernandes, V. David, P.H. Facchini, M.F.D.F. da Silva, E. Rodrigues, P.C.
Vieira, M.S. Galhiane, F.C. Pagnocca, O.C. Bueno, M.J. Hebling, S.R. Victor,
A.M.R. dos Santos, Citrus seed oils extractions and their activity against leaf
cutting ant Atta sexdens and its symbiotic fungus, Qumica Nova 25 (2002)
10911095.
[141] S. Cavero, M.R. Garca-Risco, F.R. Marin, L. Jaime, S. Santoyo, F.J. Senorans, G.

Reglero, E. Ibnez,
Supercritical uid extraction of antioxidant compounds
from oregano chemical and functional characterization via LCMS and
in vitro assays, Journal of Supercritical Fluids 38 (2006) 6269.
[142] T. Fornari, A. Ruiz-Rodriguez, G. Vicente, E. Vazquez, M.R. Garca-Risco, G.
Reglero, Kinetic study of the supercritical CO2 extraction of different plants
from Lamiaceae family, Journal of Supercritical Fluids 64 (2012) 18.

[143] S. Santoyo, S. Cavero, L. Jaime, E. Ibnez,


F.J. Senorans, G. Reglero, Supercritical carbon dioxide extraction of compounds with antimicrobial activity from
Origanum vulgare L.: determination of optimal extraction parameters, Journal
of Food Protection 69 (2006) 369375.
[144] F. Gaspar, Extraction of essential oils and cuticular waxes with compressed
CO2 : effect of extraction pressure and temperature, Industrial & Engineering
Chemistry Research 41 (2002) 24972503.
[145] F. Gaspar, T. Lu, R. Santos, B. Al-Duri, Modelling the extraction of essential oils
with compressed carbon dioxide, Journal of Supercritical Fluids 25 (2003)
247260.
[146] M.G. Bernardo-Gil, L.M.C. Lopes, Supercritical uid extraction of Cucurbita cifolia seed oil, European Food Research and Technology 219 (2004) 593597.
[147] N. Hrabovski, S. Sinadinovic-Fiser, B. Nikolovski, M. Sovilj, O. Borota, Phytosterols in pumpkin seed oil extracted by organic solvents and supercritical CO2 ,
European Journal of Lipid Science and Technology 114 (2012) 12041211.
[148] P. Mitra, H.S. Ramaswamy, K.S. Chang, Pumpkin (Cucurbita maxima) seed oil
extraction using supercritical carbon dioxide and physicochemical properties
of the oil, Journal of Food Engineering 95 (2009) 208213.
[149] J. Shi, C. Yi, X. Ye, S. Xue, Y. Jiang, Y. Ma, D. Liu, Effects of supercritical CO2 uid
parameters on chemical composition and yield of carotenoids extracted from
pumpkin, LWT-Food Science and Technology 43 (2010) 3944.
[150] W.L. Yu, Y.P. Zhao, J.J. Chen, B. Shu, Comparison of two kinds of pumpkin
seed oils obtained by supercritical CO2 extraction, European Journal of Lipid
Science and Technology 106 (2004) 355358.
[151] J.M.D. Arajo, A.P.N. Nicolino, C. Blatt, Utilization of supercritical carbon dioxide for concentration of tocopherols from soybean oil deodorizer distillate,
Pesquisa Agropecuaria Brasileira 35 (2000) 201205.
[152] C.M.J. Chang, Y.F. Chang, H.Z. Lee, J.Q. Lin, P.W. Yang, Supercritical carbon dioxide extraction of high-value substances from soybean oil deodorizer distillate,
Industrial & Engineering Chemistry Research 39 (2000) 45214525.
[153] S. Jokic, B. Nagy, Z. Zekovic, S. Vidovic, M. Bilic, D. Velic, B. Simandi, Effects
of supercritical CO2 extraction parameters on soybean oil yield, Food and
Bioproducts Processing 90 (2012) 693699.

[154] S. Jokic, Z. Zekovic, S. Vidovic, R. Sudar, I. Nemet, M. Bilic, D. Velic, Supercritical CO2 extraction of soybean oil: process optimisation and triacylglycerol
composition, International Journal of Food Science and Technology 45 (2010)
19391946.
[155] S.L. Taylor, J.W. King, L. Montanari, P. Fantozzi, M.A. Blanco, Enrichment and
fractionation of phospholipid concentrates by supercritical uid extraction
and chromatography, Italian Journal of Food Science 12 (2000) 6576.
[156] B. Matthus, L. Bruhl, Comparison of different methods for the determination
of the oil content in oilseeds, Journal of the American Oil Chemists Society 78
(2001) 95102.
[157] B. Gopalan, M. Goto, A. Kodama, T. Hirose, Supercritical carbon dioxide extraction of turmeric (Curcuma longa), Journal of Agricultural and Food Chemistry
48 (2000) 21892192.
[158] A.L. Chassagnez-Mendez, N.T. Machado, M.E. Arajo, J.G. Maia, M.A.A. Meireles, Supercritical CO2 extraction of curcumins and essential oil from the
rhizomes of turmeric (Curcuma longa L.), Industrial & Engineering Chemistry
Research 39 (2000) 47294733.
[159] A.L. Chassagnez-Mendez, N.C.F. Correa, L.F. Franca, N.T. Machado, M.E. Arajo,
A mass transfer model applied to the supercritical extraction with CO2 of
curcumins from turmeric rhizomes (Curcuma longa L.), Brazilian Journal of
Chemical Engineering 17 (2000) 315322.
[160] M.E.M. Braga, P.F. Leal, J.E. Carvalho, M.A.A. Meireles, Comparison of yield,
composition, and antioxidant activity of turmeric (Curcuma longa L.) extracts
obtained using various techniques, Journal of Agricultural and Food Chemistry
51 (2003) 66046611.
[161] G. Began, M. Goto, A. Kodama, T. Hirose, Response surfaces of total oil yield
of turmeric (Curcuma longa) in supercritical carbon dioxide, Food Research
International 33 (2000) 341345.
[162] M. Eisenmenger, N.T. Dunford, F. Eller, S. Taylor, J. Martnez, Pilot-scale supercritical carbon dioxide extraction and fractionation of wheat germ oil, Journal
of the American Oil Chemists Society 83 (2006) 863868.
[163] N. Gelmez, N.S. Kincal, M.E. Yener, Optimization of supercritical carbon dioxide extraction of antioxidants from roasted wheat germ based on yield, total
phenolic and tocopherol contents, and antioxidant activities of the extracts,
Journal of Supercritical Fluids 48 (2009) 217224.
[164] A.M. Gomez, E.M. de la Ossa, Quality of wheat germ oil extracted by liquid and
supercritical carbon dioxide, Journal of the American Oil Chemists Society 77
(2000) 969974.
[165] J.D. Hubbard, J.M. Downing, M.S. Ram, O.K. Chung, Lipid extraction from
wheat our using supercritical uid extraction, Cereal Chemistry 81 (2004)
693698.
[166] G.W. Jung, H.M. Kang, B.S. Chun, Characterization of wheat bran oil obtained
by supercritical carbon dioxide and hexane extraction, Journal of Industrial
and Engineering Chemistry 18 (2012) 360363.
[167] G. Panli, L. Cinquanta, A. Fratianni, R. Cubadda, Extraction of wheat germ
oil by supercritical CO2 : oil and defatted cake characterization, Journal of the
American Oil Chemists Society 80 (2003) 157161.
[168] B. Marongiu, A. Piras, S. Porcedda, A. Scorciapino, Chemical composition of
the essential oil and supercritical CO2 extract of Commiphora myrrha (Nees)
Engl. and of Acorus calamus L, Journal of Agricultural and Food Chemistry 53
(2005) 79397943.
[169] K.X. Chen, W.H. Yin, Effects of entrainers on the purity of andrographolide
extracted from andrographolide raw material by SC-CO2 , Separation and
Purication Technology 70 (2009) 207211.
[170] P. Tonthubthimthong, S. Chuaprasert, P. Douglas, W. Luewisutthichat, Supercritical CO2 extraction of nimbin from neem seeds an experimental study,
Journal of Food Engineering 47 (2001) 289293.
[171] P. Tonthubthimthong, P.L. Douglas, S. Douglas, W. Leuwisutthichat, W.
Teppaitoon, L. Pengsopa, Extraction of nimbin from neem seeds using supercritical CO2 and a supercritical CO2 -methanol mixture, Journal of Supercritical
Fluids 30 (2004) 287301.
[172] D. Mongkholkhajornsilp, S. Douglas, P.L. Douglas, A. Elkamel, W. Teppaitoon,
S. Pongamphai, Supercritical CO2 extraction of nimbin from neem seeds a
modelling study, Journal of Food Engineering 71 (2005) 331340.
[173] A. Ajchariyapagorn, T. Kumhom, S. Pongamphai, S. Douglas, P.L. Douglas, W.
Teppaitoon, Predicting the extraction yield of nimbin from neem seeds in
supercritical CO2 using group contribution methods, equations of state and
a shrinking core extraction model, Journal of Supercritical Fluids 51 (2009)
3642.
[174] X.G. Shi, X. Wang, D.J. Wang, Y.L. Geng, J.H. Liu, Separation and Purication of
cyperone from Cyperus rotundus with supercritical uid extraction and highspeed counter-current chromatography, Separation Science and Technology
44 (2009) 712721.
[175] M.G.D. Silva, F.J.D. Matos, P.R.O. Lopes, F.O. Silva, M.T. Holanda, Composition
of essential oils from three Ocimum species obtained by steam and microwave
distillation and supercritical CO2 extraction, Arkivoc (2004) 6671.
[176] M. Mazutti, B. Beledelli, A.J. Mossi, R.L. Cansian, C. Dariva, J.V. de Oliveira, N.
Paroul, Chemical characterization of Ocimum basilicum L. extracts obtained
by high pressure CO2 extraction, Qumica Nova 29 (2006) 11981202.
[177] P.F. Leal, N.B. Maia, Q.A.C. Carmello, R.R. Catharino, M.N. Eberlin, M.A.A. Meireles, Sweet basil (Ocimum basilicum) extracts obtained by supercritical uid
rxtraction (SFE): global yields, chemical composition, antioxidant activity,
and estimation of the cost of manufacturing, Food and Bioprocess Technology
1 (2008) 326338.
[178] P.F. Leal, F.C.M. Chaves, L.C. Ming, A.J. Petenate, M.A.A. Meireles, Global yields,
chemical compositions and antioxidant activities of clove basil (Ocimum

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

[179]

[180]

[181]

[182]

[183]

[184]

[185]

[186]

[187]

[188]

[189]

[190]
[191]
[192]

[193]

[194]

[195]
[196]

[197]

[198]

[199]

[200]

[201]

[202]

[203]

[204]

gratissimum L.) extracts obtained by supercritical uid extraction, Journal of


Food Process Engineering 29 (2006) 547559.
A. Menaker, M. Kravets, M. Koel, A. Orav, Identication and characterization
of supercritical uid extracts from herbs, Comptes Rendus Chimie 7 (2004)
629633.
B. Kayan, A.M. Gizir, Co-solvent-modied supercritical carbon dioxide extraction of 10-Deacetylbaccatin III from Needles of Taxus baccata L, Separation
Science and Technology 44 (2009) 20042021.
M.M.R. de Melo, R.M.A. Domingues, A.J.D. Silvestre, C.M. Silva, Extraction and purication of triterpenoids using supercritical uids:
from lab to exploitation, Mini-Reviews in Organic Chemistry (2014),
http://dx.doi.org/10.2174/1570193X113106660002.
R.M.A. Domingues, A.R. Guerra, M. Duarte, C.S.R. Freire, C.P. Neto, C.M.
Silva, A.J.D. Silvestre, Bioactive triterpenic acids: from agroforestry biomass
residues, to promising therapeutic tools, Mini-Reviews in Organic Chemistry
(2014), http://dx.doi.org/10.2174/1570193X113106660001.
A.M.R.C. Alexandre, A.M.A. Dias, I.J. Seabra, A.A.T.G. Portugal, H.C. de Sousa,
M.E.M. Braga, Biodiesel obtained from supercritical carbon dioxide oil of
Cynara cardunculus L, Journal of Supercritical Fluids 68 (2012) 5263.
W.H. Chen, C.H. Chen, C.M.J. Chang, Y.H. Chiu, D. Hsiang, Supercritical carbon
dioxide extraction of triglycerides from Jatropha curcas L. seeds, Journal of
Supercritical Fluids 51 (2009) 174180.

P. Kotnik, M. Skerget,
Z. Knez, Kinetics of supercritical carbon dioxide extraction of borage and evening primrose seed oil, European Journal of Lipid
Science and Technology 108 (2006) 569576.
G.L. Li, Z.W. Sun, L.A. Xia, J.Y. Shi, Y.J. Liu, Y.R. Suo, J.M. You, Supercritical CO2
oil extraction from Chinese star anise seed and simultaneous compositional
analysis using HPLC by uorescence detection and online atmospheric CIMS identication, Journal of the Science of Food and Agriculture 90 (2010)
19051913.
L.F. de Franca, M.A.A. Meireles, Modeling the extraction of carotene and lipids
from pressed palm oil (Elaes guineensis) bers using supercritical CO2 , Journal
of Supercritical Fluids 18 (2000) 3547.
M. Arshadi, A.J. Hunt, J.H. Clark, Supercritical uid extraction (SFE) as an
effective tool in reducing auto-oxidation of dried pine sawdust for power
generation, RSC Advances 2 (2012) 18061809.
M.E. Arajo, N.T. Machado, L.F. Franca, M.A.A. Meireles, Supercritical extraction of pupunha (Guilielma speciosa) oil in a xed bed using carbon dioxide,
Brazilian Journal of Chemical Engineering 17 (2000) 297306.
K. Hill, R. Hfer, Natural fats and oils, in: R. Hfer (Ed.), Sustainable Solutions
for Modern Economies, RSC, Cambridge, 2009.
H.-D. Belitz, W. Grosch, P. Schieberle, Food Chemistry, Springer Berlin, Heidelberg, Germany, 19871999.
R. Arroo, Eberhard Breitmaier. Terpenesavors, fragrances, pharmaca,
pheromones. Wiley-VCH, 2006, 214 pp ISBN 3-527-31786-4, Applied
Organometallic Chemistry 21 (2007) 377.
A.Z. Kakasy, E. Lemberkovics, B. Simandi, L. Lelik, E. Hethelyi, I. Antal, E.
Szoke, Comparative study of traditional essential oil and supercritical uid
extracts of Moldavian dragonhead (Dracocephalum moldavica L.), Flavour and
Fragrance Journal 21 (2006) 598603.
A. Peterson, S. Machmudah, B.C. Roy, M. Goto, M. Sasaki, T. Hirose, Extraction
of essential oil from geranium (Pelargonium graveolens) with supercritical carbon dioxide, Journal of Chemical Technology and Biotechnology 81 (2006)
167172.
P.B. Gomes, V.G. Mata, A.E. Rodrigues, Production of rose geranium oil using
supercritical uid extraction, Journal of Supercritical Fluids 41 (2007) 5060.
S. Quispe-Condori, D. Sanchez, M.A. Foglio, P.T.V. Rosa, C. Zetzl, G. Brunner,
M.A.A. Meireles, Global yield isotherms and kinetic of artemisinin extraction
from Artemisia annua L leaves using supercritical carbon dioxide, Journal of
Supercritical Fluids 36 (2005) 4048.

L. Cretnik, M. Skerget,
Z. Knez, Separation of parthenolide from feverfew:
performance of conventional and high-pressure extraction techniques, Separation and Purication Technology 41 (2005) 1320.
H.P. He, H. Corke, J.G. Cai, Supercritical carbon dioxide extraction of oil and
squalene from Amaranthus grain, Journal of Agricultural and Food Chemistry
51 (2003) 79217925.
P. Bhattacharjee, D. Chatterjee, R.S. Singhal, Supercritical carbon dioxide extraction of squalene from Amaranthus paniculatus: experiments
and process characterization, Food and Bioprocess Technology 5 (2012)
25062521.
S. Stavroulias, C. Panayiotou, Determination of optimum conditions for the
extraction of squalene from olive pomace with supercritical CO2 , Chemical
and Biochemical Engineering Quarterly 19 (2005) 373381.
T.F. Ko, Y.M. Weng, R.Y.Y. Chiou, Squalene content and antioxidant activity of Terminalia catappa leaves and seeds, Journal of Agricultural and Food
Chemistry 50 (2002) 53435348.
L.D. Kagliwal, A.S. Pol, S.C. Patil, R.S. Singhal, V.B. Patravale, Antioxidant-Rich
extract from dehydrated seabuckthorn berries by supercritical carbon dioxide
extraction, Food and Bioprocess Technology 5 (2012) 27682776.
L. Ciurlia, M. Bleve, L. Rescio, Supercritical carbon dioxide co-extraction of
tomatoes (Lycopersicum esculentum L.) and hazelnuts (Corylus avellana L.): a
new procedure in obtaining a source of natural lycopene, Journal of Supercritical Fluids 49 (2009) 338344.
W. Huang, Z. Li, H. Niu, D. Li, J. Zhang, Optimization of operating parameters
for supercritical carbon dioxide extraction of lycopene by response surface
methodology, Journal of Food Engineering 89 (2008) 298302.

167

[205] L.S.V. Katherine, C.C. Edgar, W.K. Jerry, R.H. Luke, C.D. Julie, Extraction
conditions affecting supercritical uid extraction (SFE) of lycopene from
watermelon, Bioresource Technology 99 (2008) 78357841.
[206] S. Machmudah, A. Martin, M. Sasaki, M. Goto, Mathematical modeling for
simultaneous extraction and fractionation process of coffee beans with supercritical CO2 and water, Journal of Supercritical Fluids 66 (2012) 111119.
[207] J. Sedlakova, B. Kocourkova, L. Lojkova, V. Kuban, Determination of essential
oil content in caraway (Carum carvi L.) species by means of supercritical uid
extraction, Plant Soil and Environment 49 (2003) 277282.
[208] S.M. Pourmortazavi, F. Sedkon, S.G. Hosseini, Supercritical carbon dioxide
extraction of essential oils from Perovskia atriplicifolia Benth, Journal of Agricultural and Food Chemistry 51 (2003) 54145419.
[209] A.H. El-Ghorab, A.F. Mansour, K.F. El-Massry, Effect of extraction methods
on the chemical composition and antioxidant activity of Egyptian marjoram
(Majorana hortensis Moench), Flavour and Fragrance Journal 19 (2004) 5461.
[210] M.E.M. Braga, P.A.D. Ehlert, L.C. Ming, M.A.A. Meireles, Supercritical uid
extraction from Lippia alba: global yields, kinetic data, and extract chemical
composition, Journal of Supercritical Fluids 34 (2005) 149156.
[211] E. Ghasemi, Y. Yamini, N. Bahramifar, F. Sedkon, Comparative analysis of the
oil and supercritical CO2 extract of Artemisia sieberi, Journal of Food Engineering 79 (2007) 306311.
[212] P. Costa, C. Grosso, S. Goncalves, P.B. Andrade, P. Valentao, M.G. Bernardo-Gil,
A. Romano, Supercritical uid extraction and hydrodistillation for the recovery of bioactive compounds from Lavandula viridis LHer, Food Chemistry 135
(2012) 112121.
[213] D. Ehlers, T. Nguyen, K.W. Quirin, D. Gerard, Analysis of essential basil oils
CO2 extracts and steam-distilled oils, Deutsche Lebensmittel-Rundschau 97
(2001) 245250.
[214] F. Yahya, T. Lu, R.C.D. Santos, P.J. Fryer, S. Bakalis, Supercritical carbon dioxide
and solvent extraction of 2-acetyl-1-pyrroline from Pandan leaf: the effect of
pre-treatment, Journal of Supercritical Fluids 55 (2010) 200207.
[215] P. Bhattacharjee, A. Kshirsagar, R.S. Singhal, Supercritical carbon dioxide
extraction of 2-acetyl-1-pyrroline from Pandanus amaryllifolius Roxb, Food
Chemistry 91 (2005) 255259.
[216] J. Rincon, A. De Lucas, I. Garca, Isolation of rock rose essential oil using
supercritical CO2 extraction, Separation Science and Technology 35 (2000)
27452763.
[217] P. Dzubak, M. Hajduch, D. Vydra, A. Hustova, M. Kvasnica, D. Biedermann,
L. Markova, M. Urban, J. Sarek, Pharmacological activities of natural triterpenoids and their therapeutic implications, Natural Product Reports 23 (2006)
394411.
[218] M.N. Laszczyk, Pentacyclic triterpenes of the lupane, oleanane and ursane
group as tools in cancer therapy, Planta Medica 75 (2009) 15491560.
[219] N. Sultana, A. Ata, Oleanolic acid and related derivatives as medicinally important compounds, Journal of Enzyme Inhibition and Medicinal Chemistry 23
(2008) 739756.
[220] P. Yogeeswari, D. Sriram, Betulinic acid and its derivatives: a review on their
biological properties, Current Medicinal Chemistry 12 (2005) 657666.
[221] L.Y. Huang, T.H. Zhong, T.W. Chen, Z. Ye, G.N. Chen, Identication of sitosterol, stigmasterol and ergosterin in A. roxburghii using supercritical uid
extraction followed by liquid chromatography/atmospheric pressure chemical ioneization ion trap mass spectrometry, Rapid Communications in Mass
Spectrometry 21 (2007) 30243032.
[222] R. Bruni, A. Medici, A. Guerrini, S. Scalia, F. Poli, M. Muzzoli, G. Sacchetti, Wild
Amaranthus caudatus seed oil, a nutraceutical resource from Ecuadorian ora,
Journal of Agricultural and Food Chemistry 49 (2001) 54555460.
[223] S.L. Taylor, J.W. King, Preparative-scale supercritical uid extraction/supercritical uid chromatography of corn bran, Journal of the
American Oil Chemists Society 79 (2002) 11331136.
[224] K.L. Nyam, C.P. Tan, R. Karim, O.M. Lai, K. Long, Y.B.C. Man, Extraction of
tocopherol-enriched oils from Kalahari melon and roselle seeds by supercritical uid extraction (SFE-CO2 ), Food Chemistry 119 (2010) 12781283.
[225] A. Boszormenyi, S. Szarka, E. Hethelyi, I. Gyurjan, M. Laszlo, B. Simandi,
E. Szoke, E. Lemberkovics, Triterpenes in traditional and supercritical-uid
extracts of Morus alba leaf and stem bark, Acta Chromatographica 21 (2009)
659669.
[226] M. Sajfrtov, I. Lickov, M. Wimmerov, H. Sovov, Z. Wimmer, -Sitosterol:
supercritical carbon dioxide extraction from sea buckthorn (Hippophae rhamnoides L.) seeds, International Journal of Molecular Sciences 11 (2010)
18421850.
[227] H. Sovov, A.A. Galushko, R.P. Stateva, K. Rochov, M. Sajfrtov, M. Brtlov, Supercritical uid extraction of minor components of vegetable oils:
-sitosterol, Journal of Food Engineering 101 (2010) 201209.
[228] V.R. Preedy, R.R. Watson, The Encyclopedia of Vitamin E, CABI, Oxon, 2007.

[229] E. Ibnez,
J. Palacios, F.J. Senorans, G. Santa-Maria, J. Tabera, G. Reglero, Isolation and separation of tocopherols from olive by-products with supercritical
uids, Journal of the American Oil Chemists Society 77 (2000) 187190.
[230] A. de Lucas, E.M. de la Ossa, J. Rincon, M.A. Blanco, I. Gracia, Supercritical
uid extraction of tocopherol concentrates from olive tree leaves, Journal of
Supercritical Fluids 22 (2002) 221228.
[231] M. Waksmundzka-Hajnos, J. Sherma, High Performance Liquid Chromatography in Phytochemical Analysis, Taylor & Francis, Boca Raton, 2010.
[232] O.I. Pokrovskii, A.A. Markoliya, F.D. Lepeshkin, I.V. Kuvykin, O.O. Parenago,
S.A. Gonchukov, Extraction of linear furocoumarins from Ammi Majus seeds
by means of supercritical uid extraction and supercritical uid chromatography, Russian Journal of Physical Chemistry B 3 (2009) 11651171.

168

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

[233] H. Sovov, L. Opletal, M. Bartlova, M. Sajfrtova, M. Krenkova, Supercritical uid


extraction of lignans and cinnamic acid from Schisandra chinensis, Journal of
Supercritical Fluids 42 (2007) 8895.
[234] M. Fullana, F. Trabelsi, F. Recasens, Use of neural net computing for statistical and kinetic modelling and simulation of supercritical uid extractors,
Chemical Engineering Science 55 (2000) 7995.
[235] Z. Solati, B.S. Baharin, H. Bagheri, Supercritical carbon dioxide (SC-CO2 ) extraction of Nigella sativa L. oil using full factorial design, Industrial Crops and
Products 36 (2012) 519523.
[236] C. Grosso, A.C. Figueiredo, J. Burillo, A.M. Mainar, J.S. Urieta, J.G. Barroso, J.A.
Coelho, A.M.F. Palavra, Enrichment of the thymoquinone content in volatile
oil from Saturejia montana using supercritical uid extraction, Journal of Separation Science 32 (2009) 328334.
[237] J. Liu, S.Y. Lin, Z.Z. Wang, C.N. Wang, E.L. Wang, Y. Zhang, J.B. Liu, Supercritical
uid extraction of avonoids from Maydis stigma and its nitrite-scavenging
ability, Food and Bioproducts Processing 89 (2011) 333339.
[238] B. Shan, J.H. Xie, J.H. Zhu, Y. Peng, Ethanol modied supercritical carbon dioxide extraction of avonoids from Momordica charantia L. and its antioxidant
activity, Food and Bioproducts Processing 90 (2012) 579587.
[239] S.-F. Miao, J.-P. Yu, Z. Du, Y.-X. Guan, S.-J. Yao, Z.-Q. Zhu, Supercritical uid
extraction and micronization of Ginkgo Flavonoids from Ginkgo biloba Leaves,
Industrial & Engineering Chemistry Research 49 (2010) 54615466.
[240] S.J. Wu, J.Y. Tsai, S.P. Chang, D.L. Lin, S.S. Wang, S.N. Huang, L.T. Ng,
Supercritical carbon dioxide extract exhibits enhanced antioxidant and antiinammatory activities of Physalis peruviana, Journal of Ethnopharmacology
108 (2006) 407413.
[241] J.Z. He, P. Shao, J.H. Liu, Q.M. Ru, Supercritical carbon dioxide extraction of avonoids from Pomelo (Citrus grandis (L.) Osbeck) peel and their
antioxidant activity, International Journal of Molecular Sciences 13 (2012)
1306513078.
[242] L.E. Laroze, B. Diaz-Reinoso, A. Moure, M.E. Zuniga, H. Dominguez, Extraction
of antioxidants from several berries pressing wastes using conventional and
supercritical solvents, European Food Research and Technology 231 (2010)
669677.
[243] A. Rajaei, M. Barzegar, Y. Yamini, Supercritical uid extraction of tea seed
oil and its comparison with solvent extraction, European Food Research and
Technology 220 (2005) 401405.
[244] F.J. Eller, S.C. Cermak, S.L. Taylor, Supercritical carbon dioxide extraction of
cuphea seed oil, Industrial Crops and Products 33 (2011) 554557.
[245] R.A. Holser, G. Bost, Hybrid hibiscus seed oil compositions, Journal of the American Oil Chemists Society 81 (2004) 795797.
[246] T. Hatami, R.N. Cavalcanti, T.M. Takeuchi, M.A.A. Meireles, Supercritical uid
extraction of bioactive compounds from Macela (Achyrocline satureioides)
owers: kinetic, experiments and modeling, Journal of Supercritical Fluids
65 (2012) 7177.
[247] J. Dai, C. Ha, M. Shen, Systematic study of -asarone-rich volatile oil
from Acori graminei rhizoma by off-line supercritical CO2 extractiongas
chromatographymass spectrometry, Journal of Separation Science 31 (2008)
714720.
[248] P.R. Venskutonis, M. Skemaite, B. Sivik, Assessment of radical scavenging
capacity of Agrimonia extracts isolated by supercritical carbon dioxide, Journal of Supercritical Fluids 45 (2008) 231237.
[249] I.H. Akgun, A. Erkucuk, M. Pilavtepe, O. Yesil-Celiktas, Optimization of total
alkannin yields of Alkanna tinctoria by using sub- and supercritical carbon
dioxide extraction, Journal of Supercritical Fluids 57 (2011) 3137.
[250] B. Simandi, A. Sass-Kiss, B. Czukor, A. Deak, A. Prechl, A. Csordas, J. Sawinsky, Pilot-scale extraction and fractional separation of onion oleoresin using
supercritical carbon dioxide, Journal of Food Engineering 46 (2000) 183188.
[251] C. Saengcharoenrat, D.E. Guyer, Effects of supercritical carbon dioxide conditions on onion oil desorption, Journal of Food Engineering 63 (2004) 3337.
[252] C.L. Ye, Y.F. Lai, Supercritical CO2 extraction optimization of onion oil using
response surface methodology, Chemical Engineering & Technology 35 (2012)
646652.
[253] A. Felfoldi-Gava, S. Szarka, B. Simandi, B. Blazics, B. Simon, A. Kery, Supercritical uid extraction of Alnus glutinosa (L.) Gaertn, Journal of Supercritical
Fluids 61 (2012) 5561.
[254] Q.H. Hu, Y. Hu, J. Xu, Free radical-scavenging activity of Aloe vera (Aloe barbadensis Miller) extracts by supercritical carbon dioxide extraction, Food
Chemistry 91 (2005) 8590.
[255] H.Y. Ju, K.C. Huang, J.H. Chen, Y.C. Liu, C.M.J. Chang, C.C. Lee, C. Chang, C.J. Shieh,
Optimization of the extraction of Alpinia oxyphylla essence oil in supercritical carbon dioxide, Journal of the American Oil Chemists Society 87 (2010)
10631070.
[256] R. Bruni, A. Guerrini, S. Scalia, C. Romagnoli, G. Sacchetti, Rapid techniques for
the extraction of vitamin E isomers from Amaranthus caudatus seeds: ultrasonic and supercritical uid extraction, Phytochemical Analysis 13 (2002)
257261.
[257] D. Westerman, R.C.D. Santos, J.A. Bosley, J.S. Rogers, B. Al-Duri, Extraction of
Amaranth seed oil by supercritical carbon dioxide, Journal of Supercritical
Fluids 37 (2006) 3852.
[258] A.C. Kumoro, M. Hasan, Modeling of supercritical carbon dioxide extraction of
andrographolide from Andrographis paniculata leaves, Chemical Engineering
Communications 195 (2008) 7280.
[259] A.L. Medina, M.E. Lucero, F.O. Holguin, R.E. Estell, J.J. Posakony, J. Simon, M.A.
OConnell, Composition and antimicrobial activity of Anemopsis californica leaf
oil, Journal of Agricultural and Food Chemistry 53 (2005) 86948698.

[260] N. Paroul, L. Rota, C. Frizzo, A.C.A. dos Santos, P. Moyna, A.E. Gower, L.A. Serani, E. Cassel, Chemical composition of the volatiles of Angelica root obtained
by hydrodistillation and supercritical CO2 extraction, Journal of Essential Oil
Research 14 (2002) 282285.
[261] Q.H. Chen, P. Li, J. He, Z. Zhang, J. Liu, Supercritical uid extraction for identication and determination of volatile metabolites from Angelica dahurica by
GCMS, Journal of Separation Science 31 (2008) 32183224.
[262] M.R. Kim, A.M. Abd El-Aty, J.H. Choi, K.B. Lee, J.H. Shim, Identication of
volatile components in Angelica species using supercritical-CO2 uid extraction and solid phase microextraction coupled to gas chromatographymass
spectrometry, Biomedical Chromatography 20 (2006) 12671273.
[263] Y.Y. Sun, S.F. Li, H.T. Song, S.J. Tian, Extraction of ferulic acid from Angelica
sinensis with supercritical CO2 , Natural Product Research 20 (2006) 835841.
[264] I. Papamichail, V. Louli, K. Magoulas, Supercritical uid extraction of celery
seed oil, Journal of Supercritical Fluids 18 (2000) 213226.
[265] S. Akay, I. Alpak, O. Yesil-Celiktas, Effects of process parameters on supercritical CO2 extraction of total phenols from strawberry (Arbutus unedo
L.) fruits: an optimization study, Journal of Separation Science 34 (2011)
19251931.
[266] J.T. Paula, L.C. Paviani, M.A. Foglio, I.M.O. Sousa, F.A. Cabral, Extraction of anthocyanins from Arrabidaea chica in xed bed using CO2 and
CO2 /ethanol/water mixtures as solvents, Journal of Supercritical Fluids 81
(2013) 3341.
[267] L. Martin, A.M. Mainar, A. Gonzalez-Coloma, J. Burillo, J.S. Urieta, Supercritical
uid extraction of wormwood (Artemisia absinthium L.), Journal of Supercritical Fluids 56 (2011) 6471.
[268] B. Marongiu, A. Piras, S. Porcedda, Comparative analysis of the oil and supercritical CO2 extract of Artemisia arborescens L. and Helichrysum splendidum
(Thunb.) less, Natural Product Research 20 (2006) 421428.
[269] C.-C. Yang, M.-R. Lee, S.-L. Hsu, C.-M.J. Chang, Supercritical uids extraction
of capillarisin from Artemisia capillaris and its inhibition of in vitro growth of
hepatoma cells, Journal of Supercritical Fluids 42 (2007) 96103.
[270] Q.H. Chen, P. Li, H.D. Yang, X.L. Li, J. Zhu, F.C. Chen, Identication of volatile
compounds of Atractylode lancea Rhizoma using supercritical uid extraction
and GC-MS, Journal of Separation Science 32 (2009) 31523156.
[271] Z. Huang, M.J. Yang, S.F. Liu, Q. Ma, Supercritical carbon dioxide extraction of
Baizhu: experiments and modeling, Journal of Supercritical Fluids 58 (2011)
3139.
[272] C.R. Piantino, F.W.B. Aquino, L.A. Follegatti-Romero, F.A. Cabral, Supercritical
CO2 extraction of phenolic compounds from Baccharis dracunculifolia, Journal
of Supercritical Fluids 47 (2008) 209214.
[273] E. Cassel, C.D. Frizzo, R. Vanderlinde, L. Atti-Serani, D. Lorenzo, E. Dellacassa, Extraction of Baccharis oil by supercritical CO2 , Industrial & Engineering
Chemistry Research 39 (2000) 48034805.
[274] R.M.F. Vargas, E. Cassel, G.M.F. Gomes, L.G.S. Longhi, L. Atti-Serani, A.C. AttiSantos, Supercritical extraction of carqueja essential oil: experiments and
modeling, Brazilian Journal of Chemical Engineering 23 (2006) 375382.
[275] D.C.M.N. Silva, L.F.V. Bresciani, R.L. Dalagnol, L. Danielski, R.A. Yunes, S.R.S.
Ferreira, Supercritical uid extraction of carqueja (Baccharis trimera) oil: process parameters and composition proles, Food and Bioproducts Processing
87 (2009) 317326.
[276] B. Klejdus, L. Lojkova, E. Kula, I. Buchta, P. Hrdlicka, V. Kuban, Supercritical uid
extraction of amino acids from birch (Betula pendula Roth) leaves and their
liquid chromatographic determination with uorimetric detection, Journal of
Separation Science 31 (2008) 13631373.
[277] B.P. Nobre, R.L. Mendes, E.M. Queiroz, F.L.P. Pessoa, J.P. Coelho, A.F. Palavra,
Supercritical carbon dioxide extraction of pigments from Bixa orellana seeds
(experiments and modeling), Brazilian Journal of Chemical Engineering 23
(2006) 251258.
[278] G.F. Silva, F.M.C. Gamarra, A.L. Oliveira, F.A. Cabral, Extraction of bixin from
annatto seeds using supercritical carbon dioxide, Brazilian Journal of Chemical Engineering 25 (2008) 419426.
[279] C.L.C. Albuquerque, M.A.A. Meireles, Defatting of annatto seeds using supercritical carbon dioxide as a pretreatment for the production of bixin:
experimental, modeling, economic evaluation of the process, Journal of
Supercritical Fluids 66 (2012) 8695.
[280] A.M. Gomez, E.M. de la Ossa, Quality of borage seed oil extracted by liquid
and supercritical carbon dioxide, Chemical Engineering Journal 88 (2002)
103109.
[281] E. Dauksas, P.R. Venskutonis, B. Sivik, Supercritical uid extraction of borage
(Borago ofcinalis L.) seeds with pure CO2 and its mixture with caprylic acid
methyl ester, Journal of Supercritical Fluids 22 (2002) 211219.
[282] C. Soto, E. Conde, A. Moure, M.E. Zuniga, H. Dominguez, Supercritical
extraction of borage seed oil coupled to conventional solvent extraction of
antioxidants, European Journal of Lipid Science and Technology 110 (2008)
10351044.
[283] J.C. Germain, J.M. del Valle, J.C. de la Fuente, Natural convection retards supercritical CO2 extraction of essential oils and lipids from vegetable substrates,
Industrial & Engineering Chemistry Research 44 (2005) 28792886.
[284] M. Cvjetko, S. Jokic, Z. Lepojevic, S. Vidovic, B. Maric, I.R. Redovnikovic,
Optimization of the supercritical CO2 extraction of oil from rapeseed using
response surface methodology, Food Technology and Biotechnology 50
(2012) 208215.
[285] H.Y. Li, J. Wu, C.B. Rempel, U. Thiyam, Effect of operating parameters on oil
and phenolic extraction using supercritical CO2 , Journal of the American Oil
Chemists Society 87 (2010) 10811089.

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176


[286] E. Arnaiz, J. Bernal, M.T. Martin, M.J. Nozal, J.L. Bernal, L. Toribio, Supercritical
uid extraction of free amino acids from broccoli leaves, Journal of Chromatography A 1250 (2012) 4953.
[287] S.M. Pourmortazavi, M. Ghadiri, S.S. Hajimirsadeghi, Supercritical uid
extraction of volatile components from Bunium persicum Boiss. (black cumin)
and Mespilus germanica L. (medlar) seeds, Journal of Food Composition and
Analysis 18 (2005) 439446.
[288] Y. Sun, L. Wei, J. Wang, J. Bi, Z. Liu, Y. Wang, Z. Guo, Optimization of
supercritical uid extraction of saikosaponins from Bupleurum falcatum
with orthogonal array design, Journal of Separation Science 33 (2010)
11611166.
[289] Y. Kong, Y.J. Fu, Y.G. Zu, W. Liu, W. Wang, X. Hua, M. Yang, Ethanol modied supercritical uid extraction and antioxidant activity of cajaninstilbene
acid and pinostrobin from pigeonpea [Cajanus cajan (L.) Millsp.] leaves, Food
Chemistry 117 (2009) 152159.
[290] M. Hamburger, S. Adler, D. Baumann, A. Frg, B. Weinreich, Preparative purication of the major anti-inammatory triterpenoid esters from Marigold
(Calendula ofcinalis), Fitoterapia 74 (2003) 328338.
[291] L.M.A.S. Campos, E.M.Z. Michielin, L. Danielski, S.R.S. Ferreira, Experimental
data and modeling the supercritical uid extraction of marigold (Calendula
ofcinalis) oleoresin, Journal of Supercritical Fluids 34 (2005) 163170.
[292] I. Zizovic, M. Stamenic, A. Orlovic, D. Skala, Supercritical carbon dioxide
extraction of essential oils from plants with secretory ducts: mathematical modelling on the micro-scale, Journal of Supercritical Fluids 39 (2007)
338346.
[293] L. Danielski, L.M.A.S. Campos, L.F.V. Bresciani, H. Hense, R.A. Yunes, S.R.S. Ferreira, Marigold (Calendula ofcinalis L.) oleoresin: solubility in SC-CO2 and
composition prole, Chemical Engineering and Processing: Process Intensication 46 (2007) 99106.
[294] M. Hamburger, D. Baumann, S. Adler, Supercritical carbon dioxide extraction
of selected medicinal plants effects of high pressure and added ethanol on
yield of extracted substances, Phytochemical Analysis 15 (2004) 4654.
[295] Y.F. Wang, D. Sun, H. Chen, L.S. Qian, P. Xu, Fatty acid composition and antioxidant activity of tea (Camellia sinensis L.) seed oil extracted by optimized
supercritical carbon dioxide, International Journal of Molecular Sciences 12
(2011) 77087719.
[296] W.-Q. Tang, D.-C. Li, Y.-X. Lv, J.-G. Jiang, Extraction and removal of caffeine
from green tea by ultrasonic-enhanced supercritical uid, Journal of Food
Science 75 (2010) C363C368.
[297] S.M. Ghoreishi, E. Heidari, Extraction of epigallocatechin gallate from green
tea via modied supercritical CO2 : experimental, modeling and optimization,
Journal of Supercritical Fluids 72 (2012) 3645.
[298] C. Da Porto, D. Decorti, F. Tubaro, Fatty acid composition and oxidation stability of hemp (Cannabis sativa L.) seed oil extracted by supercritical carbon
dioxide, Industrial Crops and Products 36 (2012) 401404.
[299] C. Da Porto, D. Voinovich, D. Decorti, A. Natolino, Response surface optimization of hemp seed (Cannabis sativa L.) oil yield and oxidation stability
by supercritical carbon dioxide extraction, Journal of Supercritical Fluids 68
(2012) 4551.
[300] A.F. Gouveia, C. Duarte, M.L.B. da Costa, M.G. Bernardo-Gil, M. MoldoMartins, Oxidative stability of olive oil avoured by Capsicum frutescens
supercritical uid extracts, European Journal of Lipid Science and Technology
108 (2006) 421428.
[301] C. Duarte, M. Moldo-Martins, A.F. Gouveia, S. Beirao da Costa, A.E. Leitao, M.G.
Bernardo-Gil, Supercritical uid extraction of red pepper (Capsicum frutescens
L.), Journal of Supercritical Fluids 30 (2004) 155161.
[302] X.J. Han, L.M. Cheng, R. Zhang, J.C. Bi, Extraction of safower seed oil by
supercritical CO2 , Journal of Food Engineering 92 (2009) 370376.
[303] M. Ahro, M. Hakala, J. Sihvonen, J. Kauppinen, H. Kallio, Low-resolution gasphase FT-IR method for the determination of the limonene/carvone ratio
in supercritical CO2 -extracted caraway fruit oils, Journal of Agricultural and
Food Chemistry 49 (2001) 31403144.
[304] M. Cabizza, G. Cherchi, B. Marongiu, S. Porcedda, Isolation of a volatile concentrate of caraway seed, Journal of Essential Oil Research 13 (2001) 371375.
[305] M. Khajeh, Y. Yamini, F. Sedkon, N. Bahramifar, Comparison of essential
oil composition of Carum copticum obtained by supercritical carbon dioxide extraction and hydrodistillation methods, Food Chemistry 86 (2004)
587591.
[306] Y. Zhang, D. Wei, S. Guo, X. Zhang, M. Wang, F. Chen, Chemical components and antioxidant activity of the volatile oil from Cassia tora L. seed
prepared by supercritical uid extraction, Journal of Food Lipids 14 (2007)
411423.
[307] A. Verma, K. Hartonen, M.L. Riekkola, Optimisation of supercritical uid
extraction of indole alkaloids from Catharanthus roseus using experimental
design methodology-comparison with other extraction techniques, Phytochemical Analysis 19 (2008) 5263.
[308] M.G. Bernardo-Gil, R. Roque, L.B. Roseiro, L.C. Duarte, F. Girio, P. Esteves,
Supercritical extraction of carob kibbles (Ceratonia siliqua L.), Journal of Supercritical Fluids 59 (2011) 3642.
[309] N.P. Povh, M.O.M. Marques, M.A.A. Meireles, Supercritical CO2 extraction
of essential oil and oleoresin from chamomile (Chamomilla recutita [L.]
Rauschert), Journal of Supercritical Fluids 21 (2001) 245256.
[310] C.S. Kaiser, H. Rompp, P.C. Schmidt, Supercritical carbon dioxide extraction
of chamomile owers: extraction efciency, stability, and in-line inclusion
of chamomile-carbon dioxide extract in beta-cyclodextrin, Phytochemical
Analysis 15 (2004) 249256.

169

[311] C.E. Vargas, M.F. Mendes, D.A. Azevedo, F.L.P. Pessoa, A.C. Uller, Extraction
of the essential oil of abajeru (Chrysobalanus icaco) using supercritical CO2 ,
Journal of Supercritical Fluids 54 (2010) 171177.
[312] B. Marongiu, A. Piras, S. Porcedda, E. Tuveri, E. Sanjust, M. Meli, F. Sollai,
P. Zucca, A. Rescigno, Supercritical CO2 extract of Cinnamomum zeylanicum:
chemical characterization and antityrosinase activity, Journal of Agricultural
and Food Chemistry 55 (2007) 1002210027.
[313] K.L. Nyam, C.P. Tan, O.M. Lai, K. Long, Y.B.C. Man, Optimization of supercritical
CO2 extraction of phytosterol-enriched oil from Kalahari melon seeds, Food
and Bioprocess Technology 4 (2011) 14321441.
[314] Y.H. Lee, A.L. Charles, H.F. Kung, C.T. Ho, T.C. Huang, Extraction of nobiletin
and tangeretin from Citrus depressa Hayata by supercritical carbon dioxide with ethanol as modier, Industrial Crops and Products 31 (2010)
5964.
[315] H. Ueno, M. Tanaka, S. Machmudah, M. Sasaki, M. Goto, Supercritical carbon
dioxide extraction of valuable compounds from Citrus junos seed, Food and
Bioprocess Technology 1 (2008) 357363.
[316] A.C. Atti-Santos, M. Rossato, L.A. Serani, E. Cassel, P. Moyna, Extraction
of essential oils from lime (Citrus latifolia Tanaka) by hydrodistillation and
supercritical carbon dioxide, Brazilian Archives of Biology and Technology 48
(2005) 155160.
[317] W.Y. Teng, C.C. Chen, R.S. Chung, HPLC comparison of supercritical uid
extraction and solvent extraction of coumarins from the peel of Citrus maxima
fruit, Phytochemical Analysis 16 (2005) 459462.
[318] A.N. Giannuzzo, H.J. Boggetti, M.A. Nazareno, H.T. Mishima, Supercritical uid
extraction of naringin from the peel of Citrus paradisi, Phytochemical Analysis
14 (2003) 221223.
[319] J. Yu, D.V. Dandekar, R.T. Toledo, R.K. Singh, B.S. Patil, Supercritical uid extraction of limonoids and naringin from grapefruit (Citrus paradisi Macf.) seeds,
Food Chemistry 105 (2007) 10261031.
[320] S. Lim, S.K. Jung, M.K. Jwa, Extraction of carotenoids from Citrus unshiu press
cake by supercritical carbon dioxide, Food Science and Biotechnology 12
(2003) 513520.
[321] C. Asis, R. Baroy, S. Bendijo, S.L. Hansen, V. Nacion, J. Tolimao, Supercritical
uid extraction to determine the oil content in copra and extracted meal,
Journal of the American Oil Chemists Society 83 (2006) 1114.
[322] A.J. Hu, S.N. Zhao, H.H. Liang, T.Q. Qiu, G.H. Chen, Ultrasound assisted supercritical uid extraction of oil and coixenolide from Adlay seed, Ultrasonics
Sonochemistry 14 (2007) 219224.
[323] A.J. Hu, Z.H. Zhang, J. Zheng, Y.M. Wang, Q.X. Chen, R. Liu, X. Liu, S.J.
Zhang, Optimizations and comparison of two supercritical extractions of
adlay oil, Innovative Food Science & Emerging Technologies 13 (2012)
128133.
[324] E. Ellington, J. Bastida, F. Viladomat, C. Codina, Supercritical carbon dioxide extraction of colchicine and related alkaloids from seeds of Colchicum
autumnale L, Phytochemical Analysis 14 (2003) 164169.
[325] B. Liu, W.J. Li, Y.L. Chang, W.H. Dong, L. Ni, Extraction of berberine from rhizome of Coptis chinensis Franch using supercritical uid extraction, Journal of
Pharmaceutical and Biomedical Analysis 41 (2006) 10561060.
[326] S. Quispe-Condori, M.A. Foglio, P.T.V. Rosa, M.A.A. Meireles, Obtaining betacaryophyllene from Cordia verbenacea de Candolle by supercritical uid
extraction, Journal of Supercritical Fluids 46 (2008) 2732.
[327] E.B. Parisotto, E.M.Z. Michielin, F. Biscaro, S.R.S. Ferreira, D. Wilhelm, R.C.
Pedrosa, The antitumor activity of extracts from Cordia verbenacea DC
obtained by supercritical uid extraction, Journal of Supercritical Fluids 61
(2012) 101107.
[328] B. Yepez, M. Espinosa, S. Lopez, G. Bolanos, Producing antioxidant fractions
from herbaceous matrices by supercritical uid extraction, Fluid Phase Equilibria 194 (2002) 879884.
[329] C. Grosso, V. Ferraro, A.C. Figueiredo, J.G. Barroso, J.A. Coelho, A.M. Palavra,
Supercritical carbon dioxide extraction of volatile oil from Italian coriander
seeds, Food Chemistry 111 (2008) 197203.
[330] V. Illes, H.G. Daood, S. Perneczki, L. Szokonya, M. Then, Extraction of coriander
seed oil by CO2 and propane at super- and subcritical conditions, Journal of
Supercritical Fluids 17 (2000) 177186.
[331] M.G. Bernardo-Gil, M. Casquilho, Modeling the supercritical uid extraction
of hazelnut and walnut oils, AIChE Journal 53 (2007) 29802985.
[332] M.G. Bernardo-Gil, J. Grenha, J. Santos, P. Cardoso, Supercritical uid extraction and characterisation of oil from hazelnut, European Journal of Lipid
Science and Technology 104 (2002) 402409.
[333] S.G. Ozkal, U. Salgin, M.E. Yener, Supercritical carbon dioxide extraction of
hazelnut oil, Journal of Food Engineering 69 (2005) 217223.
[334] S.G. Ozkal, M.E. Yener, U. Salgin, U. Mehmetoglu, Response surfaces of hazelnut oil yield in supercritical carbon dioxide, European Food Research and
Technology 220 (2005) 7478.
[335] X.L. Cao, Y. Tian, T.Y. Zhang, Y. Ito, Supercritical uid extraction of catechins
from Cratoxylum prunifolium Dyer and subsequent purication by high-speed
counter-current chromatography, Journal of Chromatography A 898 (2000)
7581.
[336] E. Sousa, J. Martnez, O. Chiavone, P.T.V. Rosa, T. Domingos, M.A.A. Meireles,
Extraction of volatile oil from Croton zehntneri Pax et Hoff with pressurized
CO2 : solubility, composition and kinetics, Journal of Food Engineering 69
(2005) 325333.
[337] M. Ismail, A. Mariod, G. Bagalkotkar, H.S. Ling, Fatty acid composition and
antioxidant activity of oils from two cultivars of Cantaloupe extracted by
supercritical uid extraction, Grasas Y Aceites 61 (2010) 3744.

170

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

[338] M.G. Bernardo-Gil, M. Casquilho, M.M. Esquivel, M.A. Ribeiro, Supercritical


uid extraction of g leaf gourd seeds oil: fatty acids composition and extraction kinetics, Journal of Supercritical Fluids 49 (2009) 3236.
[339] D.L. Heikes, B. Scott, N.A. Gorzovalitis, Quantitation of volatile oils in ground
cumin by supercritical uid extraction and gas chromatography with ame
ionization detection, Journal of Aoac International 84 (2001) 11301134.
[340] B. Daneshvand, K.M. Ara, F. Raoe, Comparison of supercritical uid extraction and ultrasound-assisted extraction of fatty acids from quince (Cydonia
oblonga Miller) seed using response surface methodology and central composite design, Journal of Chromatography A 1252 (2012) 17.
[341] B.T. Schaneberg, I.A. Khan, Comparison of extraction methods for marker compounds in the essential oil of lemon grass by GC, Journal of Agricultural and
Food Chemistry 50 (2002) 13451349.
[342] L.H.C. Carlson, R.A.F. Machado, C.B. Spricigo, L.K. Pereira, A. Bolzan, Extraction
of lemongrass essential oil with dense carbon dioxide, Journal of Supercritical
Fluids 21 (2001) 3339.
[343] Y.S. Sun, Z.B. Liu, J.H. Wang, W. Tian, H.Y. Zhou, L.X. Zhu, C.L. Zhang,
Supercritical uid extraction of paeonol from Cynanchum paniculatum
(Bge.) Kitag. and subsequent isolation by high-speed counter-current
chromatography coupled with high-performance liquid chromatographyphotodiode array detector, Separation and Purication Technology 64 (2008)
221226.
[344] M. Takahashi, H. Watanabe, J. Kikkawa, M. Ota, M. Watanabe, Y. Sato,
H. Inomata, N. Sato, Carotenoids extraction from Japanese persimmon
(Hachiyakaki) peels by supercritical CO2 with ethanol, Analytical Sciences
22 (2006) 14411447.
[345] M. Khajeh, Optimisation of supercritical uid extraction of essential oil components of Diplotaenia cachrydifolia: BoxBehnken design, Natural Product
Research 26 (2012) 19261930.
[346] M. Khajeh, M.G. Moghaddam, M. Shakeni, Application of articial neural
network in predicting the extraction yield of essential oils of Diplotaenia
cachrydifolia by supercritical uid extraction, Journal of Supercritical Fluids
69 (2012) 9196.
[347] T. Grevenstuk, S. Goncalves, J.M.F. Nogueira, M.G. Bernardo-Gil, A. Romano,
Recovery of high purity plumbagin from Drosera intermedia, Industrial Crops
and Products 35 (2012) 257260.
[348] O.J. Catchpole, N.B. Perry, B.M.T. da Silva, J.B. Grey, B.M. Smalleld, Supercritical extraction of herbs I: saw Palmetto, St Johns Wort, Kava Root, and
Echinacea, Journal of Supercritical Fluids 22 (2002) 129138.
[349] V. Sewram, M.W. Raynor, D.A. Mulholland, D.M. Raidoo, The uterotonic
activity of compounds isolated from the supercritical uid extract of Ekebergia capensis, Journal of Pharmaceutical and Biomedical Analysis 24 (2000)
133145.
[350] M.N. Hassan, N.N.A. Rahman, M.H. Ibrahim, A.K.M. Omar, Simple fractionation through the supercritical carbon dioxide extraction of palm kernel oil,
Separation and Purication Technology 19 (2000) 113120.
[351] N.N. Ab Rahman, S.S. Al-Rawi, A.H. Ibrahim, M.M. Ben Nama, M.O. Ab Kadir,
Supercritical carbon dioxide extraction of the residual oil from palm kernel
cake, Journal of Food Engineering 108 (2012) 166170.
[352] H.L.N. Lau, Y.M. Choo, A.N. Ma, C.H. Chuah, Characterization and supercritical
carbon dioxide extraction of palm oil (Elaeis guineensis), Journal of Food Lipids
13 (2006) 210221.
[353] B. Marongiu, A. Piras, S. Porcedda, Comparative analysis of the oil and supercritical CO2 extract of Elettaria cardamomum (L.) maton, Journal of Agricultural
and Food Chemistry 52 (2004) 62786282.
[354] S. Hamdan, H.G. Daood, M. Toth-Markus, V. Illes, Extraction of cardamom oil
by supercritical carbon dioxide and sub-critical propane, Journal of Supercritical Fluids 44 (2008) 2530.
[355] J.Y. Kim, K.P. Yoo, Effects of basic modiers on SFE efciencies of ephedrine
derivatives from plant matrix, Korean Journal of Chemical Engineering 17
(2000) 672677.
[356] E.M.Z. Michielin, L.F.V. Bresciani, L. Danielski, R.A. Yunes, S.R.S. Ferreira, Composition prole of horsetail (Equisetum giganteum L.) oleoresin: comparing
SFE and organic solvents extraction, Journal of Supercritical Fluids 33 (2005)
131138.
[357] A. Brachet, P. Christen, J.Y. Gauvrit, R. Longeray, P. Lanteri, J.L. Veuthey, Experimental design in supercritical uid extraction of cocaine from coca leaves,
Journal of Biochemical and Biophysical Methods 43 (2000) 353366.
[358] N.L. Rozzi, W. Phippen, J.E. Simon, R.K. Singh, Supercritical uid extraction
of essential oil components from lemon-scented botanicals, LebensmittelWissenschaft Und-Technologie-Food Science and Technology 35 (2002)
319324.
[359] V.M. Rodrigues, E. Sousa, A.R. Monteiro, O. Chiavone-Filho, M.O.M. Marques,
M.A.A. Meireles, Determination of the solubility of extracts from vegetable
raw material in pressurized CO2 : a pseudo-ternary mixture formed by cellulosic structure plus solute plus solvent, Journal of Supercritical Fluids 22
(2002) 2136.
[360] H. Li, J.Y. Hu, H. Ouyang, Y.N. Li, H. Shi, C.J. Ma, Y.K. Zhang, Extraction of Aucubin
from Seeds of Eucommia ulmoides Oliv. Using supercritical carbon dioxide,
Journal of Aoac International 92 (2009) 103110.
[361] T. Hatami, M.A.A. Meireles, G. Zahedi, Mathematical modeling and genetic
algorithm optimization of clove oil extraction with supercritical carbon dioxide, Journal of Supercritical Fluids 51 (2010) 331338.
[362] J. Martnez, P.T.V. Rosa, M.A.A. Meireles, Extraction of clove and vetiver oils
with supercritical carbon dioxide: modeling and simulation, Open Chemical
Engineering Journal (2007) 17.

[363] Y.L. Geng, J.H. Liu, R.M. Lv, J.P. Yuan, Y.L. Lin, X. Wang, An efcient method for
extraction, separation and purication of eugenol from Eugenia caryophyllata
by supercritical uid extraction and high-speed counter-current chromatography, Separation and Purication Technology 57 (2007) 237241.
[364] W. Guan, S. Li, R. Yan, S. Tang, C. Quan, Comparison of essential oils of clove
buds extracted with supercritical carbon dioxide and other three traditional
extraction methods, Food Chemistry 101 (2007) 15581564.
[365] F.S. Malaman, L.A.B. Moraes, C. West, N.J. Ferreira, A.L. Oliveira, Supercritical uid extracts from the Brazilian cherry (Eugenia uniora L.): relationship
between the extracted compounds and the characteristic avour intensity of
the fruit, Food Chemistry 124 (2011) 8592.
[366] A. Ozcan, A.S. Ozcan, Supercritical uid extraction of Euphorbia rigida, HrcJournal of High Resolution Chromatography 23 (2000) 397400.
[367] B. Liu, F. Guo, Y. Chang, H. Jiang, Q. Wang, Optimization of extraction
of evodiamine and rutaecarpine from fruit of Evodia rutaecarpa using
modied supercritical CO2 , Journal of Chromatography A 1217 (2010)
78337839.
[368] M. Khajeh, Y. Yamini, N. Bahramifar, F. Sedkon, M.R. Pirmoradei, Comparison
of essential oils compositions of Ferula assa-foetida obtained by supercritical
carbon dioxide extraction and hydrodistillation methods, Food Chemistry 91
(2005) 639644.
[369] G. Sodeian, K. Ansari, Optimization of Ferulago Angulata oil extraction with
supercritical carbon dioxide, Journal of Supercritical Fluids 57 (2011) 3843.
[370] Y. Yamini, F. Sedkon, S.M. Pourmortazavi, Comparison of essential oil composition of Iranian fennel (Foeniculum vulgare) obtained by supercritical carbon
dioxide extraction and hydrodistillation methods, Flavour and Fragrance
Journal 17 (2002) 345348.
[371] L.S. Moura, R.N. Carvalho, M.B. Stefanini, L.C. Ming, M.A.A. Meireles, Supercritical uid extraction from fennel (Foeniculum vulgare): global yield,
composition and kinetic data, Journal of Supercritical Fluids 35 (2005)
212219.
[372] J.A.P. Coelho, A.P. Pereira, R.L. Mendes, A.M.F. Palavra, Supercritical carbon
dioxide extraction of Foeniculum vulgare volatile oil, Flavour and Fragrance
Journal 18 (2003) 316319.
[373] B. Damjanovic, Z. Lepojevic, V. Zivkovic, A. Tolic, Extraction of fennel
(Foeniculum vulgare Mill.) seeds with supercritical CO2 : comparison with
hydrodistillation, Food Chemistry 92 (2005) 143149.
[374] A.S. Zarena, B. Manohar, K.U. Sankar, Optimization of supercritical carbon
dioxide extraction of Xanthones from Mangosteen Pericarp by response surface methodology, Food and Bioprocess Technology 5 (2012) 11811188.
[375] A.S. Zarena, N.M. Sachindra, K.U. Sankar, Optimisation of ethanol modied
supercritical carbon dioxide on the extract yield and antioxidant activity from
Garcinia mangostana L, Food Chemistry 130 (2012) 203208.
[376] C. Yang, Y.R. Xu, W.X. Yao, Extraction of pharmaceutical components from
Ginkgo biloba leaves using supercritical carbon dioxide, Journal of Agricultural
and Food Chemistry 50 (2002) 846849.
[377] K.-L. Chiu, Y.-C. Cheng, J.-H. Chen, C.J. Chang, P.-W. Yang, Supercritical uids
extraction of Ginkgo ginkgolides and avonoids, Journal of Supercritical Fluids
24 (2002) 7787.
[378] Y.H. Choi, J. Kim, K.P. Yoo, Supercritical-uid extraction of bilobalide and
ginkgolides from Ginkgo biloba leaves by use of a mixture of carbon dioxide,
methanol, and water, Chromatographia 56 (2002) 753757.
[379] Y.J. Fu, W. Wang, Y.G. Zu, Q.Y. Li, X.N. Liu, Study on volatile components
of seed oil from Glycyrrhiza uralensis Fisch by supercritical carbon dioxide
extraction-gas chromatographymass spectrometry, Chinese Journal of Analytical Chemistry 33 (2005) 498500.
[380] P. Bhattacharjee, R.S. Singhal, S.R. Tiwari, Supercritical carbon dioxide extraction of cottonseed oil, Journal of Food Engineering 79 (2007) 892898.
[381] B. Marongiu, A. Piras, S. Porcedda, E. Tuveri, Isolation of Guaiacum bulnesia
volatile oil by supercritical carbon dioxide extraction, Journal of Essential Oil
Bearing Plants 10 (2007) 221228.
[382] J. Ivanovic, M. Ristic, D. Skala, Supercritical CO2 extraction of Helichrysum
italicum: inuence of CO2 density and moisture content of plant material,
Journal of Supercritical Fluids 57 (2011) 129136.
[383] Y.W. Hsu, C.F. Tsai, W.K. Chen, Y.C. Ho, F.J. Lu, Determination of lutein and
zeaxanthin and antioxidant capacity of supercritical carbon dioxide extract
from daylily (Hemerocallis disticha), Food Chemistry 129 (2011) 18131818.
[384] K.W. Chan, M. Ismail, Supercritical carbon dioxide uid extraction of Hibiscus
cannabinus L. seed oil: a potential solvent-free and high antioxidative edible
oil, Food Chemistry 114 (2009) 970975.
[385] A.A. Mariod, B. Matthus, M. Ismail, Comparison of supercritical uid and
hexane extraction methods in extracting Kenaf (Hibiscus cannabinus) seed oil
lipids, Journal of the American Oil Chemists Society 88 (2011) 931935.
[386] J.Z. Yin, X.W. Sun, X.W. Ding, H.H. Liang, Modeling of supercritical uid extraction from Hippophae rhamnoides L. seeds, Separation Science and Technology
38 (2003) 40414055.
[387] J.Z. Yin, A.Q. Wang, W. Wei, Y. Liu, W.H. Shi, Analysis of the operation conditions for supercritical uid extraction of seed oil, Separation and Purication
Technology 43 (2005) 163167.
[388] L.D. Kagliwal, S.C. Patil, A.S. Pol, R.S. Singhal, V.B. Patravale, Separation of
bioactives from seabuckthorn seeds by supercritical carbon dioxide extraction methodology through solubility parameter approach, Separation and
Purication Technology 80 (2011) 533540.
[389] E. Bravi, G. Perretti, L. Montanari, F. Favati, P. Fantozzi, Supercritical uid
extraction for quality control in beer industry, Journal of Supercritical Fluids
42 (2007) 342346.

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176


[390] A. Fratianni, M.F. Caboni, M. Irano, G. Panli, A critical comparison between
traditional methods and supercritical carbon dioxide extraction for the
determination of tocochromanols in cereals, European Food Research and
Technology 215 (2002) 353358.
[391] M.P. Fernandez, J.F. Rodriguez, M.T. Garca, A. de Lucas, I. Gracia, Application of
supercritical uid extraction to brewers spent grain management, Industrial
& Engineering Chemistry Research 47 (2008) 16141619.
[392] H.M. Rui, L.Y. Zhang, Z.W. Li, Y.L. Pan, Extraction and characteristics of seed
kernel oil from white pitaya, Journal of Food Engineering 93 (2009) 482486.
[393] F.M.C. Barros, F.C. Silva, J.M. Nunes, R.M.F. Vargas, E. Cassel, G.L. von Poser,
Supercritical extraction of phloroglucinol and benzophenone derivatives
from Hypericum carinatum: quantication and mathematical modeling, Journal of Separation Science 34 (2011) 31073113.
[394] M. Mannila, Q.Y. Lang, C.M. Wai, Y.Y. Cui, C.Y.W. Ang, Supercritical uid extraction of bioactive components from St. Johns Wort (Hypericum perforatum L.)
and Ginkgo biloba, in: A.S. Gopalan, C.M. Wai, H.K. Jacobs (Eds.), Supercritical
Carbon Dioxide: Separations and Processes, 2003, pp. 130144.
[395] A. Smelcerovic, Z. Lepojevic, S. Djordjevic, Sub-and supercritical CO2 extraction of Hypericum perforatum L, Chemical Engineering & Technology
27 (2004) 13271329.
[396] E. Langa, J. Cacho, A.M.F. Palavra, J. Burillo, A.M. Mainar, J.S. Urieta, The evolution of hyssop oil composition in the supercritical extraction curve: modelling
of the oil extraction process, Journal of Supercritical Fluids 49 (2009)
3744.
[397] H. Kazazi, K. Rezaei, S.J. Ghotb-Sharif, Z. Emam-Djomeh, Y. Yamini, Supercriticial uid extraction of avors and fragrances from Hyssopus ofcinalis L.
cultivated in Iran, Food Chemistry 105 (2007) 805811.
[398] E. Cassel, R.M.F. Vargas, G.W. Brun, D.E. Almeida, L. Cogoi, G. Ferraro, R. Filip,
Supercritical uid extraction of alkaloids from Ilex paraguariensis St. Hil, Journal of Food Engineering 100 (2010) 656661.
[399] B. Marongiu, A. Piras, F. Pani, S. Porcedda, M. Ballero, Extraction, separation
and isolation of essential oils from natural matrices by supercritical CO2 ,
Flavour and Fragrance Journal 18 (2003) 505509.
[400] R. Oliveira, M.F. Rodrigues, M.G. Bernardo-Gil, Characterization and supercritical carbon dioxide extraction of walnut oil, Journal of the American Oil
Chemists Society 79 (2002) 225230.
[401] T.D. Crowe, T.W. Crowe, L.A. Johnson, P.J. White, Impact of extraction method
on yield of lipid oxidation products from oxidized and unoxidized walnuts,
Journal of the American Oil Chemists Society 79 (2002) 453456.
[402] B.M. Damjanovic, D. Skala, D. Petrovic-Djakov, J. Baras, A comparison between
the oil, hexane extract and supercritical carbon dioxide extract of Juniperus
communis L, Journal of Essential Oil Research 15 (2003) 9092.
[403] P. Chatzopoulou, A. de Haan, S.T. Katsiotis, Investigation on the supercritical
CO2 extraction of the volatile constituents from Juniperus communis obtained
under different treatments of the berries (cones), Planta Medica 68 (2002)
827831.
[404] B. Barjaktarovic, M. Sovilj, Z. Knez, Chemical composition of Juniperus communis L. fruits supercritical CO2 extracts: dependence on pressure and extraction
time, Journal of Agricultural and Food Chemistry 53 (2005) 26302636.
[405] B. Damjanovic, D. Skala, J. Baras, D. Petrovic-Djakov, Isolation of essential oil
and supercritical carbon dioxide extract of Juniperus communis L. fruits from
Montenegro, Flavour and Fragrance Journal 21 (2006) 875880.
[406] S.M. Pourmortazavi, P. Baghaee, M.A. Mirhosseini, Extraction of volatile compounds from Juniperus communis L. leaves with supercritical uid carbon
dioxide: comparison with hydrodistillation, Flavour and Fragrance Journal
19 (2004) 417420.
[407] B. Marongiu, S. Porcedda, A. Caredda, B. De Gioannis, L. Vargiu, P. La Colla,
Extraction of Juniperus oxycedrus ssp oxycedrus essential oil by supercritical
carbon dioxide: inuence of some process parameters and biological activity,
Flavour and Fragrance Journal 18 (2003) 390397.
[408] F.J. Eller, J.W. King, Supercritical carbon dioxide extraction of cedarwood oil:
a study of extraction parameters and oil characteristics, Phytochemical Analysis 11 (2000) 226231.
[409] F.J. Eller, S.L. Taylor, Pressurized uids for extraction of cedarwood oil from
Juniperus virginianna, Journal of Agricultural and Food Chemistry 52 (2004)
23352338.
[410] M. Akgun, N.A. Akgun, S. Dincer, Extraction and modeling of lavender ower
essential oil using supercritical carbon dioxide, Industrial & Engineering
Chemistry Research 39 (2000) 473477.
[411] L.T. Danh, D.A.T. Ngo, T.N.H. Le, J. Zhao, R. Mammucari, N. Foster, Antioxidant activity, yield and chemical composition of lavender essential oil
extracted by supercritical CO2 , Journal of Supercritical Fluids 70 (2012)
2734.
[412] S.M. Ghoreishi, H. Kamali, H.S. Ghaziaskar, A.A. Dadkhah, Optimization of
supercritical extraction of linalyl acetate from lavender via BoxBehnken
design, Chemical Engineering & Technology 35 (2012) 16411648.
[413] H. Kamali, M.R. Jalilvand, N. Aminimoghadamfarouj, Pressurized uid extraction of essential oil from Lavandula hybrida using a modied supercritical
uid extractor and a central composite design for optimization, Journal of
Separation Science 35 (2012) 14791485.
[414] N.A. Akgun, M. Akgun, S. Dincer, A. Akgerman, Supercritical uid extraction
of Lavandula stoechas L. ssp cariensis (Boiss.) Rozeira, Journal of Essential Oil
Research 13 (2001) 143148.
[415] W. Xu, K.D. Chu, H. Li, L.D. Chen, Y.Q. Zhang, X.C. Tang, Extraction of Lepidium
apetalum seed oil using supercritical carbon dioxide and anti-oxidant activity
of the extracted oil, Molecules 16 (2011) 1002910045.

171

[416] E. Dauksas, P.R. Venskutonis, B. Sivik, T. Nillson, Effect of fast CO2 pressure
changes on the yield of lovage (Levisticum ofcinale Koch.) and celery (Apium
graveolens L.) extracts, Journal of Supercritical Fluids 22 (2002) 201210.
[417] Y.Y. Sun, S.F. Li, Measurement and correlation of the solubility of Ligusticum
Chuanxiong oil in supercritical CO2 , Chinese Journal of Chemical Engineering
13 (2005) 796799.
[418] Q.H. Chen, P. Li, B. Li, H.D. Yang, X.L. Li, F.C. Chen, A GCMS-SIM simultaneous determination of ligustilide and butylidenephthalide from Ligusticum
chuanxiong using SFE, Chromatographia 72 (2010) 963967.
[419] E.L. Galvao, J. Martnez, H.N. Maia De Oliveira, E.M. Bittencourt Dutra De
Sousa, Supercritical extraction of linseed oil: economical viability and modeling extraction curves, Chemical Engineering Communications 200 (2013)
205221.
[420] V.J. Barthet, J.K. Daun, An evaluation of supercritical uid extraction as an
analytical tool to determine fat in canola, ax, solin, and mustard, Journal of
the American Oil Chemists Society 79 (2002) 245251.
[421] E.E. Stashenko, B.E. Jaramillo, J.R. Mart nez, Comparison of different extraction methods for the analysis of volatile secondary metabolites of Lippia alba
(Mill.) N.E. Brown, grown in Colombia, and evaluation of its in vitro antioxidant activity, Journal of Chromatography A 1025 (2004) 93103.
[422] P.F. de Oliveira, R.A.F. Machado, A. Bolzan, D. Barth, Supercritical uid extraction of hernandulcin from Lippia dulcis Trev, Journal of Supercritical Fluids 63
(2012) 161168.
[423] E.M.B.D. Sousa, O. Chiavone, M.T. Moreno, D.N. Silva, M.O.M. Marques, M.A.A.
Meireles, Experimental results for the extraction of essential oil from Lippia
sidoides Cham. using pressurized carbon dioxide, Brazilian Journal of Chemical
Engineering 19 (2002) 229241.
[424] C.F. Silva, M.F. Mendes, F.L.P. Pessoa, E.M. Queiroz, Supercritical carbon dioxide extraction of macadamia (Macadamia integrifolia) nut oil: experiments
and modeling, Brazilian Journal of Chemical Engineering 25 (2008) 175181.
[425] M.T. Fernandez-Ponce, L. Casas, C. Mantell, M. Rodriguez, E.M. de la Ossa,
Extraction of antioxidant compounds from different varieties of Mangifera
indica leaves using green technologies, Journal of Supercritical Fluids 72
(2012) 168175.
[426] H. Cao, J.B. Xiao, M. Xu, Comparison of volatile components of Marchantia
convoluta obtained by supercritical carbon dioxide extraction and petrol ether
extraction, Journal of Food Composition and Analysis 20 (2007) 4551.
[427] J.B. Xiao, J.W. Chen, M. Xu, Supercritical uid CO2 extraction of essential oil
from Marchantia convoluta: global yields and extract chemical composition
(2007).

[428] P. Kotnik, M. Skerget,


Z. Knez, Supercritical uid extraction of chamomile
ower heads: comparison with conventional extraction, kinetics and scaleup, Journal of Supercritical Fluids 43 (2007) 192198.
[429] Z.P. Zekovic, Chamomile ligulate owers in supercritical CO2 -extraction, Journal of Essential Oil Research 12 (2000) 8593.
[430] E.C. de Vasconcelos, J.H.Y. Vilegas, F.M. Lancas, Comparison of extraction and
clean-up methods for the analysis of friedelan-3-ol and friedelin from leaves
of Maytenus aquifolium Martius (Celastraceae), Phytochemical Analysis 11
(2000) 247250.
[431] A.J. Mossi, R.L. Cansian, A.Z. Carvalho, C. Dariva, J. Vladimir Oliveira, M.
Mazutti, I.N. Filho, S. Echeverrigaray, Extraction and characterization of
volatile compounds in Maytenus ilicifolia, using high-pressure CO2 , Fitoterapia
(2004) 168178.
[432] S.M. Jajaei, W.R.W. Daud, M. Markom, Z. Zakaria, M. Lo Presti, R. Costa, L.
Mondello, L. Santi, Extraction of Melaleuca cajuputi using supercritical uid
extraction and solvent extraction, Journal of Essential Oil Research 22 (2010)
205210.
[433] G. Karasova, J. Lehotay, E. Klodzinska, R. Gadzala-Kopciuch, B. Buszewski,
Comparison of several extraction methods for the isolation of benzoic acid
derivatives from Melissa ofcinalis, Journal of Liquid Chromatography &
Related Technologies 29 (2006) 16331644.
[434] M.A. Ribeiro, M.G. Bernardo-Gil, M.M. Esquivel, Melissa ofcinalis L.: study of
antioxidant activity in supercritical residues, Journal of Supercritical Fluids
21 (2001) 5160.
[435] E.M.C. Reis-Vasco, J.A.P. Coelho, A.M.F. Palavra, C. Marrone, E. Reverchon,
Mathematical modelling and simulation of pennyroyal essential oil supercritical extraction, Chemical Engineering Science 55 (2000) 29172922.
[436] N. Aghel, Y. Yamini, A. Hadjiakhoondi, S.M. Pourmortazavi, Supercritical carbon dioxide extraction of Mentha pulegium L. essential oil, Talanta 62 (2004)
407411.
[437] B. Marongiu, S. Porcedda, G. Della Porta, E. Reverchon, Extraction and isolation of Salvia desoleana and Mentha spicata subsp insularis essential oils by
supercritical CO2 , Flavour and Fragrance Journal 16 (2001) 384388.
[438] K.H. Kim, J. Hong, A mass transfer model for super- and near-critical CO2
extraction of spearmint leaf oil, Separation Science and Technology 37 (2002)
22712288.
[439] P.P. Almeida, N. Mezzomo, S.R.S. Ferreira, Extraction of Mentha spicata L.
volatile compounds: evaluation of process parameters and extract composition, Food and Bioprocess Technology 5 (2012) 548559.
[440] K. Ansari, I. Goodarznia, Optimization of supercritical carbon dioxide extraction of essential oil from spearmint (Mentha spicata L.) leaves by using Taguchi
methodology, Journal of Supercritical Fluids 67 (2012) 123130.
[441] M. Bimakr, R.A. Rahman, A. Ganjloo, F.S. Taip, L.M. Salleh, M.Z.I. Sarker, Optimization of supercritical carbon dioxide extraction of bioactive avonoid
compounds from spearmint (Mentha spicata L.) leaves by using response
surface methodology, Food and Bioprocess Technology 5 (2012) 912920.

172

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

[442] S. Lina, R. Fei, Z. Xudong, D. Yangong, H. Fa, Supercritical Carbon Dioxide Extraction of Microula sikkimensis Seed Oil, Journal of the American Oil
Chemists Society 87 (2010) 12211226.
[443] R.M.S. Celeghini, J.H.Y. Vilegas, F.M. Lancas, Extraction, quantitative, HPLC
analysis of coumarin in hydroalcoholic extracts of Mikania glomerata Spreng.
(guaco) leaves, Journal of the Brazilian Chemical Society 12 (2001) 706709.
[444] C.H. Chen, T.P. Lin, Y.L. Chung, C.K. Lee, D.B. Yeh, S.Y. Chen, Determination
of antioxidative properties of Morinda citrifolia using near supercritical uid
extraction, Journal of Food and Drug Analysis 17 (2009) 333341.
[445] H.N. Nguyen, P.A.D. Gaspillo, J.B. Maridable, R.M. Malaluan, H. Hinode, C.
Salim, H.K.P. Huynh, Extraction of oil from Moringa oleifera kernels using
supercritical carbon dioxide with ethanol for pretreatment: optimization
of the extraction process, Chemical Engineering and Processing 50 (2011)
12071213.
[446] S. Machmudah, A. Sulaswatty, M. Sasaki, M. Goto, T. Hirose, Supercritical CO2
extraction of nutmeg oil: experiments and modeling, Journal of Supercritical
Fluids 39 (2006) 3039.
[447] T.Q. Chen, J.G. Wu, Y.B. Wu, H.Y. Wang, F.H. Mao, J.Z. Wu, Supercritical uid
CO2 extraction, simultaneous determination of total sterols in the spore lipids
of Ganoderma lucidum by GCMS/SIM methods, Chemistry of Natural Compounds 48 (2012) 657658.
[448] E. Ghasemi, F. Raoe, N.M. Naja, Application of response surface methodology and central composite design for the optimisation of supercritical uid
extraction of essential oils from Myrtus communis L. leaves, Food Chemistry
126 (2011) 14491453.
[449] J.P. Louey, H. Shaeffer, N. Petersen, D. Salotti, Oil of catnip by supercritical
uid extraction, in: Abstracts of Papers of the American Chemical Society,
221, 2001, p. U215.
[450] M. Khajeh, Y. Yamini, S. Shariati, Comparison of essential oils compositions of
Nepeta persica obtained by supercritical carbon dioxide extraction and steam
distillation methods, Food and Bioproducts Processing 88 (2010) 227232.
[451] A. Ruiz-Rodriguez, M.R. Bronze, M.N. da Ponte, Supercritical uid extraction
of tobacco leaves: a preliminary study on the extraction of solanesol, Journal
of Supercritical Fluids 45 (2008) 171176.
[452] N. Radulovic, G. Stojanovic, R. Palic, S. Alagic, Chemical composition of the
ether and ethyl acetate extracts of Serbian selected tobacco types: Yaka, Prilep
and Otlja, Journal of Essential Oil Research 18 (2006) 562565.
[453] E. Dauksas, P.R. Venskutonis, B. Sivik, Comparison of oil from Nigella damascena seed recovered by pressing, conventional solvent extraction and carbon
dioxide extraction, Journal of Food Science 67 (2002) 10211024.
[454] S. Machmudah, Y. Shiramizu, M. Goto, M. Sasaki, T. Hirose, Extraction of Nigella
sativa L. using supercritical CO2 : a study of antioxidant activity of the extract,
Separation Science and Technology 40 (2005) 12671275.
[455] M.V. Rao, A.H. Al-Marzouqi, F.S. Kaneez, S.S. Ashraf, A. Adem, Comparative
evaluation of SFE and solvent extraction methods on the yield and composition of Black Seeds (Nigella sativa), Journal of Liquid Chromatography &
Related Technologies 30 (2007) 25452555.
[456] A. de Lucas, J. Rincon, I. Gracia, Inuence of operation variables on quality
parameters of olive husk oil extracted with CO2 : three-step sequential extraction, Journal of the American Oil Chemists Society 80 (2003)
181188.
[457] A. de Lucas, J. Rincon, I. Gracia, Inuence of operating variables on yield and
quality parameters of olive husk oil extracted with supercritical carbon dioxide, Journal of the American Oil Chemists Society 79 (2002) 237243.
[458] S. Sahin, M. Bilgin, M.U. Dramur, Investigation of oleuropein content in olive
leaf extract obtained by supercritical uid extraction and soxhlet methods,
Separation Science and Technology 46 (2011) 18291837.
[459] C.J. Ma, G. Li, J. Zhang, Q.S. Zheng, X. Fan, Z.H. Wang, An efcient combination
of supercritical uid extraction and high-speed counter-current chromatography to extract and purify homoisoavonoids from Ophiopogon japonicus
(Thunb.) Ker-Gawler, Journal of Separation Science 32 (2009) 19491956.
[460] W. Liu, Y.J. Fu, Y.G. Zu, M.H. Tong, N. Wu, X.L. Liu, S. Zhang, Supercritical carbon
dioxide extraction of seed oil from Opuntia dillenii Haw. and its antioxidant
activity, Food Chemistry 114 (2009) 334339.
[461] E. Vagi, E. Rapavi, M. Hadolin, K.V. Peredi, A. Balazs, A. Blazovics, B. Simandi,
Phenolic and triterpenoid antioxidants from Origanum majorana L. herb and
extracts obtained with different solvents, Journal of Agricultural and Food
Chemistry 53 (2005) 1721.
[462] E. Vagi, B. Simandi, A. Suhajda, E. Hethelyi, Essential oil composition and
antimicrobial activity of Origanum majorana L. extracts obtained with ethyl
alcohol and supercritical carbon dioxide, Food Research International 38
(2005) 5157.
[463] C. Devittori, D. Gumy, A. Kusy, L. Colarow, C. Bertoli, P. Lambelet, Supercritical
uid extraction of oil from millet bran, Journal of the American Oil Chemists
Society 77 (2000) 573579.
[464] B. Bozan, F. Temelli, Extraction of poppy seed oil using supercritical CO2 ,
Journal of Food Science 68 (2003) 422426.
[465] Y. Xie, J.Y. Peng, G.R. Fan, Y.T. Wu, Chemical composition and antioxidant
activity of volatiles from Patrinia villosa Juss obtained by optimized supercritical uid extraction, Journal of Pharmaceutical and Biomedical Analysis
48 (2008) 796801.
C. Zetzl, R.S. Mohamed, G. Brunner, Decaffeination of guarana
[466] M.D.A. Saldana,
seeds in a microextraction column using water-saturated CO2 , Journal of
Supercritical Fluids 22 (2002) 119127.
[467] M. Reddy, R. Moodley, S.B. Jonnalagadda, Fatty acid prole and elemental
content of avocado (Persea americana Mill.) oil-effect of extraction methods,

[468]

[469]
[470]

[471]

[472]

[473]

[474]

[475]

[476]

[477]

[478]

[479]

[480]

[481]

[482]
[483]

[484]

[485]

[486]

[487]

[488]

[489]

[490]

[491]

[492]

[493]

Journal of Environmental Science and Health Part B-Pesticides Food Contaminants and Agricultural Wastes 47 (2012) 529537.
L. Martin, A. Gonzalez-Coloma, C.E. Diaz, A.M. Mainar, J.S. Urieta, Supercritical
CO2 extraction of Persea indica: effect of extraction parameters, modelling and
bioactivity of its extracts, Journal of Supercritical Fluids 57 (2011) 120128.
V. Louli, G. Folas, E. Voutsas, K. Magoulas, Extraction of parsley seed oil by
supercritical CO2 , Journal of Supercritical Fluids 30 (2004) 163174.
E. Uquiche, E. Huerta, A. Sandoval, J.M. del Valle, Effect of boldo (Peumus boldus
M.) pretreatment on kinetics of supercritical CO2 extraction of essential oil,
Journal of Food Engineering 109 (2012) 230237.
J.M. del Valle, C. Godoy, M. Asencio, J.M. Aguilera, Recovery of antioxidants
from boldo (Peumus boldus M.) by conventional and supercritical CO2 extraction, Food Research International 37 (2004) 695702.
J.M. del Valle, T. Rogalinski, C. Zetzl, G. Brunner, Extraction of boldo (Peumus boldus M.) leaves with supercritical CO2 and hot pressurized water, Food
Research International 38 (2005) 203213.
P.F. Leal, M.B. Kfouri, F.C. Alexandre, F.H.R. Fagundes, J.M. Prado, M.H. Toyama,
M.A.A. Meireles, Brazilian Ginseng extraction via LPSE and SFE: global yields,
extraction kinetics, chemical composition and antioxidant activity, Journal of
Supercritical Fluids 54 (2010) 3845.
X.L. Liu, M.M. Zhao, J.S. Wang, W. Luo, Antimicrobial and antioxidant activity
of emblica extracts obtained by supercritical carbon dioxide extraction and
methanol extraction, Journal of Food Biochemistry 33 (2009) 307330.
M. Co, A. Fagerlund, L. Engman, K. Sunnerheim, P.J.R. Sjoberg, C. Turner, Extraction of antioxidants from Spruce (Picea abies) Bark using Eco-friendly Solvents,
Phytochemical Analysis 23 (2012) 111.
V.M. Rodrigues, P.T.V. Rosa, M.O.M. Marques, A.J. Petenate, M.A.A. Meireles,
Supercritical extraction of essential oil from aniseed (Pimpinella anisum L.)
using CO2 : solubility, kinetics, and composition data, Journal of Agricultural
and Food Chemistry 51 (2003) 15181523.
M. Davoody, G. Zahedi, M. Biglari, M.A.A. Meireles, A. Bahadori, Expert and
gray box modeling of high pressure liquid carbon dioxide extraction of
Pimpinella anisum L. seed, Journal of Supercritical Fluids 72 (2012) 213222.
O. Yesil-Celiktas, F. Otto, S. Gruener, H. Parlar, Determination of extractability
of pine bark using supercritical CO2 extraction and different solvents: optimization and prediction, Journal of Agricultural and Food Chemistry 57 (2009)
341347.
E. Conde, J. Hemming, A. Smeds, B.D. Reinoso, A. Moure, S. Willfr, H.
Domnguez, J.C. Paraj, Extraction of low-molar-mass phenolics and lipophilic
compounds from Pinus pinaster wood with compressed CO2 , Journal of Supercritical Fluids 81 (2013) 193199.
V.D. Carrara, L.Z. Serra, L. Cardozo, E.F. Cunha, E.C. Torres-Santos, D.A.G.
Cortez, HPLC analysis of supercritical carbon dioxide and compressed propane
extracts from Piper amalago L. with antileishmanial activity, Molecules 17
(2012) 1533.
Z.Y. Li, X.W. Liu, S.H. Chen, X.D. Zhang, Y.J. Xia, Y. Wei, F. Xiao, An experimental
and simulating study of supercritical CO2 extraction for pepper oil, Chemical
Engineering and Processing 45 (2006) 264267.
C. Perakis, V. Louli, K. Magoulas, Supercritical uid extraction of black pepper
oil, Journal of Food Engineering 71 (2005) 386393.
A.H. Goli, M. Barzegar, M.A. Sahari, Antioxidant activity and total phenolic compounds of pistachio (Pistachia vera) hull extracts, Food Chemistry 92
(2005) 521525.
R. Congiu, D. Falconieri, B. Marongiu, A. Piras, S. Porcedda, Extraction and
isolation of Pistacia lentiscus L. essential oil by supercritical CO2 , Flavour and
Fragrance Journal 17 (2002) 239244.
A. Sheibani, H.S. Ghaziaskar, Pressurized uid extraction of pistachio oil using
a modied supercritical uid extractor and factorial design for optimization,
Lwt-Food Science and Technology 41 (2008) 14721477.
L.A. Follegatti-Romero, C.R. Piantino, R. Grimaldi, F.A. Cabral, Supercritical CO2
extraction of omega-3 rich oil from Sacha inchi (Plukenetia volubilis L.) seeds,
Journal of Supercritical Fluids 49 (2009) 323329.
A. Femenia, M. Garca-Marin, S. Simal, C. Rossello, M. Blasco, Effects of
supercritical carbon dioxide (SC-CO2 ) oil extraction on the cell wall composition of almond fruits, Journal of Agricultural and Food Chemistry 49 (2001)
58285834.
I.H. Adil, M.E. Yener, A. Bayindirli, Extraction of total phenolics of sour cherry
pomace by high pressure solvent and subcritical uid and determination of
the antioxidant activities of the extracts, Separation Science and Technology
43 (2008) 10911110.
A.T. Serra, I.J. Seabra, M.E.M. Braga, M.R. Bronze, H.C. de Sousa, C.M.M. Duarte,
Processing cherries (Prunus avium) using supercritical uid technology. Part
1: recovery of extract fractions rich in bioactive compounds, Journal of Supercritical Fluids 55 (2010) 184191.
G. Bernardo-Gil, C. Oneto, P. Antunes, M.F. Rodrigues, J.M. Empis, Extraction
of lipids from cherry seed oil using supercritical carbon dioxide, European
Food Research and Technology 212 (2001) 170174.
N. Mezzomo, J. Martnez, S.R.S. Ferreira, Supercritical uid extraction of peach
(Prunus persica) almond oil: kinetics, mathematical modeling and scale-up,
Journal of Supercritical Fluids 51 (2009) 1016.
Y. Sanchez-Vicente, A. Cabanas, J.A.R. Renuncio, C. Pando, Supercritical uid
extraction of peach (Prunus persica) seed oil using carbon dioxide and ethanol,
Journal of Supercritical Fluids 49 (2009) 167173.
N. Mezzomo, B.R. Mileo, M.T. Friedrich, J. Martnez, S.R.S. Ferreira, Supercritical uid extraction of peach (Prunus persica) almond oil: process yield and
extract composition, Bioresource Technology 101 (2010) 56225632.

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176


[494] L. Leo, L. Rescio, L. Ciurlia, G. Zacheo, Supercritical carbon dioxide extraction
of oil and alpha-tocopherol from almond seeds, Journal of the Science of Food
and Agriculture 85 (2005) 21672174.
[495] E. Riera, A. Blanco, J. Garca, J. Benedito, A. Mulet, J.A. Gallego-Juarez, M. Blasco,
High-power ultrasonic system for the enhancement of mass transfer in supercritical CO2 extraction processes, Ultrasonics 50 (2010) 306309.
[496] P.M. Moura, G.H.C. Prado, M.A.A. Meireles, C.G. Pereira, Supercritical uid
extraction from guava (Psidium guajava) leaves: global yield, composition and
kinetic data, Journal of Supercritical Fluids 62 (2012) 116122.
[497] X. Wang, Y.Q. Wang, J.P. Yuan, Q.L. Sun, J.H. Liu, C.C. Zheng, An efcient new
method for extraction, separation and purication of psoralen and isopsoralen from Fructus psoraleae by supercritical uid extraction and high-speed
counter-current chromatography, Journal of Chromatography A 1055 (2004)
135140.
[498] Y.N. Lu, B.Z. Zhu, K.F. Wu, Z.P. Gou, L. Li, G.G. Chen, L. Cui, N.C. Liang, Analysis
of operation conditions for a pilot-scale supercritical CO2 extraction of diterpenoid from Pteris semipinnata L, Asia-Pacic Journal of Chemical Engineering
7 (2012) 777782.
[499] L.Z. Wang, B. Yang, X.Q. Du, C. Yi, Optimisation of supercritical uid
extraction of avonoids from Pueraria lobata, Food Chemistry 108 (2008)
737741.
[500] L.Z. Wang, B. Yang, X.Q. Du, Investigation of Supercritical Fluid Extraction of
Puerarin from Pueraria Lobata, Journal of Food Process Engineering 32 (2009)
682691.
[501] G.M. Liu, X. Xu, Q.F. Hao, Y.X. Gao, Supercritical CO2 extraction optimization of pomegranate (Punica granatum L.) seed oil using response surface
methodology, Lwt-Food Science and Technology 42 (2009) 14911495.
[502] I.M.G. Lopes, M.G. Bernardo-Gil, Characterisation of acorn oils extracted by
hexane and by supercritical carbon dioxide, European Journal of Lipid Science
and Technology 107 (2005) 1219.
[503] V. Castola, B. Marongiu, A. Bighelli, C. Floris, A. Lai, J. Casanova, Extractives
of cork (Quercus suber L.): chemical composition of dichloromethane and
supercritical CO2 extracts, Industrial Crops and Products 21 (2005) 6569.
[504] P. Iheozor-Ejidor, E.S. Dey, Extraction of rosavin from Rhodiola rosea root using
supercritical carbon dioxide with water, Journal of Supercritical Fluids 50
(2009) 2932.
[505] J.M. del Valle, S. Bello, J. Thiel, A. Allen, L. Chordia, Comparision of conventional
and supercritical CO2 -extracted rosehip oil, Brazilian Journal of Chemical
Engineering 17 (2000) 335348.
[506] J.M. del Valle, E.L. Uquiche, Particle size effects on supercritical CO2 extraction of oil-containing seeds, Journal of the American Oil Chemists Society 79
(2002) 12611266.
[507] J.M. del Valle, O. Rivera, M. Mattea, L. Ruetsch, J. Daghero, A. Flores, Supercritical CO2 processing of pretreated rosehip seeds: effect of process scale on oil
extraction kinetics, Journal of Supercritical Fluids 31 (2004) 159174.
[508] K. Szentmihalyi, P. Vinkler, B. Lakatos, V. Illes, M. Then, Rose hip (Rosa canina L.) oil obtained from waste hip seeds by different extraction methods,
Bioresource Technology 82 (2002) 195201.
[509] R. Eggers, A. Ambrogi, J. von Schnitzler, Special features of scf solid extraction
of natural products: deoiling of wheat gluten and extraction of rose hip oil,
Brazilian Journal of Chemical Engineering 17 (2000) 329334.
[510] E. Reverchon, A. Kaziunas, C. Marrone, Supercritical CO2 extraction of hiprose
seed oil: experiments and mathematical modelling, Chemical Engineering
Science 55 (2000) 21952201.
[511] E. Langa, G. Della Porta, A.M.F. Palavra, J.S. Urieta, A.M. Mainar, Supercritical uid extraction of Spanish sage essential oil: optimization of the process
parameters and modelling, Journal of Supercritical Fluids 49 (2009) 174181.
[512] L. Wang, Y. Song, Y. Cheng, X. Liu, Orthogonal array design for the optimization of supercritical uid extraction of tanshinones from Danshen, Journal of
Separation Science 31 (2008) 321328.
[513] E. Dauksas, P.R. Venskutonis, V. Povilaityte, B. Sivik, Rapid screening of antioxidant activity of sage (Salvia ofcinalis L.) extracts obtained by supercritical
carbon dioxide at different extraction conditions, Nahrung-Food 45 (2001)
338341.
[514] B. Marongiu, A. Piras, S. Porcedda, E. Tuveri, Extraction of Santalum album and
Boswellia carterii Birdw. volatile oil by supercritical carbon dioxide: inuence of some process parameters, Flavour and Fragrance Journal 21 (2006)
718724.
[515] C. Grosso, A.C. Figueiredo, J. Burillo, A.M. Mainar, J.S. Urieta, J.G. Barroso,
J.A. Coelho, A.M.F. Palavra, Supercritical uid extraction of the volatile oil
from Santolina chamaecyparissus, Journal of Separation Science 32 (2009)
32153222.
[516] G. Cherchi, D. Deidda, B. De Gioannis, B. Marongiu, R. Pompei, S. Porcedda,
Extraction of Santolina insularis essential oil by supercritical carbon dioxide:
inuence of some process parameters and biological activity, Flavour and
Fragrance Journal 16 (2001) 3543.
[517] M. Khajeh, Optimization of process variables for essential oil components
from Satureja hortensis by supercritical uid extraction using Box-Behnken
experimental design, Journal of Supercritical Fluids 55 (2011) 944948.
[518] S. Plander, L. Gontaru, B. Blazics, K. Veres, A. Kery, S. Kareth, B. Simandi, Major
antioxidant constituents from Satureja hortensis L. extracts obtained with different solvents, European Journal of Lipid Science and Technology 114 (2012)
772779.
[519] C. Grosso, A.C. Oliveira, A.M. Mainar, J.S. Urieta, J.G. Barroso, A.M.F. Palavra,
Antioxidant activities of the supercritical and conventional Satureja montana
extracts, Journal of Food Science 74 (2009) C713C717.

173

[520] B. Marongiu, A.P.S. Porcedda, R. Casu, P. Pierucci, Chemical composition of


the oil and supercritical CO2 extract of Schinus molle L., Flavour and Fragrance
Journal 19 (2004) 554558.
[521] L.H. Wang, Y.S. Chen, Y.T. Song, Y. Chen, X.S. Liu, GCMS of volatile components of Schisandra chinensis obtained by supercritical uid and conventional
extraction, Journal of Separation Science 31 (2008) 32383245.
[522] Y. Chang, B. Liu, B. Shen, Orthogonal array design for the optimization of supercritical uid extraction of balicalin from roots of Scutellaria baicalensis Georgi,
Journal of Separation Science 30 (2007) 15681574.
[523] Q.H. Hu, J. Xu, S.B. Chen, F.M. Yang, Antioxidant activity of extracts of black
sesame seed (Sesamum indicum L.) by supercritical carbon dioxide extraction,
Journal of Agricultural and Food Chemistry 52 (2004) 943947.
[524] B. Marongiu, A. Piras, S. Porcedda, E. Tuveri, A. Maxia, Isolation of Seseli bocconi
Guss., subsp praecox Gamisans (Apiaceae) volatile oil by supercritical carbon
dioxide extraction, Natural Product Research 20 (2006) 820826.

[525] M. Hadolin, M. Skerget,


Z. Knez, D. Bauman, High pressure extraction of vitamin E-rich oil from Silybum marianum, Food Chemistry 74 (2001) 355364.
[526] U. Salgin, A. Calimli, B.Z. Uysal, Supercritical uid extraction of jojoba oil,
Journal of the American Oil Chemists Society 81 (2004) 293296.
[527] T.H.J. Beveridge, M. Cliff, P. Sigmund, Supercritical carbon dioxide percolation
of sea buckthorn press juice, Journal of Food Quality 27 (2004) 4154.
[528] B. Liu, H.L. Jiang, B. Shen, Y.L. Chang, Supercritical uid extraction of
sinomenine from Sinomenium acutum (Thumb) Rehd et Wils, Journal of Chromatography A 1075 (2005) 213215.
[529] J.Y. Ling, G.Y. Zhang, Z.J. Cui, C.K. Zhang, Supercritical uid extraction of quinolizidine alkaloids from Sophora avescens Ait. and purication by high-speed
counter-current chromatography, Journal of Chromatography A 1145 (2007)
123127.
[530] A.M.A. Dias, P. Santos, I.J. Seabra, R.N.C. Jnior, M.E.M. Braga, H.C. de Sousa,
Spilanthol from Spilanthes acmella owers, leaves and stems obtained by
selective supercritical carbon dioxide extraction, Journal of Supercritical Fluids 61 (2012) 6270.
[531] A. Erkucuk, I.H. Akgun, O. Yesil-Celiktas, Supercritical CO2 extraction of glycosides from Stevia rebaudiana leaves: identication and optimization, Journal
of Supercritical Fluids 51 (2009) 2935.
[532] S.K. Yoda, M.O.M. Marques, A.J. Petenate, M.A.A. Meireles, Supercritical uid
extraction from Stevia rebaudiana Bertoni using CO2 and CO2 plus water:
extraction kinetics and identication of extracted components, Journal of
Food Engineering 57 (2003) 125134.
[533] L. Ruetsch, J. Daghero, M. Mattea, Supercritical extraction of solid matrices,
Model formulation and experiments, Latin American Applied Research 33
(2003) 103107.
[534] Y.X. Gao, B. Nagy, X. Liu, B. Simandi, Q. Wang, Supercritical CO2 extraction of
lutein esters from marigold (Tagetes erecta L.) enhanced by ultrasound, Journal
of Supercritical Fluids 49 (2009) 345350.
[535] B. Marongiu, A. Piras, S. Porcedda, E. Tuveri, S. Laconi, D. Deidda, A. Maxia,
Chemical and biological comparisons on supercritical extracts of Tanacetum
cinerariifolium (Trevir) Sch Bip. with three related species of chrysanthemums
of Sardinia (Italy), Natural Product Research 23 (2009) 190199.
[536] M. Kaplan, M.R. Simmonds, G. Davidson, Comparison of Supercritical uid
and solvent extraction of feverfew (Tanacetum parthenium), Turkish Journal
of Chemistry 26 (2002) 473480.
[537] B. Simandi, S.T. Kristo, A. Kery, L.K. Selmeczi, I. Kmecz, S. Kemeny, Supercritical
uid extraction of dandelion leaves, Journal of Supercritical Fluids 23 (2002)
135142.
[538] A.B.A. de Azevedo, U. Kopcak, R.S. Mohamed, Extraction of fat from fermented
Cupuacu seeds with supercritical solvents, Journal of Supercritical Fluids 27
(2003) 223237.
[539] S. Sonsuzer, S. Sahin, L. Yilmaz, Optimization of supercritical CO2 extraction
of Thymbra spicata oil, Journal of Supercritical Fluids 30 (2004) 189199.
[540] Z. Zekovic, Z. Lepojevic, A. Tolic, Modeling of the thyme-supercritical carbon dioxide extraction system. 1. The inuence of carbon dioxide ow rate
and grinding degree of thyme, Separation Science and Technology 36 (2001)
34593472.
[541] R.F. Rodrigues, A.K. Tashima, R.M.S. Pereira, R.S. Mohamed, F.A. Cabral,
Coumarin solubility and extraction from emburana (Torresea cearensis) seeds
with supercritical carbon dioxide, Journal of Supercritical Fluids 43 (2008)
375382.
[542] S.M. Ghoreishi, E. Bataghva, A.A. Dadkhah, Response surface optimization of
essential oil and diosgenin extraction from Tribulus terrestris via supercritical
uid technology, Chemical Engineering & Technology 35 (2012) 133141.
[543] B. Klejdus, L. Lojkova, O. Lapcik, R. Koblovska, J. Moravcova, V. Kuban, Supercritical uid extraction of isoavones from biological samples with ultra-fast
high-performance liquid chromatography/mass spectrometry, Journal of
Separation Science 28 (2005) 13341346.
[544] T. Tapia, F. Perich, F. Pardo, G. Palma, A. Quiroz, Identication of volatiles from
differently aged red clover (Trifolium pratense) root extracts and behavioural
responses of clover root borer (Hylastinus obscurus) (Marsham) (Coleoptera:
Scolytidae) to them, Biochemical Systematics and Ecology 35 (2007) 6167.
[545] R. Yang, H. Wang, N. Jing, C. Ding, Y. Suo, J. You, Trigonella foenum-graecum L.
seed oil obtained by supercritical CO2 extraction, Journal of the American Oil
Chemists Society 89 (2012) 22692278.
[546] H. Li, S. Li, Y. Zhang, H. Duan, New supercritical uid extraction treatment method for determination of tripterine in Tripterygium wilfordii Hook.
F, Journal of Liquid Chromatography & Related Technologies 31 (2008)
14221433.

174

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

[547] M.O.P. Crespo, M.A.L. Yusty, Comparison of supercritical uid extraction and
Soxhlet extraction for the determination of aliphatic hydrocarbons in seaweed samples, Ecotoxicology and Environmental Safety 64 (2006) 400405.
[548] D. Shohet, R.B.H. Wills, Characteristics of extracted valerenic acids from valerian (Valeriana ofcinalis) root by supercritical uid extraction using carbon
dioxide, International Journal of Food Properties 9 (2006) 325329.
J. Ivanovic,
A. Orlovic,
M. Ristic,
S. Djordjevic,
S.D.
[549] I. Zizovic, M. Stamenic,
D. Skala, Supercritical carbon dioxide extraction of sesquiterpenes
Petrovic,
from valerian root, Journal of Supercritical Fluids 43 (2007) 249258.
[550] A. Safaralie, S. Fatemi, A. Salimi, Experimental design on supercritical extraction of essential oil from valerian roots and study of optimal conditions, Food
and Bioproducts Processing 88 (2010) 312318.
[551] B.K. Huang, L.P. Qin, Q.C. Chu, Q.Y. Zhang, L.H. Gao, H.C. Zheng, Comparison of
Headspace SPME with Hydrodistillation and SFE for Analysis of the Volatile
Components of the Roots of Valeriana ofcinalis var. latifolia, Chromatographia
69 (2009) 489496.
[552] J.W. King, A. Mohamed, S.L. Taylor, T. Mebrahtu, C. Paul, Supercritical uid
extraction of Vernonia galamensis seeds, Industrial Crops and Products 14
(2001) 241249.
[553] J. Martnez, P.T.V. Rosa, C. Menut, A. Leydet, P. Brat, D. Pallet, M.A.A. Meireles,
Valorization of Brazilian vetiver (Vetiveria zizanioides (L.) Nash ex Small) oil,
Journal of Agricultural and Food Chemistry 52 (2004) 65786584.
[554] L.T. Danh, P. Truong, R. Mammucari, N. Foster, Extraction of vetiver essential
oil by ethanol-modied supercritical carbon dioxide, Chemical Engineering
Journal 165 (2010) 2634.
[555] L.T. Danh, R. Mammucari, P. Truong, N. Foster, Response surface method
applied to supercritical carbon dioxide extraction of Vetiveria zizanioides
essential oil, Chemical Engineering Journal 155 (2009) 617626.
[556] T.M. Takeuchi, P.F. Leal, R. Favareto, L. Cardozo-Filho, M.L. Corazza, P.T.V. Rosa,
M.A.A. Meireles, Study of the phase equilibrium formed inside the ash tank
used at the separation step of a supercritical uid extraction unit, Journal of
Supercritical Fluids 43 (2008) 447459.
[557] E. Talansier, M.E.M. Braga, P.T.V. Rosa, D. Paolucci-Jeanjean, M.A.A. Meireles,
Supercritical uid extraction of vetiver roots: a study of SFE kinetics, Journal
of Supercritical Fluids 47 (2008) 200208.
[558] D. Cossuta, B. Simandi, E. Vagi, J. Hohmann, A. Prechl, E. Lemberkovics, A.
Kery, T. Keve, Supercritical uid extraction of Vitex agnus castus fruit, Journal
of Supercritical Fluids 47 (2008) 188194.
[559] L. Arce, A.G. Lista, A. Ros, M. Valcrcel, Screening of polyphenols in grape marc
by on-line supercritical uid extraction ow through sensor, Analytical
Letters 34 (2001) 14611476.
[560] M.C. Pascual-Mart , A. Salvador, A. Chafer, A. Berna, Supercritical uid extraction of resveratrol from grape skin of Vitis vinifera and determination by HPLC,
Talanta 54 (2001) 735740.
[561] S. Zhang, Y.-G. Zu, Y.-J. Fu, M. Luo, W. Liu, J. Li, T. Efferth, Supercritical carbon dioxide extraction of seed oil from yellow horn (Xanthoceras sorbifolia
Bunge.) and its anti-oxidant activity, Bioresource Technology 101 (2010)
25372544.
[562] L.A. Xia, J.M. You, G.L. Li, Z.W. Sun, Y.R. Suo, Compositional and antioxidant
activity analysis of Zanthoxylum bungeanum seed oil obtained by supercritical
CO2 uid extraction, Journal of the American Oil Chemists Society 88 (2011)
2332.
[563] H. Ebrahimzadeh, Y. Yamini, F. Sedkon, D. Chaloosi, S.M. Pourmortazavi,
Chemical composition of the essential oil and super critical CO2 extracts of
Zataria multiora Boiss, Food Chemistry 83 (2003) 357361.
[564] S. Rebolleda, N. Rubio, S. Beltran, M.T. Sanz, M.L. Gonzalez-Sanjose, Supercritical uid extraction of corn germ oil: Study of the inuence of process
parameters on the extraction yield and oil quality, Journal of Supercritical
Fluids 72 (2012) 270277.
[565] Z.N. Yang, S.Q. Luo, Q.C. Peng, C. Zhao, Z.W. Yu, GCMS analysis of the essential
oil of coral ginger (Zingiber corallinum Hance) Rrhizome obtained by supercritical uid extraction and steam distillation extraction, Chromatographia
69 (2009) 785790.
[566] M.J.H. Akanda, M.Z.I. Sarker, S. Ferdosh, M.Y.A. Manap, N.N.N. Ab Rahman,
M.O. Ab Kadir, Applications of supercritical uid extraction (SFE) of palm oil
and oil from natural sources, Molecules 17 (2012) 17641794.
[567] R. Davarnejad, K.M. Kassim, A. Zainal, S.A. Sata, Supercritical uid extraction
of beta-carotene from crude palm oil using CO2 , Journal of Food Engineering
89 (2008) 472478.
[568] C.P. Passos, M.A. Coimbra, F.A. Da Silva, C.M. Silva, Modelling the supercritical
uid extraction of edible oils and analysis of the effect of enzymatic pretreatments of seed upon model parameters, Chemical Engineering Research
and Design 89 (2011) 11181125.
[569] H. Kubat, U. Akman, O. Hortacsu, Semi-batch packed-column deterpenation of
origanum oil by dense carbon dioxide, Chemical Engineering and Processing
40 (2001) 1932.
[570] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases & Liquids, 5th ed.,
McGraw-Hill Professional, New York, 2001.
[571] J.R. Elliott, C.T. Lira, Introductory Chemical Engineering Thermodynamics, 2nd
ed., Prentice Hall, New York, 2012.
[572] K.S. Pitzer, D.R. Schreiber, Improving equation-of-state accuracy in the critical
region equations for carbon-dioxide and neopentane examples, Fluid Phase
Equilibria 41 (1988) 117.
[573] J.C. Giddings, M.N. Myers, L. McLaren, R.A. Keller, High pressure gas chromatography of nonvolatile species. Compressed gas is used to cause migration
of intractable solutes, Science 162 (1968) 6773.

[574] L. McLaren, M.N. Myers, J.C. Giddings, Dense-gas chromatography of nonvolatile substances of high molecular weight, Science 159 (1968) 197199.
[575] W.-J. Kim, J.-D. Kim, J. Kim, S.-G. Oh, Y.-W. Lee, Selective caffeine removal
from green tea using supercritical carbon dioxide extraction, Journal of Food
Engineering 89 (2008) 303309.
[576] E.L.G. Oliveira, A.J.D. Silvestre, C.M. Silva, Review of kinetic models for supercritical uid extraction, Chemical Engineering Research and Design 89 (2011)
11041117.
[577] H. Sovov, R.P. Stateva, Supercritical uid extraction from vegetable materials,
Reviews in Chemical Engineering 27 (2011) 79156.
[578] J.M. del Valle, J.C. de la Fuente, D.A. Cardarelli, Contributions to supercritical
extraction of vegetable substrates in Latin America, Journal of Food Engineering 67 (2005) 3557.
[579] S. Angus, B. Amstrong, K.M. De Reuck, Internation Thermodynamic Tables of
the Fluid State: Carbon Dioxide, Pergamon Press, Oxford, 1976.
[580] M. Pilavtepe, O. Yesil-Celiktas, Mathematical modeling and mass transfer considerations in supercritical uid extraction of Posidonia oceanica residues,
Journal of Supercritical Fluids 82 (2013) 244250.
[581] M. Sauceau, J.J. Letourneau, D. Richon, J. Fages, Enhanced density-based
models for solid compound solubilities in supercritical carbon dioxide with
cosolvents, Fluid Phase Equilibria 208 (2003) 99113.
[582] K. Stephan, K. Lucas, Viscosity of Dense Fluids, Plenum Press, Lafayette, 1979.
[583] C.M. Silva, H. Liu, Modelling of transport properties of hard sphere uids and
related systems, and its application, chapter 9, in: A. Mulero (Ed.), Theory
and Simulation of Hard Sphere Fluids and Related Systems, Lecture Notes in
Physics 753, Springer, Berlin, 2008, pp. 383501.
[584] W.D. Monnery, W.Y. Svrcek, A.K. Mehrotra, Viscosity a critical-review of
practical predictive and correlative methods, Canadian Journal of Chemical
Engineering 73 (1995) 340.
[585] H. Sovov, J. Prochazka, Calculations of compressed carbon dioxide viscosities,
Industrial & Engineering Chemistry Research 32 (1993) 31623169.
[586] V.V. Altunin, M. Sakhabetdinov, Viscosity of liquid and gaseous carbondioxide at temperatures of 2201300 K and pressures up to 1200 Bar, Thermal
Engineering 19 (1972) 124129.
[587] V. Vesovic, W.A. Wakeham, Prediction of the viscosity of uid mixtures over
wide ranges of temperature and pressure, Chemical Engineering Science 44
(1989) 21812189.
[588] C.C. Lai, C.S. Tan, Measurement of molecular diffusion coefcients in supercritical carbon dioxide using a coated capillary column, Industrial & Engineering
Chemistry Research 34 (1995) 674680.
[589] A.L. Magalhes, R.V. Vaz, R.M.G. Goncalves, F.A. Da Silva, C.M. Silva, Accurate
hydrodynamic models for the prediction of tracer diffusivities in supercritical
carbon dioxide, Journal of Supercritical Fluids 83 (2013) 1527.
[590] R.V. Vaz, A.L. Magalhes, C.M. Silva, Improved StokesEinstein based models for diffusivities in supercritical CO2 , Journal of the Taiwan Institute of
Chemical Engineers (2014), http://dx.doi.org/10.1016/j.jtice.2013.1012.1005.
[591] R.V. Vaz, A.L. Magalhes, C.M. Silva, Improved hydrodynamic equations for
the accurate prediction of diffusivities in supercritical carbon dioxide, Fluid
Phase Equilibria 360 (2013) 401415.
[592] R.V. Vaz, A.L. Magalhes, C.M. Silva, Prediction of binary diffusion coefcients in supercritical CO2 with improved behavior
near the critical point, Journal of Supercritical Fluids (2014),
http://dx.doi.org/10.1016/j.supu.2014.1003.1011.
[593] Y. Zhu, X.H. Lu, J. Zhou, Y.R. Wang, J. Shi, Prediction of diffusion coefcients for
gas, liquid and supercritical uid: application to pure real uids and innite
dilute binary solutions based on the simulation of LennardJones uid, Fluid
Phase Equilibria 194 (2002) 11411159.
[594] H.B.E. Dymond, E. Vogel, W.A. Wakeham, V. Vesovic, M.J. Assael,
TheoryDense Fluids, Cambridge University Press, Cambridge, 2005.
[595] T. Funazukuri, N. Wakao, AIChE Annual Meeting, 1993.
[596] H. Liu, C.M. Silva, E.A. Macedo, New Equations for tracer diffusion coefcients
of solutes in supercritical and liquid solvents based on the LennardJones
uid model, Industrial & Engineering Chemistry Research 36 (1997)
246252.
[597] A.L. Magalhes, F.A. Da Silva, C.M. Silva, Free-volume model for the diffusion
coefcients of solutes at innite dilution in supercritical CO2 and liquid H2 O,
Journal of Supercritical Fluids 74 (2013) 89104.
[598] P.F. Lito, A.L. Magalhes, J.R.B. Gomes, C.M. Silva, Universal model for accurate calculation of tracer diffusion coefcients in gas, liquid and supercritical
systems, Journal of Chromatography A 1290 (2013) 126.
[599] A.L. Magalhes, F.A. Da Silva, C.M. Silva, New models for tracer diffusion coefcients of hard sphere and real systems: application to gases, liquids and
supercritical uids, Journal of Supercritical Fluids 55 (2011) 898923.
[600] A.L. Magalhes, F.A. Da Silva, C.M. Silva, New tracer diffusion correlation for
real systems over wide ranges of temperature and density, Chemical Engineering Journal 166 (2011) 4972.
[601] A.L. Magalhes, F.A. Da Silva, C.M. Silva, Tracer diffusion coefcients of polar
systems, Chemical Engineering Science 73 (2012) 151168.
[602] A.L. Magalhes, P.F. Lito, F.A. Da Silva, C.M. Silva, Simple and accurate correlations for diffusion coefcients of solutes in liquids and supercritical uids
over wide ranges of temperature and density, Journal of Supercritical Fluids
76 (2013) 94114.
[603] A.L. Magalhes, S.P. Cardoso, B.R. Figueiredo, F.A. Da Silva, C.M. Silva, Revisiting
the LiuSilvaMacedo model for tracer diffusion coefcients of supercritical,
liquid, and gaseous systems, Industrial & Engineering Chemistry Research 49
(2010) 76977700.

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176


[604] J.M. Del Valle, J.C. De La Fuente, Supercritical CO2 extraction of oilseeds:
review of kinetic and equilibrium models, Critical Reviews in Food Science
and Nutrition 46 (2006) 131160.
[605] N. Wakao, T. Funazkri, Effect of uid dispersion coefcients on particle-touid mass transfer coefcients in packed beds correlation of Sherwood
number, Chemical Engineering Science 33 (1978) 13751384.
[606] O.J. Catchpole, R. Bernig, M.B. King, Measurement and correlation of packedbed axial dispersion coefcients in supercritical carbon dioxide, Industrial &
Engineering Chemistry Research 35 (1996) 824828.
[607] D. Yu, K. Jackson, T.C. Harmon, Dispersion and diffusion in porous media under
supercritical conditions, Chemical Engineering Science 54 (1999) 357367.
[608] H. Sovov, Mathematical model for supercritical uid extraction of natural
products and extraction curve evaluation, Journal of Supercritical Fluids 33
(2005) 3552.
[609] J. Chrastil, Solubility of solids and liquids in supercritical gases, Journal of
Physical Chemistry 86 (1982) 30163021.
[610] . Gcl-stndag, F. Temelli, Correlating the solubility behavior of minor
lipid components in supercritical carbon dioxide, Journal of Supercritical Fluids 31 (2004) 235253.
[611] Y. Adachi, B.C.Y. Lu, Supercritical uid extraction with carbon dioxide and
ethylene, Fluid Phase Equilibria 14 (1983) 147156.
[612] J.M. del Valle, J.M. Aguilera, An improved equation for predicting the solubility of vegetable oils in supercritical CO2 , Industrial & Engineering Chemistry
Research 27 (1988) 15511553.
[613] J. Mndez-Santiago, A.S. Teja, The solubility of solids in supercritical uids,
Fluid Phase Equilibria 158160 (1999) 501510.
[614] H.D. Sung, J.J. Shim, Solubility of C. I. Disperse Red 60 and C. I. Disperse Blue
60 in supercritical carbon dioxide, Journal of Chemical and Engineering Data
44 (1999) 985989.
[615] K.D. Bartle, A.A. Clifford, S.A. Jafar, G.F. Shilstone, Solubilities of solids and
liquids of low volatility in supercritical carbon dioxide, Journal of Physical
and Chemical Reference Data 20 (1991) 713756.
[616] S.K. Kumar, K.P. Johnston, Modelling the solubility of solids in supercritical
uids with density as the independent variable, Journal of Supercritical Fluids
1 (1988) 1522.
[617] Z.-R. Yu, B. Singh, S.S.H. Rizvi, J.A. Zollweg, Solubilities of fatty acids, fatty acid
esters, triglycerides, and fats and oils in supercritical carbon dioxide, Journal
of Supercritical Fluids 7 (1994) 5159.
[618] M.D. Gordillo, M.A. Blanco, A. Molero, E. Martnez de la Ossa, Solubility of the
antibiotic Penicillin G in supercritical carbon dioxide, Journal of Supercritical
Fluids 15 (1999) 183190.
[619] C. Garlapati, G. Madras, Solubilities of solids in supercritical uids using
dimensionally consistent modied solvate complex models, Fluid Phase Equilibria 283 (2009) 97101.
[620] J.C. Gonzalez, M.R. Vieytes, A.M. Botana, J.M. Vieites, L.M. Botana, Modied
mass action law-based model to correlate the solubility of solids and liquids
in entrained supercritical carbon dioxide, Journal of Chromatography A 910
(2001) 119125.
[621] J. Mendez-Santiago, A.S. Teja, Solubility of solids in supercritical uids: consistency of data and a new model for cosolvent systems, Industrial & Engineering
Chemistry Research 39 (2000) 47674771.
[622] R. Thakur, R.B. Gupta, Rapid expansion of supercritical solution with solid
cosolvent (RESS-SC) process: formation of griseofulvin nanoparticles, Industrial & Engineering Chemistry Research 44 (2005) 73807387.
[623] H. Sovov, Solubility of ferulic acid in supercritical carbon dioxide with
ethanol as cosolvent, Journal of Chemical & Engineering Data 46 (2001)
12551257.
[624] S. Garnier, E. Neau, P. Alessi, A. Cortesi, I. Kikic, Modelling solubility of solids
in supercritical uids using fusion properties, Fluid Phase Equilibria 158160
(1999) 491500.
[625] K. Sepassi, P.B. Myrdal, S.H. Yalkowsky, Estimating pure-component vapor
pressures of complex organic molecules: part II, Industrial & Engineering
Chemistry Research 45 (2006) 87448747.

[626] M. Skerget,
Z. Knez, M. Knez-Hrncic, Solubility of solids in sub- and supercritical uids: a review, Journal of Chemical and Engineering Data 56 (2011)
694719.
[627] B. Diaz-Reinoso, A. Moure, H. Dominguez, J.C. Parajo, Supercritical CO2 extraction and purication of compounds with antioxidant activity, Journal of
Agricultural and Food Chemistry 54 (2006) 24412469.
[628] S. Vafai, B.D. Drake, R.L. Smith, Solid molar volumes of interest to supercritical extraction at 298 K: atropine, berberine hydrochloride hydrate, brucine
dihydrate, capsaicin, ergotamine tartrate dihydrate, naphthalene, penicillin
V, piperine, quinine, strychnine, theobromine, theophylline, and yohimbine
hydrochloride, Journal of Chemical & Engineering Data 38 (1993) 125127.
[629] S.N. Vaidya, G.C. Kennedy, Compressibility of 18 molecular organic solids to
45 kbar, Journal of Chemical Physics 55 (1971) 987.
[630] ChemSpider, Available from: http://www.chemspider.com
[631] C.-S. Su, Correlation and estimation of solubilities of fatty acids in supercritical
carbon dioxide using solution model approach, Journal of Supercritical Fluids
81 (2013) 7985.
[632] D.H. Ziger, C.A. Eckert, Correlation and prediction of solid supercritical uid
phase-equilibria, Industrial & Engineering Chemistry Process Design and
Development 22 (1983) 582588.
[633] P. Subra, S. Castellani, P. Jestin, A. Aou, Extraction of -carotene with supercritical uids: experiments and modelling, Journal of Supercritical Fluids 12
(1998) 261269.

175

[634] M.M. Esquvel, M.G. Bernardo-Gil, M.B. King, Mathematical models for supercritical extraction of olive husk oil, Journal of Supercritical Fluids 16 (1999)
4358.
[635] S.N. Naik, H. Lentz, R.C. Maheshwari, Extraction of perfumes and avours from
plant materials with liquid carbon dioxide under liquidvapor equilibrium
conditions, Fluid Phase Equilibria 49 (1989) 115126.
[636] C.S. Tan, D.C. Liou, Modeling of desorption at supercritical conditions, AIChE
Journal 35 (1989) 10291031.
[637] J. Crank, The Mathematics of Diffusion, 2nd ed., Clarendon Press, Oxford,
England, 1975.
[638] G. Brunner, Mass-transfer from solid material in gas extraction, Berichte
Der Bunsen-Gesellschaft-Physical Chemistry Chemical Physics 88 (1984)
887891.
[639] H. Sovov, Steps of supercritical uid extraction of natural products and their
characteristic times, Journal of Supercritical Fluids 66 (2012) 7379.
[640] H. Sovov, Rate of the vegetable oil extraction with supercritical CO2 I. Modelling of extraction curves, Chemical Engineering Science 49 (1994) 409414.
[641] H. Sovov, Rate of the vegetable oil extraction with supercritical CO2 . 1. Modeling of extraction curves, Chemical Engineering Science 49 (1994) 409414.
[642] M. Goto, B.C. Roy, T. Hirose, Shrinking-core leaching model for supercriticaluid extraction, Journal of Supercritical Fluids 9 (1996) 128133.
[643] L. Fiori, D. Basso, P. Costa, Supercritical extraction kinetics of seed oil: a new
model bridging the broken and intact cells and the shrinking-core models,
Journal of Supercritical Fluids 48 (2009) 131138.
[644] Z. Huang, X.-h. Shi, W.-j. Jiang, Theoretical models for supercritical uid
extraction, Journal of Chromatography A 1250 (2012) 226.
[645] C.M. Silva, C.P. Passos, M.A. Coimbra, F.A. Da Silva, Numerical simulation of
supercritical extraction processes, Chemical Product and Process Modeling 4
(2009), Article 9.
[646] N. Hasan, B. Farouk, Mass transfer enhancement in supercritical uid extraction by acoustic waves, Journal of Supercritical Fluids 80 (2013) 6070.
[647] L. Fiori, D. Basso, P. Costa, Supercritical extraction kinetics of seed oil: a new
model bridging the broken and intact cells and the shrinking-core models,
Journal of Supercritical Fluids 48 (2009) 131138.
[648] G. Nimet, E.A. da Silva, F. Pal, C. Dariva, L.d.S. Freitas, A.M. Neto, L.C. Filho,
Extraction of sunower (Heliantus annuus L.) oil with supercritical CO2 and
subcritical propane: experimental and modeling, Chemical Engineering Journal 168 (2011) 262268.
[649] A.A. Jesus, L.C. Almeida, E.A. Silva, L.C. Filho, S.M.S. Egues, E. Franceschi, M.
Fortuny, A.F. Santos, J. Arajo, E.M.B.D. Sousa, C. Dariva, Extraction of palm
oil using propane, ethanol and its mixtures as compressed solvent, Journal of
Supercritical Fluids 81 (2013) 245253.
[650] E. Reverchon, L.S. Osseo, Modelling the supercritical extraction of basil oil, in:
M. Perrut, G. Brunner (Eds.), Third International Symposium on Supercritical
Fluids, vol. 2, 1994, p. p189.
[651] E. Reverchon, Mathematical modeling of supercritical extraction of sage oil,
AIChe Journal 42 (1996) 17651771.

[652] M. Skerget,
Z. Knez, Modelling high pressure extraction processes, Computers
& Chemical Engineering 25 (2001) 879886.
[653] I.K. Hong, S.W. Rho, K.S. Lee, W.H. Lee, K.P. Yoo, Modeling of soybean oil
bed extraction with supercritical carbon dioxide, Korean Journal of Chemical
Engineering 7 (1990) 4046.
[654] B. Honarvar, S.A. Sajadian, M. Khorram, A. Samimi, Mathematical modeling of
supercritical uid extraction of oil from canola and sesame seeds, Brazilian
Journal of Chemical Engineering 30 (2013) 159166.
[655] M. Mukhopadhyay, Natural Extract Using Supercritical Carbon Dioxide, CRC
Press, Boca Raton, 2000.
[656] M. Goto, M. Sato, T. Hirose, Extraction of peppermint oil by supercritical carbon dioxide, Journal of Chemical Engineering of Japan 26 (1993) 401407.
[657] K. Araus, E. Uquiche, J.M. del Valle, Matrix effects in supercritical CO2 extraction of essential oils from plant material, Journal of Food Engineering 92
(2009) 438447.
[658] R.N. Almeida, R.G. Neto, F.M.C. Barros, E. Cassel, G.L. von Poser, R.M.F. Vargas,
Supercritical extraction of Hypericum caprifoliatum using carbon dioxide and
ethanol + water as co-solvent, Chemical Engineering and Processing: Process
Intensication 70 (2013) 95102.
[659] M. Akgun, Investigation of Thermodynamic and Transport Properties in
Supercritical Fluid Extraction, Yildiz Technical University, Instanbul, Turkey,
1999.
[660] E. Reverchon, Supercritical uid extraction and fractionation of essential oils
and related products, Journal of Supercritical Fluids 10 (1997) 137.
[661] K.D. Bartle, A.A. Clifford, S.B. Hawthorne, J.J. Langenfeld, D.J. Miller, R. Robinson, A model for dynamic extraction using a supercritical uid, Journal of
Supercritical Fluids 3 (1990) 143149.
[662] C.S.G. Kitzberger, R.H. Lomonaco, E.M.Z. Michielin, L. Danielski, J. Correia,
S.R.S. Ferreira, Supercritical uid extraction of shiitake oil: curve modeling
and extract composition, Journal of Food Engineering 90 (2009) 3543.
[663] H. Peker, M.P. Srinivasan, J.M. Smith, B.J. McCoy, Caffeine extraction rates
from coffee beans with supercritical carbon dioxide, AIChE Journal 38 (1992)
761770.
[664] M.B. King, T.R. Bott, Estimation of separation cost, in: M.B. King, T.R. Bott (Eds.),
Extraction of Natural Products using Near-critical Solvents, Blackie Academic
& Professional, Bishopbriggs, Glasgow, 1993.
[665] E. Reverchon, G.D. Porta, F. Senatore, Supercritical CO2 extraction and fractionation of lavender essential oil and waxes, Journal of Agricultural and Food
Chemistry 43 (1995) 16541658.

176

M.M.R. de Melo et al. / J. of Supercritical Fluids 92 (2014) 115176

[666] Z.R. Lazic, Design of Experiments in Chemical Engineering, John Wiley & Sons,
Weinheim, 2006.
[667] R. Mead, The Design of Experiments: Statistical Principles for Practical Applications, Cambridge University Press, Cambridge, 1990.
[668] R.K. Roy, Design of Experiments Using The Taguchi Approach: 16 Steps to
Product and Process Improvement, Wiley, USA, 2001.
[669] R.L. Mason, R.F. Gunst, J.L. Hess, Statistical Design and Analysis of Experiments: With Applications to Engineering and Science, Wiley, New Jersey,
2003.
[670] J. Lawson, Design and Analysis of Experiments with Examples of SAS, Taylor
& Francis, USA, 2010.
[671] I. Forrest, W. Breyfogle, Implementing Six Sigma: Smarter Solutions Using
Statistical Methods, John Wiley & Sons, New Jersey, 2003.
[672] G. Franceschini, S. Macchietto, Model-based design of experiments for parameter precision: state of the art, Chemical Engineering Science 63 (2008)
48464872.
[673] M. Perrut, J.Y. Clavier, M. Poletto, E. Reverchon, Mathematical modeling of
sunower seed extraction by supercritical CO2 , Industrial & Engineering
Chemistry Research 36 (1997) 430435.
[674] E.J. Beckman, Supercritical and near-critical CO2 in green chemical synthesis
and processing, Journal of Supercritical Fluids 28 (2004) 121191.
[675] R.M.A. Domingues, E.L.G. Oliveira, C.S.R. Freire, R.M. Couto, P.C. Simes, C.P.
Neto, A.J.D. Silvestre, C.M. Silva, Supercritical uid extraction of Eucalyptus
globulus barka promising approach for triterpenoid production, International Journal of Molecular Sciences 13 (2012) 76487662.
[676] Essential Oils Direct, http://www.essentialoilsdirect.co.uk/, 22.03.2014.
[677] C.E.O. N.D. Aromatics, Available from: http://www.newdirectionsaromatics.
ca, December 2013.
[678] D.T. Santos, P.C. Veggi, M.A.A. Meireles, Optimization and economic evaluation of pressurized liquid extraction of phenolic compounds from jabuticaba
skins, Journal of Food Engineering 108 (2012) 444452.
[679] C.G. Pereira, M.A.A. Meireles, Supercritical uid extraction of bioactive compounds: fundamentals, applications and economic perspectives, Food and
Bioprocess Technology 3 (2010) 340372.

[680] Sigma-Aldrich, http://www.sigmaaldrich.com/, 22.03.2014.


[681] R. Turton, R.C. Bailie, W.B. Whiting, J.A. Shaeiwitz, Analysis, Synthesis and
Design of Chemical Processes, 2nd ed., Prentice Hall, Upper Saddle River, 2003.
[682] E. Lack, T. Gamse, R. Marr, in: A. Bertucco, G. Vetter (Eds.), Separation
Operations and Equipment, Elsevier, Amsterdam, The Netherlands, 2001,
p. 383.
[683] M. Peters, K. Timmerhaus, Plant Design and Economic for Chemical Engineering, 5th ed., McGraw-Hill Book Company, London, 2003.
[684] A.C. Aguiar, J.V. Visentainer, J. Martnez, Extraction from striped weaksh
(Cynoscion striatus) wastes with pressurized CO2 : global yield, composition, kinetics and cost estimation, Journal of Supercritical Fluids 71 (2012)
110.
[685] A.M. Faras-Campomanes, M.A. Rostagno, M.A.A. Meireles, Production of
polyphenol extracts from grape bagasse using supercritical uids: yield,
extract composition and economic evaluation, Journal of Supercritical Fluids
77 (2013) 7078.
[686] N.C.M.C.S. Leito, G.H.C. Prado, P.C. Veggi, M.A.A. Meireles, C.G. Pereira, Anacardium occidentale L. leaves extraction via SFE: global yields, extraction
kinetics, mathematical modeling and economic evaluation, Journal of Supercritical Fluids 78 (2013) 114123.
[687] L. Fiori, Supercritical extraction of grape seed oil at industrial-scale: plant
and process design, modeling, economic feasibility, Chemical Engineering and
Processing: Process Intensication 49 (2010) 866872.
[688] S.S.H. Rizvi, J.A. Daniels, A.L. Benado, J.A. Zollweg, Supercritical uid extraction operating principles and food applications, Food Technology 40 (1986)
5764.
[689] R.M. Smith, Supercritical uids in separation science the dreams, the reality
and the future, Journal of Chromatography A 856 (1999) 83115.
[690] CEPI, Unfold the future the two team project, in: Confederation of European
Paper Industries Brussels, 2013.
[691] T. Lu, F. Gaspar, R. Marriott, S. Mellor, C. Watkinson, B. Al-Duri, J. Seville, R.
Santos, Extraction of borage seed oil by compressed CO2 : effect of extraction parameters and modelling, The Journal of Supercritical Fluids 41 (2007)
6873.

Anda mungkin juga menyukai