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University of Belgrade, Faculty of Technology and Metallurgy, Karnegijeva 4, 11120 Belgrade, Serbia
Institute for Medical Plant Research Dr Josif Pancic, Tadeusa Koscuska 1, 11000 Belgrade, Serbia
a r t i c l e
i n f o
Article history:
Received 21 December 2010
Received in revised form 13 February 2011
Accepted 14 February 2011
Keywords:
Helichrysum italicum
Supercritical extraction
Kinetics
Mathematical modelling
Process optimization
Moisture content inuence
a b s t r a c t
Kinetics and selectivity of supercritical carbon dioxide (SC CO2 ) extraction of Helichrysum italicum owers
were analyzed at pressures in the range of 1020 MPa and temperatures of 40 C and 60 C (density of SC
CO2 from 290 to 841 kg/m3 ) and also at 10 MPa and 40 C using owers with different moisture contents
(10.5% and 28.4%). Increased moisture content of H. italicum owers resulted in enchased solubility of
solute enabling decrease of SC CO2 consumption necessary for achieving desired extraction yield. The
most abundant compounds in the supercritical extracts are sesquiterpenes and waxes while monoterpenes and sesquiterpenes are the main constituents of essential oil obtained by hydrodistillation. The
optimal set of working parameters with respect to extraction yield, SC CO2 consumption and chemical
composition of extract were dened related to moisture content of raw material and SC CO2 density.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The genus Helichrysum belonging to Asteraceae family include
approximately 600 species widespread all over the world. It is represented in the Mediterranean area by nearly 25 native species [1].
Helichrysum italicum (commonly known as curry plant, Italian everlasting or immortelle) is widespread along the coast and on the
islands of the Adriatic Sea. It is a dwarf aromatic shrub with yellow
owers, up to 5070 cm high, growing on dry cliffs and sandy soil
[2]. Metabolites isolated from H. italicum and especially its volatile
oil have been found to display many biological properties, such as
the anti-inammatory [3,4], antiallergic, antibacterial, antifungal
[510], antioxidant [3,1113] and antiviral [4,14].
The essential oil of Helichrysum species for commercial applications is traditionally obtained by steam and hydrodistillation
[1,2,6,10,1520]. Since high temperature during distillation process can induce thermal degradation, hydrolysis and solubilization
of some compounds some authors suggest low temperature processing techniques for isolation of bioactive principles from H.
italicum such as extraction with water [2123], organic solvents
[3,79,11,13,14,2124] and supercritical carbon dioxide (SC CO2 )
[12,17,18]. Process of extraction with SC CO2 is optimally performed at mild pressure (910 MPa) and temperature (4050 C)
in order to isolate essential oil rich extracts [17,18,25]. In the
130
moisture is in the range between 3% and 12% [27] (or for some
plant material up to 18% [26]). Normal moisture content of tobacco
had to be increased by up to 25% to affect nicotine extraction, presoaking of coffee beans aids the removal of caffeine and also to
increase the extraction of vanilla from vanilla beans [32]. Varying
bed moisture levels can differently affect mass transfer of solute in
the solid phase [33]. In the case of Origanum vulgare L. discontinuous addition of water led to increase in the extraction degree of
essential oils and reduction in the yield of the co-extracted waxy
material [33]. They observed that extraction was enhanced due to
changes in the transport properties of the solvent and a decrease
in intraparticle resistance of the solute inside the particles. Five
times higher predicted effective diffusivity for less brous fresh
ginger from the water-rich new season compared to the value for
the freeze-dried ginger samples previously reported was explained
by the structure of the matrix [32]. Increased moisture level in
oilseeds and paprika samples had negative effect on extraction efciency and time of extraction necessary for obtaining desired yield
of extract [26,28], or increased the loss of volatile compounds [29].
Yoda et al. [31] reported different inuence 510% moisture in the
Stevia rebaudiana on extraction yield at supercritical and subcritical
conditions.
Up to now there are no data about inuence of the moisture content in the plant material on kinetics of SFE of H. italicum and on
chemical composition of the supercritical extracts. Therefore, the
goal of this study was also to analyze the inuence of moisture content of H. italicum owers on the kinetics of SFE and, to analyze the
chemical composition of the obtained extracts isolated at 10 MPa
and 40 C (CO2 = 630 kg/m3 ).
In this paper, Sovovs mass transfer model [28,3437] was
used for simulation of experimentally obtained extraction curves
in order to analyze the inuence of the SC CO2 density and moisture
content in the plant material on the solubility of extracts and mass
transfer parameters.
2.2. Hydrodistillation
The milled owers of H. italicum (50 g) were distilled using
1000 ml distilled water according to Clevenger standard method
(4 h) and volatile essential oil was collected. The obtained essential
oil was kept in a sealed vial at 4 C.
as deviation of the yield calculated by model and those experimentally determined [34].
131
Table 1
Chemical composition of the essential oil of H. italicum owers.
Constituents
RIa
RT/MSb
932
1020
1020
1024
1095
1135
1165
1174
1186
1227
1359
7.3
8.53
10.5
10.6
13.03
13.9
15.27
15.68
16.17
16.97
21.56
1373
1374
1405
1410
1411
1417
1481
1479
1489
1498
1500
1505
1513
1522
1582
1600
1644
1649
21
21.83
23.22
23.43
23.56
23.69
24.92
25.78
25.85
25.86
26.21
26.44
26.61
26.87
28.21
28.91
30.24
30.5
1100
13.17
15.41
2056
40.72
Monoterpenes
-Pinene
p-Cymene
Limonene
1,8-Cineole
Linalool
trans-Pinocarveol
Endoborneol
Terpinene-4-ol
-Terpineol
Nerol
Neryl acetate
Sesquiterpenes
-Ylangene
-Copaene
Italicene
-Cedrene
cis--Bergamotene
trans--Caryophyllene
-Curcumene
ar-Curcumene
-Selinene
-Selinene
Murolene
-Bisabolene
-Cadinene
-Cadinene
Caryophyllene oxide
Viridiorol
-Murolool
-Eudesmol
Hydrocarbon aldehydes, ketones and esters
Nonyl aldehyde
2-Methyl, 2-butenoic acid, isopentyl ester
Diterpenes
Manool
ID (%)
Number of constituents
a
EOc
% (w/w)d
10.38
2.8
0.28
0.64
0.22
0.42
0.49
0.3
0.43
0.49
0.21
3.1
61.3
0.52
3.61
4.62
0.96
2.19
6.91
12.4
4.01
9.94
5.91
1.15
1.21
1.36
0.85
0.63
3.01
0.74
1.07
1.03
0.35
0.29
4.22
4.22
76.8
46
Kovats index.
Retention time (min) of corresponding constituent obtained by GC/MS.
Essential oil.
Percentage >0.2% (w/w).
Fig. 1. Extraction yield as a function of the specic amount of SC CO2 for SFE at
different p and t (IVI, Table 2); solid line presents the yield calculated according to
Sovovs model.
132
133
Table 2
Contextual and model parameters for SFE from H. italicum owers.
Contextual parameters
Units
Temperature, t
Pressure, p
Density of CO2 , CO2
Viscosity of CO2 , CO2 105
Moisture content
Bed porosity,
Mass ow rate, qCO2 104
Supercial velocity, u 104
Specic interfacial area, a0 103
Total extraction yield, ytot a
Binary diffusion coefcient, D12 108
Mass transfer coefcient in the CO2 phase, kf 104
Sovovs model parameters
Solubility, yr 103
Mass transfer coefcient in the solid phase, ks 107
Mass of inaccessible solute per mass of solute-free solid phase, xk 102
Mass transfer coefcient in the solid phase, ks,eff 109 b
Z
W
AARD
Sample
I
a
b
C
MPa
kg/m3
Pa s
%, w/w
kg/s
m/s
m/m3
%, w/wa
m2 /s
m/s
kgoil /kgCO2
m/s
m/s
III
IV
VI
40
10
630
4.68
10.5
0.45
1.81
4.02
0.856
2.45
2.19
0.712
II
40
10
630
4.68
28.4
0.45
1.5
3.33
0.904
2.78
2.19
0.609
40
15
781
6.7
10.5
0.45
1.28
2.84
1.133
4.25
2.19
0.446
40
20
841
7.84
10.5
0.45
1.19
2.64
1.252
4.1
2.19
0.388
60
10
290
2.41
10.5
0.45
1.67
3.71
0.629
1.37
2.19
0.928
60
20
725
5.89
10.5
0.45
1.18
2.62
1.087
3.79
2.19
0.445
2
5
2.2
11.00
72.2
0.113
10
4
2.75
11.00
62.70
0.094
20
2.3
4.2
9.66
102.9
0.095
25
1.8
4
7.20
114.8
0.089
1.5
3.2
1.36
4.35
34.86
0.058
20
2.5
3.7
9.25
109.7
0.108
5.42
5.21
1.80
5.56
1.30
3.40
134
Table 3
Chemical composition of the supercritical extracts of H. italicum owers.
Components
RIa
RT/MSb
II
III
VI
5.483
1.279
0.305
0.918
1.702
21.278
1.157
1.617
0.46
0.498
3.04
4.308
1.347
0.374
0.498
0.58
0.914
0.486
0.996
0.821
0.151
1.595
0.481
0.798
2.431
0.242
1.337
0.531
22.457
0.348
22.109
28.000
2.228
3.116
8.176
0.851
10.392
1.527
4.305
1.015
0.398
0.959
0.441
23.643
1.136
1.673
0.251
0.557
3.463
4.939
1.675
0.488
0.543
0.555
1.325
0.394
0.708
0.684
0.297
0.111
1.335
0.461
0.732
3.613
0.39
1.878
0.778
18.738
0.404
18.334
25.448
2.192
3.022
7.792
0.73
8.517
1.109
5.312
0.0762
2.495
1.044
0.573
26.422
0.827
1.333
0.397
0.488
3.287
4.846
1.437
0.578
0.622
0.62
0.733
0.639
0.851
1.058
0.628
0.367
2.191
0.664
0.912
1.15
21.397
0.179
21.217
27.357
1.789
2.826
8.048
0.767
10.459
1.679
0.565
0.193
20.668
0.681
19.986
23.069
1.821
3.794
7.718
0.617
7.371
0.638
5.317
2.56
0.135
0.94
0.151
21.929
1.23
1.586
0.291
0.576
2.984
4.558
1.511
0.373
0.49
0.561
1.365
0.401
0.912
0.668
0.315
0.707
0.634
0.416
0.739
1.431
0.629
0.349
0.15
20.393
0.312
20.081
27.039
2.034
2.807
7.435
1.086
9.972
1.677
76.921
59
75.746
65
76.677
59
76.622
59
76.108
58
%, w/w
Monoterpenes
-Pinene
Pugenol
Neryl acetate
Geranyl tiglate
Sesquiterpenes
-Copaene
Italicene
trans--Caryophyllene
9-Epi-(E)-caryophyllene
ar-curcumene
-Selinene
-Selinene
-Bisabolene
-Cadinene
-Cadinene
Caryophyllene oxide
Cedrol
Globulol
Rosifoliol
Muurola-4,10(14)-dien-1-beta-ol
-Eudesmol
Eudesm-7(11)-en-4-ol
Xanthorrhizol
(Z)-Lanceol
Hydrocarbon acids and esters
2.5-Dimethyl-2-hexanold
Methyl oleate
Methyl linoleate
Other
Dihidroangelicin(2 ,3 ,3 -trimethyl-2 ,3 -)c
Mw = 242274d
Waxes
Pentacosane
Heptacosane
Nonacosane
Triacontane
Untriacontane
Dotriacontane
932
1356
1359
1696
7.04
21.42
21.56
31.26
1374
1405
1417
1464
1479
1489
1498
1505
1513
1522
1582
1599
1590
1598
1630
1649
1652
1760
1767
21.83
22.7
23.019
24.94
25.21
25.28
25.54
25.98
26.11
26.4
28.11
28.56
28.75
28.85
29.43
30.03
30.16
33.67
33.9
2082
2095
17.37
41.13
41.27
1893
19312203
36.23
2500
2700
2900
3000
3100
3200
51.75
55.38
59.33
61.04
63.22
68.58
ID%
Number of constituents
a
b
c
d
3.478
0.479
0.33
0.897
0.914
20.557
1.034
1.361
0.219
0.456
3.027
4.218
1.45
0.369
0.464
0.502
0.811
0.4
0.927
0.633
0.206
1.135
0.446
0.696
1.163
0.519
0.162
Kovats index.
Retention time of corresponding constituent obtained by GC/MS.
Only the most abundant components from different classes of compounds are presented.
Tentative identication (MS).
135
4. Conclusion
Present study provides new data on supercritical extraction of
H. italicum owers in the range of SC CO2 densities from 290 to
0.840 kg/m3 . It was shown that increase of SC CO2 density resulted
in the faster extraction and higher extraction yields due to positive
effect of higher density on solubility of extract in the SC CO2 . On the
other hand, increasing SC CO2 density above 630 kg/m3 had adverse
effect on selectivity toward terpenes extraction.
Increased moisture content positively inuences solubility of
lighter and oxygenated compounds in SC CO2 enabling a higher rate
of extraction and thus, the reduction of SC CO2 consumption. For the
same time of extraction, the increased moisture of H. italicum owers changes selectivity of SC CO2 to aroma compounds particularly
to the higher content of sesquiterpenes in supercritical extract.
Results obtained using raw material with different moisture
contents and SC CO2 density was used for dening optimal working
parameters with respect to extraction yield, time of extraction, SC
CO2 consumption and chemical composition of extracts.
Acknowledgements
Authors thank to Dr Sandra Glisic for valuable assistance during
experimental work.
Financial support of this work by the Serbian Ministry of Science,
Project No. 142073, is gratefully acknowledged.
References
Fig. 5. Inuence of (a) SC CO2 density and (b) moisture content in the plant material
on selectivity of extraction to mono- and sesquiterpene compounds.
136