J.

of Supercritical Fluids 110 (2016) 265274

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

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

Extraction of oil from Pistacia khinjuk using supercritical carbon

dioxide: Experimental and modeling
Gholamhossein Sodeian , Sajad Ghorbandoost, Seyed Ali Sajadian,
Nedasadat Saadati Ardestani
Department of Chemical Engineering, Faculty of Engineering, University of Kashan, 87317-51167, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In the present work supercritical uid extraction (SFE) with carbon dioxide was performed to obtain
Received 30 September 2015 oil from Pistacia khinjuk (P. khinjuk) stocks fruit, for the rst time. Response surface methodology (RSM)
Received in revised form 5 December 2015 was used to optimize the process and evaluate the effect of different operating parameters including
Accepted 5 December 2015
pressure (1224 MPa), temperature (3555 C), ow rate (26 g/min) and extraction time (0300 min)
Available online 9 December 2015
on the total oil yield. The relationship between the yield of P. khinjuk fruit oil and the extraction variables
was determined by a second order poly-nominal equation applying the central composite design (CCD).
Keywords:
The maximum oil yield was found to be 78.10 wt% under optimal conditions pressure of 23.39 MPa,
Supercritical uid extraction
Pistacia khinjuk oil
temperature of 55 C, CO2 ow rate of 4.37 g/min and dynamic extraction time of 286.45 min. Sovovs
Prediction mathematical model was applied to describe adequately the kinetic behavior of the extraction process.
RSM The concentration of hardly accessible solute (xk ), the mass transfer coefcients in the uid phase (kf )
Mathematical modeling and solid phase (ks ) as well as the oil solubility in supercritical CO2 (yr ) were used as tting parameters.
The chemical composition of the extracts was identied by gas chromatography spectrum (GC) analysis.
Moreover the physicochemical properties of the oil samples were measured to characterize the oil quality.
The desired and promised nutritional properties of the oil proposed that it can be considered as a good
product in the future food industry.
2015 Elsevier B.V. All rights reserved.

1. Introduction extraction techniques such as pressurized-hot water extraction

Pistacia khinjuk Stock is one of the large number species of the
genus Pistacia in the Anacardiaceae family which wildly grows in
some Asian countries such as Iran, Iraq and Syria [1]. This plant
is traditionally used as a herbal treatment for stomach related
illnesses, motion disease [2], and skin lesions [3]. Different phar-
macological properties of P. khinjuk including anticholinesterase,
antitumor, antidiabetic, antifungal and antimicrobial activities
have been studied [4]. Also antioxidant effects of P. khinjuk was
conrmed through investigating phenolic and avonoid content in
the plant extract [5,6]. The major constituents of P. khinjuk hull oil
are palmitic, palmitoleic, stearic, oleic, linoleic and linolenic acid.
The plant hull oil is suitable as an edible vegetable oil because of
its high amount of Tocols (tocopherol and tocotrienol), low value
of saponication number and high oxidative stability [7]. Addi-
tionally the main fatty acid components of oil from kernel of P.
khinjuk fruit are the same as its hull oil [8]. Recently, various novel
Corresponding author. Tel.: +98 3155912406; fax: +98 3155912930.
E-mail address: sodeian@kashanu.ac.ir (G. Sodeian).
(PHWE), supercritical uid extraction (SFE) and ultra-sonication
assisted extraction (USE) have been developed for extraction of
different compounds from natural sources [9]. Among the new
methods, supercritical uid extraction has been extensively stud-
ied as a noteworthy alternative to conventional techniques of
oil extraction including organic solvent extraction and hydro-
distillation. It has been proven that SFE can achieve extraction yield
relatively equal to those gained by conventional Soxhlet extrac-
tion using n-hexane [10]. The most commonly used solvent in
SFE is carbon dioxide because of its unique characteristics namely
non-toxic, non-ammable, non-polar, non-explosive, inexpensive,
easily removed from the extract, higher extraction rate [11,12]
and also high selectivity by manipulating the process pressure and
temperature[13,14].
Response surface methodology (RSM) as an effective and pow-
erful statistical approach has been frequently used to optimize
various operating conditions such as pressure, temperature, ow
rate and dynamic time of the SFE processes. The main methods of
experimental design applied in the optimization of SFE are Taguchi,
Central Composite Design (CCD) and BoxBehnken Design (BBD)
[15,16].

http://dx.doi.org/10.1016/j.supu.2015.12.004
0896-8446/ 2015 Elsevier B.V. All rights reserved.
266 G. Sodeian et al. / J. of Supercritical Fluids 110 (2016) 265274

Fig. 1. Schematic diagram of supercritical CO2 extraction set-up.

Simulation of a supercritical extraction process via mathemati- the extracted oil were determined to evaluate the suitability of P.
cal modeling is required to determine the parameters which used khinjuk fruit oil as an edible nutritional oil.
in the prediction, optimization and scale up of the process. Wide
variety of kinetic models have been established and developed to be 2. Material and methods
employed in supercritical uid extraction [17]. The models gener-
ally divided into three main groups based on different approaches: 2.1. Materials
empirical models, models developed by analogies between heat
The P. khinjuk fruits used in this study were picked from wild
and mass transfer, and models based on differential mass balances
plants during September 2014 from high-areas (graphical coor-
integration [18,19].
dinate included 39 29 north latitude and 51 39 east longitude)
Scientic sources reviews showed that many attempts have
of Kazerun in the Fars province, Iran. The CO2 gas (99.90% purity)
been made on extraction of oil and essential oil from different parts
was purchased from Aboughaddareh Gas Factory. Hexane with a
of P. khinjuk applying distillate water [20] and organic solvents such
purity of 99.99% was provided by Merck (German Company). To
as ethanol [5], methanol [21] and n-hexane [22]. But there has not
prepare the samples before performing the tests, the samples were
yet been any reports on supercritical uid extraction of oil from
washed with distilled water, to remove possible dusts or other
P. khinjuk fruit in the literature. For this purpose, response surface
major surcial pollutions, and dried in shadow under ambient
methodology (RSM) with Central Composite Design (CCD) was used
temperature until the associated unbound water was completely
to realize the effect of process variables (pressure, temperature, sol-
removed. Moisture of fruit is one of the most important factors
vent ow rate and dynamic time) on the extraction yield and then to
inuencing extraction yield. Therefore, moisture content of seeds
determine optimal conditions. A mathematical model was utilized
were determined directly by oven drying at 100105 C for 10 h.
to investigate the kinetic behavior of the SFE. The model parame-
The seeds were placed in desiccator until constant weight was
ters consisting of mass transfer coefcient in solid and uid phases,
achieved (measured at less than 4% for original sample). They were
oil solubility into SC-CO2 and initial oil content in intact cells were
crushed in a mill and then granulated based on a desired size using
optimized by differential evolution (DE) algorithm. The predictive
a sieve and shaker.
ability of the model was validated by comparing the experimental
data with the model results through a statistical parameter of abso- 2.2. Methods
lute average relative deviation (AARD). Fatty acids composition of
the extracts, obtained with SFE and Soxhlet methods, was specied 2.2.1. Extraction of oil by classical method
by gas chromatography. Finally the physicochemical properties of Fifty grams of ground P. Khinjuk fruits were put into a glass thim-
ble and moved to a Soxhlet apparatus in order to extract the oil of
Table 1 the sample. Five hundred mililiter of n- hexane was used as an
Coded and uncoded values of the independent variables applied in the experimental extraction solvent at 78 C for 8 h. The residual solvent was elim-
design. inated from the extract under vacuum at 40 C applying a rotary
Coded levels Pressure Temperature Mass-ow rate Extraction vacuum evaporator. After evaporation of the solvent, the mass of
(MPa) ( C) (g/min) time (min) the recovered oil was measured gravimetrically, and then the oil
2 12 35 2 60
sample was kept in dark until being needed for analysis.
1 15 40 3 120
0 18 45 4 180 2.2.2. Supercritical uid extraction procedure
1 21 50 5 240 The extraction experiments were carried out in a bench scale SC-
2 24 55 6 300
CO2 apparatus shown in Fig. 1. Ground P. khinjuk fruits (5 g), mixed
 G. Sodeian et al. / J. of Supercritical Fluids 110 (2016) 265274 267

Table 2
Experimental results and predicted yields obtained from RSM design for extraction of P. khinjuk fruit oil.

Std. run Point type Pressure (x1 ) Temperature (x2 ) Flow rate (x3 ) Time (x4 ) Experimental yield Predicted yield

1 Factorial 15 40 3 120 26.63 26.76

2 Factorial 21 40 3 120 44.90 46.18
3 Factorial 15 50 3 120 29.91 29.46
4 Factorial 21 50 3 120 49.03 48.20
5 Factorial 15 40 5 120 42.01 40.50
6 Factorial 21 40 5 120 57.48 57.32
7 Factorial 15 50 5 120 44.03 43.20
8 Factorial 21 50 5 120 59.04 59.34
9 Factorial 15 40 3 240 44.34 45.44
10 Factorial 21 40 3 240 58.65 60.42
11 Factorial 15 50 3 240 48.86 48.14
12 Factorial 21 50 3 240 61.34 62.44
13 Factorial 15 40 5 240 54.59 55.42
14 Factorial 21 40 5 240 66.89 67.80
15 Factorial 15 50 5 240 58.88 58.12
16 Factorial 21 50 5 240 69.94 69.82
17 Axial 12 45 4 180 32.65 33.96
18 Axial 24 45 4 180 66.98 65.08
19 Axial 18 35 4 180 60.83 58.88
20 Axial 18 55 4 180 62.23 63.60
21 Axial 18 45 2 180 35.56 34.12
22 Axial 18 45 6 180 54.34 55.24
23 Axial 18 45 4 60 33.09 34.52
24 Axial 18 45 4 300 65.90 63.88
25 Central 18 45 4 180 55.20 55.36
26 Central 18 45 4 180 53.24 55.36
27 Central 18 45 4 180 56.58 55.36
28 Central 18 45 4 180 54.27 55.36
29 Central 18 45 4 180 56.98 55.36
30 Central 18 45 4 180 55.91 55.36

uniformly with 1 mm diameter glass beads, and were loaded into
the extraction vessel. The extractor had a capacity of 74 ml with
internal diameter and height of 0.025 m and 0.15 m respectively.
Carbon dioxide was fed from a gas tank equipped with a condenser
to keep CO2 liqueed. A pump was used to put the liqueed carbon
dioxide under the needed pressure. The high pressure carbon diox-
ide was passed through a surge tank before feeding to the packed
bed vessel. The surge tank and the vessel were designed as shell and
tube where the warm water was circulated in their shell at constant
temperature. In this study, the static time was considered about
30 min by feeding SC-CO2 to the vessel while the outlet back pres-
sure valve was closed. The dynamic conditions were then initialized
by opening the back pressure valve. To prevent the back pressure
valve from freezing, it was wrapped with heating element. The tem-
perature of sample collection was kept at below 0 C by using ice
and salt bath during the dynamic extraction time. The quantity of
samples was measured gravimetrically, subsequently the samples
stored in a sealed dark container which was maintained in a freezer
until needed for analysis. Each experiment was performed in trip-
licate and nally their mean values were reported. The extraction
yield was calculated according to Eq. (1)
Oil yield (%)
Amount of extracted oil (g)
= 100%
Amount of total oil in initial ground sample (g)
and maintained at this temperature for 35 min. Helium (of 99.99%
purity) was utilized as the carrier gas, with a ow rate of 1 cm3 /min.
The analysis was performed with a detector temperature of 250 C
and an injector temperature of 220 C and a 1 L sample, with split
injection (1:20).
2.4. Design of experiments
The response surface methodology (RSM) was utilized to deter-
mine the optimal conditions for supercritical carbon dioxide
extraction of oil from the P. khinjuk fruit. The effects of four inde-
pendent variables, namely pressure (X1 , MPa), temperature (X2 ,
C), mass-ow rate (X , g/min) and dynamic time (X , min) on
3 4
the extraction yield were investigated using the Central Composite
Design (CCD). The coded values of the variables and their related
un-coded levels used in the experimental design are presented in
Table 1. As introduced in Table 2, a total number of 30 experiments
with the four factors at ve levels of variation were dened from
CCD, which includes 16 factorial points (point 1 to point 16), 8 axial
points (point 17 to point 24) and 6 central points (point 25 to point
30).
Relevance of the oil yield (Y) to the coded independent variables
is expressed by the following second-order polynomial model:
(1) 
4 
4 
4 
4
Y = 0 + i Xi + ii Xi2 + ij Xi Xj + Error (2)
i=1 i=1 i=1 j>1

2.3. Gas chromatography
The quantitative determination of fatty acids in the P. khin-
juk fruit oil was performed in a gas chromatograph (YL CLARITY,
model 6500), equipped with a split 1/20 injector and FID detec-
tor, using a Wcot Fused Silica Coating CPsil 88 for FAME capillary
column (0.25 mm i.d. 100 m, lm thickness 25 mChompack
the Nethrlands). The initial temperature of the column was main-
tained at 110 C for 10 min and raised to 200 C at a rate of 10 C/min,
where, 0 is a constant, i , ii and ij are the linear, quadratic
and interaction terms, respectively. Xi and Xj are the coded
degrees of independent parameters. The stated unknown regres-
sion coefcients were established by tting the model with respect
to experimental data points. All experiments were randomly car-
ried out in triplicate in order to minimize systematic errors, and
the validity of the model was assessed through analysis of variance
(ANOVA), coefcient of determination (R2 ) and adjusted coefcient
of determination (adj. R2 ). The design matrix of CCD and the oil
268 G. Sodeian et al. / J. of Supercritical Fluids 110 (2016) 265274
yield measured at different experimental conditions are shown in
Table 2. Analysis of the results was carried out by Design expert
(trial version 7.0.0, Stat Ease, USA) software.
2.5. Mathematical modeling
In this section, the extended Lacks plug ow model proposed
by Sovov [23] was used to study the extraction of oil from a milled
solid matrix into supercritical uid. In the model a part of total ini-
tial solute within solid phase is considered to be trapped in intact
cells and is hardly accessible while the rest existing in broken cells
is readily exposed to the solvent on the surface of the particles.
Extraction time is divided into three periods which is attributed to
the above description. During the rst period the easily accessible
solute covers the external surface of the solid particles through-
out the bed and the extraction happens at a constant rate which is
controlled by the resistance of the solvent lm surrounding the par-
ticles. After the rst period the free solute of the particles at the bed
entrance is fully exhausted and the inaccessible solute which is pre-
sented in interior sections of these particles begins to be extracted
based on the diffusion mechanism. This trend is consistent dur-
ing the second extraction period from the inlet to the outlet of the
bed, so the extraction rate is simultaneously determined by the
diffusion and convection rates. When the second period nishes,
the all particles have only the inaccessible solute which is situated
deeper inside them, and the extraction process is affected just by
the internal mass transfer resistance. The model assumes that the
ow regime is a plug and axial dispersion is negligible. Particle size
distribution and initial solute content are uniform in the extractor.
Finally the bed porosity, pressure and temperature are constant.
According to the differential mass balance equations for the solid
and uid phases, Sovov developed the following expressions to
describe the specic amount of extracted solute e (g solute/g solute-
free feed) as a function of a specic quantity of solvent q (g solvent/g
solute-free feed) which is consumed during the three different
periods:
qyr [1 exp (Z)]
q < qm
yr [q qm exp (Zw Z)]
e= qm q < qn
 
extraction regions x0 is the initial total concentration of the solute
in the bed (g solute/g solute-free feed). xk is the initial content of
barely accessible solute inside the particles (g solute/g solute-free
feed). s and f are the densities of solid and uid phases (kg/m3 ),
respectively. is the void fraction of the bed (m3 /m3 ), a is the spe-
cic interfacial area of the solid particles (m2 /m3 ), yr is the extract
solubility in SC-CO2 (g solute/g solvent), t is extraction time (s). ks
and kf are the solid and uid phases mass transfer coefcients (m/s),
respectively. x0 was determined by Soxhlet extraction technique,
solid density was calculated according to Rahman [24], bed poros-
ity was easily calculated considering the mass and the density of
particles and the extractor volume. Finally, the oil solubility was
taken as an adjustable parameter of the model.
2.6. Differential evolution (DE) algorithm
Differential evolution (DE) method, an almost novel optimiza-
tion technique, uses a simple evolution strategy signicantly
making it easy to use, fast and capable in terms of numerical opti-
mization which is more likely to nd the true global optimum
of a function. Similar to genetic algorithms (GAs), the DE algo-
rithm is based on population, using similar operators like crossover,
mutation, and selection. While simple GA uses a binary coding to
represent problem parameters, DE uses real coding of oating point
numbers. In DE, the mutation operator is addition instead of bit-
wise ipping which is used in GA. In order to create new solution
strings, DE utilizes non-uniform crossover and tournament selec-
tion operators. DEs main advantages are as follows: ease of use,
its simple structure, robustness, and speed. Functions can be opti-
mized through this technique with real variables and many local
optima. Depending upon the type of problem for which DE is used,
one can adopt different strategies. These can vary based on the
vector for perturbation, the number of vectors considered to be
perturbed, and nally the type for crossover to be used. Depending
on the specic problem applied, choosing number of population
(NP), scaling factor (F), and crossover constant (CR) would vary and
is often difcult, but some general guidelines are available. Nor-
mally, NP should be about 510 times the number of parameters
in a vector. As for F, it lies in the range 0.41.0. Initially F = 0.5 can
be tried then F and/or NP is increased if the population converges
prematurely. As a rst choice for CR, 0.1 is good, but generally CR
 


x0 yr ln 1 + exp Wx0 1 exp [W (qm q)] xk qn q should be as large as possible [25]. Babu and Munawar [25] reported
W yr x0 more details of basic version of DE (pseudo code), its strategies, and
(3) selection of operating parameters. In the current work, the parame-
ter values used for DE are: Population size (NP)=100; Scaling factor
(F) = 0.8; Crossover constant (CR)=1. As of now, DE has been suc-
Where cessfully applied for solving several complex problems which in
(x0 xk ) turn is now being known as a potential technique for more precise
qm = (4)
yr Z and faster optimization [26]. In this study, DE was utilized to deter-
  mine adjustable parameters of the mathematical model, such as
1 x + (x0 xk ) exp(Wx0 /yr )
qn = qm + ln k (5) mass transfer coefcient in uid and solid phase, oil solubility and
W x0 initial mass fraction of oil in intact cells through minimizing error
Zw yr
 x exp  between the model results and experimental values of oil yield.
0 [W (q qm )] xk
= ln (6)
Z Wx0 x0 xk
3. Result and discussion
kf af
Z= (7)
q(1
)s 3.1. Analysis of the RSM model
ks a
W= (8) The analysis of variance (ANOVA) was performed using the
)
q(1
data listed in Table 2 with the purpose of examining signicance
qm and qn are q values when extraction of the solute within the of the variables as linear, quadratic, or interaction coefcients of
particles begins and the easily accessible solute is fully extracted, the RSM model. Those variables and their interactions with higher
respectively. q is specic mass ow rate of the solvent. Z and W are regression coefcient and smaller p-value (p < 0.05) have a remark-
dimensionless mass transfer parameters in solid and solvent phases able inuence on the oil yield [27]. Therefore the non-signicant
being proportional to the mass transfer coefcients of two phases. variables (p > 0.05) were removed from the initial model and the
zw is dimensionless boundary coordinate between slow and fast experimental data retted with respect to the signicant variables
 G. Sodeian et al. / J. of Supercritical Fluids 110 (2016) 265274 269

Table 3
RSM model adequacy and ANOVA analysis.

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

Linear 4.34 0.8799 0.8607 0.8221 0.0067 696.87

2FI 4.75 0.8907 0.8332 0.8109 0.0039 740.79
Quadratic 1.69 0.9890 0.9788 0.9480 0.3094 203.69
Cubic 1.27 0.9971 0.9881 0.9542 0.7651 179.34

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

Model 3874.37 14 276.74 96.64 <0.0001 Signicant
X1 1452.06 1 1452.06 507.06 <0.00010 Signicant
X2 33.46 1 33.46 11.69 0.0038 Signicant
X3 669.50 1 669.50 233.79 <0.0001 Signicant
X4 1291.84 1 1291.84 451.12 <0.0001 Signicant
X1 X2 0.45 1 0.45 0.16 0.6977 Insignicant
X1 X3 6.68 1 6.68 2.33 0.1474 Insignicant
X1 X4 19.62 1 19.62 6.85 0.0194 Signicant
X2 X3 0.86 1 0.86 0.30 0.5927 Insignicant
X2 X4 0.79 1 0.79 0.28 0.6066 Insignicant
X3 X4 14.03 1 14.03 4.90 0.0428 Signicant
X1 X1 58.17 1 58.17 20.31 0.0004 Signicant
X2 X2 59.47 1 59.47 20.77 0.0004 Signicant
X3 X3 195.90 1 195.90 68.41 <0.0001 Signicant
X4 X4 64.73 1 64.73 22.61 0.0003 Signicant
Residual 42.95 15 2.86
Lack of t 32.83 10 3.28 1.62 0.3094 Insignicant
Pure error 10.12 5 2.02
Core total 3917.33 29

in order to gain the nal appropriate response model. According Table 4

Estimated regression coefcients of the RSM model.
to the analysis results which summarized in Table 3, the variables
which statistically indicated highly signicant impact on the Term Coefcient SE Coefcient
extraction yield were linear term of pressure, CO2 ow rate and Constant 55.36 0.69
time (p < 0.0001), followed by the quadratic term of ow rate X1 7.78 0.35
(p < 0.0001). The quadratic term of time (p = 0.0003), the linear term X2 1.18 0.35
of temperature (p = 0.0038) as well as the quadratic term of pressure X3 5.28 0.35
X4 7.34 0.35
and temperature (p = 0.0004), represented signicant inuence on
X1 X2 0.17 0.42
the oil yield. It can be clearly inferred from the model F-value of X1 X3 0.65 0.42
96.64 (p < 0.0001) that the model was considerably signicant and X1 X4 1.11 0.42
extremely appropriate for the present experimental results. Con- X2 X3 0.23 0.42
X2 X4 0.22 0.42
sequently the below equation illustrated the total extraction yield
X3 X4 0.94 0.42
as a function of the coded independent variables: X1 X1 1.46 0.32
X2 X2 1.47 0.32
X3 X3 2.67 0.32
Yield = 55.36 + 7.78x1 + 1.18x2 + 5.28x3 +
X4 X4 1.54 0.32
7.34x4 1.46x12 + 1.47x22 2.67x32 1.54x42 0.17x1 x2 (9)

0.65x1 x3 1.11x1 x4 0.23x2 x3 + 0.22x2 x4 0.94x3 x4
The model summary statistics were carried out on the experi-
mental data in this present study and the results are given in Table 3.
From the results, it was found that, quadratic model was suitable
for prediction of experiments.
The high adequacy of the model can be easily evidenced by R2
and Adj. R2 of 0.9890 and 0.9788, respectively. The adjusted R2
value of the model exhibits that 0.9788 of total variations related
to the extraction yield caused by the effective operating parame-
ters including pressure, temperature, CO2 ow rate and dynamic
extraction time. The low value of coefcient variation (C.V = 3.25)
showed the reliability of experiments conducted. Adequate pre-
cision 36.06 indicated an adequate signal as this value should be
above 4 explaining the signal to noise to navigate the design space
excellently. The p-value of the lack of t is 0.3094, which suggests
that insignicant lack of t is good for data tness to the model.
This result shows that the RSM model is capable to predict the
experimental data in the range of operating conditions. The opti-
mized parameters were determined by applying Eq. (9) as follows:
pressure = 23.39 MPa, temperature = 55 C, ow rate = 4.37 g/min,
time = 286.45 min which resulted in oil yield of 78.10%. The results
of the complete analysis of variance (ANOVA) are presented in the
Table 3, and the estimated regression coefcients with standard
errors are shown in Table 4.
3.2. Effect of operating parameters
In this section the inuences of various independent parameters
on the extraction yield are shown through response surface plots
which presented in Fig. 2af the surface plots were obtained by
changing two parameters within their experimental ranges while
the other parametes were maintained at their respective central
levels as shown in Table 1. The solid particle size was considered
to be constant in all experiments at 0.6 mm. Fig. 2a as a response
surface graph illustrates the interactive effect of pressure and tem-
perature on the total oil yield at a xed CO2 mass ow rate of 4 g/min
and an extraction time of 180 min. At a constant temperature the
yield of oil was considerably affected by increasing pressure until
about 21 MPa and then the slope of the graph decreased. As the
pressure went up, the density of the solvent would increase, caus-
ing an enhancement in SC-CO2 solvating power and therefore led to
higher oil recovery. On the other hand, higher pressure had a neg-
ative quadratic effect on the oil yield. This was probably due to the
facilitated solute-solvent repulsion resulting from the highly com-
pressed CO2 [28,29]. Therefore, it should be taken into account that
270 G. Sodeian et al. / J. of Supercritical Fluids 110 (2016) 265274

55

Fig. 2. Response surface plots for the oil yield as a function of: (a) pressure and temperature; (b) pressure and CO2 ow; (c) pressure and dynamic time; (d) CO2 ow rate
and temperature; (e) dynamic time and temperature; (f) dynamic time and CO2 ow rate.

very high pressures showed little impact on the oil yield because
of the explained opposing effects of pressure. Temperature has two
counteracting effects on the oil yield, for this reason evaluation of its
inuence on the process is more complicated than that of pressure.
When the temperature rises, the density of SC-CO2 reduces, result-
ing in a decreased solvent power. Conversely, the extract vapor
pressure is raised with increasing temperature, which leads to an
enhancement in the supercritical uid solubility. Thus increasing
temperature changes the solubility of the SC-CO2 depending on
whether the solvent density or the extract vapor pressure is pre-
vailing factor [30,31]. At a selected pressure the oil yield gradually
lessened as temperature increased before critical value of 45 C,
 G. Sodeian et al. / J. of Supercritical Fluids 110 (2016) 265274 271

conrming that density is more effective than the extract vapor (a) 90
pressure. Further increase in temperature above the critical point 80
favored the efciency of the extract. The effect of SC-CO2 ow 70
rate and pressure on the extraction yield at 45 C and 180 min

Extraction yield %
60
are depicted in Fig. 2b. Increasing the ow rate from 2 g/min to 50 Model results
about 4.37 g/min decreased the lm thickness around the particles 40
15 MPa
throughout the bed which lowered the external mass transfer resis- 30
tance; consequently the extraction efciency was enhanced. The 20 21 MPa
oil recovery seemed to be constant for ow rates above 4.37 g/min 10 Optimal conditions
due to two intersection effects happened in this region. The resi- 0
dence time of the uid decreased while the external mass transfer 0 50 100 150 200 250 300
coefcient increased, so these opposite phenomena canceled their Time (min)
effects out leading to the almost constant oil yield [32]. The reason
(b) 80
was that the SC-CO2 ow rate had a reciprocal highly positive linear
70
(p < 0.0001) and signicantly negative quadratic effect (p < 0.0001)
on the oil recovery. According to the Fig. 2b the interaction effect 60

Extraction yield %
of extraction pressure and the solvent ow rate is clearly signif- 50
icant in the range of the lower amount of the variables. Fig. 2c 40 35 C
shows the effects of pressure and dynamic time on the extrac- 30 55 C
tion yield at xed 4 g/min and 45 C. In this research, prior to
20 Optimal conditions
dynamic extraction a static time of 30 min was considered for all
10 Model prediction
experiments in order to improve the extract yield due to possible
equilibrating impact on the extract transfer from the solid parti- 0
0 20 40 60 80 100 120 140 160 180 200
cles to the supercritical solvent [33]. Increasing extraction dynamic
Time (min)
time makes improvement in the oil yield because of consuming
fresh solvent passing through the bed until there is inuential (c) 90
mass transfer driving force between the solid and uid phases. As 80
summarized in Table 3, dynamic time has an extremely positive
70
linear effect (p < 0.0001) and signicant negative quadratic effect
Extraction yield %

60
(p < 0.05) on the extraction yield. At the higher range of dynamic
time, the stated dual counter effects cancel each other and the driv- 50 Model prediction
ing force is slightly removed, therefore the enhancing trend of the 40
oil recovery is almost stopped [33,34]. The interaction of dynamic 3 g/min
30
timepressure and dynamic time-ow rate displayed signicant 20 5 g/min
effect (p < 0.05) while the interaction of ow rate-temperature
10
and timetemperature showed insignicant effect (p > 0.05) on the Optimal conditions
0
total yield as visualized by response surfaces plots which indicated
0 50 100 150 200 250 300
in Fig. 2. Time (min)

Fig. 3. Effect of process parameters on the extraction yield of P. khinjuk fruit oil
3.3. The mathematical modeling of the supercritical extraction versus time. (a) 50 C and 5 g/min: (b) 18 MPa and 4 g/min; (c) 40 C and 21 MPa.

The SC-CO2 extraction modeling is an effective approach to

determine the extraction yield and mass transfer parameters,
nally to optimize and scale-up the process. In order to apply
the BIC model equations, the following parameters which exper-
imentally determined were required: solid phase density (s )
1100 kg/m3 ; initial oil concentration (x0 ) 0.859 g oil/g oil
free feed; bed porosity () 0.4 m3 /m3 ; solid particle size (dp )
0.6 mm; diameter of the extractor (d) 0.025 m; bed height (h)
0.1 m. The solvent density (f ) was obtained from NIST chem-
istry book (http://webbook.nist.gov/chemistry/). According to the
results depicted in Fig. 3a-c, the calculated values of total yield
by Sovovs model were highly consistent to the experimental
data points. The adjusted model parameters including an initial
mass fraction of the solute in intact cells, oil solubility into SC-CO2
and mass transfer coefcients in the solid and liquid phases are
shown in Table 4. The mass transfer coefcient in the uid phase,
kf decreased with rising pressure because of a reduction in the
supercritical solvent velocity which led to increasing external mass
transfer resistance. The solvent ow rate showed a positive effect
on kf due to the decrease in the mass transfer resistance. Addi-
tionally, kf was raised by increasing the extraction temperature
which caused an increase in the extract diffusivity into the super-
critical carbon dioxide. The mass transfer coefcient in the solid
phase, ks increased with increasing pressure and the resistance
in the solid particles decreased. Furthermore, the increase in
solvent ow rate led to an increase in ks , indicating that the
extraction yield was mainly affected by the convection in the
uid phase. The same result has been reported in the literature
[35,36]. The BIC model has been extensively used for simulating
SFE of different vegetable matrices where the internal and exter-
nal mass transfer coefcients taken as model parameters regressed
against the experimental data. For example the reported results
indicated that the values of ks and kf were 1.63.65 109 and
2.173.61 106 m/s for soybean oil [36], 1.271.77 108 and
0.971.38 106 m/s for rosemary oil [37], 0.920.7 109 and
2.918.47 106 m/s for Plumula nelumbinis oil [38], 1.1 108
and 4.66 106 m/s for pumpkin seed oil [39], 5.1 1010 and
1.02 106 m/s for paprika fruit seed oil [39], respectively. Anal-
ysis of the results revealed that kf was generally 24 orders of
magnitude larger than ks for all experiments. The solute located
on the surface of the solid particle moves across the uid lm more
rapidly than the solute restricted with the solid matrix [40], caus-
ing a smaller mass transfer coefcient in the solid phase. The BIC
model has four tuning parameters including kf , ks , xk and yr that
were computed by minimizing the errors between experimental
and calculated yield values (Table 5). The average absolute relative
272 G. Sodeian et al. / J. of Supercritical Fluids 110 (2016) 265274

3.5. Fatty acid composition of the extracted oil

The fatty acid (FA) prole of P. khinjuk fruit oil extracted by

Fig. 4. SEM images of the surface of the dry P. khinjuk fruit: (a) before extraction
and (b) after extraction.
the Soxhelt method with n-hexane and by SFE at optimized condi-
tions are presented in Table 6. It can be concluded from the results
that the FA content of the oil obtained by the Soxhlet and SC-CO2
extraction are approximately similar. Since CO2 and n-hexane used
in the SFE and the Soxhelt extraction were both non-polar sol-
vents, so they extracted the oil from the solid matrix in a same
way. Gas chromatography disclosed that the amount of unsatu-
rated fatty acids (UFA) consisting palmitoleic (C16:1), oleic (C18:1),
linoleic (C18:2) and linolenic acids (C18:3), identied in the all sam-
ples, was more than that of saturated ones (SFA) including palmitic
(C16:0) and stearic acids (C18:0). The unsaturated fatty acids (UFA)
content was around 76% of total FAs which can focus attentions
on the signicance of this plant oil. A criterion for evaluating the
nutritional and functional properties of oil is the proper ratio of sat-
urated to unsaturated (S/U) FA. The average value of S/U FA ratios
of the samples extracted by the various methods was 0.32 which
is noticeably low when compared with some other vegetable oils
like soybean, peanut, olive and corn [4143]. The main compo-
nent of the UFA was oleic acid with concentration averagely at
57%, followed by linolenic acid, while stearic acid with average
content of 22% was the most prevalent constituent of saturated
fatty acids. Several medicinal properties of oleic acid was recently
investigated, for instance it can lower the risk of cardiovascular
diseases by decreasing the level of lipoprotein cholesterol in blood
plasma and control genes that trigger cancers [4446]. Additionally,
P. khinjuk fruit oil is substantially resistant to oxidative rancidity,
both at ambient storage and high temperatures due to abundance
of oleic acid [47,48]. Furthermore, a moderate content of linoleic
acid as a polyunsaturated omega-6 fatty acid, presented in the oil
samples, improves skin, bone and hair growth, protects the repro-
ductive system and regulates different metabolism taking place in
the human body. Also the nervous system, brain and muscle growth
are affected positively by Omega-6 [49].
3.6. Physicochemical properties of the obtained extract samples

The chemical properties of P. khinjuk fruit oil extracted by the

deviation (AARD), dened by following equation, was used to eval- SFE and Soxhelt techniques, including iodine value, peroxide value,
uate the mathematical model results: acid value, saponication value, oxidative stability index, specic
extinction values K232 and K270 were measured in order to char-
 
 Y Y  
1
n acterize the oil quality. Based on the results listed in Table 7, the low
 i,cal i,exp 
AARD (%) =     100% (10) peroxide values (0.9 and 1 meq of O2 /kg of oil) of the fruit oil were
n  Yi,exp  indicating the high oxidative stability of the oil for a long period
i=1
without rancidity. Higher iodine value designates higher degree
where, n is the number of experimental data, Yi,cal and Yi,exp are of unsaturation [50]. The iodine values were relatively high (76.2
the oil yield obtained by the model and by the experimental data, and 75.3 g of I2 /100 g of oil) and fairly close to that of some com-
respectively. mon high-oleic oils like olive oil (80 g of I2 /100 g of oil) [51] and
sunower oil (80 g of I2 /100 g of oil) [52] representing proper unsa-
turation of the samples. The combination of low peroxide value and
3.4. Evaluating the structure of samples high iodine value proves that the P. khinjuk fruit oil has the highly
suitable qualities of an edible oil. A valuable parameter to evaluate
The structure and surface morphology of non-extracted and the chain length (molecular weight) of fatty acids existing in the
extracted P. khinjuk fruit samples were evaluated by scanning elec- triacylglycerols in oil is saponication number. The saponication
tron microscopy (SEM). The fruit samples were rst coated with numbers of the samples (183 and 177.6 mgKOH/g oil) were within
goldpalladium alloy and then analyzed using scanning electron normal range measured for other seed oils like safower, sunower,
microscope (TESCAN, VEGA II XMU, Czech Republic). Fig. 4 presents corn and raspberry [53]. Therefore, the results showed that sam-
two micrographs of P. khinjuk fruit of 0.6 mm particle size diame- ples consist mainly of unsaturated fatty acids. The relatively low
ter before extraction (a) and after supercritical extraction (b). The specic extinction values K270 and K232 indices revealed that
electron micrograph of non-extracted samples show an uneven and the small amount of primary and secondary oxidation products
rough surface covered uniformly with a layer of oil. The structure such as hydroperoxides, -diketones and -unsaturatedketones
of the treated samples seems more porous and the surface is clearly existed in the oil samples [54]. The refractive index of the sam-
deated and depleted of oil signifying high extraction efciency by ples (1.46 and 1.41) was lower than that of common oils such
supercritical CO2 . as canola (1.4651.469), sunower (1.4611.468) and soybean
 G. Sodeian et al. / J. of Supercritical Fluids 110 (2016) 265274 273

Table 5
Adjusted parameters for mathematical model at different experimental conditions.

Pressure (MPa) Temperature ( C) Mass ow rate (g/min) Xk /X0 kf 106 (m/s) ks 109 (m/s) yr AARD (%)

15 50 5 0.62 4.80 4.74 0.0035 3.22

21 50 5 0.48 3.95 5.09 0.0067 2.07
18 35 4 0.52 2.02 5.42 0.0074 1.86
18 55 4 0.56 2.43 5.30 0.0066 2.54
21 40 3 0.64 2.98 4.64 0.0068 2.66
21 40 5 0.52 3.78 4.96 0.0068 1.33
23.64 55 4.34 0.45 7.85 6.56 0.0086 1.30

Table 6 Acknowledgment
Fatty acids composition of P. khinjuk oil obtained by the SC-CO2 and Soxhlet extrac-
tion methods.
The authors gratefully acknowledge the University of Kashan,
Fatty acids (wt%) n-Hexane SFE especially deputy of research, for their nancial support. Also, the
Palmitic acid (C16:0) 22.43 21.70 authors would like to thank laboratory of Nargesoil company, Shi-
Palmitoleic acid (C16:1) 4.50 4.70 raz city, for their cooperation in this project.
Stearic acid (C18:0) 2.10 2.00
Oleic acid (C18:1) 57.60 57.30
Linoleic acid (C18:2) 12.10 13.10
Linolenic acid (C18:3) 0.64 0.90 References
Other 0.63 0.30
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