J.

of Supercritical Fluids 28 (2004) 11–19

Modeling of extraction of ␤-carotene from apricot bagasse

using supercritical CO2 in packed bed extractor
O. Döker, U. Salgın, İ. Şanal, Ü. Mehmetoğlu, A. Çalımlı∗
Faculty of Engineering, Department of Chemical Engineering, Ankara University, 06100 Tandoğan, Ankara, Turkey

Received 26 May 2002; received in revised form 2 December 2002; accepted 10 January 2003

Abstract

This work investigates the modeling of ␤-carotene extraction from industrial waste product of apricot bagasse at the production
of fruit juice. Shrinking core model was selected as the best mathematical model, which characterize the extraction process, after
take into consideration of mass transfer mechanisms such as adsorption, diffusion, solubility, and desorption. Effect of main
separation parameters such as pressure, temperature, CO2 flow rate, and particle size on the extraction yields were researched
at the supercritical fluid extraction system of laboratory scale and the results were compared with the results obtained from the
solution of mathematical model.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Supercritical CO2 ; Supercritical CO2 extraction; Mathematical modeling; Shrinking core model; ␤-carotene

1. Introduction from porous solid materials by supercritical fluids usu-

Most of the works have been devoted to experimen-
tal study, where they focused on the natural materials
to consider industrial. Although most of biochemical
and chemical productions which have produced natu-
ral and synthetic methods sensitive to heat, supercrit-
ical fluid extraction (SFE) is an alternative method to
be produced that materials. This method is more suit-
able than crystallization, adsorption, chromatography,
and evaporation methods for environment conditions.
Fine chemicals in plant, can be found in cell, or out
of the cell wall as synthesized. The extraction process
∗ Corresponding author. Tel.: +90-312-212-6720/1314;
fax: +90-312-212-1546.
E-mail address: calimli@eng.ankara.edu.tr (A. Çalımlı).
ally includes dissolution of solid or liquid component
into pore liquid, diffusion in porous materials, and ex-
ternal mass-transfer around the solid particle [1].
Extraction system involves a bulk solid phase and a
fluid phase. The fluid phase comprises the supercriti-
cal solvent and the dissolved extract. In many cases,
the fluid can be assumed identical with the supercrit-
ical solvent. However, this has to be examined for
each case. The solid phase remains within the extrac-
tion vessel (semi-continuous operation). Mass trans-
port occurs between the two phases. Substances are
transported from the solid to the fluid phase. Follow-
ing parameters, such as dispersion of extract concen-
tration along extractor and depend time, concentration
of the extractable substance in the bulk phase, and ra-
dial and axial dispersion, pretreatment of the solid and

0896-8446/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0896-8446(03)00006-8
12 O. Döker et al. / J. of Supercritical Fluids 28 (2004) 11–19

Nomenclature
a model’s constant (vR2 /(DL L))
b model’s constant (b = Csat /q0 )
c model’s constant (c = DL /De )
Cb solute concentration in the bulk phase (mol m−3 )
Cp solute concentration in the pore volume (mol m−3 )
Csat solubility of ␤-carotene in supercritical CO2 (mol m−3 )
De effective diffusivity (m2 s−1 )
DL axial dispersion coefficient (m2 s−1 )
kf film mass-transfer coefficient (m s−1 )
L bed length (m)
q solid phase concentration (mol m−3 )
qavr average solid phase concentration (mol m−3 )
qo initial solid phase concentration (mol m−3 )
qv volumetric flow rate (m3 s−1 )
r radial coordinate in particle (m)
rc critical radius of the core (m)
R initial radial coordinate of the solid phase (m)
Rp particle diameter (m)
t time (s)
xb dimensionless concentration in the bulk phase (Cb /Csat )
xp dimensionless concentration in the pore volume (Cp /Csat )
y dimensionless solid phase concentration (q/q0 )
yo dimensionless initial solid phase concentration
z axial distance (m)
Z dimensionless axial distance (z/L)
Bi biot number (kf r/De )
Pe peclet number (Lv/DL )
ε volid fraction in bed
εp porosity of the solid
ξ dimensionless radial coordinate in particle (r/R)
ξc dimensionless critical radius of the core (rc /R)
υ interstitial velocity of solvent in bed (m s−1 )
θ dimensionless time

operation parameters, have interest for the extraction
processes [2,3].
Mathematical modeling of complex phenomena,
such as the extraction of natural materials, is an ac-
tivity of increasing importance due to the economic
potentials in offers. It is important to develop models
for the extraction process when the extraction op-
erations are optimized for commercial applications.
However, such predictions require the establishment
of model predicting the phase behavior, equilibrium,
solubility, adsorption, desorption etc. Relationships,
as well as models for equipment design including the
effects of fluid flow, mass and heat transfer, and phase
contacting mechanisms.
The distribution of the natural materials with in
the solid structure affects the selection of the possi-
ble models. The extractable materials may be free on
the surface of the solid matrix, adsorbed on the outer
surface, located with in pores, or distributed with in
plant cell. Each different description equivalents to a
different model. In literature, the extraction models
proposed for extraction of natural materials in plants,
 O. Döker et al. / J. of Supercritical Fluids 28 (2004) 11–19
could be classified in two main groups and afterwards
into their subgroups as:
i) Empirical models [4,5]
ii) Differential mass balance models
a) Model based on heat transfer analogy [6,7]
b) Model based on mass transfer balance [8,9]
c) Shrinking core model [2,3,10].
Identification for mathematical equations based on
experimental results is determined with separation
parameters such as temperature, pressure, solvent
velocity, particle size, and physical properties of su-
percritical fluids [4,5]. When the information on the
mass transfer mechanisms and on the equilibrium re-
lationships are missing, the empirical model approach
can be useful for define of the extraction process.
In the model based on heat transfer analogy, SFE
beware towards as a heat transfer phenomenon. Ev-
ery single plant particles were assumed spherical and
equations that apply to the cooling hot sphere in a cool
medium were used to describe the concentration pro-
file inside the particles as function of time [11]. Main
assumption of this model, all particles are assumed to
be at the same extraction conditions. For this reason,
this model considers the ideal extraction behavior for
each single particle because the interactions between
the particles can be neglected.
In fixed bed extractors, widely proposed model is
based on differential mass balance because it can be
describe the SFE process as well as. This model can
be included the resistances of the bulk phase, external
mass-transfer resistance, and internal mass-transfer
resistance of particle. However, at this model equi-
librium relationship have to propose between the
concentration of the particle and bulk phase. At most
of SFE processes, linear relationship is used due
to the lack of experimental phase equilibrium data
[11].
Shrinking core model describes the situation of
the irreversible desorption followed by diffusion in
porous solid through the pores. Where there is a sharp
boundary within a particle between extracted part and
nonextracted part, the shrinking core model may be
useful [2,10].
In this work, modeling of the natural product ex-
traction by supercritical fluid was studied. ␤-carotene
was selected as a model the extraction of natural prod-
ucts by supercritical CO2 . Shrinking core model was
13
selected the best mathematical model, which charac-
terize the extraction process, after the take into consid-
eration of mass transfer mechanisms such as diffusion
and solubility.
2. Experimental
In this study, ␤-carotene was extracted from apricot
bagasse, which was got from Fruit Juice Management
of Faculty of Agriculture at Ankara University, by su-
percritical fluid extraction system (ISCO, SFX 220).
Firstly, apricot bagasse was dried with the freeze
drier, ground up the specific particle dimension by
grinder and kept in a deep freezer at 253 K. The
experiments were carried out in 10 × 10−3 m3 ex-
traction column with 2 × 10−3 kg material [12]. The
extraction of ␤-carotene from apricot bagasse occurs
in semi-continuous flow extractor. At the end of the
extraction, ␤-carotene was collected in the petroleum
ether at the collection tube and extract collected in
the tube analyzed at 451 nm by UV–Vis spectropho-
tometer (Shimadzu UV-VIS 1201). The temperature,
pressure, and flow rate of supercritical CO2 were
monitored at the control system.
3. Mathematical model
In this study, mass transfer equations, which charac-
terize the extraction of ␤-carotene in industrial waste
product of apricot bagasse by supercritical CO2 , were
proposed and solved.
This model describes the situation of the irreversible
desorption followed by diffusion in the porous solid
through the pores. When the mass transfer rate of the
solute in the nonextracted inner part is much slower
than that in outer part where most of the solute has
been extracted, or solute concentration is much higher
than the solubility of the solute in the solvent phase,
a shape boundary may exit between outer and inner
region. A core of inner region shrinks with the progress
of the extraction. These situations can be modeled by
shrinking core model [2].
The following criteria are assumed:
i) The system is isothermal and isobaric,
ii) The matrix is a porous material where ␤-carotene
is uniformly distributed throughout the particle,
14 O. Döker et al. / J. of Supercritical Fluids 28 (2004) 11–19

iii) The physical properties of the supercritical fluid The following equations were derived by rearrang-
are constant during the extraction, ing with Eqs. (1)–(11).
iv) Radial dispersion is neglected,
v) Extraction is irreversible desorption, ∂xb ∂xb a ∂ 2 xb (1 − ε)
+a = − 3Bi
∂θ ∂Z Pe ∂Z 2 ε
Based on these assumptions, the dimensionless ma-
xb − 1
terial balances in the bulk phase and solid phase are × (12)
described as; (1 − Bi (1 − 1ξc ))
Bulk phase:
∂xb ∂xb a ∂ 2 xb (1 − ε)
 ∂ξc cBi(1 − xb )
+a = − 3Bi x b
− x p
(1) =    
∂θ ∂Z Pe ∂Z2 ε ∂θ εp Bi xb −1 + 1−εp bξc (ξc +Bi (1−ξc ))
(1) (13)
Solid phase: These differential equations coupled with bound-
 p
∂xp   ∂y c ∂ 2 ∂x
ary and initial conditions were solved numerically
εp + 1 − εp b = 2 ξ (2) by Crank-Nicholson’s method [13]. Proposed model
∂θ ∂θ ξ ∂ξ ∂ξ
equations solved at matlab 6.0.
Dimensionless diffusion in outer region is given by
 p
c ∂ 2 ∂x
ξ = 0 (3) 4. Parameters
ξ 2 ∂ξ ∂ξ
Solid phase solute exists within the core. The parameters involved in the model are the mass
y = ξ 3
(4) transfer coefficient to the bulk phase, the axial dis-
persion coefficient in the fluid phase, the effective
Dimensionless boundary conditions are given as fol- pore diffusivity in the particles and the solubility of
lows. At the core boundary, the concentration in the ␤-carotene in supercritical CO2 . These were evaluated
fluid phase is at its saturated value. using existing correlations and available data.
p
xp = xsat at ξ = ξc (5) The mass transfer coefficient in a packed bed super-
critical extractor was estimated with using empirical
Diffusion flux at the outer surface of a particle is correlation [14];
equal to mass transfer through external film.
 p
 Sh = 2 + 1.1Sc1/3 Re0.6 (14)
∂x
= Bi xb − xp (1) (6)
∂ξ ξ = 1 where;
Dimensionless initial conditions are given as fol- 2Rkf
Sh = (15)
lows: De
xb = 0 at θ = 0 (7) η
Sc = (16)
ρDe
ξc = 1 at θ = 0 (8)
2Rυρ
y = y0 at θ = 0 (9) Re = (17)
η
Dimensionless Danckwerts’ boundary conditions at
the inlet and exit of extractor are given by Eq. (14) was developed for conventional process but
it has been used successfully for supercritical extrac-
1 ∂xb tion systems [15].
xb − = 0 at Z = 0 (10)
Pe ∂Z The axial dispersion coefficient in the supercritical
∂xb phase was approximated as follows [16,8].
= 0 at Z = 1 (11)
∂Z Pe = 0.187Re0.265 Sc−0.919 (18)
 O. Döker et al. / J. of Supercritical Fluids 28 (2004) 11–19 15

Where, diffusivity (De ), and solubility of ␤-carotene (Csat )

2Rυ
Pe =
DL
The effective diffusivity in the particle given by
[14];
εp
De = DAB (20)
τ 5. Results and discussions
In Eq. (20), τ is the tortuosity factor of solid and it
is usually in the range of 2–8. In this study, it was held
constant at a value of 3 and D+ AB is calculated with
Fuller equation [17]. Thus, the effective pore diffusiv-
ity was calculated from Eq. (20) using the binary dif-
fusivity, tortuosity, and porosity values. Where DAB is
the binary diffusivity of solute and solvent, and which
is calculated by Eq. (21)[17].
DAB P
= f(Tr , Pr ) (21)
(DAB P)+
The solubility of ␤-carotene in supercritical CO2
given by Sakaki [18];
H
ln(Csat ) = klnρ − +A (22)
RT
Where k is the number of gas molecules associat-
ing with one molecule of solute to from a solvatocom-
pex. For ␤-carotene, k = 9.3 in supercritical CO2 . In
Eq. (22) A is a variable that is function of molecular
weights of the solute and the gas and equal to −34.28.
H was measured 7.2 × 104 J mol−1 [18].
The physical properties of both the solvent and
solute at the experimental conditions are shown
in Table 1. The density of CO2 was estimated by
Hankinson–Brobst–Thomson method (HBT) [17].
The viscosity of CO2 was calculated by the viscosity
correlation of Makhopadyay [19]. Mass transfer coef-
ficient (kf ), axial dispersion coefficient (DL ), effective
in supercritical CO2 were calculated using Eqs. (14),
(19) (18), (20) and (22), respectively. The particle poros-
ity of apricot bagasse and bed void fraction were
determined 0.12 and 0.8, respectively.
In this study, the effects of particle size of apri-
cot bagasse, supercritical CO2 flow rate, pressure, and
temperature on the extraction yield were investigated
and the experimental and model results were com-
pared.
5.1. Effect of particle size
Effect of particle size (106 and 300 ␮m) on ex-
traction yield is shown in Fig. 1. Intraparticle diffu-
sion resistance is small for small particle because of
the smaller diffusion path. For this reason, extraction
yield increased with decreasing of the particle size.
For large particle size, the mathematical model satis-
factorily described the experimental data.
5.2. Effect of supercritical CO2 flow rate
Effect of CO2 flow rate is shown in Fig. 2. The ex-
traction yield increases with the increase of the flow
rate. This behavior can be explain as that by the way
of the increasing of the flow rate, thickness of the
film layer around the solid particles reduced and mass
transfer resistance surrounding the solid particle is be-
come small. As a result, extraction yields increase via
CO2 flow rate increase. The mathematical model sat-
isfactorily described the experimental data.

Table 1
Physical properties of supercritical CO2 and ␤-carotene at the experimental conditions
P (MPa) T (K) ρ (kg m−3 ) µ × 10−5 De × 10−11 kf × 10−11 DL × 10−11 Csat × 10−3
(kg m−1 s−1 ) (m2 s−1 ) (m2 s−1 ) (m2 s−1 ) (kg m−3 )
30.4 313 921 3.30 7.77 1.55 4.71 4.6
333 839 2.77 8.66 1.70 3.87 10.2
40.5 313 964 4.44 5.83 1.20 8.24 7.1
333 897 3.79 6.50 1.32 6.74 19.0
50.7 313 1002 5.70 4.66 0.97 13.01 10.1
333 943 4.89 5.19 1.07 10.56 30.3
16 O. Döker et al. / J. of Supercritical Fluids 28 (2004) 11–19

Fig. 1. Effect of particle size on the extraction yield of ␤-carotene at T = 333 K, P = 40.5 MPa, qv = 3.33 × 10−8 m3 CO2 s−1 .

5.3. Effect of pressure time, internal and external mass-transfer resistances

The influence of the pressure has been studied at a
temperature of 313 and 333 K, particle size of 300 ×
10−6 m and CO2 flow rate of 3.3 × 10−8 m3 s−1 . The
corresponding yield data are reported in Fig. 3.
Effective diffusivity and mass transfer coefficient
decrease but solubility of ␤-carotene and axial dis-
persion coefficient increase by the way of increasing
pressure at constant temperature (Table 1). At the same
increase by the decreasing of the effective diffusivity
and mass transfer coefficient. For this reason, super-
critical CO2 did not disperse in solid particles easily.
In the result of, increasing of saturation concentra-
tion of ␤-carotene in fluid phase showed a positive
effect on the extraction process. On the contrary,
increasing of internal and external mass-transfer
resistance showed a negative effect. At constant
temperature (T = 313 K), extraction yield increased by

Fig. 2. Effect of CO2 flow rate on the extraction yield of ␤-carotene at P = 40.5 MPa, T = 333 K.
 O. Döker et al. / J. of Supercritical Fluids 28 (2004) 11–19 17

Fig. 3. Effect of pressure on the extraction yield of ␤-carotene at T = 313 K, qv = 3.3 × 10−8 m3 CO2 s−1 .

the increasing pressure. This behavior was explained
as, at the increasing pressure, the positive effects on
the extraction process overcome the negative effects.
At pressure values of 40.5 and 50.7 MPa, the mathe-
matical model satisfactorily described the experimen-
tal data.
5.4. Effect of temperature
Effect of temperature at 30.4 MPa is shown in
Fig. 4. It is evident from this figure that the extrac-
tion rate increased with an increase in temperature at
30.4 MPa.
In constant pressure, axial dispersion coefficient
decreased while effective diffusivity, mass transfer
coefficient and saturation concentration of ␤-carotene
increased by the increasing temperature. Internal and
external mass-transfer resistances are decreased by
the increased of the effective diffusivity and mass
transfer coefficient. For this reason, supercritical CO2
shows better penetrate behavior in solid particles. In
addition, increasing of saturation concentration of

Fig. 4. Effect of temperature on the extraction yield of ␤-carotene at P = 30.4 MPa, qv = 3.3 × 10−8 m3 CO2 s−1 .
18 O. Döker et al. / J. of Supercritical Fluids 28 (2004) 11–19
␤-carotene in fluid phase and decreasing of internal
and external mass-transfer resistance showed positive
effects on the extraction process.
Finally, at 30.4 MPa, by the increasing temperature
from 313 to 333 K, the positive effects influence the
extraction process. At the 333 K, the mathematical
model satisfactorily described the experimental data.
6. Conclusions
␤-carotene from freeze-dried apricot bagasse was
extracted by using supercritical CO2 as a solvent to
measure the effects of supercritical CO2 flow rate,
particle size, temperature, and pressure on the extrac-
tion yield. The experimental data were described by
shrinking core model. The mass transfer coefficient to
the bulk phase, the axial dispersion coefficient in the
fluid phase, the effective pore diffusivity in the par-
ticle and the solubility of ␤-carotene in supercritical
CO2 , which is involved proposed model, were evalu-
ated using existing correlations and available data.
Mathematical model equations coupled with bound-
ary and initial conditions were solved numerically by
Crank-Nicholson’s method at matlab 6.0.
Investigated of the harmony with the mathematical
model and experimental data which got different val-
ues of main separation parameters such as pressure,
temperature, particles size, and CO2 flow rate;
i) As a result of experimental study, external and
internal mass-transfer resistances are important.
ii) Investigation of effect of operation pressure on
extraction process, the mathematical model fitted
well the experimental data at 40.5 and 30.4 MPa.
iii) Investigation of effect of operation temperature on
extraction process, at the 313 K, the mathematical
model seen fit the experimental model.
iv) At the effect of particle size on extraction process,
the mathematical model satisfactorily described
the experimental data.
v) Investigation of effect of CO2 flow rate on extrac-
tion process, the mathematical model more suit-
able with experimental data by the way of the de-
creasing the CO2 flow rate.
vi) Regression coefficients between the proposed
model and experimental data were estimated
0.97–0.99.
Acknowledgements
The author wish to thank to Ankara University
Research Fund, project no: 2001-07-05-046 for their
financial support.
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