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2.doker - Modeling of Extraction of Carotene From Apricot Bagasse
2.doker - Modeling of Extraction of Carotene From Apricot Bagasse
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
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 as well as models for equipment design including the
processes [2,3]. effects of fluid flow, mass and heat transfer, and phase
Mathematical modeling of complex phenomena, contacting mechanisms.
such as the extraction of natural materials, is an ac- The distribution of the natural materials with in
tivity of increasing importance due to the economic the solid structure affects the selection of the possi-
potentials in offers. It is important to develop models ble models. The extractable materials may be free on
for the extraction process when the extraction op- the surface of the solid matrix, adsorbed on the outer
erations are optimized for commercial applications. surface, located with in pores, or distributed with in
However, such predictions require the establishment plant cell. Each different description equivalents to a
of model predicting the phase behavior, equilibrium, different model. In literature, the extraction models
solubility, adsorption, desorption etc. Relationships, proposed for extraction of natural materials in plants,
O. Döker et al. / J. of Supercritical Fluids 28 (2004) 11–19 13
could be classified in two main groups and afterwards selected the best mathematical model, which charac-
into their subgroups as: terize the extraction process, after the take into consid-
eration of mass transfer mechanisms such as diffusion
i) Empirical models [4,5]
and solubility.
ii) Differential mass balance models
a) Model based on heat transfer analogy [6,7]
b) Model based on mass transfer balance [8,9] 2. Experimental
c) Shrinking core model [2,3,10].
Identification for mathematical equations based on In this study, -carotene was extracted from apricot
experimental results is determined with separation bagasse, which was got from Fruit Juice Management
parameters such as temperature, pressure, solvent of Faculty of Agriculture at Ankara University, by su-
velocity, particle size, and physical properties of su- percritical fluid extraction system (ISCO, SFX 220).
percritical fluids [4,5]. When the information on the Firstly, apricot bagasse was dried with the freeze
mass transfer mechanisms and on the equilibrium re- drier, ground up the specific particle dimension by
lationships are missing, the empirical model approach grinder and kept in a deep freezer at 253 K. The
can be useful for define of the extraction process. experiments were carried out in 10 × 10−3 m3 ex-
In the model based on heat transfer analogy, SFE traction column with 2 × 10−3 kg material [12]. The
beware towards as a heat transfer phenomenon. Ev- extraction of -carotene from apricot bagasse occurs
ery single plant particles were assumed spherical and in semi-continuous flow extractor. At the end of the
equations that apply to the cooling hot sphere in a cool extraction, -carotene was collected in the petroleum
medium were used to describe the concentration pro- ether at the collection tube and extract collected in
file inside the particles as function of time [11]. Main the tube analyzed at 451 nm by UV–Vis spectropho-
assumption of this model, all particles are assumed to tometer (Shimadzu UV-VIS 1201). The temperature,
be at the same extraction conditions. For this reason, pressure, and flow rate of supercritical CO2 were
this model considers the ideal extraction behavior for monitored at the control system.
each single particle because the interactions between
the particles can be neglected.
3. Mathematical model
In fixed bed extractors, widely proposed model is
based on differential mass balance because it can be
In this study, mass transfer equations, which charac-
describe the SFE process as well as. This model can
terize the extraction of -carotene in industrial waste
be included the resistances of the bulk phase, external
product of apricot bagasse by supercritical CO2 , were
mass-transfer resistance, and internal mass-transfer
proposed and solved.
resistance of particle. However, at this model equi-
This model describes the situation of the irreversible
librium relationship have to propose between the
desorption followed by diffusion in the porous solid
concentration of the particle and bulk phase. At most
through the pores. When the mass transfer rate of the
of SFE processes, linear relationship is used due
solute in the nonextracted inner part is much slower
to the lack of experimental phase equilibrium data
than that in outer part where most of the solute has
[11].
been extracted, or solute concentration is much higher
Shrinking core model describes the situation of
than the solubility of the solute in the solvent phase,
the irreversible desorption followed by diffusion in
a shape boundary may exit between outer and inner
porous solid through the pores. Where there is a sharp
region. A core of inner region shrinks with the progress
boundary within a particle between extracted part and
of the extraction. These situations can be modeled by
nonextracted part, the shrinking core model may be
shrinking core model [2].
useful [2,10].
The following criteria are assumed:
In this work, modeling of the natural product ex-
traction by supercritical fluid was studied. -carotene i) The system is isothermal and isobaric,
was selected as a model the extraction of natural prod- ii) The matrix is a porous material where -carotene
ucts by supercritical CO2 . Shrinking core model was 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
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 .
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 tion rate increased with an increase in temperature at
as, at the increasing pressure, the positive effects on 30.4 MPa.
the extraction process overcome the negative effects. In constant pressure, axial dispersion coefficient
At pressure values of 40.5 and 50.7 MPa, the mathe- decreased while effective diffusivity, mass transfer
matical model satisfactorily described the experimen- coefficient and saturation concentration of -carotene
tal data. increased by the increasing temperature. Internal and
external mass-transfer resistances are decreased by
5.4. Effect of temperature the increased of the effective diffusivity and mass
transfer coefficient. For this reason, supercritical CO2
Effect of temperature at 30.4 MPa is shown in shows better penetrate behavior in solid particles. In
Fig. 4. It is evident from this figure that the extrac- 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
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tical and Biomedical Analysis 24 (2001) 1037–1048. York, 2001.
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Penniger, M. Radosz, M.A. McHugh, V.J. Krukonis (Eds.), and nitrous oxide from 308 to 323 K and from 9.6 to 30
Supercritical Fluid Technology, Elsevier, Amsterdam, 1985, MPa, Journal of Chemical Engineering Data 37 (1992) 249–
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