128 The Journal of Supercritical Fluids, 1996, 9, 128-133

Shrinking-Core Leaching Model for Supercritical-

Fluid Extraction
Motonobu Goto,* Bhupesh C. Roy, and Tsutomu Hirose

Department of Applied Chemistry, Kumamoto University, Kumamoto 860, Japan

Received August 18, 1995; accepted in revised form December 28, 1995

Extraction or leaching of a solute from a solid material is a process involving mass transfer in the
solid matrix. When the solute content in the solid material is sufficiently large as compared to the solubil-
ity in fluid phase, the process is similar to that of irreversible desorption. The shrinking-core model was
applied to the modeling of the extraction process. The model including axial dispersion in the extraction
column was solved numerically. Quasi-steady-state solution without axial dispersion was derived, and
the accuracy was discussed in comparison with the numerical solutions. The model calculations gave a
good agreement with the experimental extraction curve reported in literature.
Keywords: supercritical extraction, leaching, shrinking core, modeling, mass transfer

INTRODUCTION natural materials is not well understood and is not always

Supercritical-fluid extraction has been applied to
natural materials to separate the desired components from
a solid matrix in several industries such as the food, per-
fumery, pharmaceuticals, and the petroleum industry.
Most of the work has been devoted to experimental stud-
ies where the focus has been on the composition of the
extracts or application to new materials.
The extraction process from natural materials such
as plants, beans, or seeds involves the release of solutes
from the porous or cellular matrix into the solvent. It is
a mass-transfer process. The solutes fixed or trapped in a
matrix by physical or chemical forces must be released
and transferred to the supercritical fluid by dissolving.
Then, the dissolved solutes diffuse through the matrix to
the surface of a particle. Finally, they move across stag-
nant film around a particle to the bulk fluid-phase.
The solutes of interest vary from small to large
molecules, or low to high boiling compounds such as
flavor components, or essential oil to lipids or
carotenoids. Their content in a feed material may be
small (less than 1%) or large (40% for seed oil). Thus,
rate-limiting process for the extraction of these materials
may differ from material to material. The dissolution ki-
netics involved in a model may depend on the ratio of the
solute content to the saturation concentration in the fluid
phase, the bound state of the solute on a matrix, and the
association with coexisting materials.
It is important to model the extraction process when
the extraction operation is to be optimized for commercial
application. Unfortunately, the extraction process for
operated at the optimal conditions.
Several attempts have been devoted for the modeling
of the extraction process. 1*2 The extraction of oil from
seeds has been most intensively modeled. Since oil con-
tent of seeds is relatively high and oil consists of similar
compounds, mass-transfer model was often employed.
Fick’s diffusion model has been applied.2,3 A simpler
model has been also applied where mass transfer was ex-
pressed by a linear driving-force mode1.4+5 The driving
force for the mass transfer may be the difference of the so-
lute concentration between saturated concentration in fluid
phase and local concentration in pores in the matrix of a
particle. It is evident that natural materials are different
from uniformly porous materials such as adsorbents but
are cellular structures with partial destruction taking place
during the crushing process. Sovova6v7considered a parti-
cle consisting of crushed cells and uncrushed cells. The
solutes can be easily extracted from the crushed cell,
whereas the extraction from the uncrushed cell is much
more difficult.
Desorption models have been developed where local
dissolving process is considered to be desorption of so-
lutes adsorbed on a matrix. Recasens et al.* developed a
model accounting for local adsorption/desorption kinetics,
intraparticle diffusion, and external mass transfer. Goto et
a1.9 applied the desorption model to the extraction of es-
sential oils where local adsorption equilibrium was as-
sumed.
When there is a sharp boundary within a particle be-
tween extracted part and nonextracted part, the shrinking-

0896-8446/96/0902-0128$7.50/O 0 1996 PRA Press

The Journal of Supercritical Fluids, Vol. 9, No. 2, 1996 Shrinking-Core Leaching Model 129

core leaching model may be useful. The shrinking-core

model has been used in solid-fluid reaction,‘O adsorp- (4)
tion,” and ion exchange. t2 The shrinking-core leaching
model was used for a single particleI and for a packed
Boundary conditions are given as follows. At the
bed.14 King and Catchpolet4 derived quasi-steady-state an-
core boundary, the concentration in the fluid phase is at
alytical solution assuming negligible axial dispersion in a
its saturation value.
bed.
In this paper we derive a shrinking-core leaching
Ci = C,,, at r = r, (5)
model accounting for intraparticle diffusion, external fluid
film mass transfer, and axial dispersion. The model is
further simplified to derive an analytical solution. The ef- Diffusion flux at the outer surface of a particle is equal to
fect of parameters involved in the model is discussed. The the mass transfer through external film.
model was applied to the experimental data for oil extrac-
tion from seeds. Dac,
e -& _ = kf[c-cml (6)
( 1 r-R
THEORETICAL DEVELOPMENT
Model Including Axial Dispersion. This Initial conditions are given as follows:
model describes the situation of the irreversible desorption
followed by diffusion in the porous solid through the rc=R at t=O (7)
pores. When mass transfer rate of the solute in the
nonextracted inner part is much slower than that in the C=O at t=O. (8)
outer part where most of the solute has been extracted, or
the solute concentration is much higher than the solubil- Danckwert’s boundary condition at the inlet of column and
ity of the solute in the solvent phase, a sharp boundary the exit condition are given by
may exit between the outer and the inner region. A core
of inner region shrinks with the progress of the extrac-
tion. These situations can be modeled by the shrinking-
vC-D z=O at z=O (9)
L az
core model. An example of these situations is the super-
critical-fluid extraction of vegetable oils.
&=O at z=L.
The following assumptions have been made to de-
rive the fundamental equations. The solvent flows axially
with interstitial velocity, v, through a packed bed in a Following dimensionless groups are defined to derive di-
cylindrical extractor of height, L. Pure solvent enters the mensionless formulae of the fundamental equations: x =
bed. The process is isothermal. Considering axial disper- C/C,, 9Xi = CilCs,, v 5 = t-JR, Z = zlL, a = vR21D,L, 0 =
sion, the material balance on the bulk fluid-phase in the (D,lR2)t, y = qlqo, b = C,,,/g,, Pe = LvlDL, Bi = kfRID,.
extractor is With these dimensionless groups, eqs l-3 become

dC
+XD a2C l-&3k, 3X 2X
---R[C-Ci(R)]. (1) a fi-53Bi[x-xi(l)] (11)
at az Laz2 & -+a5g=KdZ2
ae

Time variation of the solid-phase concentration

(average oil concentration in a particle) is equated with the g=3Bib[x-x,(l)] (12)
rate of mass transfer of solute within external film sur-
rounding the particle.
+& p$ =o, (13)
( 1
(2)
Dimensionless boundary and initial conditions are
The diffusion in outer region is given by
xi = 1 at 5 = 5, (14)

=Bi[x-xi(l)] (15)
<=I
Solid phase solute exists within the core, the average
value of solid-phase concentration 4 being given by
(16)
130 Goto et al. The Journal of Supercritical Fluids, Vol. 9, No. 2, 1996

{,=l at 8=0 (17) TABLE I

Parameters for Example Calculation
x=0 at 8=0 (18)
0, 1.5 x lO-‘Om2 s-’
L 70x 10.‘rn
x-J-$=0 at Z=O (19) 1 X 1O-3m s-l
I;; 1 X 10e3m
& 0.4
$=O at Z=l. % 250 kg m-3
Csat qdlO0
a 100 (value calculated with
The following equations were derived by rearranging these above parameters is 95)
equations. b 0.01
Bi 100
ax dx a ---
a2x l--E 3Bi(x - 1) Pe 1000
%+“Z=KdZ2 E l-Bi(l-l/t,) (21)

ag,- bBi( x - 1)
(22) b = 0.01
&I - cz[l--Bi(l-lit,)]

These differential equations coupled with boundary and 0.6

initial conditions were solved numerically by Crank x
Nicholson’s method. 0.4
The yield, that is, cumulative amount of extract up
to time 8 is given by
9

xde . (23)

Quasi-Steady-State Solution Without Figure 1. Effect of parameter a on the extracted concen-

Axial Dispersion. When axial dispersion is negligi- tration.
ble, a quasi-steady-state solution can be obtained by as-
suming that changes in & during the residence time of 3bBXJ* l--E 3BiZ
solvent in the column are negligible and that changes in “=l~~~~i(l~~/~,)exp a& 1-Bi(l-115,) (26)
the axial direction of the column at any given time are I
small. By introducing the dimensionless time B* = 8 -
Z/a, integration of eq 2 1 gives This solution is identical to that derived by Catchpole.14
The time required for complete equilibrium extrac-
tion is given by eqs 27 and 28 on an assumption of equi-
3BiZ
(24) librium extraction, that is, rate processes do not interfere
l-Bi(l-115,) 1’ with the extraction.

By substitution of x into eq 22 and integration

(27)

4,.
(25)

1 PARAMETRIC ANALYSIS
e, =-
1-&
ab&

AND ACCURACY
(28)

The symbolic integration was done with a computer alge-

bra system (MathematicaTM, Wolfram Research Inc.), OF SIMPLIFIED MODELS
which gives analytical solution in terms of the exponen- Values of the Parameters Used in the
tial integral function. For example computations, numer- Model. The parameter values used in model calculation
ical values were obtained directly from the analytical solu- were taken from the literature.13 Table I shows the pa-
tion. rameters used in this work.
When 5, is further assumed to be constant during The Effect of Parameter a. One of the im-
integration of eq 22 with eq 24, the folIowing simplified portant operation parameters is a = (v/L)(R2/D,) which is
solution can be obtained: an inverse of dimensionless residence time. The value of
The Journal of Supercritical Fluids, Vol. 9, No. 2, 1996 Shrinking-Core Leaching Model 131

a increases with flow rate and particle size, and decreases

with extractor length and intraparticle diffusivity. Figure
1 shows variations of effluent concentration, x, at the exit
b I 0.01
of the extractor as a function of dimensionless time, e/e,.
Pe-loo0
Bi-100
- Figure 2 shows average solid-phase concentration, 7,
which is equivalent to <i, at three locations in the extrac-
tor column. These curves were calculated by the numeri-
cal solution, eqs 21 and 22 at three values of a (=
0.2 vR21D&L). Solid-phase concentration, 7, decreases more
rapidly for smaller value of a. The wave of sharp decrease
0 in jj propagates from inlet to exit of the extractor in case
0 1 2 3 4 5 of small a where extraction proceeds from inlet to outlet
@B. in the extractor. On the other hand, extraction occurs
similarly for entire region in the extractor for larger a.
Figure 2. Effect of parameter a on the solid-phase con-
centration. This behavior is reflected in the effluent concentration at
the exit of the column. Thus, the extraction is more ef-
a-10 fective for smaller a, that is, smaller particle size and
b- 0.01
Bi-100 - larger residence time.
The Effect of Peclet Number. Peclet
number, Pe, is an index of axial dispersion. Figure 3
x shows effluent concentration at the exit of the extractor, x
calculated by numerical solution at various Peclet num-
bers. Since the influence of the axial dispersion is ob-
served only when there is a sharp distribution along the
extractor column in flow direction, the results are com-
pared at a = 10. For smaller Peclet number, the exit con-
0 0.5 1 1.5 2 2.5 centration becomes broader due to the axial dispersion.
wee When Peclet number is larger than 100, the effect of axial
dispersion becomes insignificant. For larger value of a,
Figure 3. Effect of Peclet number (Pe) on the extracted axial dispersion becomes less influential.
concentration.

1
a-70 : a-200
- Numerical solution
--------- QSS solution
- - SQSS solution

1;
a=500
0.8 0.8 :

0.8 0.6
X

0.4

0.2
ot- - 1
1 3 4 5
2 e/e,

Figure 4. Comparison of models at various a (b = 0.01, Bi = 100).

132 Goto et al. The Journal of Supercritical Fluids, Vol. 9, No. 2, 1996

6
CO, flow rate: 0.2 m3/h (S
0.8
35 MPa, 316 K I
0.6
X

0.4

- Model (eqs 21-23)

0.8 0.2 0.3 0.4 0.5

Gas flow [m3 (STP)]
0.6
X Figure 6. Comparison of model calculation and experi-
0.4 mental extraction curve of oil from rape seeds with carbon
dioxide.
0.2
31 I I I I I

1 2 3 4 5
“0
- I 35 MPa, 316 K q 0 Experimental data
(Brunner. 19841
1; ~2~+&\~ - %~’ ‘1
Model (eqs 21-22)
Bi=l
0.8

0.6 :
X

0.4

0.2 :

o--- --- .--- -- ---..- -

0 0.1 0.2 0.3 0.4 0.5
1 4 5
2 O/8, 3 Gas flow [m3 (STP)]

Figure 5. Comparison of models at various Biot number
(a = 100, b = 0.01).
Accuracy of Quasi-Steady-State Solu-
tions. Figure 4 shows the comparisons of dimension-
less effluent concentration, x at the extractor exit among
the numerical solution, quasi-steady-state (QSS) solution,
eq 24 and simplified quasi-steady-state (SQSS) solution,
eq 26. Comparison is made for four different values of a
in Figures 4 (a), (b), (c), and (d). The SQSS solution
gives always larger value of x. For larger value of a (a >
200), QSS solution agreed well with the numerical solu-
tion for the entire range of dimensionless time, 0/e,.
However, for smaller value of a, the QSS solution devi-
ates from the numerical solution at smaller time. In these
cases accuracy of the QSS solution is worse than the
SQSS solution at smaller time.
The Effect of Biot Number. Relative im-
portance of intraparticle diffusion to external fluid-solid
mass transfer is represented by Biot number, Bi = kfR/D,.
Figure 5 shows the effect of Bi on the accuracy of the so-
lutions. When Bi is small, external mass transfer signifi-
cantly affects to the extraction behavior. Thus, the exit
Figure 7. Comparison of model calculation and experi-
mental extraction rate of oil from rape seeds with carbon
dioxide.
concentration at the initial time is smaller than unity for
smaller Bi. The accuracy of quasi-steady-state solutions
increases with decrease in Bi. When intraparticle diffusion
controls the extraction process for large Bi, sudden change
of the concentration at the surface of a particle at the ini-
tial stage of the extraction results in inadequate situation
for quasi-steady-state assumption.
COMPARISON WITH EXPERIMENTAL
DATA
The shrinking-core model was applied to the exper-
imental data. The extraction data of oil from rape seed
with supercritical carbon dioxide measured by Brunner2
was used to compare with the model calculation. Radius
of the crashed rape seed was 0.25 mm and the extractor
was 17 mm dia. and 220 mm long. Figure 6 shows the
extraction curve, that is, cumulative amount extracted ver-
sus carbon dioxide flowed at two operating conditions.
Figure 7 shows the extraction rate, which corresponds to
The Journal of Supercritical Fluids, Vol. 9, No. 2, 1996 Shrinking-Core Leaching Model 133

the differentials of the cumulative extraction curve. All NOTATION

the parameters necessary for model calculation were ob- Bi Biot number = k,RID,
c concentration in bulk fluid-phase, mol mm3
tained from the literature* except for effective intraparticle concentration in pores, mol mm3
ci
diffusivity, D,, and axial dispersion coefficient, DL. c Sal saturation concentration, mol rnA3
External mass-transfer coefficient estimated by Wakao and effective intraparticle diffusivity, m2 s-r
Kaguei’s correlation15 was adopted as used by Brunner.* $ axial dispersion coefficient, m* s-r
Estimation method of axial dispersion in supercriti- external mass-transfer coefficient, m s-l
L’ length of extractor, m
Cal-fluid extractor is not available in literature. Erkey and Pe Peclet number, LvlD,
Akgermani6 measured axial dispersion by the chromato- 9 solid-phase concentration, mol mm3
graphic technique. They obtained particle Peclet number ? average value of q, mol me3
(=2Rv/DL) in range from 0.058 to 0.244 for naphthalene- initial solid-phase concentration, mol mm3
alumina system. When these values are converted to 2 particle radius, m
r radial coordinate
Peclet number (=Lv/DL), one obtains Pe = 25-107 for the radius of unleached core, m
r,
experimental condition. Thus, we adopted the value of 50 t time, s
for Peclet number. Axial dispersion did not influence to V interstitial fluid velocity, m s-r
the extraction curve in this case. x dimensionless concentration in bulk fluid-phase, C/C,,,
xi dimensionless concentration in pores, CilC,,
Intraparticle effective diffusivity is most important
Y dimensionless solid-phase concentration, q/q0
parameter for the extraction process from solid materials. average value of y
L
However, accurate value of the intraparticle effective diffu- z axial coordinate in extractor
sivity can not be estimated, because the value changes de- & bed voidage
pending on the material and environment. We adopted 1.5 dimensionless time, (D,lR*)t
dimensionless radial coordinate, r/R
x IO-i0 m* s-i as an initial value for intraparticle effective
Ec dimensionless radius of unleached core, r,lR
diffusivity as given in Table I. By fitting the calculated
results with the experimental data, we optimized the value REFERENCES
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