The Journal of Supercritical Fluids 127 (2017) 146–157

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The Journal of Supercritical Fluids

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

Experimental optimization and mathematical modeling of the supercritical MARK

fluid extraction of essential oil from Eryngium billardieri: Application of
simulated annealing (SA) algorithm
⁎
Gholamhossein Sodeifian , Seyed Ali Sajadian, Nedasadat Saadati Ardestani
Department of Chemical Engineering, Faculty of Engineering, University of Kashan, 87317-53153, Kashan, Islamic Republic of Iran

A R T I C L E I N F O A B S T R A C T

Keywords: This article presents experimental results and mathematical modeling predictions of the extraction of essential
Eryngium billardieri oil from Eryngium billardieri, for the first time, using supercritical carbon dioxide (SCeCO2) method. Design of
Supercritical fluid extraction experiments and experimental optimization were carried out with a response surface methodology (RSM) to
Experimental optimization investigate the effects of different operating parameters including pressure (100–300 bar), temperature
Mathematical modeling
(308–328 K), particle size (0.45–1.05 mm) and extraction time (30–150 min). The maximum extraction yield
Simulated annealing (SA) algorithm
was found to be 0.8522% w/w at the optimum conditions 300 bar, 308 K, 0.75 mm and 130 min. Moreover, in
order to describe the kinetic behavior of extraction process, a mathematical model based on the Brunauer-
Emmett-Teller (BET) theory of adsorption with three adjustable parameters was developed for correlating
experimental data. Model parameters have been optimized by applying simulated annealing (SA) algorithm. The
obtained results from model predictions were consistent with experimental data in the different extraction
conditions.

1. Introduction tical industries. In comparison with the traditional extraction method,

Eryngium billardieri from the umbliferae family is a native plant from
Asia and widely grows in various provinces of Iran, at an altitude of
2600 m above sea level [1,2]. Eryngium billardieri (commonly known
as “booghnagh”) is a plant with medicinal and antimicrobial properties.
Eryngium billardieri (E. billardieri) have been used in folk medicine for
various purposes, including root extracts for the treatment of rheuma-
tism, inflammations of mucous membranes and wounds. The aerial
parts of E. billardieri is used for heling colds by sniffing and also its
powdered root mixed with tobacco is consumed to stop smoking [3–5].
The essential oils of plants have usually been separated by either
hydrodistillation (HD) or solvent extraction. The disadvantages of all
these techniques are: low yield, losses of volatile compounds, long
extraction times, toxic solvent residues, degradation of unsaturated
compounds, lead to thermal degradation, partial hydrolysis of some
essential oil compounds and easily deteriorate the heat-sensitive
compounds [6].
Supercritical fluid (SCF) technology has been considered as a green
separation process in the several various fields such as extraction of
natural materials [7]. In recent years, supercritical carbon dioxide
(SCeCO2) extraction plays an important role in food and pharmaceu-
SCeCO2 technique is more rapid because of solvent’s low viscosity and
high diffusivity. By adjusting the pressure and temperature parameters
to near the critical point, the low polarity and density changes
drastically. The best chosen solvent for SCFs is carbon dioxide because
it is non-toxic, non-flammable, non-corrosive and non-explosive. More-
over, it is also bacteriostatic, inexpensive and can be easily removed
from the extract. The only disadvantage of carbon dioxide is that it is a
non-polar solvent, however, this can be considered as a good solvent for
the extraction of non-polar compounds [6–10]. Additionally, it is worth
mentioning that the SCFs have liquid-like densities, gas-like viscosities
and diffusivities, and zero surface tension that cause superior mass
transfer characteristics and the solvent effectiveness with density
control [11].
Response surface methodology (RSM) with centered composite
design (CCD) has been widely confirmed to optimize various operating
conditions of the extraction process, as well as to explain of extraction
yield obtained by suggested experimental runs in terms of recovered
mass. Between multivariate statistical techniques, RSM is the most
powerful and effective mathematical and statistical approach to
determine the effects of process parameters [12–14].
Mathematical models are beneficial tools for the design, improve-

⁎
Corresponding author.
E-mail address: sodeifian@kashanu.ac.ir (G. Sodeifian).

http://dx.doi.org/10.1016/j.supflu.2017.04.007
Received 5 January 2017; Received in revised form 7 April 2017; Accepted 10 April 2017
Available online 14 April 2017
0896-8446/ © 2017 Elsevier B.V. All rights reserved.
G. Sodeifian et al.
Nomenclature
asf Specific surface area for mass transfer (1/m)
cal Refers to calculated
cf Concentration of the solute in the bulk phase (kg/m3)
cf* Concentration of solute in the fluid-phase (kg/m3)
Dm Diffusion coefficient of solute (m2/s)
dp Particle size (mm)
Dsf Axial dispersion coefficient of the solute in the fluid phase
(m2/s)
exp Refers to experimental
K Ratio between the adsorption equilibrium constants of the
solute in the first monolayer and that in subsequent layers
k sf Mass transfer coefficient (m/s)
L Length of extractor (m)
m0 Initial mass of the solute extracted (kg)
n Number of data
P Pressure (bar)
Qco2 Mass flow rate of CO2 (kg/s)
Re Reynolds number ρνdp/μ
ment and scale-up of extraction processes from laboratory to pilot and
industrial scales [15]. There are several models in the literature to
describe the supercritical fluid extraction of oils and volatile oils, which
have been reviewed by some authors [15–19]. In general, these models
are divided into four significant groups: empirical models, models
based on heat transfer analogies, shrinking core model and models
based on differential mass balances. The last class of models has
distinctive physical significance and encompasses mass transfer coeffi-
cients to fluid and solid phases or in just one phase. They consider the
characteristics of the material matrix such as the particle size and the
bed porosity. In comparison with the empirical models, various
coefficients must be determined, however, these models describe the
trends and mechanisms carried out by the extraction process [20].
During the past two decades, a few researchers had attempted to
optimize a SF process by some good optimization methods such as
genetic algorithm (GA) [21,22], Levenberg–Marquardt training algo-
rithm (L-M) [6,23,24], differential evolution (DE) [25], simulated
annealing (SA) [26], grey wolf optimization (GWO) [6], ant colony
optimization (ACO) [27], Nelder-Mead simplex method [28], particle
swarm optimization (PSO) [29], etc.
Scientific sources review showed that there is no report on the
extraction of E. billardieri via the SFE technique so far. Therefore, the
first objective of this work was the optimization of the extraction
process considering the effective variables of pressure, temperature,
particle size and dynamic time on the essential oil yield. The second aim
of this study relied on the mathematical modeling by the differential
mass balances approach to demonstrate the behavior of the experi-
mental kinetic curves. Additionally, simulated annealing (SA) algo-
rithm was employed to obtain the optimized adjustable parameters of
the model. Finally, ability of model predictions and its validation was
evaluated by fitted experimental data.
2. Material and methods
2.1. Materials
The aerial parts E. billardieri used in this study were gathered by
hand during June 2016 from 2500 to 3000 m-high areas (graphical
coordinate included 33°44′38″ north latitude and 51°24′57″ east long-
itude) of Qamsar (Kashan) located in the Esfahan Province, Iran.
Liquefied CO2 of purity 99.99% is supplied by Fadak Gas Factory in
pressurized deep tube cylinders.
147
The Journal of Supercritical Fluids 127 (2017) 146–157
Sc Schmidt number μ/ρDm
Sh Sherwood number dpk sf / Dm
t Time (s)
T Temperature (K)
u Solvent velocity (m/s)
x Mass ratio
x Solute mass fraction in the first monolayer. Adjustable
parameter
y Yield
yf Mass fraction of the solute in the SCF
yf * Solute mass fraction in the SCF film
ysat Solute mass fraction in the saturated fluid phase (kg/kg)
Greek letters
μ Viscosity (kg/ms)
ρ Density (kg/m3)
ε Bed porosity
2.1.1. Samples preparation
To prepare the samples before performing the tests, the samples
were washed with distilled water. Moisture of the plant is one of the
most important factors influencing extraction yield. Therefore, they
were dried in an ambient temperature until all the unbound water was
removed. The sample was placed in desiccator until moisture of the
plant was decreased to its minimum content. They were crushed in a
mill and then granulated to the desired size using a laboratory sieve and
shaker. To prevent the samples from over-temperature, the grinding
time was kept short with no use of jet mills.
2.2. Methods
2.2.1. Extraction of essential oil by hydrodistillation (Clevenger)
The dried samples (100 g) of E. billardieri were hydrodistilled using
a glass Clevenger-type apparatus for four hours according to the
standard procedure described in the European pharmacopoeia [30].
The yellowish oil was then dried over anhydrous sodium sulfate and
stored in a dark glass bottle at 4 °C under nitrogen gas until the time of
analysis. Experiments were carried out in triplicates. The yield of
essential oil extracted by hydrodistillation method was
0.8330 ± 0.0052 (w/w%).
2.2.2. Supercritical fluid extraction (SFE) apparatus
The SFE pilot plant used in this study, consisted of an extraction
vessel with internal diameter of 0.015 m and height of 0.2 m. The other
equipment of SFE pilot were carbon dioxide liquefied cylinder; high
pressure pump (Haskel pump, maximum pressure up to 600 bar) to
locate the liquefied CO2 under the demanded pressure; surge tank; the
packed bed vessel (extraction vessel) both made of stainless steel, inside
vessel the glass beads of diameter 5 mm; shell-and-tube heat exchanger
that hot water was revolved within the shell at fixed temperature; back-
pressure valve to control the extraction pressure, in which a heating
element was used to avoid freezing. In the present work, 10 g sample
was loaded into the extraction cell. Carbon dioxide from a gas cylinder
(standard cylinder) was passed to refrigerator unit. In this unit, CO2 was
cooled and liquefied. The liquefied CO2 was pressurized by the high
pressure pump. The compressed CO2 exited was passed into a surge
tank and then was transferred to the main extraction column. A heat
exchanger, shell and tube type, where the water was circulated in its
shell with constant temperature, provided the required temperature of
the extraction process. Volume of packed bed vessel is 35 ml which was
filled out with the samples and glass beads to prevent flow channeling
G. Sodeifian et al.
Fig. 1. Schematic diagram of supercritical CO2 extraction set-up.
in the packed bed and the dead volume. The pressure and temperature
were maintained to be constant within a desired operating condition.
The static time was determined for all experiments by closing a back
pressure valve for about 30 min and the dynamic conditions were
adjusted by opening the back pressure valve. At the dynamic time, the
extraction cell temperature was held at 0 °C by using the ice bath
chamber. To prevent the back pressure valve from freezing, it was
heated by a heating electrical jacket. The obtained essential oil was
collected carefully, since it was a little and very sensitive and after
weighing, samples kept in a sealed murky vial in a cool place like a
fridge or ice box up to the analysis. The extracted essential oil was then
measured and based on which results the extraction yield was
calculated. Each extract sample obtained by at the different experi-
mental conditions was tested in triplicate and finally their mean values
were reported. The SCeCO2 apparatus has been shown in Fig. 1. Total
yield (y) of the SCeCO2 extraction can be calculated through dividing
the essential oil weight by the dried powder weight.
weight of extracted essentil oil(g)
Yield(%) = × 100
weight of dried plant powder(g)
2.2.3. Gas chromatography (GC) analysis
In this science, an Agilent HP-6890 gas chromatograph (Agilent
Technologies, Palo Alto, CA, USA), equipped with a FID detector, with a
HP-5MS 5% phenylmethyl siloxane capillary column (30 m × 0.25 mm,
0.25 μm film thickness; Restek, Bellefonte, PA) was applied to perform
chemical analysis. The oven temperature was hold at 60 °C for 3 min
before being raised, at the rate of 3 °C/min, to 246 °C. Injector and
detector temperatures were both set at 250 °C. Helium was used as the
carrier gas at a flow rate of 1.5 ml/min with the samples being injected
manually under a split ratio of 1:100. Peaks’ area percentages were used
to obtain quantitative data [31].
2.2.4. Gas chromatography/mass spectrometry (GC/MS) analysis
GC/MS analysis of the oil was carried out on an Agilent HP-6890 gas
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The Journal of Supercritical Fluids 127 (2017) 146–157
chromatograph (Agilent Technologies, Palo Alto, CA, USA) with a HP-
5MS 5% phenylmethyl siloxane capillary column (30 m × 0.25 mm,
0.25 μm film thickness; Restek, Bellefonte, PA) equipped with an
Agilent HP-5973 mass selective detector in electron impact mode
(ionization energy: 70 eV) operating under the same conditions as
described above. Retention indices were calculated for all components
using a homologous series of n-alkanes injected under the same
conditions as those of samples. Identification of essential oil compo-
nents was based on the retention indices (RI) relative to n-alkanes,
matching the results using a computer to Wiley 275.L and Wiley 7n.L
libraries, as well as comparisons of the fragmentation patterns of the
mass spectra to the available data in the literature [31,32].
2.3. Experimental design
The response surface central composite design (RSM-CCD) method
was selected to determine the experimental conditions providing the
highest extraction yield of E. billardieri. The four factors independent
variables were developed in statistical software package ‘Design Expert
7.0′ with 30 runs to include 16 factorial points, 6 center points and 8
axial points at five different levels (−α, −1, 0, 1, +α). For this
purpose, the levels of the factors were chosen according to previous
experiments. The extraction parameter of pressure (x1), temperature
(x2), particle size (x3) and dynamic time (x4) in five levels were
performed for extraction of E. billardieri. The parameter of supercritical
CO2 flow rate was considered to be constant (4 g/min). The resultant
range of experimental conditions, including their coded levels, can be
observed in Table 1. A multiple regression analysis of data was used to
calculate the coefficients of the second order polynomial equation
proposed to express yield of essential by a quadratic equation (Eq. (1)):
Y = β0 + β1x1 + β2x2 + β3x3 + β4x4
+ β11x12 + β22x22 + β33x32 + β44x42
+ β12x1x2 + β13x1x3
+ β14x1x4 + β23x2x3 + β24x2x4 + β34x3x4 + Error (1)
G. Sodeifian et al. The Journal of Supercritical Fluids 127 (2017) 146–157

Table 1 Integrating within the usual limits for a packed extractor (at
Coded and uncoded values of the independent variables used in the experimental design. z = 0 → yf = 0, z = L → yf = k fl ), the following relationship was ob-
tained:
Independent Pressure (x1) Temperature (x2) Particle size Time (x4)
variables (x3) ⎡ ⎛ kL ⎞⎤
y f = yf *⎢1 − exp⎜ − ⎟⎥
Coded levels Level of factor l ⎣ ⎝ uε ⎠⎦ (5)
−2 100 308 0.45 30
−1 150 313 0.6 60 where y f is the solute mass fraction in the bulk fluid phase at the outlet
l
0 200 318 0.75 90 of the extraction cell and L is the length of the extractor.
1 250 323 0.9 120
2 300 328 1.05 150
2.4.1. BET-based model
The modeling approach based on thermodynamic and mass transfer
where Y is the predicted response and x1 − x4 are the coded indepen- phenomena videlicet Brunauer–Emmett–Teller (BET) theory of adsorp-
dent parameters. The β0 is the intercept term, β1 − β4 are the linear tion [35] that suggested by Pardo [33] were developed in this study for
coefficients, β12, β13, β14, β23β24 and β34 are the interaction coeffi- correlating SFE data of E. billardieri. Mathematical model represents the
cients, β11, β22, β33 and β44 are the quadratic coefficients. The statistical extraction yield as a function of time using one individual equation
significance of each regression coefficient on the yield of extraction was with three fitting parameters, each one with an obvious physical
carried out using analysis of variance (ANOVA). The determination meaning. The model with three adjustable parameters is shown in Eq.
coefficients, R2, and their adjusted value, R2 adj., were used to evaluate (6):
the fit adequacy of the regression models.
m 0 ⎛⎜ ⎡ ⎛ α ⎞⎤ ⎡ α′ ⎤⎞
t= ⎜ x 0 − x′ + (2 − K )⎢x − xm ln⎜ ⎟⎥ + Kxm ln⎢ ⎥⎟
2 ⎟
*
2Qco2y ⎝ ⎣ ⎝ β ⎠⎥⎦ ⎣ β′(1 − x ) ⎦⎠
2.4. Mathematical modeling
(6)
A packed bed of the E. billardieri particles mixed with glass beads as where:
the stationary phase and the flowing SCeCO2 as the mobile phase was
considered. The extraction process consists of two successive stages of x 0' = a+b+c (7)
static and dynamic periods. Based on the shell mass balance approach,
governing differential equation for the solute in the SCF around a x′ = a(1 − x )2 + b(1 − x ) + c (8)
differential element along the axial direction of the extractor can be 2
a=K (9)
written as [19]:
b = 2(2 − K )Kxm (10)
∂cf ∂cf ∂ 2cf (1 − ε )
+u = Dsf + asf k sf (cf * − cf ) 2
∂t ∂z ∂z 2 ε (2) c = (Kxm ) (11)

where cf is the concentration of the solute in the bulk phase, u is the α = x′ + K (1 − x ) + (2 − K )xm (12)
interstitial velocity of the solvent, ε is the void fraction of the bed, Dsf is
the axial dispersion coefficient of the solute in the fluid phase, asf is the α′ = x′ + (2 − K )(1 − x ) + Kxm (13)
effective solid-fluid contact area for mass transfer, k sf is the mass β = x 0' + K + (2 − K )xm (14)
transfer coefficient for transport of the solute through the external fluid
film around the solid particles and cf* is the concentration of solute in β′ = x 0' + (2 − K ) + Kxm (15)
the fluid-phase film (SCF film) that is in equilibrium with the solid
surface. ⎡ ⎛ kL ⎞⎤
y* = ysat ⎢1 − exp⎜ − ⎟⎥
According to the approach used by Pardo [33], it is necessary to ⎣ ⎝ uε ⎠⎦ (16)
simplify the above partial differential equation. Hence, the simplifying
assumptions was used as follows: (I) the accumulation of solute in the k = (1 − ε )asf k sf (17)
bulk phase in comparison with the amount of solute in the solid
As stated before, this model (Eq. (6)) has three meaningful
material is negligible; (II) axial dispersion is insignificant, this condition
adjustable parameters including y*, xm and K which are the solubility
is satisfied when the Reynolds number is greater than 10 and the
of the solute in SCeCO2 reformed by diffusion restrictions (kg/kg), the
length/diameter ratio of the packed bed is larger than 50 [34]; (III) the
solute mass fraction in the first monolayer (kg/kg), and the ratio
concentration of the solute in the solid is approximately constant in the
between the adsorption equilibrium constants of the solute in the first
axial or radial directions; (IV) an adsorption situation is responsible for
monolayer and that in next layers (kg/kg), respectively. In this regard x
the solute-matrix interaction; (V) isothermal and isobaric process along
is the mass ratio between the solute extracted at time t and the
the entire extractor is considered; (VI) the process sharply reaches the
extractable solute initially present in the SFE packed bed (kg/kg); m0
equilibrium conditions and the model is mono dimensional and only the
is the initial extractable mass of solute extracted in the SFE packed bed
axial coordinate is regarded. With these assumptions and conditions,
(kg); QCO2 is the mass flow rate of CO2 (kg/s); ysat is the solute mass
the mass balance equation for the essential oil in the fluid phase is
fraction in the saturated SCeCO2 phase (kg/kg); L is the length of
reduced to the following equation:
extraction cell (m); u is the interstitial solvent velocity (m/s); ε is the
∂yf ⎛ ⎞ SFE bed porosity; asf is the effective solid-fluid contact area for mass
uε = k ⎜yf * − yf ⎟
∂z ⎝ ⎠ (3) transfer (m−1); k sf is the external mass transfer coefficient for the
transport of solute through the external fluid film around the solid
where k is presented by particles (m/s), that the external mass transfer coefficient was calcu-
k = (1 − ε )asf k sf lated using the following equation [36]:
(4)
ShDm
yf is the mass fraction of the solute in the SCF and yf* is the solute mass k sf =
dp (18)
fraction in the SCF film that is in equilibrium with the solid–fluid
interface. Sherwood number can be represented by several relationships.

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G. Sodeifian et al. The Journal of Supercritical Fluids 127 (2017) 146–157

Here, two correlations have been given, depending on the ranges of the 3) The algorithm systematically storing the best point found so far. The
dimensionless numbers Re and Sc: objective function uses to update the current amount. The annealing
(1): Re(0.26 − 1.90) & Sc(7.24 − 21.93) parameters depend on the values of estimated gradients of the
objective function in each dimension. The basic formula is:
Sh = 0.030Re0.75Sc0.33 (19)
⎛ T max(Si ) ⎞
[36] ki = log⎜ 0 ⎟
⎝ Ti Si ⎠ (26)
(2): Re(2 − 40) & Sc(2 − 40)

Sh = 0.38Re0.83Sc0.33 (20) where, ki is annealing parameter for component i, T0 is the initial

amount of component i, Ti is the current amount of component i and Si
[37] is the gradient of objective in the direction i.
The dimensionless parameters present in the above equations,
namely Re, Sc, and Sh are calculated by the following equations: 4) The algorithm stops when:
ρνdp
Re = i) The average change in the objective function is small relative to
μ (21)
function tolerance
μ ii) It reaches any other stopping criterion
Sc =
ρDm (22) In this study, SA was utilized to determine adjustable parameters of
dpk sf the mathematical model to minimize the error between the model
Sh = results and experimental data.
Dm (23)
The model performance (the error) was evaluated using a well- 3. Results and discussion
known statistical parameter called average absolute relative deviation
(AARD%) that is defined as follows: 3.1. Comparison of hydrodistillation (HD) and supercritical extraction
(SFE) techniques
n ⎛ y −y ⎞
1 ⎜ i,cal i,exp ⎟ × 100%
AARD% = ∑ ⎜ ⎟ The chemical compositions of essential oils obtained under optimal
n ⎝ y ⎠
i=1 i,exp (24)
SCeCO2 conditions were compared with the components extracted by
where, n is the number of experimental data, and yi;exp and yi;cal refer Clevenger. Twenty-seven components were identified using Clevenger
to experimental and calculated yields/times for the data i, respectively. which comprised 97.68% of the essential oils. Twenty-four constituents
Also, yi,cal corresponds to xi in Eq. (6). were extracted by the SCeCO2 extraction method in this study for the
first time that comprised 95.62% of the essential oil. The values
2.4.2. Simulated annealing (SA) algorithm (optimization algorithm) procured from the SCeCO2 and hydrodistillation methods were
Simulated Annealing (SA) is based on a statistical approach, a 0.8522 ± 0.0032 (w/w%) and 0.8330 ± 0.0052 (w/w%), respec-
Monte Carlo method, proposed by Kirkpatrick et al., and Cerny [38,39]. tively, supercritical extraction yield was slightly higher. Based on the
This technique has been widely utilized to solve several complex results presented in Table 2, the quality and type of the essential oil
problems [40,41]. SA is a probabilistic technique specifically, a
metaheuristic algorithm to approximate global optimization of a Table 2
function (optimal) or discrete space in a wide range of problems. The Comparison between essential oils extracted by the SFE and hydro-distillation methods,
identified by GC/Mass.
SA algorithm is based on a practical approach in materials processing
science. In fact, annealing is a thermal process for accessing low energy Number Component RI Area H.D. Area SFE
states in a material. In this process, at the first, the temperature is
increased to a value at which a solid melts, then the temperature is 1. α-pinene 942 0.57 0.97
slowly decreased until all particles have arranged themselves randomly, 2. Furan 972 1.06 1.48
3. β-pinene 976 0.38 –
if the cooling step of the material is sufficiently slow. These random 4. Octanal 984 3.45 4.95
fluctuations will allow the material to escape from local energy minima 5. dl-Limonene 1013 0.93 1.46
and are frozen in a configuration with some residual energy that 6. α-Thujone 1060 – 0.75
characterize the thermal stresses in material. In fact, annealing is a 7. Fenchone 1075 0.72 1.70
8. Nonal 1091 1.96 0.97
process where hardness of a mechanically deformed microstructure is
9. Camphor 1133 1.47 1.46
reduced at high temperature. There are four stages in annealing 10. β-Safranal 1156 0.57 –
process: cold work, recovery, recrystallization and grain growth [42]. 11. Anethole 1285 12.43 11.23
The goal of SA is to determine the minimum of the objective function of 12. Camphene 1325 0.72 1.66
the model parameters. The performance of the algorithm is as follows 13. Citronellyl acetate 1345 0.87 –
14. δ-elemene 1330 3.86 4.97
[43,44]: 15. Durylaldehyde 1367 16.85 7.70
16. β-caryophyllene 1413 2.74 7.55
1) The algorithm generates a random initial point. 17. β-gurjunene 1443 0.65 1.48
2) The algorithm determines the new point and compares them with 18. γ-muurolene 1468 2.85 –
19. germacrene D 1471 8.93 10.80
the current point, then algorithm chooses the best points to
20. β-selinene 1477 3.25 2.40
acceptance function (objective function). The probability of accep- 21. valencene 1488 2.20 1.68
tance is: 22. β-Ionone 1492 1.56 1.46
23. α-gurjunene 1498 1.18 3.61
1 24. Germacrene B 1496 3.31 1.52
⎛ Δ ⎞ 25. γ-cadinene 1512 13.91 14.14
1 + exp⎜ max(T ) ⎟
⎝ ⎠ (25) 26. caryophyllene oxide 1563 0.97 2.63
27. α-cadinol 1660 0.95 1.66
where Δ is new objection, T0 is the initial amount of component and T is 28. Spathulenol 1651 9.35 7.37
the current amount. 29. Total 97.68 95.62

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G. Sodeifian et al. The Journal of Supercritical Fluids 127 (2017) 146–157

compounds in both techniques were approximately the same. The Yield= + 0.66 + + 0.082x1 − 0.034x2 + 0.042x3 + 0.10x4 − 0.034x12
major components were anethole, spathulenol, durylaldehyde, germa-
− 0.003490x22 − 0.030x32 − 0.028x24 − 0.020x1x2 − 0.025x1x3
crene D, γ-cadinene, δ-elemene. On the other hand, a study on the
chemical composition of the essential oil of E. billardieri from Iran − 0.001187x1x4 − 0.008437x2x3 + 0.016x2x4 − 0.017x3x4 (25)
revealed forty- two compounds. The identified major components were
The analysis of variance (ANOVA) was used to indicate which terms
found to be α-muurolene, β- gurjunene, δ-cadinene and valencene [1].
are statistically significant and which one have a positive or a negative
effect on the extraction yield of essential oil from E. billardieri. Also, the
ANOVA result, F-values and corresponding p-values along with the
3.2. Prediction and optimization using RSM
estimated coefficients are presented in Table 4. The higher model F-
value (61.87) and the associated lower p-values (p < 0.0001) demon-
3.2.1. Experimental data analysis
strated the corresponding coefficients would be more significant and
RSM-CCD was applied to optimize SCeCO2 extraction conditions
also illustrate the best fit of the developed model. From statistical
and investigate the single and interactive effect of the process variables
analysis pressure (x1), temperature (x2), particle size (x3), and extrac-
including pressure (100–300 bar, x1), temperature (308–328 K, x2),
tion time (x4) affected the essential oil yield highly significantly
particle size (0.45–1.05 mm, x3) and time (30–150 min, x4) on the
(P < 0.0001). The pressure (x1), particle size (x3), and extraction time
maximum yield of essential oil from E. billardieri. Experimental data
(x4) (p = 0.0001) had a positive linear effect (p < 0.05) on the yield
obtained according to the RSM-CCD is presented in Table 3. The
of extraction as exhibited from the positive linear coefficients. The
experimental data was analyzed and fitted to linear, interactive (2FI),
linear effect of temperature (x2) (p = 0.0001) had a negative linear
quadratic and cubic models. Adequacy of model tested for response
effect on the extraction yield. Moreover, all of the extraction para-
(essential oil yield) is shown in Table 4. The results showed that linear
meters (x1–x3) had a negative quadratic effect (p = 0.0001) on the
and interactive (2FI) models had lower R2, adjusted R2, predicted R2
extraction yield. The interaction between (x1 × x2) (p < 0.05),
and high F-values to compare with quadratic model. Also, cubic model
(x1 × x3) (p < 0.05), (x2 × x4) (p < 0.05) as well as (x3 × x4)
was found to be aliased. Therefore, the quadratic model incorporating
(p < 0.05) was significant. The interaction between (x2 × x3) and
linear, interactive and quadratic terms was selected to describe the
(x1 × x4) was insignificant. A negative sign of the interaction coeffi-
current study.
cient between (x1 × x2), (x1 × x3) described a negative effect on the
essential oil yield. The goodness of fit of the regression model was
evaluated by the estimated value of the coefficient of determination,
3.2.2. Model fitting and statistical analysis
(R2), adjusted coefficient of determination, (R2 adj.) and predicted
A second-order polynomial equation was fitted to the experimental
coefficient of determination, (R2pred.), that were calculated to be
data. In fact, this empirical model was determined by fitting the
0.9830, 0.9671 and 0.9108, respectively. The high value of (R2) and
constants and coefficients into Eq. (1), so that the regression equation
(R2pred.) obviously shows the model precision in demonstrating the
as a function of the independent parameters, namely pressure (x1),
relationship between the response and independent variables. The
temperature (x2), particle size (x3), and extraction time (x4) was
value of adjusted R2 indicates that only 3.29% of the total variation
obtained as follows (in terms of coded levels):
was not explained by the model. Also, low value of the mean square
(0.040) displays the highest degree of precision and good reliability of

Table 3
The design matrix of CCD and the oil yield measured at different experimental conditions and predicted responses.

Std.order Pressure (x1) Temperature (x2) Particle size (x3) Time (x4) Experimental yield Predicted yield

1. 150.00 313.00 0.60 60.00 0.303 0.3189

2. 250.00 313.00 0.60 60.00 0.564 0.5753
3. 150.00 323.00 0.60 60.00 0.281 0.2758
4. 250.00 323.00 0.60 60.00 0.466 0.4521
5. 150.00 313.00 0.90 60.00 0.509 0.5038
6. 250.00 313.00 0.90 60.00 0.684 0.6601
7. 150.00 323.00 0.90 60.00 0.455 0.4269
8. 250.00 323.00 0.90 60.00 0.456 0.5033
9. 150.00 313.00 0.60 120.00 0.566 0.5233
10. 250.00 313.00 0.60 120.00 0.76 0.7749
11. 150.00 323.00 0.60 120.00 0.534 0.5441
12. 250.00 323.00 0.60 120.00 0.708 0.7158
13. 150.00 313.00 0.90 120.00 0.64 0.6401
14. 250.00 313.00 0.90 120.00 0.781 0.7918
15. 150.00 323.00 0.90 120.00 0.635 0.6273
16. 250.00 323.00 0.90 120.00 0.729 0.6989
17. 100.00 318.00 0.75 90.00 0.346 0.3600
18. 300.00 318.00 0.75 90.00 0.712 0.6880
19. 200.00 308.00 0.75 90.00 0.719 0.7140
20. 200.00 328.00 0.75 90.00 0.586 0.5780
21. 200.00 318.00 0.45 90.00 0.475 0.4560
22. 200.00 318.00 1.05 90.00 0.62 0.6240
23. 200.00 318.00 0.75 30.00 0.36 0.3480
24. 200.00 318.00 0.75 150.00 0.749 0.7480
25. 200.00 318.00 0.75 90.00 0.665 0.6600
26. 200.00 318.00 0.75 90.00 0.654 0.6600
27. 200.00 318.00 0.75 90.00 0.645 0.6600
28. 200.00 318.00 0.75 90.00 0.675 0.6600
29. 200.00 318.00 0.75 90.00 0.687 0.6600
30. 200.00 318.00 0.75 90.00 0.657 0.6600

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Table 4
Response surface model adequacy and ANOVA analysis.

Source Std. Dev R-square Adjusted R-square Predicted R-square p-Value PRESS

Linear 0.063 0.8714 0.7993 0.7610 0.0016 0.14

2FI 0.062 0.8830 0.8070 0.7359 0.0015 0.15
Quadratic 0.025 0.9832 0.9671 0.9108 0.0818 0.051
Cubic 0.015 0.9973 0.9887 0.8965 0.4787 0.059

Source Sum of squares df Mean-square F-value p-value Significance

Model 0.56 14 0.040 61.87 < 0.0001 Significant

X1 0.16 1 0.16 246.96 < 0.0001 Significant
X2 0.027 1 0.027 42.20 < 0.0001 Significant
X3 0.041 1 0.041 64.10 < 0.0001 Significant
X4 0.24 1 0.24 375.46 < 0.0001 Significant
X1* X2 0.006281 1 0.006281 9.72 0.0071 Insignificant
X1* X3 0.010 1 0.010 15.71 0.0012 Significant
X1* X4 0.00002256 1 0.00002.256 0.035 0.8543 Insignificant
X2* X3 0.001139 1 0.001139 1.76 0.2041 Insignificant
X2* X4 0.004258 1 0.004258 6.59 0.0215 Insignificant
X3* X4 0.004658 1 0.004658 7.21 0.0170 Significant
X1* X1 0.032 1 0.032 50.13 < 0.0001 Significant
X2* X2 0.0003340 1 0.00003340 0.52 0.4832 Insignificant
X3* X3 0.024 1 0.024 37.54 < 0.0001 Significant
X4* X4 0.021 1 0.021 33.25 < 0.0001 Significant
Residual 0.009692 15 0.0006462
Lack of fit 0.008532 10 0.0008532 3.67 0.0818 Insignificant
Pure error 0.001161 5 0.0002322
Core total 0.57 29

the conducted experiments. The lack-of-fit (0.0818) measures the
failure of the model to represent data in the experimental domain at
points which are not included in the regression.
3.2.3. Diagnostics of model adequacy
Data were evaluated with the aim of that the fitted model gives a
qualified (normal) approximation to the actual values and shows a
satisfactory fit. Also, residual (difference between the observed and the
predicted response value) gives poor or misleading results. In addition,
the small residual value indicates that model prediction is accurate.
Normal probability diagrams of these residuals are a suitable graphical
method for advising residuals normality that are shown in (Fig. 2a). The
data points on this plot lie reasonably close to the straight line which
shows an adequate agreement between real data and the data obtained
from the developed empirical models. It can be confirmed that the data
are normally distributed. Furthermore, by constructing the residuals
plot, a check was made to analyze the experimental data to find out its
satisfactory fit and the plot demonstrates that all the data points lie
within the limits (Fig. 2b). Diagnostic plots such as predicted against
actual (Fig. 2c) was used to evaluate the model compatibility and to
investigate the relationship between predicted and experimental data
[45,46]. It is worth mentioning that the optimized process conditions
was found to be pressure: 300 bar, temperature: 308 K, particle size:
0.75 mm and dynamic time: 130 min. The optimum yield of extraction
from the RSM was predicted to be 0.861 w/w%. The average extraction
yield was 0.8522 ± 0.0032 w/w%, indicating that very close to
estimated values.
3.3. Effects of process parameters on the extraction yield
Response surface methodology (RSM) taken into account the
individual and interaction effect of independent variables on the
extraction yield by three-dimensional (3D) plots and contour plots with
the response as a function of two independent variables, while the other
variables maintained at its respective fixed middle level, corresponding
to coded as zero. It is observable by the yield of extraction in relation to
the extraction pressure (x1: P), temperature (x2: T), particle size (x3: dp)
and dynamic time (x4: time) in Figs. 3–6 . Fig. 3 demonstrates the 3D
graphic response surface and contour plots for the influence of pressure
and temperature. Pressure is one of the important factors in extraction
of essential oil using SFE technique. From the results, it was observed
that the extraction yield increased with increasing pressure from 100 to
300 bar. Increase in pressure up to 300 bar could increase the fluid
density, decreasing the distance between the molecules, increasing
solvent power and solubility of the extract. This experimental observa-
tion was attributed to the increased solute/solvent attractive interac-
tions resulting from the highly compressed CO2 at high operating
pressures. As shown in Fig. 4, increment of temperature had a negative
effect on the extraction yield of essential oil. The variation of
temperature during the SFE can be attributed to retrograde solubility
in which the counter effect of solute vapor pressure and supercritical
fluid density are affecting the extraction yield. The effect of reducing
density and solubility prevails on the increase of vapor pressure; hence,
extraction yields slightly decreased by increasing the extraction tem-
perature. Similar results have been reported in the different of scientific
articles [25,47]. It is readily clear that particle size may inflict a dual
effect on the extraction yield. Increasing the available surface area for
the supercritical fluid across which to contact with the samples, cause
enhanced the yield of extraction. Moreover, the extraction yield
elevates when the particle size of the samples is small because the
diffusion path into the plant matrices was shorten, through which the
extract was to pass, decreasing in trap article mass transfer resistance.
In addition, the effect of particle size on cumulative extraction yield can
be pointed out in term of mass transfer resistances. The extraction of
solute from the solid matrix provides two types of mass transfer
resistances, namely internal mass transfer resistance and external mass
transfer resistance. In this case, extraction from different particle sizes
will largely depend on the length of the diffusion path [14,48,49]. In
Fig. 5, one can observe the effect of particle size and time on the
essential oil yield from E. billardieri. The extraction yield was increased
dramatically with increasing extraction time and reached a maximum
value at 130 min of extraction time (Fig. 6). It can be clearly seen that
higher amount of extraction process at initial extraction time was
caused by the higher extractable compounds contained in the surface of
the plant. Additionally, the supercritical fluid flows continuously
through the sample and it may be due to the extractible components

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Fig. 2. Diagnostic plots of model adequacy (Model fitting).

being easily accessible to the SCeCO2 [50]. into account diffusion, to calculate mass transfer from the SCF and to
investigate radial and axial dispersion in the extractor. Therefore, BET
approach can be usuful for the SFE process of natural matter
3.4. Mathematical modeling results
[33,51–53]. The empirical significant parameters of the BET developed
model and the physical properties are: solid phase density (s) 600 kg/
The adsorption based models such as BET have been used to take

Fig. 3. 3D graphic surface and contour plot for the effects of temperature and pressure on the yield of extraction.

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Fig. 4. 3D graphic surface and contour plot for the effects of temperature and extraction time on the yield of extraction.

Fig. 5. 3D graphic surface and contour plot for the effects of particle size and time on the yield of extraction.

Fig. 6. 3D graphic surface and contour plot for the effects of time and pressure on the yield of extraction.

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Table 5
The required and dimensionless parameters calculated during modeling.

Experiments The required parameters for model

Pressure (bar) Temperature(K) Particle size (mm) Dm ksf Re Sh Sc

300 318 0.75 7.5932 × 10−9 2.1422 × 10−5 2.8378 2.1160 13.1967
100 318 0.75 1.8752 × 10−8 4.6197 × 10−5 3.9296 1.8477 3.8590
200 318 0.75 8.9670 × 10−9 2.5218 × 10−5 3.1470 2.1693 10.0768
200 318 0.75 8.9670 × 10−9 2.5218 × 10−5 3.1470 2.1693 10.0768
200 328 0.75 1.0508 × 10−8 2.8877 × 10−5 3.3366 2.0612 8.1108
200 308 0.75 7.7489 × 10−9 2.2114 × 10−5 2.9427 2.1403 12.4704
200 318 0.75 8.9670 × 10−9 2.5218 × 10−5 3.1470 2.1693 10.0768
200 318 0.45 8.9670 × 10−9 2.0639 × 10−6 4.4057 2.7888 10.0768
200 318 1.05 8.9670 × 10−9 2.3816 × 10−5 3.1470 2.1093 10.0768

Table 6
Adjusted parameters for mathematical model at different experimental conditions.

Adjustable parameters

Experiments Viscosity(μ) Density (ρ) ysat K xm AARD%

−5
Exp. 1 8.9274 × 10 890.92 0.0079 12.818 0.5102 4.22
Exp. 2 3.6367 × 10−5 502.57 0.0045 27.960 0.5102 5.45
Exp. 3 7.3509 × 10−5 813.52 0.0076 14.587 0.5102 3.51
Exp. 4 7.3509 × 10−5 813.52 0.0076 14.587 0.5102 3.51
Exp. 5 6.4366 × 10−5 755.25 0.0047 5.660 0.5102 5.00
Exp. 6 8.3729 × 10−5 866.48 0.0090 21.813 0.5102 6.72
Exp. 7 7.3509 × 10−5 813.52 0.0076 14.587 0.5102 3.51
Exp. 8 7.3509 × 10−5 813.52 0.0040 14.587 0.5102 5.67
Exp. 9 7.3509 × 10−5 813.52 0.0067 14.587 0.5102 9.46

m3; initial oil concentration (x0) 0.011 g oil/g solid; bed porosity (ε)
0.4 m3/m3; diameter of the extractor (d) 0.015 m; bed height (h) 0.2 m.
Furthermore, the solvent density (ρf), solvent viscosity and critical
temperature (Tc), critical pressure (Pc), were obtained from NIST
chemistry web book in operational conditions (http://webbook.nist.
gov/chemistry/). The experimental conditions have been reported in
Table 5. Also, Table 5 shows the modeling results procured for the
following parameters: molecular diffusion coefficient, Reynolds num-
ber, Schmidt number, Sherwood number and finally mass transfer
coefficient (ksf). The calculated values of the model were compared
with the experimental data for extractions with SFE under the different
conditions. The results of analogy between the BET based model and
the experimental data was presented in Tables 5 and 6 and Figs. 7–9 . In
these figures, the solid lines are the model prediction and the points are
the experimental data.
The BET based model has three fitting parameters containing xm,
ysat and K that was determined by minimizing the errors between
experimental data and calculated yield (model) values (Table 6). The
average absolute relative deviation (AARD) was used to evaluate the
mathematical model results. Concentrating on the adjustable para-
meters, xm was obtained to illustrate all of data set in the SFE process. In
the other words, xm is the constant in different operating conditions due
to the fact that this parameter is independent of temperature, pressure
and it is dependent on the solid-solute interaction. Additionally,
because the initial mass of solute transferable relative to the mass of
solute in the first monolayer is more, the xm value was obtained less
than one. The similar behavior for xm parameter has been reported in
the literature for SCeCO2 extraction of other plants[33,54]. As can be
seen in Table 6, at the same temperature (318 K), the ysat values
increases approximately with increasing the pressure (100–300 bar) or
increasing the solvent density and the K parameter is reduced sig-
nificantly. Since the solid-solute molecular forces was declined with
increasing the solubility of the solute in the supercritical extraction and
ysat is directly proportional to solubility can also expect that the K

Fig. 7. Comparison between the model results and experimental SFE data for temperature Fig. 8. Comparison between the model results and experimental SFE data for pressure
(318 K) and particle size (0.75 mm). (200 bar) and particle size (0.75 mm).

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G. Sodeifian et al.
Fig. 9. Comparison between the model results and experimental SFE data for temperature
(318 K) and pressure (200 bar).
reduced. These results are compatible with the literature [33,54,55].
Fig. 7 exhibits the kinetics of the experimental data and calculated
values obtained at 100–300 bar and 318 K through SFE using the BET
based model, where the three stages (CER, FER and DC) can be
considered. Fig. 7 shows the most yield of extraction by SFE was
determined in pressure of 300 bar and temperature of 318 K during the
entire extraction time. The curves procured for the extraction using SCF
under the conditions of 100–300 pressure illustrated the three phases
(typical behavior of extraction curves). The first step of the curve
indicates the constant extraction rate (CER) and the second step, a
falling extraction rate (FER). Also, the third step demonstrates diffusion
controlled (DC) which is slow and the governing extraction mechanism
(diffusion). The third step, of course, has not been achieved in this
experiment and it was not obviously completed. Other researchers also
did not acquire the third stage using SFE [56–58]. The kinetic curves
shown in Fig. 8, represents that the highest extraction rate of essential
oil was achieved under the conditions of 308 K (The lowest tempera-
ture) and 200 bar. In the kinetic evaluations, the BET-based model
reveals where the three steps CER, FER and DC can be distinguished.
4. Conclusion
Extraction of essential oil from E. billardieri using supercritical
carbon dioxide (SFE) and hydrodistillation methods have been carried
out. Response surface methodology (RSM) based on a central composite
design (CCD) was utilized to evaluate the effect of operating conditions
such as pressure, temperature, particle size and dynamic time on the
SCeCO2 extraction. The maximum yield of essential oil was found to be
0.8522% and obtained at pressure of 300 bar, temperature of 308 K,
particle size 0.75 mm and extraction time of130 min. The predicted
results were revealed that the RSM method has the adequately agreed
with the experimental data. In sequence, the developed model of the
BET adsorption equilibrium equation has been employed to describe
the SFE process. The three adjustable parameters of the model, namely
xm, ysat and K were obtained via best fitting procedure applying
simulated annealing (SA) algorithm. Furthermore, the simple mathe-
matical model has a considerable good performance and might be used
as a first approximation for correlating experimental data on SFE. In the
other words, this model is capable of predicting the kinetic behavior of
the SFE process of essential oil from E. billardieri.
Acknowledgements
The authors would like to thank the research deputy of University of
Kashan for providing financial support for this project (Grant #1395/
6). Moreover, the authors express their thanks to the laboratory of
supercritical fluids of University of Kashan for providing experimental
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The Journal of Supercritical Fluids 127 (2017) 146–157
facilities. Furthermore, the authors would like to appreciate Senior
Engineer Mr. Allahyar Farrokhi, CEO of Aber Afarin Company, for
positive supports.
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