Innovative Food Science and Emerging Technologies 38 (2016) 32–40

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Innovative Food Science and Emerging Technologies

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

Fitting of broken and intact cell model to supercritical fluid extraction

(SFE) of sunflower oil
Amit Rai a,⁎, Bikash Mohanty b, Ravindra Bhargava b
a
Department of Chemical Engineering, NIT Hamirpur, Hamirpur, Himachal Pradesh 177001, India
b
Department of Chemical Engineering, IIT Roorkee, Roorkee, Uttarakhand 247667, India

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

Article history: The present work is focused on the supercritical extraction and kinetic study of sunflower oil. The effect of oper-
Received 22 March 2016 ating parameters, namely pressure (20–40 MPa), temperature (333–373 K), solvent mass flow (0.83 × 10−4 to
Received in revised form 26 August 2016 2.50 × 10−4 kg/s), particle size (0.50–1.00 mm) and ethanol as co-solvent (0–10%) have been studied by a set
Accepted 30 August 2016
of experiments. The outcomes of work show, extraction yield increases with increasing pressure, solvent mass
Available online 31 August 2016
flow and co-solvent. The retrograde phenomenon is also observed between 333 and 353 K. The experimental
Keywords:
data have been used to simulate the broken and intact cell model and fitting parameters are optimized by the
Sunflower oil global optimization method. The model successfully fitted the experimental data at high pressure with lower par-
Broken and intact cell ticle size.
Model optimization Industrial relevance: The sunflower seeds are a major source of good quality, high oleic acid, vegetable oil and Vi-
Kinetics tamin E. Hence, largely used in beauty care products, production of vegetable oil based fuel oil and lubricants.
SFE There are also many other applications of rich–oleic acid oils such as food, cosmetics, pharmaceuticals, biodiesel
production, and also as a feedstock for the oleo-chemical industry. In recent years, due to rigid environmental
regulation and health concern, high pressure extraction of the vegetable oil with supercritical carbon dioxide
has received considerable attention as a promising alternative to conventional solvent extraction and mechanical
process. Hence, the present work is focused on extraction of seed oil by supercritical CO2.
Moreover, for industrial application of supercritical fluid extraction, it is very important to study the kinetic
model that gives large scale extraction curves with minimum error by using model fitting parameters with
small scale experiment. There are large numbers of models based on different approach suggested by various re-
searchers to fit experimental data of supercritical fluid extraction. Amongst them, the broken and intact cell
model proposed by Sovova's (1994) is widely used to fit the experimental data of vegetable oil extraction. The
broken and intact cell model has three fitting parameters and many authors have applied different optimization
techniques to optimize these fitting parameters. Therefore, in the present work the optimized kinetic parameters
of Sovová's model for sunflower oil extraction are obtained by applying the Box complex optimization method to
study the influence of pressure, temperature, particle size, co-solvent and solvent flow rate of extraction yield.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction
The sunflower seeds (Heliantus annuus L.) are a major source of good
quality, high oleic acid vegetable oil which is largely used for human
consumption in India as well as in many Western countries due high
ratio of polyunsaturated to saturated fatty acids (Salgin, Doker, &
Calimli, 2006; Shahidi, 2005). Also, sunflower oil is a major source of Vi-
tamin E and hence, largely used in beauty care products (Nimet et al.,
2011). Moreover, it is also used for the production of vegetable oil
based fuel oil and lubricants (Tomic, Savin, Micic, Simikic, & Furman,
2014). Extraction of vegetable oils from seed material is mostly per-
formed by some traditional methods such as by organic solvent.
⁎ Corresponding author.
E-mail address: mit.rai123456@gmail.com (A. Rai).
However, these traditional methods have some drawbacks, like long ex-
traction time, large amounts of organic solvent and high temperature is
required due to which loss or degradation of active compounds occurs
(Mukhopadhyay, 2000). Hence, the SFE is an attractive alternative tech-
nique has several advantages, including the use of non-flammable, non-
toxic, non-explosive, cost efficient, non-polar green solvent, which gives
faster and more selective separation with low degradation of chemical
compounds (Mukhopadhyay, 2000).
Moreover, for industrial application of SFE, it is very important to
study the kinetic model that gives large scale extraction curves with
minimum error by using model fitting parameters with small scale ex-
periment (Casas, Mantell, Rodriguez, Lopez, & Ossa, 2009). There are
large numbers of models based on different approach suggested by var-
ious researchers to fit experimental data of SFE. Amongst them, the bro-
ken and intact cell model proposed by Sovová's (1994) is widely used to

http://dx.doi.org/10.1016/j.ifset.2016.08.019
1466-8564/© 2016 Elsevier Ltd. All rights reserved.
 A. Rai et al. / Innovative Food Science and Emerging Technologies 38 (2016) 32–40 33

fit the experimental data of vegetable oil extraction. The broken and in- of easily accessible solute (P) and the inaccessible solute (K) inside the
tact cell model has three fitting parameters and many authors have ap- solid particle. Thus, the overall extraction process includes three differ-
plied different optimization techniques to optimize these fitting ent stages. First is the constant extraction rate (CER): governed by con-
parameters. Mira, Blasco, and Subirats (1996) fitting parameters by vection and extraction rate is proportional to the solubility, second is the
Excel solver, Louli, Folas, Voutsas, and Magoulas (2004) used fourth transition extraction step or falling extraction rate (FER): extraction rate
order Runga-Kutta method, Moura, Carvalho, Stefanini, Ming, and is governed by diffusion and convection, third is the slow extraction pe-
Meireles (2005) steepest descent and Newton method, Pederssetti et riod: governed by only diffusion. The analytical solution of broken and
al. (2011) used Nelder-Mead simplex method to minimize an error ob- intact cell model is described by the following equations, where the ex-
jective function but all these methods may not give optimum value and tractions curve as a function of time.
can be trapped at local minima. Similarly, Martinez and Martinez (2008) 8
used the lexicographical grid method to obtain the global optimum so- >
> Q CO y ½1− expð−ZÞt if 0≤ t ≤tCER
< Q y ½t−t 2 rexpðz −ZÞ if tCER≤ t≤tFER
lution, but this method required good programming skills. Therefore, yðt Þ ¼
CO2 r CER
W 

>
> y expðWx0 Þ WQ CO2 x
: mSI x0 − r ln 1 þ −1 exp ðtCER −tÞ k if t NtFER
the objectives of the present work are to obtain the optimized kinetic W tr mSI x0
parameters of Sovová's model for sunflower oil extraction using super- ð3Þ
critical carbon dioxide by applying the Box complex optimization meth-
od to study the influence of pressure, temperature, particle size, co- where x0, xp and xk represent the total oil, easily accessible and inacces-
solvent and solvent mass flow of extraction yield. sible oil present in the solid with respect to non-extractable solid and
express by x0 = xp + xk, QCO2 is solvent mass flow, mSI is mass of non-ex-
2. Material and methods tractable solid. In the second extraction period, the depletion of easily
accessible oil in the raw material is given by a dimensionless variable
The sunflower seed had been purchased from local markets. In order zw and given by the Eq. (4).
to reduce the water content the seed have been unsealed and dried  


under daylight. All the seed has been crushed in a domestic kitchen Zyr x0 exp WQ CO2 ðt−t CER Þ=mSI −xk
zW ¼ ln ð4Þ
mixer grinder and sample based on three different sizes of particle has Wx0 x0 −xk
been prepared by sieved analysis as discussed in our previous paper of
sunflower and watermelon seed oil extraction (Rai, Mohanty, & Here tCER is the end of the first extraction period and the start of the
Bhargava, 2016; Rai, Mohanty, & Bhargava, 2015). The supercritical ex- second extraction period. Also tFER represent the end of the transition
traction grade CO2 is supplied by Sigma gases, India in a deep tube cyl- period with zW = 0 at the start and zW = Z of the transition period. The
inder. Analytical grade ethanol is procured from Merck Ltd. value of tFER and tCER is given by Eqs. (5) and (6) respectively.
(Darmstadt, Germany). A Soxhlet extraction with n-hexane has been
performed to determine total hexane-extractable sunflower oil content ðx0 −xk ÞmSI
t CER ¼ ð5Þ
of unsieved crushed seed as discussed in our previous paper (Rai et al., yr ZQ CO2
2015; Rai et al., 2016) and 54.87 ± 0.22% oil has been obtained. The


value of hexane-extractable oil is referred as total oil content in the mSI x þ ðx0 −xk Þ expðWx0 =yr Þ
t FER ¼ t CER þ ln k ð6Þ
present work and calculated by the Eq. (1). WQ CO2 x0

Oil Extracted The parameters Z and W are directly proportional to fluid and solid
Yield ð%Þ¼ 100 ð1Þ
Total Sample Taken phase mass transfer coefficient respectively, and given by Eqs. (7) and
(8)
Similarly, moisture and ash content of sunflower seed are obtained
as suggested by standard method 926.12 (AOAC, 1995) and ISO 749 k f a0 ρ mSI kYa ρCO2 FmSI
Z¼
¼ ¼ ð7Þ
(ISO, 1977) and found approximately 5.31 ± 0.73% and 9.61 ± 0.59% re- Q CO2 Q CO2 ð1−ε Þρs Q CO2
ð1−ε Þρs
spectively. Moreover, the porosity, density and bulk density of the par- mSI
ticle bed are obtained by the apparatus supplied by Macro scientific
works, New Delhi by the following procedure. 50 g dry seed has been ks a0 mSI kXa SmSI Zy
W¼
¼ ¼ ¼k r ð8Þ
taken into a graduated cylinder and set the time around 3 min to take Q CO2 Q CO2 ð1−ε Þ Q CO2 xk
ð1−ε Þ
100 stoke as per the standard requirement. After 100 St ± 5% the mSI
timer switch off the motor automatically. Read the volume of a cylinder
and calculate the bulk density by the following formula. where kXa and kYa are fluid and solid phase mass transfer coefficient re-
spectively, a0 shows the specific interfacial area, ρs and ρCO2 represents
Bulk Density¼ðweight of the seed particle Þ=ðvolume Þ ð2Þ the density of the sunflower seed material and the density of supercrit-
ical carbon dioxide respectively, ε represents bed void fraction. This
Now, to obtain the particle density, take a 100 ml of water (density model is used to fit the SFE experimental data of sunflower oil. In the
1000 kg/m3) into a measuring cylinder and pour 50 g sample of seed present investigation, the broken and intact cell model fitting parame-
particle into it. Note down the increased in volume. This is the volume ters (Z, W and xk) have been optimize by minimizing the average abso-
of the seed particles. Now calculate the particle density by dividing lute relative deviation (AARD) as objective function given by Eq. (9) the
the weight of sample by volume of seed particle. Moreover, the porosity Box complex optimization method has been used to optimize the model
is also calculated by the formula discussed in Section 4. parameters.
 
2.1. Broken and intact cell model 100 N yieldpredicted −yieldexperimental 
AARD ð%Þ ¼ ∑  ð9Þ
N i¼1  yieldexperimental 
The broken and intact cell model proposed by Sovová's has been
used to explain the behavior of the extraction process of various natural 2.2. Optimization technique
products (Pederssetti et al., 2011). This model considers that the solute
is protected by non-extractable solid cell walls inside the cell and also In the present work, a global optimization technique known as the
considered that the total extractable solute in the solid (O) is composed Box complex optimization method has been used to optimize the fitting
34 A. Rai et al. / Innovative Food Science and Emerging Technologies 38 (2016) 32–40

parameter of broken and intact cell model because it is a very simple given by Eq. (13).
and reliable method to optimize the problems with explicit and implicit
constraints (Erdogdu & Balaban, 2009). This method does not require Xk
1
gradient calculation and is a direct pattern search method includes gen- X¼ XL ð13Þ
k−1
eration and maintenance of search (trial) points. To obtained new L¼1
search point, all remaining search points are projected toward the cen- L≠k
ter (centroid, X) (Ravindran, Ragsdell, & Reklaitis, 2006). The flow chart
of a Box complex optimization method is shown in Fig.1 and principal Step 3: A new reflected point (XR) is now again check for feasibility. If
calculation steps are given below: f(XR) b f(XH) and satisfy all constrains the new search point replaceable
Step 1: Start with the generation of k (~2n) sequential and random and XH is replaced by XR and go to step 2. It XR is not a feasible, then a
search points by using pseudo-random variables distributed in the in- new trial point is obtained by redirecting the reflected point by half
terval of (0, 1) given as Eq. (10) the value of α.

Step 4: If at any step, reflected point XR obtained in step (3) not fol-
ðlÞ
xi; j ¼ xi þ ri; j xui −xli ; i ¼ 1; 2; :::::; n j ¼ 2; 3; :::::::; k ð10Þ low any of the constrain, it must move toward the centroid until it be-
comes feasible as given in Eq. (14)
where xi,j is the ith component of point Xj and ri,j is the random var-
iable. It is noted that, each generated point must satisfy all m constraints 1 
ðX R Þnew ¼ XR þ X ð14Þ
and if not, trial point moved the centroid (X) of remaining accepted 2
point. The centroid of accepted point is given by Eq. (11)
This search procedure continues until the vertices of the simplex
1 X j¼1 made by the value of objective function at trial points shrink so that
X¼ L¼1 L
X ð11Þ
j−1 the generations of new search point are not possible by reflection or
redirection.
This process is repeated until all feasible search points are found and Step 5: In the last step, the search point is checked for convergence
must follow all m constrains. by satisfying the following criteria
Step 2: The objective function (f) is evaluated at each trial points
(vertices of simplex) and the search point corresponds highest ( )1=2
(worst) value of the objective function is reflected toward the center 1X k     2
f X −f X J ≤ε ð15Þ
and the new search point (XR) is obtained as k J¼1

X R ¼ ð1 þ α ÞX 0 −αX H ð12Þ
where, X is the center of all vertices and ε ≤10−6. The above procedure
where, XR is the new reflected point, XH represent the worst point, α≥ 1 leads to find the global optimum since the initial complex (set of the ini-
(normally taken as 1.2) and X is the centroid of all vertices except XH and tial trial points) is randomly scattered through the feasible space.

Find out the centriod of all search points except

Start

Set the value Constant & variable

(n, α, m, x0, ε, XL, XU ) Reflection of worst search point

Variable Initialization
(X1=W, Z, Xk)
Yes

Generate the k=2n search points randomly

No
Yes

Constrain violation No

No

Find out the centriod of accepted search points

Yes

Evaluate the objective function at each search points.

, ,…………….,

Find the worst point with the highest function value Find the second highest point with
Find the favorable point with the lowest function value the highest function value

Stop

Fig. 1. Flow chart of Box complex optimization method.

 A. Rai et al. / Innovative Food Science and Emerging Technologies 38 (2016) 32–40 35

30
have a bulk density of 506.12, 510.30, 509.14 kg/m3 and corresponding
Sim. (333 K) particle density of 960.03, 1090.93, 1081.6 kg/m3 respectively is obtain-
Cumulative Extraction Yield x 10 -3 (kg)

Exp. (333 K) ed. Furthermore, the values of bed porosity are 0.52, 0.47, 0.45 and the
25
Sim. (353 K) values of corresponding particle porosity (1 − (ρb / ρp)) are 0.47, 0.53,
Exp. (353 K) 0.47 for particle sizes of 1.00, 0.75 and 0.50 mm respectively has been
20 Sim. (373 K) obtained. The amount of initial oil content (xo) in the sunflower seed
Exp. (373 K) is 1.2153 g of oil per g of non-extractable matter. In the present work,
the values of sunflower oil solubility (0.009330 g/g of CO2 at 333 K
15 and 30 MPa) are found larger than reported by Salgin et al. (2006) as
0.00669 g/g of CO2 at 333 K and 30 MPa. The higher value of solubility
is due to fact that, in the present study, co-solvent (5% and 10% of super-
10 critical carbon dioxide mass flow) is used with supercritical carbon di-
Pressure : 30 M Pa oxide, which increases the polarity of supercritical carbon dioxide. As
Particle Size: 0.75 mm a result, interactions between the molecules of solute and supercritical
5
CO2 flow rate: 1.67 x 10-4 kg/s carbon dioxide are increased and hence, solubility increases. The total
Co-solvent (EtOH) : 5% of CO2 amounts of seed kernel used in the work of Salgin et al. (2006) are 4 g
and the supercritical carbon dioxide mass flow was about 3 g/min at
0
30 MPa and 353 K. Hence, the space time (τ) of supercritical carbon di-
0 50 100 150 200 250
Time/60 (s) oxide is approximately [4 g seed/3(g/min) CO2 ≈ 1.33 min g seed g CO ].
2

Fig. 2. Effect of temperature on cumulative extraction yield of sunflower seed oil.
3. Supercritical fluid extraction (SFE)
The supercritical CO2 extraction experiments have been performed
on an extraction system supplied by Thar Technologies Inc. Pittsburgh.
The process flow diagram and working principal are discussed in detail
in our previous paper of watermelon seed oil extraction (Rai et al.,
2015). To perform the extraction of sunflower oil from seed particles
of different size, a cylindrical basket of 7.5 cm diameter and 9 cm height
has been used. The 50 g seed particles of particular diameter, glass
beads, glass wool are used in each experiment and detail procedure
adopted for preparing the bed of seed particle are given in the author's
previous paper (Rai et al., 2015). The amount of extracting oil with co-
solvent is collected in a sample vial in every five minutes and ethanol
is removed by vacuum evaporator. The amount of extracted oil is ob-
tained gravimetrically and cumulative extraction yield is obtained by
the sum of all samples.
Whereas, in the present case 50 g of seed kernel are used in each exper-
iment with 5, 10 and 15 g/min supercritical carbon dioxide mass flow.
Hence, the minimum space time are 10, 5 and 3.33 min for 5, 10 and
15 g/min supercritical carbon dioxide mass flow respectively, which is
minimum three times larger than used by Salgin et al. (2006), which
provide large contact time between seed kernel and supercritical carbon
dioxide. As a result, value of cumulative extraction yield (g oil/g kernel)
increases. The model equation for second and third extraction periods
proposed by Sovová (1994) suggests that, they strongly depend on ini-
tial oil content and the solubility of oil in supercritical carbon dioxide. In
the present case, for sunflower oil, the value of initial oil content is very
high (xo = 1.21533) and at low pressure, the value of solubility is very
low which leads to very high value of tCER and tFER. As the value of tCER is
very high, the model equation which should cover the first extraction
period only, now covers all data points on the cumulative extraction
curve. The model equation for first extraction period is a straight line
with the slope of QCO2yr(1 − exp (‐Z)). Hence, the model does not fit
well for seeds with the extraction at lower pressure with high initial
oil content.

4. Result and discussion 4.1. Effect of operating parameters on extraction yield

The solubility (yr) of sunflower oil in supercritical CO2 and supercrit-
ical CO2 modified with co-solvent (ethanol) has been obtained from
first and linear part of the extraction curve, which shows that solubility
is directly proportional to the extraction rate. In the implementation of
Box complex optimization method, the fitting parameters are subjected
to four constraints: 0 b Z b 10, 0 b W b 10, 0 b xk b xo and xp b xo. Where,
xo is the highest possible value of xp. The value of mass transfer coeffi-
cients in solid phase (kXa) and in the fluid phase (kYa), is calculated
with the help of the optimized values of Z, W and xk by the Eqs. (7)
and (8). Ferreira and Meireles (2002) suggested that k-value is directly
proportional to the ratio of solid-phase and the fluid phase mass trans-
fer coefficients, i.e. k =kXaρsxk/kYaρCO2yr and is a measure of the relative
importance of intraparticle diffusion (diffusion-controlled period) with
respect to convection during the extraction process. As the value of ‘k’
increases the intraparticle diffusion plays a dominant role in the extrac-
tion process. For the particle sizes of 1.00, 0.75, 0.50 mm, the fixed bed
4.1.1. Effect of temperature
The Fig. 2 demonstrate the effect of temperature on the extraction
yield at a constant pressure, mean particle size, supercritical CO2 mass
flow and co-solvent mass flow. In the critical region, temperature
shows the nonlinear and complex effect on extraction yield. As temper-
ature increases the cumulative extraction yield of sunflower oil also in-
creases with time. The probable reason for the increasing cumulative
extraction yield with increasing temperature is that, the solubility of
fatty acid present in the sunflower oil increases with the increase in
temperature. This can also be observed from the first and linear part
of extraction curve. The solubility of the solute is a function of tempera-
ture as well as the density of the supercritical CO2, which intern is a
function of pressure as well as temperature (Mukhopadhyay, 2000).
Further, with temperature vapor pressure of solute also increases affect-
ing the solubility. As in the present case, pressure is constant at 30 MPa,
hence, the solubility will be a function of temperature only. At low

Table 1
Variation of mass transfer coefficients for sunflower oil extraction with temperature.

Temperature Z W xk tCER/60(s) tFER/60(s) kYa (s−1) kXa (s−1) k

−3
333 K 1.016044 0.011021 0.733793 51.875410 115.748090 2.568026 × 10 0.452901 × 10−4 0.405307
353 K 3.000000 0.021326 0.990699 11.971004 86.065194 8.437684 × 10−3 0.876378 × 10−4 0.523648
373 K 4.452837 0.030665 0.960285 7.5045910 80.296195 14.107574 × 10−3 1.260159 × 10−4 0.403116
36
30
Sim. (20 M Pa)
Exp. (20 M Pa)
Cumulative Extraction Yield x 10 -3 (kg)
Sim. (30 M Pa)
25 Exp. (30 M Pa)
Sim. (40 M Pa)
Exp. (40 M Pa)
20
15
10
5
0 1997), Rose hip seed, physic nut seed (Machmudah et al., 2008), hiprose
0 50 100 150
Time/60 (s)
Fig. 3. Effect of pressure on cumulative extraction yield of sunflower seed oil.
temperature, such as 333 and 353 K, the cumulative extraction yield is
almost same for starting 120 min and after that, it is increases with
time. The increase in extraction yield with temperature can be ex-
plained through the values of mass transfer coefficients shown in
Table 1. The mass transfer coefficient in the fluid phase (kYa) and that
in the solid phase (kXa), increases with increase in temperature due to
increase in molecular and effective diffusivity of sunflower oil in super-
critical carbon dioxide. At temperature of 333 K, the total oil extracted at
the end of the transition period (t = tFER, tFER = 115.7 min) is about
69.05 wt% of total oil extracted. Up to transition period mass transfer
is governed by convection as well as intraparticle diffusion. The remain-
ing 30.95 wt% oil at 333 K is extracted in the third period (t ≥ tFER) in
which mass transfer is governed by diffusion. Whereas, at a tempera-
ture of 353 K, the total oil extracted at the end of the transition period
(t = tFER, tFER = 86.1 min) is about 54.10 wt% of total oil extracted.
The remaining 45.90 wt% oil is extracted in the third period (t ≥ tFER)
in which mass transfer is governed by diffusion. It can be seen from
the Table 1 that the value of kXa which governs the diffusion phenomena
after t ≥ tFER at 353 K is nearly twice of that at 333 K and hence the cu-
mulative extraction curves are distinctly separate. Salgin et al. (2006)
also found that the extraction of sunflower oil has been very fast at
30 MPa however, they did not get sufficient information to show the ef-
fect of temperature on cumulative extraction yield (g oil/g kernel). Var-
ious authors reported that, the solubility of oil derived from different
seeds such as apricot, amaranth seed, almond, sunflower also increase
with extraction temperature specially at higher pressures i.e. at
30 MPa or above (Salgin et al., 2006; Eggers, 1996; Ozkal, Yener, &
Bayindirli, 2005a, 2005b; Marrone, Poletto, Reverchon, & Stassi, 1998;
Westerman, Santos, Bosley, Rogers, & Al-Duri, 2006). Fig. 2 also shows,
the broken and intact cell model is well fitted with the experimental
data. The total extraction yield obtained after 250 min is about 1.3
times as temperature increases from 333 to 373 K.
4.1.2. Effect of pressure
The effect of operating pressure varying from 20 to 40 MPa on the
sunflower oil extraction is studied by using particle size of diameter
Table 2
Variation of mass transfer coefficient for sunflower oil extraction with pressure.
Pressure Z W
20 MPa 2.057369 0.835874
30 MPa 3.000000 0.021326
40 MPa 3.998800 0.053728
(Due to bad fitting of model observed value is not tuned with experiment).
A. Rai et al. / Innovative Food Science and Emerging Technologies 38 (2016) 32–40
0.750 mm at temperature of 353 K, supercritical CO2 mass flow of
1.67 × 10−4 kg/s with 5% co-solvent (ethanol) and shown in Fig. 3 as
a function of time. The result shows that as the pressure increases the
cumulative extraction yield of sunflower oil increases and also at
20 MPa, extracted a quantity of sunflower oil is very small. This behavior
is well known and explain by the fact that the density of supercritical
CO2 reached to the density of liquid with increasing pressure which im-
Temperature: 353 K proves the solvation capacity of supercritical CO2 (Mukhopadhyay,
Particle Size: 0.75 mm
2000). This fact is also supported by the initial part of the extraction
CO2 flow rate: 1.67 x 10-4 kg/s
curve that the value of the tangent of extraction curve increases as the
Co-solvent : 5% of CO2
operating pressure increases. The solubility of sunflower oil increases
from 0.003904 kg oil/kg CO2 to 0.0279352 kg oil/kg CO2 as pressure
moves from 20 MPa to 40 MPa. The various investigators also studied
the effect of operating pressure on extraction yield at constant temper-
ature and found the similar trend for neem seed (Johnson & Morgan,
200 250 300 seed oil (Reverchon, Kaziunas, & Marrone, 2000). As the pressure in-
creases from 20 to 30 MPa and 30 MPa to 40 MPa an increment of 3.5
and 1.2 times in the total extraction yield is observed. However, at
20 MPa, the total extraction yield is very low due to very low solubility
of sunflower oil and proposed, broken and intact cell model does not
agree with experimental data, particularly in the second half of extrac-
tion period. This behavior is also observed by Salgin et al. (2006) for
sunflower oil extraction. Table 2 shows mass transfer coefficient values
in the fluid phase (kYa), and in the solid phase (kXa) for different pres-
sure values. As the pressure increases from 30 to 40 MPa, the value of
mass transfer coefficient increases due to decrease in resistances in
the solid and the fluid phase. The similar trend is also observed by var-
ious researchers for the extraction of different type of oil such as canola
seed at 30 MPa and 33.5 MPa (Pederssetti et al., 2011), marigold at 12
and 15 MPa (Campos, Michielin, Danielski, & Ferreira, 2005). However,
some authors also reports the decreasing value of fluid phase mass
transfer coefficient (kYa) for the extraction of β-carotene (Doker,
Salgın, Sanal, Mehmetoglu, & Calimli, 2004), apricot oil (Ozkal et al.,
2005a, 2005b), rosemary (Bensebia, Barth, Bensebia, & Dahmani,
2009) and nutmeg oil (Machmudah, Sulaswatty, Sasaki, Goto, &
Hirose, 2006). At higher pressure of 40 MPa, the broken and intact cell
model agrees with absolute average relative deviation of 1.62%. More-
over, about 99.6 wt% of the total oil has been extracted within a time
of 250 min and about 95% of the total oil has been extracted with in
the first 165 min of experiment. The mathematical model proposed by
Sovová (1994) agrees with the experimental data very well at high
pressure with the average relative error of 1.62%.
4.1.3. Effect of particle size
The effect of mean particle size on the cumulative extraction yield
has been demonstrated through Fig. 4, when pressure, temperature, su-
percritical carbon dioxide mass flow and added co-solvent (%) rate is
kept at 30 MPa, at 353 K, at 1.67 × 10−4 kg/s and 5% of the CO2 mass
flow respectively. The extractor feed during experiments uses average
particle size of 0.50 or 0.75 or 1.00 mm to see the effect on cumulative
extraction yield. As particle size decreases surface area per unit mass in-
creases, hence extraction yield increases. Further, during grinding of the
seed kernel to create small particles, the cell walls are disrupted and this
increases the ratio of broken to intact cells and subsequently offers more
accessible oil to the supercritical carbon dioxide. Contrary to this, as the
size of seed particles increases, cumulative extraction yield decreases,
xk tCER/60 (s) tFER/60 (s) kYa (s−1) kXa (s−1) k
−3
0.016199 320.849849 989.839839 7.264519 × 10 34.34973 × 10−4 1.685564
0.990699 11.971004 86.065194 8.437684 × 10−3 0.876378 × 10−4 0.523648
0.866394 6.714385 58.904932 10.186670 × 10−3 2.207918 × 10−4 0.416710

30
Sim. (1.00 mm)
Cumulative Extraction Yield x 10-3 (kg)
Exp. (1.00 mm)
25
Sim. (0.75 mm)
Exp. (0.75 mm)
Sim. (0.50 mm)
20
Exp. (0.50 mm)
15
10
5 Pressure : 30 M Pa
0 three different levels, i.e. 0.833 × 10− 4, 1.67 × 10− 4 and
0 50 100
Time/60 (s)
Fig. 4. Effect of particle size on cumulative extraction yield of sunflower seed oil.
which indicate that, oil is not easily transported from unbroken cell
walls, and only accessible oil present on the surface is coming out
with the supercritical carbon dioxide. Salgin et al. (2006) obtained sim-
ilar results for the extraction of sunflower oil using supercritical carbon
dioxide. Table 3 shows, the magnitudes of fluid side mass transfer coef-
ficient (kYa) are sufficiently large as compared to mass transfer coeffi-
cient (kXa) in the solid phase. The mass transfer coefficient in the solid
phase (kXa) contributes toward the diffusion of inaccessible oil in the
seed particles and hence, it depends on the properties of the kernel,
the permeability of cell walls, and the capacity of the supercritical car-
bon dioxide to access the inner parts of the particles (Ozkal et al.,
2005a, 2005b). Fig. 4 clearly shows that, the cumulative extraction
yield has not reached up to the asymptotic value for 1.00 mm and
0.75 mm particle size, which reveals that penetration of supercritical
carbon dioxide in to seed particle has been very low and hence, diffusion
is also very low due to the physical structure of the seed. This behavior is
also observed by various researchers for different type of seed particles
such as apricot (Ozkal et al., 2005a, 2005b), sunflower Salgin et al.
(2006), black pepper (Sovová, Jez, Bartlova, & Stastova, 1995), sea buck-
thorn berries (Stastova, Jez, Bartlova, & Sovová, 1996). They also con-
cluded that supercritical carbon dioxide is not able to reach all of the
oil inside the cells.
The Table 3 shows that, mass transfer coefficient in the fluid phase,
(kYa), and mass transfer coefficient in the solid phase, (kXa), increases
with the decrease in the particle size. The probable reason for this incre-
ment is due to the fact that, the increase in the surface area and the de-
crease in the diffusion path length (Ozkal et al., 2005a, 2005b). For the
large size particle, the extraction in considerably less in the third extrac-
tion period, which is diffusion controlled and hence the particle size re-
duction is necessary to decrease the extraction time. In the present
study, for large size particles the broken and intact cell model is fitted
with the AARD of 3.95%, which is quite large as compared to small size
particle which offers a value of AARD as 0.53%. The broken and intact
cell model fits the experimental result with the average relative error
of 0.53% and 1.67% for 0.50 mm and 0.75 mm particle sizes respectively.
The highest cumulative extraction yield has been obtained from the
Table 3
Variation of mass transfer coefficient for sunflower oil extraction with particle size.
Particle size Z W
0.50 mm 4.191138
0.75 mm 3.000000
1.00 mm 2.057369
(Due to bad fitting of model observed value is not tuned with experiment).
A. Rai et al. / Innovative Food Science and Emerging Technologies 38 (2016) 32–40 37
seed of the low mean particle size (0.50 mm). The lowest particle size
(0.50 mm) gives approximately 93.45 wt% cumulative extraction yield
at 250 min whereas 78.17 wt% and 55.00 wt% cumulative extraction
yields has been obtained for 0.75 and 1.00 mm mean particle sizes re-
spectively in the same time of extraction.
4.1.4. Effect of solvent mass flow
The effect of the solvent mass flow on the cumulative extraction
yield has been studied using Fig. 5(a–b), when pressure, temperature,
particle size and co-solvent mass flow are kept at 30 MPa, at 353 K, at
0.75 mm and at 5% of supercritical carbon dioxide mass flow respective-
Temperature: 353 K ly. The Fig. 5(a) are plotted for cumulative extraction yield as a function
of time and Fig. 5(b) are plotted for cumulative extraction yield as a
CO2 flow rate: 1.67 x 10-4 kg/s function of the amount of supercritical carbon dioxide consumed. The
Co-solvent (EtOH) : 5% of CO2 mass flow of supercritical carbon dioxide for experiments is varied at
150 200 250
2.5 × 10−4 kg/s. the Fig. 5(a) shows as the solvent mass flow is in-
creased, the extraction rate, which is denoted by the tangent of the
curve is also increased and at higher mass flow, such as 2.5 × 10−4 kg/
s, extraction curve reaching to an asymptotic value. Fig. 5(a) clearly
shows that extraction rate is higher for larger flow rate because more
carbon dioxide passes through the fixed bed of the sample and hereby
more sunflower oil extracting. However, Fig. 5(b) shows that the extrac-
tion rate is constant and not influenced by the flow rate at the beginning
of the all experiments and is only a function of the quantity of carbon di-
oxide that passes through the fixed bed of the sample. This indicates, at
the beginning, that the exit concentration of sunflower oil is indepen-
dent of flow rate, and hence equilibrium is assumed to exist. The various
researchers suggested that, if solid phase mass transfer resistance
(intraparticle diffusion resistance) is considered to be important, the
slop of the extraction curve in the Fig. 5(b) becomes smaller for higher
flow rate, but in our case it appears little bit higher for higher flow
rate, which conform that intraparticle diffusion also have some impact
on the extraction (Goto, Sato, & Hirose, 1996; Salgin et al., 2006;
Tonthubhimthong, Chuaprasert, Douglas, & Luewisutthichat, 2001).
Hence, the model simulated values for solid phase mass transfer coeffi-
cient shows some increments. Moreover, as discussed earlier, the mini-
mum space time are 10, 5 and 3.33 min for 5, 10 and 15 g/min
supercritical carbon dioxide mass flow respectively, The Fig. 5(b) clearly
shows that, the first part of the extraction curve almost coincided with
each other which means during the aforementioned space time, the su-
percritical carbon dioxide is totally saturated with extracted oil during
the all three experiments. Hence, low space time for large flow rate
does not affect the extraction rate.
Table 4 demonstrates that, as the solvent mass flow increases the
value of solid phase mass transfer coefficient (kXa) and supercritical
phase mass transfer coefficient (kYa) increases and consequently the
value of resistances to mass transfer decreases. The reason of decreasing
mass transfer resistances is due to increase in convection and decrease
in the film thickness around the seed particle. This explanation is in con-
formity to the finding of various researchers for different seed oil extrac-
tion, such as apricot oil (Ozkal et al., 2005a, 2005b), grape seed oil
(Sovová, Kucera, & Jez, 1994), parsley seed oil (Louli et al., 2004) and
egg yolk oil (Wu & Hou, 2001). Hence, higher solvent mass flow should
be used to obtain maximum efficiency of the SFE process.
The broken and intact cell model predictions and the experimental
data are in good agreement for the given experimental conditions. The
xk tCER/60 (s) tFER/60 (s) kYa (s−1) kXa (s−1) k
−3
0.042508 1.041692 5.348764 75.918572 12.204885 × 10 1.812758 × 10−4 0.634585
0.021326 0.990699 11.971004 86.065194 8.437684 × 10−3 0.876378 × 10−4 0.523648
0.835874 0.016199 320.84984 989.839839 7.264519 × 10−3 34.47515 × 10−4 1.685564
38 A. Rai et al. / Innovative Food Science and Emerging Technologies 38 (2016) 32–40

30 30
Temperature: 353 K
Sim. (0.0% of CO2)
Pressure : 30 M Pa
Cumulative Extraction Yield x 10 (kg)

Particle Size: 0.75 mm Exp. (0.0% of CO2)

Cumulative Extraction Yield x 10 -3 (kg)

25
Co-solvent (EtOH) : 5% of CO2 25 Sim. (5.0% of CO2)
-3

Exp. (5.0% of CO2)

20 Sim. (10% of CO2)
Exp. (10% of CO2)
20
15

15
10 Sim. (0.83 x 10-4 kg/s)
Exp. (0.83 x 10-4 kg/s)
Sim. (1.66 x 10-4 kg/s)
5 Exp. (1.66 x 10-4 kg/s) 10
Sim. (2.50 x 10-4 kg/s)
Exp. (2.50 x 10-4 kg/s) Temperature: 353 K
0
5 Pressure : 30 M Pa
0 50 100 150 200 250
Time/60 (s) Particle Size: 0.75 mm
CO2 flow rate: 1.67 x 10-4 kg/s
0
0 50 100 150 200 250
Time/60 (s)

Fig. 6. Effect of co-solvent on cumulative extraction yield of sunflower seed oil.

(1996) found that solubility of sunflower oil is almost directly propor-

Fig. 5. (a): Effect of flow rate on cumulative extraction yield of sunflower seed oil. (b):
Effect of flow rate on cumulative extraction yield of sunflower seed oil.
experimental data for the mass flow of 0.833 × 10−4, 1.67 × 10−4 and
2.5 × 10− 4 kg/s is fitted with the average relative errors of 1.40%,
1.67% and 0.9% respectively.
4.1.5. Effect of co-solvent
There are lot of chemicals may be used as a co-solvent such as meth-
anol, ethanol, isopropanol, formic acid etc. Out of these chemicals, etha-
nol is one of the most commonly used polar organic solvent to enhance
the extraction yield of vegetable oils because it is safe for human con-
sumption. Fig. 6 shows the effect of the increasing percentage of ethanol
in supercritical CO2 on extraction yield when pressure, temperature,
mean size particle and supercritical carbon dioxide mass flow are kept
at 30 MPa, at 353 K, at 0.75 mm, and at 1.67 × 10−4 kg/s respectively.
The addition of co-solvent to the supercritical carbon dioxide is varied
from 0%, 5% and 10% of supercritical carbon dioxide mass flow to ob-
serve the effect on cumulative extraction yield. As co-solvent percent-
age increases the overall cumulative extraction yield also increases
and at a higher percentage of co-solvent, such as 10%, cumulative ex-
traction yield curve reaches to asymptotic value. Cocero and Calvo
tional to co-solvent amount. As co-solvent (ethanol) concentration in-
creases in the supercritical carbon dioxide, initial slopes of the
extraction curves also increases, indicating that the solubility of sun-
flower oil in supercritical carbon dioxide is increasing due to increase
in the polarity of supercritical carbon dioxide. The addition of 5% ethanol
to supercritical carbon dioxide increases the overall cumulative extrac-
tion yield of sunflower oil 1.45 times compared to cumulative extraction
yield in the pure supercritical carbon dioxide. Similarly, the addition of
10% ethanol to supercritical carbon dioxide increased the cumulative
extraction yield of sunflower oil 1.79 times compared to cumulative ex-
traction yield in the pure supercritical carbon dioxide. Table 5 shows
that mass transfer coefficients in the fluid side (kYa) and in the solid
phase (kXa) increase with the addition of co-solvent. The probable rea-
son for the increase in mass transfer coefficient is due to possible in-
creases in the diffusivity of sunflower oil in supercritical carbon
dioxide and as a result, the increase in effective diffusivity of solvent
in particle. Similar effects of co-solvent (ethanol) addition to supercrit-
ical carbon dioxide are reported for the extraction of apricot oil (Ozkal
et al., 2005a, 2005b), pistachio nut oil (Palazoglu & Balaban, 1998),
bioresidues from Posidoniaocenanica (Pilavtepe & Celiktas, 2013). In
the present study, for the addition of 5% co-solvent, the mass transfer
coefficient in the solid phase increases, as shows in Table 5. The Broken
and Intact cell model fit the experimental data quite well for 0 and 5%
addition of co-solvent. The experimental data for the co-solvent amount
equal to 0%, and 5% of supercritical carbon dioxide mass flow is fitted
with the average relative error of 0.89% and 1.66% respectively.
5. Conclusion
The experimental and modelling results show that the operating
process parameters taken in the present study have important effect

Table 4
Variation of mass transfer coefficient for sunflower oil extraction with solvent flow rate.

Supercritical carbon dioxide Z W xk tCER/60 (s) tFER/60 (s) kYa (s−1) kXa (s−1) k
−4 −3
0.83 × 10 kg/s 2.664029 0.021807 0.842861 31.962000 163.41136 3.746372 × 10 0.448072 × 10−4 0.3668931
1.67 × 10−4 kg/s 1.999459 0.022276 0.711812 38.653800 158.13000 5.623601 × 10−3 0.915418 × 10−4 0.5662887
2.50 × 10−4 kg/s 2.726000 0.043773 0.622147 28.419125 136.70183 11.50056 × 10−3 2.698236 × 10−4 0.6706789
 A. Rai et al. / Innovative Food Science and Emerging Technologies 38 (2016) 32–40 39

Table 5
Variation of mass transfer coefficient for SF oil extraction with co-solvent.

Co-solvent (% of CO2 flow rate) Z W xk tCER/60 (s) tFER/60 (s) kYa (s−1) kXa (s−1) k

0 2.899034 0.007950 0.9263144 19.696139 98.859801 7.324007 × 10−3 0.295890 × 10−4 0.233485
5 3.000000 0.021326 0.990699 11.971004 86.065194 8.437684 × 10−3 0.876378 × 10−4 0.5236485
10 2.424300 1.253118 0.044081 53.556860 188.221308 7.130195 × 10−3 53.85021 × 10−4 1.2310455

(Due to bad fitting of model observed value is not tuned with experiment).

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