Research Article 2123

Zoran Zeković1
Mathematical Modeling of Ocimum
Snežana Filip2
Senka Vidović1 basilicum L. Supercritical CO2 Extraction
Stela Jokić3
Sandra Svilović4 The effects of pressure and temperature on supercritical extraction of Ocimum ba-
silicum L. in terms of extraction yield and aromatic compounds were investigated.
1
Faculty of Technology, Linalool, eugenol, and d-cadinene were indentified as three main compounds of
University of Novi Sad, the prepared extracts. The dominant compound in all investigated supercritical
Novi Sad, Serbia. basil extracts was linalool. Within the experimental range the extraction parame-
2
Technical Faculty ‘‘Mihajlo
ters had a significant influence on the extraction yield. The obtained results for
Pupin’’ Zrenjanin, University the sweet basil total extract, cadinene, and linalool best matched with the Gordillo
of Novi Sad, Zrenjanin, Serbia. et al. model, therefore, the solubility of total extract, linalool, and cadinene in
3
supercritical CO2 at investigated temperatures is described as a function of pres-
Faculty of Food Technology sure.
Osijek, Osijek, Croatia.
4
Faculty of Chemistry and Keywords: Eugenol, Linalool, Mathematical modeling, Ocimum basilicum L., Supercritical
Technology, Split, Croatia. CO2 extraction
Received: May 26, 2014; revised: October 01, 2014; accepted: October 06, 2014
Supporting Information
DOI: 10.1002/ceat.201400322
available online

1 Introduction solvent, so products extracted with food-grade CO2 are safe

Ocimum basilicum L. (sweet basil) belongs to the Lamiaceae
family and is the most cultivated variety in the world, especially
in Mediterranean countries. The O. basilicum leaves can be
used in fresh or dried form as a spice to enhance the flavor of
foods. Essential oils extracted from fresh leaves and flowers can
be employed as aroma additives in food, pharmaceuticals, and
cosmetics [1]. There are several types of basil oil traded com-
mercially. Extracted from different varieties of sweet basil, these
are known as European (French or sweet basil), Egyptian, Re-
union (Comoro), Bulgarian, and Java basil oil [2]. Linalool and
methylchavicol (estragole) are the two major components of
O. basilicum L. and its essential oil [3, 4]. These components
together with various sesquiterpenes are responsible for the
fresh, minty, and sweet flavor of this plant [4]. Eugenol and/or
methyl cinnamate together with linalool and methylchavicol
are considered as major compounds of basil essential oil [4–7].
Supercritical fluid extraction (SFE) is regarded as a promis-
ing alternative technique to steam distillation and solvent ex-
traction of flavor and fragrance compounds from natural mate-
rials. CO2 is the most commonly used supercritical fluid in
food and pharmaceutical industries. It is nontoxic, nonexplo-
sive, easily removable from the product, and possesses a low
critical temperature and pressure (Tc = 31.1 C, Pc = 73.8 bar).
The low critical point of CO2 allows the preservation of ther-
molabile compounds present in the essential oil during the ex-
traction process. CO2 is generally recognized as safe (GRAS)
with respect to human health. The solvent properties of CO2
can be described as a function of fluid density [8]. Extraction
pressure and temperature range are important factors affecting
the final composition of the extract and process yield, since the
solubility of every component in the fluid depends on these
parameters [9]. This is the reason why the selection of the
operating conditions for supercritical CO2 extraction for spe-
cific applications is an area of intense scientific research.
Mathematical modeling of SFE can help to better understand
the extraction mechanism, to fast optimization/calculation of
the extraction conditions, and to simulate the overall extraction
curves [10, 11]. For industrial application, it is essential to test
the applicability of the appropriate model for SFE that will
facilitate the scale-up of laboratory data to industrial design
purposes [12].
The influence of pressure and temperature on the extraction
yield of Ocimum basilicum L. obtained by supercritical CO2
were studied. Possible commercial application of SFE of sweet
basil extracts requires testing of appropriate model applicabil-
ity. This enables correlation and extrapolation of the experi-
mental data. The experimental data were used to adjust the
parameters of kinetics and solubility models.
2 Experimental
2.1 Materials and Sample Preparation

Commercial CO2 (Messer, Novi Sad, Serbia) was used for labo-
– ratory SFE. All other chemicals were of analytical reagent
Correspondence: Dr. Snežana Filip (filipsnezana@gmail.com), Techni- grade.
cal Faculty ‘‘Mihajlo Pupin’’ Zrenjanin, University of Novi Sad, Ðure O. basilicum L. was cultivated at the Institute of Biodiversity
Ðakovića b.b., 23000 Zrenjanin, Serbia. Bački Petrovac, Serbia, in 2011. The collected plant material,

Chem. Eng. Technol. 2014, 37, No. 12, 2123–2128 ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
2124
i.e., leaves and flowers, were air-dried and stored at room tem-
perature. The moisture content of O. basilicum L. was analyzed
by the standard procedure, i.e., by drying the plant sample at
105 C until constant weight. This analysis was performed in
three replicates. The dried basil was ground and the particle
size of the ground material was determined by sieve sets (Erwe-
ka, Germany). Using the standard procedure, the moisture
content of the investigated plant material was determined as
11.44 wt %.
2.2 Steam Distillation
The content of essential oil in the ground plant material was
determined by steam distillation according to the standard
Ph. Jug. IV procedure [13]. The essential oil was collected in a
Clevenger apparatus for 3 h and stored at 4 C until analysis.
According to the standard procedure, the content of essential
oil was determined as 0.565 % (v/w).
2.3 Soxhlet Extraction
A sample of 20.0 g sweet basil was extracted by 130 mL methy-
lene chloride using a Soxhlet apparatus. After 15 exchanges of
the extract, the solvent was evaporated under vacuum, and the
obtained extract was stored in a glass bottle at 4 C. The extrac-
tion yield was determined as 1.950 wt %.
2.4 Supercritical CO2 Extraction
The extraction process was carried out on a laboratory-scale
high-pressure extraction plant (HPEP, NOVA, Swiss, Efferikon,
Switzerland; Fig. 1) as described in detail elsewhere [14]. The
main plant parts and properties according to the manufacturer
specification were: gas cylinder with CO2, diaphragm-type
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Research Article
compressor with pressure range up to 1000 bar, extractor with
heating jacket for heating medium with 200 mL internal vol-
ume and maximum operating pressure of 700 bar, separator
with heating jacket for heating medium with 200 mL internal
volume and maximum operating pressure of 250 bar, pressure
control valve, temperature regulation system, and regulation
valves.
The ground sample of basil (50.0 g) was placed in the extrac-
tor vessel. The extraction process was carried out and extrac-
tion yield was measured at regular time intervals of 0.5, 1.0,
2.0, 3.0, and 4.0 h. The flow rate of CO2, expressed under nor-
mal conditions, was 97.725 dm3h–1. Investigated pressures were
100, 150, 200, and 300 bar, while the temperature varied from
40 C to 60 C during the extraction time of 4 h. Separator con-
ditions were 15 bar and 23 C. After extraction, the obtained
extract was placed in the glass bottles, sealed, and stored at 4 C
to prevent any possible degradation.
2.5 Chromatographic Procedure
GC/MS analysis was run on an Agilent GC6890N system
coupled to a mass spectrometer model Agilent MS 5795.
An HP-5MS column with 30 m length, 0.25 mm inner dia-
meter, and 0.25 mm film thickness was used. The injected
volume of sample solution in methanol was 5 mL with split
ratio 30:1. The GC/MS operating conditions were as follows:
injector temperature 250 C, temperature program from 60 C
to 150 C (4 C min–1), carrier gas He with a flow rate of 2 mL
min–1. The compounds were identified using the NIST 05 and
Wiley 7n mass data base and by comparing their retention
times to those in mass spectral libraries. Quantifications of aro-
matic compounds were performed by an FID detector and cali-
bration curve for the main compounds. The GC/FID operating
conditions were: injector temperature 250 C, temperature pro-
gram from 60 C to 150 C (4 C min–1), detector temperature
300 C.
Figure 1. Laboratory-scale high-
pressure extraction plant. GC –
gas cylinder, CU – compressor
unit, C – compressor with dia-
phragm, E – extractor, S – se-
parator, HE – heat exchanger,
UT – ultra thermostat, RV – reg-
ulation valve, V – on-off valve,
MF – microfilter, CV – cutoff
valve, RD – rapture disc, PI –
pressure indicator, TI – tempera-
ture indicator, FI – flow indica-
tor.
Chem. Eng. Technol. 2014, 37, No. 12, 2123–2128
 Research Article 2125

2.6 Mathematical Modeling where c0–c5 are the model constants and P is the pressure
(bar).
The extraction curves of sweet basil oil were adjusted using The parameters of all models were calculated by nonlinear
three models presented in the literature. regression method using software Mathcad 14.
Brunner [15] expressed the global model as:
 
YE ¼ x0 1  ekt (1) 2.7 Statistical Analysis
where YE is the extraction yield, k is the constant rate, and t is The accordance between the experimentally determined extrac-
the time at which the extraction from the particle core starts. tion yield and calculated value obtained by different mathemat-
The second model was proposed by Kandiah and Spiro [16]: ical models was established by the average absolute relative de-
viation (AARD) as follows:
YE ¼ x0 f1  ½f1 expðk1 tÞ þ f2 expðk2 tÞg (2)
n  
1X 
yexp  ycal 
where f1 and f2 are the fractions of the solute extracted with AARD ¼ (9)
n i¼1  yexp 
rate constant k1 and k2, respectively.
The empirical model from Esquivel et al. [17] is represented
by the following equation:
 
t 3 Results and Discussion
mext ¼ x0 F (3)
bþt
3.1 Effect of Pressure and Temperature on
where mext is the mass of the extract, F is the mass of the solid Extraction Yield of Total Extracts and Aromatic
material (kg), t is the extraction time (s), x0 is the initial solute Compounds
mass ratio in the solid phase (kg kg–1), and b is an adjustable
parameter (s). The effects of pressure and temperature on the supercritical
Empirical models for solubility determination are based on CO2 extraction of sweet basil total extracts (TE) were investi-
simple error minimization where there is no need for physico- gated at pressures from 100 to 300 bar and temperatures of
chemical properties. The commonly used equation for correlat- 40 C, 50 C, and 60 C. The CO2 flow rate was maintained con-
ing the solubility behavior is proposed by Chrastil [18] in the stant at 97.725 dm3h–1, and the main particle size of ground
form: material was determined to be 0.657 ± 0.012 mm. Tab. 1 sum-
 marizes the results of the supercritical extraction process. The
a  extraction yield (EY) of sweet basil TE achieved with supercriti-
S ¼ rk exp a2 þ 3 (4)
T cal CO2 was the highest with 1.879 % at 300 bar and 60 C. The
lowest extraction yield of 0.719 % was obtained at 100 bar and
where S is the solubility (g L–1), r is the density of CO2 (g L–1),
40 C.
and T is the temperature (K).
Other researchers reported similar extraction yields from
Del Valle and Aquilera [19] gave the improved form of this
0.42 to 1.95 wt % using liquid and supercritical CO2 [23, 24].
equation in the following form:
The extraction kinetics was monitored every hour during the
 a a  process. The fast extraction period was expressed during the
S ¼ rk exp a2 þ 3 þ 42 (5) first 2 h, after which the slow extraction period started and the
T T
obtained extraction yield was lower compared with the first
The units are the same as in the Chrastil equation. 2 h.
Adachi and Lu [20] proposed another empirical equation in Using the NIST 05 and Wiley 7n mass data base and by
the form: comparing the retention times to those in mass spectral libra-
 a  ries, some other compounds beside those given in Tab. 2 were
S ¼ rða1 þa2 rþa3 r Þ exp a4 þ 5
2
(6) identified. Percentages on this way identified compounds in 12
T
investigated supercritical basil extracts ranged from 71.91 % to
The equation from Adachi and Lu can be simplified to the 85.62 %. The following compounds were detected: bornylace-
following form [21]: tate, eugenol, b-elemene, trans-caryophyllene, a-bergamotene,
 a  a-humulene, b-cubebene, germacrene D, b-selinene, g-cadi-
S ¼ rða1 þa2 rÞ exp a3 þ 4 (7) nene, a-selinene, spathulenol, and d-cadinene.
T
The dominant compound in all investigated supercritical ba-
In Eq. (7), k is expressed as a linear function of density. sil extracts was linalool. Its content ranged from 6.99 to 15.11 g
The empirical solubility model proposed by Gordillo et al. per 100 g of extract. The highest content of this constituent was
[22] was used for correlating the solubility behavior of soybean determined in the extract obtained using CO2 at 200 bar and
oil and five main fatty acids. 40 C. In basil extracts, eugenol was present in the range from
The model from Gordillo et al. is defined as: 3.74 to 9.87 g per 100 g. The highest content of this compound
was measured in the extract achieved with CO2 at 100 bar and
ln S ¼ c0 þ c1 P þ c2 P2 þ c3 PT þ c4 T þ c5 T 2 (8) 50 C. The content of d-cadinene ranged from 3.20 to 7.21 g

Chem. Eng. Technol. 2014, 37, No. 12, 2123–2128 ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
2126 Research Article

Table 1. Kinetics of supercritical O. basilicum extraction. a These results were used in another still unpublished manuscript.

Extraction conditions EY [%] after 0.5 h EY [%] after 1.0 h EY [%] after 2.0 h EY [%] after 3.0 h EY [%] after 4.0 h
a
100 bar, 40 C 0.220 0.387 0.558 0.671 0.719
a
100 bar, 50 C 0.176 0.478 0.673 0.802 0.894

100 bar, 60 C 0.064 0.156 0.200 0.267 0.382

150 bar, 40 C 0.019 0.463 0.707 1.158 1.238

150 bar, 50 C 0.113 0.392 1.031 1.368 1.568

150 bar, 60 C 0.343 0.421 0.692 1.335 1.401

200 bar, 40 C 0.698 0.828 1.148 1.259 1.322

200 bar, 50 C 0.234 0.671 0.878 1.173 1.447

200 bar, 60 C 0.083 0.496 1.025 1.445 1.666

a
300 bar, 40 C 0.268 0.498 0.836 1.073 1.287
a
300 bar, 50 C 0.298 0.798 1.307 1.568 1.715

300 bar, 60 C 0.177 0.893 1.347 1.633 1.879

Table 2. Quantification of aromatic compounds (g per 100 g) present in supercritical O. basilicum L. extracts obtained after 4 h at differ-
ent extraction parameters. a These results were used in another still unpublished manuscript.

Extraction conditions Eugenol Eucalyptol Linalool a-Terpineol Methyl-chavicol Geraniol d-Cadinene

a
100 bar, 40 C 9.29 0.23 16.6 0.60 0.87 0.81 6.95

100 bar, 50 C 9.78 0.25 11.79 0.79 0.62 0.65 7.21

a
100 bar, 60 C 8.97 0.10 10.00 0.69 0.46 0.63 6.48

150 bar, 40 C 6.48 0.35 13.23 0.47 0.73 0.59 5.13

150 bar, 50 C 7.97 0.32 11.35 0.51 0.63 0.53 5.58

150 bar, 60 C 8.80 0.33 10.63 0.62 0.62 0.53 6.18

200 bar, 40 C 7.64 0.44 15.11 0.51 0.86 0.67 5.51

200 bar, 50 C 7.40 0.68 9.58 0.69 0.52 0.43 5.09

200 bar, 60 C 7.28 0.47 9.66 0.53 0.54 0.44 5.01

a
300 bar, 40 C 6.61 1.10 10.72 0.80 0.66 0.44 4.38

300 bar, 50 C 5.91 0.45 10.14 0.54 0.60 0.56 3.94

a
300 bar, 60 C 3.74 0.28 6.99 0.28 0.42 0.71 3.20

per 100 g. The highest content of this constituent was mea-
sured, as in the case of eugenol, in the extract obtained using
CO2 at 100 bar and 50 C.
3.2 Kinetic Study
The kinetics of the supercritical CO2 extraction of sweet basil
TE was investigated by modeling the extraction curves by the
model described by Brunner, Kandiah, and Spiro and Esquivel
et al. [15–17]. The values for the adjustable model parameters
and AARD values for the investigated temperature and pres-
sure ranges are presented in Tabs. 3–5. The lowest AARD val-
ues were obtained using the Kandiah and Spiro model (Tab. 4)
and the best adjustments of the experimental results were
achieved at 150 bar and 40 C, with the lowest AARD value.
Conducting a successful supercritical fluid process requires
knowledge of the solute solubility. Different equations have
been presented in the literature for mathematical modeling of
solubility data in supercritical CO2. Information on the solu-
bility behavior of different components in supercritical CO2
is necessary for the design and development of supercritical
extraction and fractionation as well as in analytical applica-
tions.
The parameters as well as average absolute relative devia-
tions of all used solubility models in this study (Eqs. (4)–(8))
are presented in Tab. S1 in the Supporting Information. The
models have been tested for the solubility of sweet basil TE and

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 Research Article 2127

Table 3. Calculated parameters of the Brunner model for sweet Table 5. Calculated parameters of the Esquivel et al. model for
basil extraction. sweet basil extraction.

Extraction conditions k [h–1] AARD [%] Extraction conditions b [h–1] AARD [%]

100 bar, 40 C 0.1407 17.455 100 bar, 40 C 5.5971 12.2306

100 bar, 50 C 0.1812 10.459 100 bar, 50 C 4.1378 9.173

100 bar, 60 C 0.0541 10.492 100 bar, 60 C 16.898 9.6977

150 bar, 40 C 0.260 8.527 150 bar, 40 C 2.7402 17.644

150 bar, 50 C 0.3549 40.899 150 bar, 50 C 1.9309 59.639

150 bar, 60 C 0.3026 14.036 150 bar, 60 C 2.280 17.248

200 bar, 40 C 0.4103 17.068 200 bar, 40 C 1.3967 7.186

200 bar, 50 C 0.3246 9.306 200 bar, 50 C 2.0451 15.011

200 bar, 60 C 0.3857 50.169 200 bar, 60 C 1.7451 83.538

300 bar, 40 C 0.2745 20.342 300 bar, 40 C 2.5242 7.155

300 bar, 50 C 0.5849 12.810 300 bar, 50 C 1.1647 22.9154

300 bar, 60 C 0.5685 31.458 300 bar, 60 C 1.0632 48.9251

Table 4. Calculated parameters of the Kandiah and Spiro model 4 Conclusions

for sweet basil extraction.
The effects of pressure and temperature on supercritical CO2
Extraction f1 f2 k1 [h–1] k2 [h–1] AARD [%]
conditions extraction of sweet basil total extracts were investigated at pres-
sures ranging from 100 to 300 bar and at temperatures of
100 bar, 40 C 0.4756 0.4754 0.1207 0.1204 8.947 40 C, 50 C, and 60 C. The highest extraction yield of sweet
100 bar, 50 C 0.4719 0.4829 0.1660 0.1660 11.795 basil TE was obtained with supercritical CO2 at 300 bar and
60 C, being 1.879 %. Linalool, eugenol, and d-cadinene were
100 bar, 60 C 0.4950 0.4950 0.0505 0.0505 7.688 identified as the three main compounds in the obtained basil
150 bar, 40 C 0.5054 0.5064 0.2654 0.2654 7.516 extracts. The dominant compound in all investigated supercrit-
ical basil extracts was linalool. The highest content of linalool
150 bar, 50 C 0.5368 0.3906 0.5360 0.3906 25.227 with 15.11 g per 100 g was determined in the extract obtained
150 bar, 60 C 0.5145 0.3071 0.4952 0.3071 14.235 using CO2 at 200 bar and 40 C. Within the experimental
range, the extraction parameters had a significant influence on
200 bar, 40 C 0.4450 0.3343 0.4385 0.3343 11.319 the extraction yield.
200 bar, 50 C 0.4974 0.3231 0.4996 0.3231 9.522 The solubility data for sweet basil TE and main aromatic
compounds were correlated using different empirical models.
200 bar, 60 C 0.5398 0.4258 0.5399 0.4258 38.211
According to the obtained results for the TE, cadinene, and
300 bar, 40 C 0.4952 0.4953 0.2700 0.2700 16.213 linalool, the Gordillo et al. model best agreed with the obtained
experimental data, while for eugenol the best fit was obtained
300 bar, 50 C 0.5271 0.5157 0.6139 0.6139 10.603
using the Del Vale and Aguilera model. Therefore, the solubili-
300 bar, 60 C 0.5323 0.5323 0.6104 0.6104 25.452 ty of TE, linalool, and cadinene in supercritical CO2 at temper-
atures of 40 C, 50 C, and 60 C is given as a function of pres-
sure, while the solubility of eugenol is presented as a function
its three main components. According to the obtained results of density.
for the TE, cadinene, and linalool, the Gordillo et al. model
provided the best agreement with the experimental data while
for eugenol the best fit was obtained using the Del Vale and Acknowledgment
Aguilera model. In Fig. 2, the accordance of experimental solu-
bility data of TE and specified components of TE and the best The authors gratefully acknowledge the financial support of
fit model are presented. The solubility of TE, linalool, and cadi- this work by the Serbian Ministry of Education, Science and
nene in supercritical CO2 at temperatures of 313, 323, and Technological Development, Project No. TR31013.
333 K is indicated as a function of pressure, while the solubility
of eugenol is presented as a function of density. The authors have declared no conflict of interest.

Chem. Eng. Technol. 2014, 37, No. 12, 2123–2128 ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
2128 Research Article

Total extract Linalool

−3 −3
9×10 2×10
313 K 313 K
model 313 K model 313 K
−3
6×10 323 K 323 K
S (g/L)
model 323 K −3 model 323 K
1×10
333 K 333 K
−3
3×10 model 333 K model 333 K

0 0
0 100 200 300 400 0 100 200 300 400

P (bar) P (bar)

Cadinene Eugenol
−3 −3
1×10 2×10
313 K 313 K
model 313 K model 313 K
323 K 323 K
S (g/L)

−4 model 323 K −3 model 323 K

5×10 1×10
333 K 333 K
model 333 K model 333 K

0 0
0 100 200 300 400 3
0 200 400 600 800 1×10
P (bar) ρ (g/L)
–1
Figure 2. Solubility (g L ) of sweet basil TE and the main aromatic compounds in supercritical CO2; experimental results and results ob-
tained by the model which gave the best results.

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