Chemical Engineering Communications

ISSN: 0098-6445 (Print) 1563-5201 (Online) Journal homepage: http://www.tandfonline.com/loi/gcec20

Experimental Modeling and Simulation of

Supercritical Fluid Extraction of Moringa oleifera
Seed Oil by Carbon Dioxide

Amit Rai, Bikash Mohanty & Ravindra Bhargava (Late)

To cite this article: Amit Rai, Bikash Mohanty & Ravindra Bhargava (Late) (2017): Experimental
Modeling and Simulation of Supercritical Fluid Extraction of Moringa oleifera Seed Oil by Carbon
Dioxide, Chemical Engineering Communications, DOI: 10.1080/00986445.2017.1328415

To link to this article: http://dx.doi.org/10.1080/00986445.2017.1328415

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Chemical Engineering Communications, 0:1–8, 2017
Copyright © Taylor & Francis Group, LLC
ISSN: 0098-6445 print/1563-5201 online
DOI: 10.1080/00986445.2017.1328415

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Experimental Modeling and Simulation of Supercritical Fluid

Extraction of Moringa oleifera Seed Oil by Carbon Dioxide
AMIT RAI1, BIKASH MOHANTY2, and RAVINDRA BHARGAVA (LATE)2
1
Department of Chemical Engineering, Sant Longowal Institute of Engineering & Technology, Longowal, Punjab, India
2
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand, India

Moringa oleifera seed is an important source of high oleic acid in vegetable oil. In the present work, supercritical extraction of Moringa
seed oil has been carried out to study the influence of operating temperature, pressure, particle size, carbon dioxide flow rate, and
co-solvent addition by performing experiments in the range of 333–373 K, 20–40 MPa, 0.50–1.00 mm, 0.83 � 10−4–2.50 � 10−4 kg/s,
and 0–10% ethanol. The extraction data have been successfully modeled by extended Lack’s model and fitting parameters are optimized
by the Box global optimization technique. The results showed that pressure has a significant effect followed by temperature, co-solvent,
solvent flow rate, and particle size.
Keywords: Fluid phase mass transfer coefficient; Moringa oleifera; Optimization; Solid phase mass transfer coefficient; Supercritical
extraction

Introduction
The supercritical carbon dioxide extraction of oil from natural
products has become very attractive and viable alternative
techniques as compared to conventional methods because of
its non-toxicity, non-inflammability, and non-solvent residue
in the extract together with higher mass transfer properties
(Mukhopadhyay, 2000). Moringa oleifera is considered to be
the most important tree species because of large application of
fruits, oil, flowers, leaves, and immature pods in medical,
chemical (natural adsorbents, coagulants), lubrication, biodiesel,
and vegetable oil production. The M. oleifera seed has a high oil
content ranging from 34% to 40% with 22%–38% protein,
30–54% fat, and abundant of fatty acid such as oleic acid
(60–75%), stearic acid (8–10%), behenic acid (3–6%), linoleic
acid (2–6%), and palmitic acid (3.5–6.0%) which makes it good
as edible oil (Zhao and Zhang, 2013; Abdulkarim et al., 2005;
Palafox et al., 2012). Apart from this, many vegetable oils
can be used for food, oleo-chemical industries and/or bio-diesel
production; hence it is very important to select the seed based on
health, technical, and economical consideration.
M. oleifera is mostly cultivated in southern parts of India due
to its high nutritional value but the latest studies show that, it has
large potential of vegetable oil production (Burlando et al.,
2010). Hence, this work focuses on experimental studies of
extraction of oil from M. oleifera seeds. Moreover, it is very
Address correspondence to Amit Rai, Department of Chemical
Engineering, Sant Longowal Institute of Engineering &
Technology, Longowal, Sangrur-148106, Punjab, India. E-mail:
mit.rai123456@gmail.com
important to study the kinetic model that will help to scale up
the small scale experimental data to the industrial scale with
minimum possible errors. Many researchers have used various
models to scale up small scale experimental data to large scale
pilot plant (Casas et al., 2009; Naik et al., 1989; Spiro and
Kandiah, 1990; Reverchon et al., 1993; Goto et al., 1993;
Sovova, 1994; Sovova et al., 1994; Goto et al., 1996;
Reverchon, 1996; Goodarznia and Eikani, 1998; Reverchon
and Osseo, 1994; Goto et al., 1998). Amongst them, the broken
and intact cell model proposed by Sovova (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. The Box complex optimiza-
tion technique (Box, 1965) to minimize an objective function
(F) is the most simplest and direct pattern search global optimi-
zation method for fitting the model parameters. This method
gives very quick and suitable optimum value. To the best of
our knowledge, till now no work has been reported in kinetic
studies of M. oleifera seed oil extraction by supercritical carbon
dioxide. Therefore, the objectives of the present work are to
obtain the optimized kinetic parameters of the broken and intact
cell model for M. oleifera oil extraction using supercritical
carbon dioxide by applying the Box complex optimization
method to study the influence of pressure, temperature, particle
size, co-solvent, and solvent flow rate on extraction yield. The
extended Lack’s plug flow model proposed by Sovova (1994)
has been used to explain the extraction of oil from M. oleifera
seeds. This model considers both solid and liquid phase
mass transfer coefficients together with the overall extraction
2 A. Rai et al.

composed of three extraction period, namely the constant by Equation (7) by the Box complex optimization method.
extraction rate (CER): governed by convection and extraction N �� �
rate is proportional to the solubility, falling or transition extrac- 100 X � yieldpredicted yieldexperimental ��
AARDð%Þ ¼ ð7Þ
tion rate (FER): extraction rate is governed by diffusion and N i¼1 � yieldexperimental �
convection, slow extraction period: governed by only diffusion.
The amount of extraction yield related to these three extraction In the present study, a direct search global optimization
periods is given by Equation (1) as a function of time. technique known as the Box complex optimization method
8 has been used to optimize the fitting parameter of extended
> QCO2 yr ½1 expð Z Þ�t if 0 � t � tCER Lack’s plug flow model because it is a very simple and reliable
>
>
>
> QCO2 yr ½t tCER expðzW Z Þ� if tCER � t � tFER method to optimize the problems with explicit and implicit
>
> � �
< h i constraints (Erdogdu and Balaban, 2009). This method does
yðtÞ ¼ mSI x0 W yr
ln 1 þ expðtWx0Þ
1 not require gradient calculation and includes generation and
>
> r
>
> �� maintenance of search (trial) points. The flow chart of a Box
>
> h i
>
: WQ
exp mSICO2 ðtCER tÞ xx0k if t > tFER complex optimization method is shown in Figure 1 and steps
of the algorithm are given below:
ð1Þ Step 1: start with the initial feasible point and generate
a complex of k (∼2n) sequential corner points by using
where x0 is the initial concentration of oil related to non- pseudo-random variables distributed in the interval of (0, 1)
extractable solid. xp and xk represent the easily accessible (P) given as Equation (8).
and inaccessible (K) oil present in the solid with respect to ðlÞ �
non-extractable solid (N) and expressed by x0 ¼ xp þ xk. During xi;j ¼ xi þ ri;j xui xli ; i ¼ 1; 2;:::::; n j ¼ 2; 3;:::::::; k ð8Þ
the extraction process, as the concentration of oil decreases to where xi, j is the ith component of point Xj and ri, j is the random
xk, the extraction process becomes diffusion control. QCO2 is variable. It is noted that, each generated point must satisfy all m
the supercritical carbon dioxide flow rate, mSI is the mass constraints and if not, trial point shifted toward the centroid (X )
of the non-extractable solid. Parameters tCER and tFER represent of remaining accepted point using the bisection step given by
the boundary of these three extraction period. The value of tFER Equation (10) until obtained all feasible points. The centroid
and tCER is given by Equation (2) and (3), respectively. In the of accepted point is given by Equation (9)
second extraction period, the depletion of easily accessible oil
in the raw material is given by a dimensionless axial coordinate 1 Xj¼1
X ¼ X
L¼1 L
ð9Þ
zw which indicates the plane of the extractor bed where the j 1
concentration of oil is equal to xk and given by Equation (4). �
xi ¼ 0:5 xi þ X ð10Þ
ðx0 xk ÞmSI
tCER ¼ ð2Þ
yr ZQCO2 Step 2: Determine the value of objective function at all k points
of the complex and the point with highest (worst) function value
� �
mSI xk þ ðx0 xk Þ expðWx0 =yr Þ is reflected toward the center using a reflection parameter (a)
tFER ¼ tCER þ ln ð3Þ and new search point (XR) is obtained as
WQCO2 x0
� � XR ¼ ð1 þ aÞX0 aXH ð11Þ
Zyr x0 exp½WQCO2 ðt tCER Þ=mSI � xk
zW ¼ ln ð4Þ where XR is the new reflected point, XH represents the
Wx0 x0 xk worst point, reflection parameter a ≥ 1 (normally taken as 1.2),
Parameters Z and W are directly proportional to fluid and solid and X is the centroid of all vertices except XH and given by
phase mass transfer coefficients, respectively, and given by Equation (12).
Equations (5) and (6) 1 X
k

kf a0 q mSI kYa qCO2 FmSI X ¼ XL ð12Þ

Z ¼ hQ i¼ ¼ ð5Þ k 1 L¼1
CO2
ð1 eÞqs QCO2 ð1 eÞqs QCO2 L6¼k

mSI
Step 3: A check for feasibility of new reflected point (XR) is now
ks a0 mSI kXa SmSI Zyr conducted. If f(XR) < f(XH) and satisfy all constrains the new
W ¼ hQ i¼ ¼ ¼k ð6Þ search point is feasible and XH is replaced by XR and go to step
CO2
ð1 eÞ QCO2 ð1 eÞ QCO2 xk 2. If XR is not a feasible, then a new trial point is obtained by
mSI
redirecting the reflected point by half the value of a.
where kXa and kYa are fluid and solid phase mass transfer Step 4: If at any step, reflected point XR obtained in step (3)
coefficients, respectively, yr is the apparent solubility of oil into not follow any of the constrain (s), it must move toward the
supercritical carbon dioxide, a0 is a specific interfacial area, qs centroid until it becomes feasible as given in Equation (13)
and qCO2 represents the density of M. oleifera seed and the �
1
density of supercritical carbon dioxide respectively, e ðXR Þnew ¼ XR þ X ð13Þ
represents bed void fraction. In this study, three parameters Z, 2
W, and xk have been optimized by minimizing the average This search procedure continues until the vertices of the simplex
absolute relative deviation (AARD) as objective function given made of the value of objective function at trial points shrink so
Optimization of SFE Parameters for M. oleifera Seed oil
Fig. 1. Flow chart of Box complex optimization method.
that the generations of new search point are not possible by
reflection or redirection.
Step 5: In the last step, the search points are checked for
convergence by satisfying the following criteria
( )1=2
1X k � � �2
f X f ðXJ Þ �e ð14Þ
k J¼1
where X is the center of all vertices. If this is less than a
e � 10−6, convergence is achieved and stop the iteration, if not
go to step 1. The above procedure leads to find the quick and
global optimum since the initial complex (set of the initial trial
points) is randomly scattered through the feasible space.
Materials and Methods
The dried M. oleifera pods have been collected from the campus
of Indian institute of Technology Roorkee. The shelled and dried
seeds are separated from the pods. In order to reduce the water
content the seed have been unshelled and dried under daylight.
All the collected seed has been crushed in a mixer grinder and
sample based on three different sizes of particle has been
prepared by sieved analysis as discussed in our previous paper
(Rai et al., 2015). The supercritical extraction grade CO2 is
supplied by Sigma gases, India in a deep tube cylinder.
Analytical grade ethanol is procured from Merck Ltd.
(Darmstadt, Germany). A Soxhlet extraction with n-hexane
has been performed to determine total hexane extractable
M. oleifera oil content of unsieved crushed seed as discussed
in our previous paper (Rai et al., 2015). The supercritical carbon
dioxide extractions have been carried out at a pilot unit supplied
by Thar Technologies Inc. Pittsburgh. The detail working and
process flow diagram of extraction unit are discussed in our
3
previous paper (Rai et al., 2015). To perform the extraction of
M. oleifera oil from seed particles of different size, a cylindrical
basket of 7.5 mm diameter and 9 cm height has been used. The
50 gram seed particles of selected size, glass beads and glass
wool are used in each experiment and detail procedure for
preparing the extraction bed are given in the author’s previous
paper (Rai et al., 2015). The amount of extracted oil with
co-solvent is collected in a sample vial in every 5 min and
ethanol is removed by vacuum evaporator. The amount of
extracted oil is obtained gravimetrically and cumulative
extraction yield is obtained by the sum of all samples.
Results and Discussion
The main aim of this work is to evaluate the model parameters
for extraction of M. oleifera seed oil which may help to scale-up
the process. For these purposes, three different levels of each
parameter, namely pressure, temperature, particle size, solvent
flow rate, and co-solvent are selected to optimize the extraction
process. The experimental conditions and corresponding mass
transfer coefficient, absolute average relative deviation are
presented in Table I. For comparison purpose, organic solvent
extraction is performed as given in author’s previous work
(Rai et al., 2015). The oil content obtained from organic solvent
extraction is 35.76% and is treated as total oil present in the
solid metrics for the present study. As discussed earlier,
solubility (yr) is directly proportional to the extraction rate dur-
ing the constant extraction period and hence, for optimization
purpose solubility has been obtained from the linear part of
the constant extraction curve. The optimizing parameters
are subjected to four inequality constraints: 0 < Z < 10,
0 < W < 10, 0 < xk < xo and xp < xo. Where, xo is the highest
possible value of xp. The value of solid phase (kXa) and fluid
 Table I. Parameters for broken and intact cell model based on experimental extraction of Moringa oleifera seed oil

CO2 flow
Temp. Press. P. S. rate Co-solvent tCER/ tFER/ kYa kXa AARD
(K) (M Pa) (104 � m) (104 � kg/s) (%) Z W xk 60 (s) 60 (s) (103 � s−1) (104 � s−1) k* (%)
SET-1: Effect of temperature
333 30 7.5 1.67 5 3.9980 0.0085 0.4349 18.73 126.16 11.116807 0.369160 0.1862352 01.28
353 30 7.5 1.67 5 3.9984 0.0198 0.3793 25.10 201.38 12.371746 0.855383 0.3460741 01.48
373 30 7.5 1.67 5 4.0000 0.0236 0.4743 09.90 101.22 13.941782 1.026460 0.4416617 00.73
SET-2: Effect of pressure
353 20 7.5 1.67 5 2.8419 1.8243 0.0157 383.39 1504.5 11.0394 79.21587 6.6395214 02.55
353 30 7.5 1.67 5 3.9984 0.0198 0.3793 25.10 201.38 12.371746 0.855383 0.3460741 01.48
353 40 7.5 1.67 5 4.9966 0.0404 0.2336 15.01 112.41 14.003228 1.754690 0.1434436 01.10
SET-3: Effect of particle size

4
353 30 5.0 1.67 5 3.9076 0.2019 0.4105 12.82 92.38 14.561811 0.977582 0.2583722 00.91
353 30 7.5 1.67 5 3.9984 0.0198 0.3793 25.10 201.38 12.371746 0.855383 0.3460741 01.48
353 30 10.0 1.67 5 3.4244 0.0066 0.4456 22.50 129.49 7.266795 0.255870 0.1994921 01.63
SET-4: Effect of solvent flow rate
353 30 7.5 0.83 5 4.0000 0.8842 0.4006 32.14 482.08 6.188348 19.19619 11.932709 01.15
353 30 7.5 1.67 5 3.9984 0.0198 0.3793 25.10 201.38 12.371746 0.855383 0.3460741 01.48
353 30 7.5 2.50 5 3.9986 0.0348 0.4712 7.0006 92.67 18.558552 2.272475 0.6613995 01.05
SET-5: Effect of co-solvent (%)
353 30 7.5 1.67 0 3.9999 0.1420 0.4293 24.020 206.06 11.740093 5.848613 3.5808892 00.36
353 30 7.5 1.67 5 3.9984 0.0198 0.3793 25.10 201.38 12.371746 0.855383 0.3460741 01.48
353 30 7.5 1.67 10 0.4786 0.0320 0.2721 243.81 417.89 1.548601 1.457196 2.5636372 06.67
Optimization of SFE Parameters for M. oleifera Seed oil
phase (kYa) mass transfer coefficients is calculated from the
optimized values of Z, W, and xk given by Equations (5) and
(6). The value of a parameter k ¼ kXa qs xk =kYa qCO2 yr is
proportional to the ratio of solid to fluid phase mass transfer
coefficients and is a measure of the relative importance of
diffusion with respect to convection (Ferreira and Meireles,
2002). The larger value of ‘k’ indicates diffusion plays a
dominant role in the extraction process. For the particle sizes
of 1.00, 0.75, and 0.50 mm, the fixed bed offers the bulk density
of 408.12, 531.32, and 623.21 kg/m3 and corresponding particle
density of 1184.1, 1115.04, and 1428.8 kg/m3, respectively. Fur-
thermore, the values of bed porosity are 0.50, 0.44, and 0.425
and the values of corresponding particle porosity (1 − (qb/qp))
are 0.65, 0.52, and 0.56 for particle sizes of 1.00, 0.75, and
0.50 mm, respectively. The seed properties such as, size of
particles, bulk density, particle geometry, and porosity have a
considerable effect on mass transfer during SFE of oil seed. If
bulk density is too high, in the case of small size particle, due
to compression of charged material an inhomogeneous extrac-
tion may occur because of channeling in fixed bed. On the other
hand, if the bulk density is too low, larger pressure vessel will
require. Similarly, the microstructure (porosity and diameters
of pores) is of great importance, the internal porosity of oilseeds
is nearly exclusively determined by macropores which leads the
diffusion process in the solid. Moreover, due to small specific
surface area, larger particle lead to a distinct, diffusion–
domination extraction and long processing time. The amount
of initial oil content (xo) in the M. oleifera seed is 0.5566 g of
oil per g of non-extractable matter.
Effect of Operating Parameters on Extraction Yield
Effect of Temperature
To study the effect of temperature on the extraction yield of
M. oleifera seed oil a set of experiments is performed and demon-
strated in Figure 2, while the other parameters are maintained at
fixed values. These experiments are performed at 333, 353, and
373 K. Unlike traditional extraction techniques, it is necessary to
Fig. 2. Effect of temperature on extraction yield.
5
work at lower temperature to reduce the degradation of thermally
labile compounds. It can be seen from Figure 2, as the operating
temperature increases the extraction yield also increases. In the
supercritical carbon dioxide extraction process, the change in
temperature largely affects the some properties such as density
of carbon dioxide, volatile property of solutes and desorption
of solute from solid matrices (Mukhopadhyay, 2000). As tem-
perature increases, the vapor pressure of solute increases and
become more volatile, but the density of supercritical carbon
dioxide decreases. Normally, at higher pressure, the operating
temperature has a large impact on the solubility of solute as com-
pared to density variation of supercritical carbon dioxide. On the
other hand, at low pressure, the density variation shows a large
impact on extraction yield as compared to operating temperature.
The supercritical fluid extraction of oil from solid metrics is also
treated as a desorption process and it is well known fact that the
kinetic constant of desorption process is increased with tempera-
ture. Moreover, the solute is strongly bounded with non-
extractable solid and hence the some extra energy is needed to
the extraction process. Thus, the rate of the desorption process
increases at high temperatures and support the higher extraction
rate. It is also clear from Figure 2 that at constant pressure, such
as 30 MPa, the extended Lack’s model proposed by Sovova
(1994) agrees well with the experimental data. The yield
obtained at the end of the extraction period is about 1.48 times
when the temperature is increased from 333 to 373 K. In the
present work, At 333 K, the 66.84 wt% of total oil is extracted
up to the end of the transition period (t ¼ tFER, tFER ¼ 126.15 min)
which is due to convection (in first extraction period) and due to
a combination of convection as well as diffusion (transition
period). The remaining 33.16 wt% oil is extracted in the
third diffusion control period (t ≥ tFER). Whereas, at 353 K and
373 K, the total oil extracted at the end of the transition period
(tFER ¼ 210.38 min and 101.22 min) is about 86.18 wt% and
49.2 wt% of the total oil extracted, respectively. The remaining
13.82 wt% and 51.8 wt% oil is extracted in the third period
(t ≥ tFER) in which mass transfer is governed by diffusion. It
can be seen from Table I that the value of mass transfer
coefficient in solid (kXa) and fluid phase (kYa) are increases as
temperatures increased from 333 K to 373 K. Zhao and Zhang
(2013) also found that the extraction of M. oleifera oil increased
as the temperature was increased at 30 MPa and below 30 MPa
retrograde behavior was observed as temperature increased.
Moreover, Nguyen et al. (2001) also reported that, at constant
pressure of 26.38 MPa and higher, the solubility increased as
the temperature increased.
Effect of Pressure
Another set of experiments is performed to study the effect of
pressure on 20, 30, and 40 MPa while other operating para-
meters are kept at a constant value as shown in Figure 3. The
result shows that the pressure has a noticeable effect on extrac-
tion yield and as the pressure increases the extraction yield also
increases. Moreover, at 20 MPa, extraction is not favorable
because extracted quantity of M. oleifera oil is very small. How-
ever, at fixed temperature, the density of supercritical solvent
increases and vapor pressure of the oil decreases with increase
in pressure. Thus, the density of supercritical carbon dioxide
is an important factor in the dissolution of oil. This can be
6 A. Rai et al.
Fig. 3. Effect of pressure on extraction yield.
explained in term of interaction between oil and supercritical
carbon dioxide molecules. If the interactions are sufficient, the
cohesive forces between the same molecules are broken down
and as a result solubility increase. Therefore, solubility of solute
in supercritical carbon dioxide is a function of interaction
between the solute molecules and supercritical carbon dioxide.
Thus, the variation in supercritical carbon dioxide density plays
a dominant role as compare to the effect of variation in solute
vapor pressure. From Figure 3, the slope of extraction curve
increases with increased extraction pressure, which indicates
an increase in oil solubility with pressure. The solubility of
M. oleifera oil increases from 0.001518 kg oil/kg of CO2 at
20 MPa to 0.013171 kg oil/kg of CO2 at 40 MPa. This behavior
is attributed to supercritical carbon dioxide density enhance-
ment, as a result increase in solvation power of supercritical car-
bon dioxide increases. Zhao and Zhang (2013) and Nguyen et al.
(2001) also found that the solubility of M. oleifera oil increased
as the pressure was increased from 20 to 30 MPa at a constant
temperature. As pressure increases 20 to 30 MPa, the extraction
yield increase nearly 3.41 times and for 30 to 40 MPa this
increment is nearly 1.44 times. It is clearly evident that, at the
lower pressure, such as 20 MPa, the extraction is very low. This
may be primarily due to the fact that M. oleifera oil has very low
solubility in supercritical carbon dioxide at 20 MPa. The
extended Lack’s model proposed by Sovova (1994) is not in
good agreement with experimental data at lower pressure.
Table I shows the mass transfer coefficient in the fluid (kYa)
and solid phase (kXa) at different extraction pressure and
considerable increase is observed with pressure. At maximum
pressure, approximately 93.5% of total extractable oil has been
obtained after 250 min experiment and approximately 95% of
the extracted oil (93.5% of total) has been obtained after
165 min. At higher pressure of 40 MPa Sovova’s model fits the
experimental data with absolute average relative error of 3.28%.
Effect of Co-Solvent
The results of experimental run to show the effect of co-solvent
on extraction yield of M. oleifera seed oil at different levels
Fig. 4. Effect of co-solvent on extraction yield.
while other parameters are kept at constant values shown in
Figure 4. As expected, the effect of ethanol addition has a posi-
tive impact on extraction yield. As the ethanol concentration
increases the density of supercritical carbon dioxide also
increases, which improves the solubility of oil (Gurdial et al.,
1993). Also, the addition of co-solvent to supercritical carbon
dioxide increases the polarity which helped to extract polar
compounds. For instance, extraction with pure supercritical car-
bon dioxide gives only 0.1784 kg oil/kg CO2 oil while addition
of 5% ethanol gives 0.2314 kg oil/kg CO2 which is 1.29 times
larger. Similarly, 10% ethanol gives 1.85 times extraction yield
as compared to pure supercritical carbon dioxide extraction.
These results show that the intermolecular interaction between
oil and ethanol increases, which favors solubility increments
in non-polar carbon dioxide. Also, mass transfer coefficients
in solid phase (kXa) increase with the addition of co-solvent
from 0 to 5% as shown in Table I. The probable reason for
the increase in mass transfer coefficient is due to possible
increases in the diffusivity of M. oleifera oil in supercritical car-
bon dioxide and as a result, the increase in effective diffusivity
in particle. However, for the 10% co-solvent addition model
under predict the experimental data.
Effect of Particle Size
Figure 5 is plotted to demonstrate the effect of particle size on
extraction yield with time and other operating parameters are
maintained at a constant value as shown in figure. As expected,
extraction yield increases with decrease in particle diameter
because of easy availability of accessible oil. Moreover, a small
particle offers low diffusion resistances due to shorter diffusion
path and also offers a large surface area per unit mass as a result
extraction increases. On the other hand, largest particle size
(1.00 mm) offers large intra-particle diffusion resistance and
has a significant effect on extraction yield. It can also explain
in term of simulated value of mass transfer coefficient given
in Table I. The value of kXa and kYa decreases as the particle size
increases. The solid phase mass transfer coefficient (kXa)
contributes toward the diffusion of inaccessible oil in the seed
particles and hence, mass transfer due to diffusion is larger for
Optimization of SFE Parameters for M. oleifera Seed oil
Fig. 5. Effect of particle size on extraction yield.
small size particle due to the short diffusion path, whereas mass
transfer due to diffusion is small for large size particle due to the
long diffusion path. For the large size particle, the extraction in
considerably less in the third extraction period, which is
diffusion controlled and hence the particle size reduction is
necessary to decrease the extraction time. In the present study,
for the larger size particles the broken and intact cell model is
fitted with the absolute average relative deviation of 1.63%,
which is quite large as compared to small size particle which
offers a value of the absolute average relative deviation as
0.91%. The broken and intact cell model fits the experimental
result with the absolute average relative deviation of 0.91%
and 1.48% for 0.50 mm and 0.75 mm particle sizes respectively.
The highest cumulative extraction yield has been obtained for
the seed of the low mean particle size (0.50 mm). The lowest
particle size (0.50 mm) gives highest cumulative extraction
yield, approximately 72.76 mass%, at 250 min, whereas 64.54
and 39.22 wt% cumulative extraction yields has been obtained
for 0.75 and 1.00 mm mean particle sizes, respectively.
Fig. 6. Effect of solvent flow rate on extraction yield.
7
Effect of Solvent Flow Rate
The performance of supercritical extraction process against
supercritical carbon dioxide flow rate has been illustrated in
Figure 6 and the results are presented in Table I. This result
clearly indicates supercritical carbon dioxide flow rate has
significant and positive effect on M. oleifera seed oil extraction.
It is found that, at lower flow rate 250 min of extraction are not
sufficient for complete or maximum extraction while at higher
flow rate (2.5 � 10−4 kg/s) extraction rate increases and after
250 min of extraction reaching to an asymptotic value. More-
over, with the increase in supercritical carbon dioxide flow rate
the resistance to mass transfer decreases proportionately and
thus the extraction yield increases. Table I shows that, mass
transfer coefficient in solid phase (kXa) and in the fluid phase
(kYa) increases with increase in supercritical carbon dioxide
flow rate and hence, extraction yield increases. The broken
and intact cell model predictions and the experimental data
are in good agreement for the given experimental conditions.
The experimental data for the flow rate of 0.833 � 10−4,
1.6 � 10−4 and 2.5 � 10−4 kg/s is fitted with the average
relative errors of 1.15%, 1.48%, and 1.05% respectively.
Conclusion
The extraction of oil from M. oleifera seed using supercritical
carbon dioxide has been performed. For M. oleifera oil extrac-
tion, the maximum extraction 0.3341 kg oil/kg CO2 is found at
40 MPa, 353 K, 0.75 mm, 1.67 � 10−4 kg/s with 5% co-solvent
addition. Similarly, minimum extraction 0.0676 kg oil/kg CO2
is found at 20 MPa, 353 K, 0.75 mm, 1.67 � 10−4 kg/s with
5% co-solvent addition for 250 min experiment which clearly
indicates that the pressure has a higher impact on extraction as
compared to other operating parameters. Moreover, the physical
aspects of supercritical extraction are investigated and modeling
of the experimental data using broken and intact cell model
proved to be adequate for M. oleifera seed oil extraction.
Nomenclature
F objective function
K the mass of inaccessible solute inside the solid particle
kf solvent-phase mass transfer coefficient, m s−1
ks solid-phase mass transfer coefficient, m s−1
kXa mass transfer coefficient in solid phase
kYa mass transfer coefficient in fluid phase
N mass of the solute-free solid phase, kg;
P total mass of extractable solute in the solid
QCO2 mass flow rate of solvent, kg/s;
Q mass flow rate of solvent related to N, s−1
X oil concentration in seeds, kg oil/kg oil free seeds
X center of all search points except XH
x0 overall initial concentration related to solute-free
solid phase
xk hardly or inaccessible solute
xp easily accessible solute
XU upper bounds of the explicit constraints
XL lower bounds of the explicit constraints
XR reflected Point
V volume
8 A. Rai et al.

W parameter of slow-extraction period Goto, M., Roy, B. C., and Hirose, T. (1996). Shrinking-core leaching model
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K easily accessible solute;
Gurdial, G. S., Foster, N. R., Yun, S. L. J., and Tilly, K. D. (1993). Phase
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O overall initial concentration Mukhopadhyay, M. (2000). Natural Extracts Using Supercritical Carbon
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qs density of seeds, kg m−3 115–126.
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with ethanol for pretreatment: Optimization of the extraction process,
AARD average absolute relative deviation
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CEY cumulative extraction yield terization of oil from Moringa oleifera using supercritical Co2 and
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