J.

of Supercritical Fluids 97 (2015) 165173

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

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

Simple models for supercritical extraction of natural matter

Camilo Pardo-Castano, Manuel Velsquez, Gustavo Bolanos
School of Chemical Engineering, Universidad del Valle, CL 13 100-00 Building 336, Cali, Colombia

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

Article history: Based on the BrunauerEmmettTeller (BET) theory of adsorption, two mathematical models for cor-
Received 6 May 2014 relating supercritical extraction data were developed. Each one of the models expresses the extraction
Received in revised form yield as a function of time through one simple equation, which contains only three or two adjustable
26 September 2014
parameters, respectively, each one with a clear physical meaning. A comparison of the performance of
Accepted 27 September 2014
the new models with those of Sovovs and VT-II models shows that the rst proposed model, with three
Available online 13 October 2014
adjustable parameters, produces in many cases an average deviation that is similar to that produced by
the Sovovs model, and is lower than that by the VT-II model, a remarkable result given the simplicity of
Keywords:
Supercritical extraction
the model. In addition, the second proposed model, which only has two adjustable parameters, performs
Mathematical models well as compared to the rigorous models especially in the rst period of the extraction and can be useful
Extraction kinetics for generating rst estimates of the parameters for data correlation with the rst model. These results
Adsorption indicate that the proposed models are simple, useful and quick tools for correlating experimental data
BET on supercritical extraction of natural matters.
Natural matters 2014 Elsevier B.V. All rights reserved.

1. Introduction 2. Mathematical model

Mathematical models for correlating experimental data on
supercritical extraction of natural matter are important tools for
scaling laboratory data up to industrial level, in order to make esti-
mates of protability or to design processing equipment. Many
models have thus been proposed, as referenced in comprehensive
literature reviews that have been published [16]. Among them,
that by Sovov [1] and the so-called VT-II [2] are examples of rig-
orous models. Sovovs model is based on the representation of
diffusive and convective transport phenomena that occur during
the extraction and has three analytical equations, one for each
extraction period. The VT-II model represents the same phenomena
through a set of differential equations that has to be numer-
ically integrated. These models have three and four adjustable
parameters, respectively, which have to be tted to each experi-
mental data set measured at constant temperature and pressure.
In this work we propose two simple models that have three and
two adjustable parameters, respectively, and explicitly express the
relation between extraction yield and time; i.e., no differential
equations are present in the nal expression.
Corresponding author. Tel.: +57 23 31 2935; fax: +57 23 39 2335.
E-mail addresses: camilo.pardo@correounivalle.edu.co (C. Pardo-Castano),
gustavo.bolanos@correounivalle.edu.co (G. Bolanos).
2.1. Material balance in the bulk uid phase
Based on the general model for the supercritical uid (SCF)
extraction of a solid substrate in a packed bed [5], we initially con-
sider a packed extractor, shown in Fig. 1, and write the material
balance for the solute in the supercritical uid, around a differential
element along the axial direction of the extractor:
Cf Cf 2 Cf (1 )  
+ u = Dsf + asf ksf Cf Cf (1)
t z z 2
where Cf is the concentration of the solute in the SCF, u is the inter-
stitial velocity of the solvent, is the void fraction of the bed, Dsf
is the axial dispersion coefcient of the solute in the SCF, asf is the
effective soliduid contact area for mass transfer, Ksf is the mass
transfer coefcient for transport of the solute through the external
uid lm around the solid particles, and Cf is the concentration of
solute in the SCF lm that is in equilibrium with the solid surface.
The balance equation is well known, and we use it here assuming
that the term that represents the axial dispersion (i.e., the rst term
on right hand side of Eq. (1) is negligible. According to Carberry
and Wendel [7], this approximation is valid when the length of the
extractor is at least 50 times the average particle diameter and the
Reynolds number is greater than 10, which are conditions usually
accomplished in the SCF extraction of natural matter [8]. We also
consider that the term that represents the solute accumulation in

http://dx.doi.org/10.1016/j.supu.2014.09.044
0896-8446/ 2014 Elsevier B.V. All rights reserved.
166 C. Pardo-Castano et al. / J. of Supercritical Fluids 97 (2015) 165173

Integrating within the usual limits for a packed extractor (at

Nomenclature z = 0, yf = 0 and at z = L, yf = yfL ), we obtain:
  kL 
asf effective soliduid contact area for mass transfer
yfL = yf 1 exp (3)
AARD average absolute relative deviation u
Bi Biot number
where yfL is the solute mass fraction in the bulk uid phase at the
cal refers to calculated
exit of the extractor and L is the length of the extractor.
Cf concentration of the solute in the SCF
Cf concentration of solute in the SCF lm that is in
2.2. Overall material balance in the packed solid
equilibrium with the solid surface
dp particle size
We now use a material balance of the solute in the solid that is
D diffusion coefcient of the solute
packed into the extractor, which is given by:
Dsf axial dispersion coefcient of the solute in the SCF 
exp refers to experimental dms mfl
h mass transfer coefcient = mf (4)
dt mfT mfl
K ratio between the adsorption equilibrium constants
of the solute in the rst monolayer and that in sub- where ms is the mass of the solute in the solid at time t, mf is the
sequent layers. Adjustable parameter ow rate of the SCF, m is the mass of solute in the SCF at the exit
ksf mass transfer coefcient for transport of the solute of the extractor, and mfT is the mass of solute + SCF.
through the external uid lm around the solid par- Assuming that mfT  m which is reasonable for low solute con-
ticles centrations, we can simplify Eq. (4) as follows:
L length of the extractor
dxs mf
mf ow rate of the SCF = y (5)
dt mo fL
m mass of solute in the SCF at the exit of the extractor
mfT mass of solute + SCF where xs is the solute mass fraction in the solid at time t, and mo
mo initial extractable mass of the solute in the packed is the initial extractable mass of the solute in the packed bed. We
bed assume that xs do not change considerably in the axial direction,
ms mass of the solute in the solid at time t because the amount of extracted solute from the solid matrix in
n number of data the differential element is very low, and it is much lower than the
Re Reynolds number solubility of the solute in the SCF.
Sc Schmidt number Replacing Eq. (4) into Eq. (5) we obtain:
t extraction time
dxs mf
 kL
 
ti time for data i = y 1 exp (6)
dt mo f u
u interstitial velocity of the solvent
W adjustable parameter of Sovovs model related to The latter equation can be coupled with a BET-type equilibrium
diffusion in the solid phase of the extraction bed relationship, as follows.
x extraction yield
xk adjustable parameter of Sovovs model related to 2.3. BET-type equilibrium equation
the amount of solute in the solid matrix that is inac-
cessible to the SCF, relative to initial solute The equilibrium relationship relates the concentration of the
xm solute mass fraction in the rst monolayer. solute in a lm of SCF located at an innitesimal distance from the
Adjustable parameter solid substrate surface, yf , with the concentration of the solute in
xs solute mass fraction in the solid at time t the solid matrix. This relationship depends upon the relative attrac-
yf mass fraction of the solute in the SCF tion forces exerted by the solid and SCF over the solute.
yfL solute mass fraction in the bulk uid phase at the A BET-type equilibrium relationship for SCF processes was used
exit of the extractor in order to consider the solute interaction with the solid matrix
y* adjustable parameter related to the solubility of the [9,10]:
solute in the SCF corrected by diffusional limita-
tions. Dened by Eq. (22). xs K
= (7)
yf solute mass fraction in the SCF lm that is in equi- xm [1 ] [1 + (K 1) ]
librium with the solid surface where  is the ratio between the solute mass fraction in equilib-
ysat solute mass fraction in a saturated SCF phase rium, yf , and the solute mass fraction in a saturated SCF phase, ysat .
z axial position along the extractor  
xm is the solute mass fraction in the rst monolayer mm /mo and
Z adjustable parameter of Sovovs model related to
K is the sorption equilibrium coefcient.
convection in the uid phase of the extraction bed
Eq. (7) can be arranged to obtain a quadratic equation:
  xm
 
(1 K) 2 + K 1+ 2 +1=0 (8)
the SCF (the rst term on left hand side) is negligible as compared to xs
the amount of solute in the solid material. With these assumptions which can be solved to give:
 

we obtain:

     2
yf   K 1 + xm /xs 2 K 1 + xm /xs 2 4 (1 K)
u =k yf yf (2) = (9)
z 2 (1 K)

where k = (1 ) asf ksf , yf is the mass fraction of the solute in the

 limiting situation when the SCF
Taking into consideration the
SCF and yf is the solute mass fraction in the SCF lm that is in is saturated with the solute yf ysat , in which the num-
equilibrium with the solid surface. ber of molecules adsorbed on the solid becomes very large
 C. Pardo-Castano et al. / J. of Supercritical Fluids 97 (2015) 165173 167

Fig. 1. Schematic representation of a packed bed extractor.

(mo 0, xs ), we obtain an expression for  as a function Eq. (12) expresses a relationship between time and extraction
of K: yield, and has three adjustable parameters: y*, K, and xm , which
2K K have a clear physical meaning. y* is related to the solubility of
= (10) the solute in the SCF corrected by diffusional limitations, K is the
2 (1 K)
ratio between the adsorption equilibrium constant of the solute
Because K 1 (and 0  1), only the root that is obtained with in the rst monolayer and that in subsequent layers (when the
the negative sign in the expression above is physically possible, and solutesolid interactions are strong, K , and when they are
thus in this case  = 1. weak, K 0), and xm is the ratio between the mass of solute present
Now, in any case, replacing Eq. (9) in Eq. (6) we get: in the rst monolayer and the initial mass of solute that can be
extracted.

   
   
K 1+(xm /xs ) 2 + K 1 + xm /xs 2 2 4 (1 K) Notice that according to Eq. (22), for situations where diffusional
dxs
=
mf
y limitations are negligible (i.e., u, L , or k ), y* ysat , and
dt mo 2 (K 1) in these cases knowing the solubility of the solute in the SCF, the
number of adjustable parameters would reduce to two. On the other
(11) hand, note that xm , which is a parameter that represents properties
of the solid, might take values greater than 1 for cases where the
where y* is dened by Eq. (22) (see below). initial amount of solute is lower than the amount that can conform
the rst monolayer in the solid.
The argument of the exponential term in Eq. (22) is dimension-
2.4. Proposed models
less and can thus be expressed in terms of dimensionless numbers,
to give:
Eq. (11) can be analytically integrated using the initial condition:
at t = 0, xso = 1, to obtain, after several arrangements:   Bi

      y = ysat 1 exp (23)
mo  ReSc
t= xo x + (2 K) x xm ln + Kxm ln (12)
2mf y  (1 x) 2

where Bi, Re and Sc are the Biot, Reynolds and Schmidt numbers,
where: respectively. These numbers are dened as:

xo = a+b+c (13) hL KL
 Bi = = (24)
 2 D
x = a(1 x) + b (1 x) + c (14)
udp
a = K2 (15) Re = (25)

b = 2 (2 K) Kxm (16)

2
Sc = (26)
c = (Kxm ) (17) D

= x + K (1 x) + (2 K) xm (18) where D is the diffusion coefcient of the solute, h is a mass transfer

coefcient, dp is the particle size and v is the kinematic viscosity.
 = x + (2 K) (1 x) + Kxm (19) Eq. (23) allows one to correlate or to estimate the effect of changes
= xo + K + (2 K) xm (20) in the ow conditions (Re), the mass transfer characteristics due to
properties of the solid (Bi) or to properties of the uid (Sc) from one
 = xo + (2 K) + Kxm (21) experimental condition to another, or for scaling up purposes.
  kL  In the case when the equilibrium constant for the rst mono-
y = ysat 1 exp (22) layer and for subsequent layers are approximately equal, K 1 and
u
Eq. (12) reduces to a simpler model:
x is the extraction yield; i.e., the ratio between the mass of the
solute extracted at time t, and the mass of solute initially present mo
t= [x xm ln (1 x)] (27)
in the packed bed that can be extracted. mf y
168 C. Pardo-Castano et al. / J. of Supercritical Fluids 97 (2015) 165173
Fig. 2. Correlation of data for supercritical CO2 extraction of cocoa butter from cocoa powder. The numbers indicate the operating conditions from Table 1. () Proposed
model 1 (AARD = 3.81%), () Sovovs model (AARD = 3.02%).
This equation has only two adjustable parameters (y* and xm ),
and might be useful as a rst approximation for correlating exper-
imental data
3. Performance of the models and discussion
Some characteristics of the described models were initially
explored by applying them to the correlation of data obtained in
our laboratory for the supercritical CO2 extraction of cocoa butter
from cocoa powder, a byproduct of the mechanical expression of
cocoa seeds. Extraction yields as a function of time were experi-
mentally determined at ve sets of temperature and CO2 density
[11,12]. The model proposed by Sovov [1], and also those pro-
posed in this work were tted to these data, using a generalized
reduced gradient algorithm for nonlinear optimization, which was
implemented in the Visual Basic solver for Excel 2013. The objec-
tive function was dened as the average absolute relative deviation
(AARD) referred to time, because this is the variable that is explicit
in the proposed models, and is expressed by the equation:
 
100   ti,exp ti,cal 
n
AARD =  ti,exp 
n
i=1
where AARD is the average absolute relative deviation (%), n is the
number of data (54), ti is time for data i, and subscripts exp and cal
refer to experimental and calculated, respectively.
In our computations we normalized time dividing this variable
by the maximum experimental time. This avoided possible com-
putational problems that might arise from using absolute values of
time, and reduced the number of iterations required by the tting
routine. The initial values of the parameters for the proposed
model 1 were obtained by tting rst the proposed model 2 to the
data. The initial values for y* were numbers close to the solubility
of the solute in the SCF (e.g., for cocoa butter is 0.45 wt%, which is
an approximated value according to the data presented by Saldana
et al. [13]), and for the xm parameter we used 0.5. The routine was
allowed to run until the difference in the objective function calcu-
lated in the last two iterations was 108 . Due to the fast convergence
of the algorithm, no limit on the number of iterations was
imposed.
Figs. 2 and 3 show the correlation of data for the supercritical
CO2 extraction of cocoa butter from cocoa powder. Notice that both
proposed models apparently perform similarly, and they represent
the data adequately. Proposed model 1 looks like a more convenient
choice because it represents adequately the whole set of data by
using only one equation, in contrast to the Sovovs model, which
uses three equations, one per period of extraction. Notice that the
AARD of the proposed model 1 (3.81%) compares well with that of
Sovovs (3.02%).
Fig. 3 shows that the proposed model 2 and Sovovas model per-
form similarly in the rst period of the extraction (i.e., in the linear
part of the extraction yield vs. time curve). This is because in this
region external mass transfer domains, and both models include the
solubility of the solute in the SCF, ysat . In contrast, at higher extrac-
tion yields, important deviations occur for the proposed model 2
probably because an internal mass transfer mechanism dominate
(e.g. diffusion or desorption of the solute from the solid matrix) and
important simplifying assumptions related to this part were done
during the derivation of proposed model 2. In fact, the deviation
(28) obtained for the proposed model 2 was 5.75%, which is in contrast
with 3.02% that was obtained for Sovovs model. However, the
proposed model 2 might be useful for providing rst estimates of
the y* and xm parameters for correlating experimental data with
the proposed model 1.
Table 1 shows the correlation of data on supercritical CO2
extraction of cocoa butter from cocoa powder. The values of the
adjustable parameters were obtained by tting the models to the
54 experimental data points. For the proposed models, a single
value of xm was obtained to represent the whole set of data because
it was observed that this parameter does not strongly depend
upon the operating conditions. In fact, this parameter is in essence
a property of the solidsolute pair, so we did not expect a major
effect of the operating conditions on the value of this parameter. In
this case the values of xm were smaller than one, which indicates
that the initial mass of solute that is removable is greater than
the mass of solute in the rst monolayer. In other cases (i.e., for
 C. Pardo-Castano et al. / J. of Supercritical Fluids 97 (2015) 165173 169

Fig. 3. Correlation of data for supercritical CO2 extraction of cocoa butter from cocoa powder. The numbers indicate the operating conditions from Table 1. () Proposed
model 2 (AARD = 5.75%), () Sovovs model (AARD = 3.02%).

other systems) the opposite situation might be conceivable, and
the values of xm might be larger than one.
Notice that as the y* parameter increases, K decreases. Because
y* is directly related to solubility, when solubility of the solute in the
SCF increases it is expected that the solidsolute molecular forces
become relatively weaker, decreasing K.
For the Sovovs model, the three adjustable parameters (xk , Z,
and W) were tted assuming that the values of Z and W depend
upon the operating conditions and that xk is independent of such
variables. In fact, Z and W are directly related to the mass transfer
coefcient, both in the SCF and in the solid matrix, respectively.
These coefcients must change with the extraction conditions. On
the other hand, the xk parameter refers to the amount of solute in
the solid matrix that is inaccessible to the SCF (i.e., xk = inaccessible
solute/initial solute), and thus it might be taken as a constant.
As a second example of the performance of the proposed mod-
els, we present a comparison of results obtained with the Sovovs
model and the so-called VT-II model for correlating data on super-
critical CO2 extraction of theobromine from cocoa seed shells
that were presented by Brunner [2]. The VT-II model is also a
rigorous, phenomenological model that uses the Freundlich
isotherm to model the change in solute concentration in the solid.
If no axial dispersion is taken into account, it has four adjustable
parameters. These are: two Freundlich coefcients, the effective
diffusivity of the extract in the solid, and a mass transfer coefcient
in the uid.
Table 2 and Fig. 4 show the correlation of the experimental data
for supercritical CO2 extraction of theobromine from cocoa seed
shells at laboratory scale that were presented by Brunner [2]. Note
that both proposed models perform similarly to the Sovovs and
VT-II models for three of the four data sets reported at different
Reynolds numbers. During the correlation with the models, the K
parameter was kept constant for the whole data set, as in this case
temperature and pressure are constant and K is a parameter that
represents the adsorption equilibrium.
Fig. 5 shows the same information than Fig. 4, except that in
this case the parameter K for the proposed model 1 was allowed
to vary from one data set to another. Clearly, this improves the
performance of the model to the point that despite the smaller
number of parameters and the simplicity of its equation, the pro-
posed model 1 ts the experimental data to an accuracy similar to
those of the other models. In fact, in this case, deviations (AARD) of
the proposed model 1, Sovovas and VT-II models were 1.97, 1.82,
and 6.02%, respectively. These results indicate that the proposed
model 1 compares favorably to the VT-II and Sovovs models.
Fig. 6 shows predictions by the proposed and VT-II models and
data for the supercritical CO2 extraction of theobromine from cocoa
seed shells at pilot-plant scale. The deviations were 11.03% for VT-
II, 12.52% for the proposed model 1, and 13.43% for the proposed
model 2. Brunner [2] has shown that for this system the VT-II model
can be used with reasonable accuracy for scaling purposes using the
parameters obtained at laboratory scale. Although rigorous models

Table 1
Correlation of data on supercritical CO2 extraction of cocoa butter from cocoa powder.

Data set Operating conditions Adjustable parameters

CO2 density (g/cm3 ) Temperature ( C) Proposed model 1 Proposed model 2 Sovovs model

xm K y 10
* 5
xm y 10
* 5
xk Z 104 W 105

1 0.7 35.0 79.46 4.15 4.44 100.69 0.18

2 0.7 50.0 74.51 21.66 23.62 513.05 49.99
3 0.8 42.5 0.044 55.00 84.23 0.126 91.16 0.005 2626.1 1001.39
4 0.9 35.0 30.61 159.67 179.64 7305.23 7685.60
5 0.9 50.0 4.61 227.16 284.52 13251.35 16452.72
AARD (%) 3.81 5.91 3.02
170 C. Pardo-Castano et al. / J. of Supercritical Fluids 97 (2015) 165173

Table 2
Correlation of experimental data for supercritical CO2 extraction of theobromine from cocoa seed shells at laboratory scale. Experimental data by Brunner [2].

Operating conditions Adjustable parameters

Proposed model 1 Proposed model 2 Sovovs model

Temperature ( C) Pressure (MPa) Re xm K y 10
* 4
xm y 10
* 4
xk Z 101 W 104

136 1.588 1.29 5.870 1.85 4.06 2.22

226 0.890 0.44 6.790 1.25 2.14 2.56
80 30 3.77 0.013
390 0.556 0.37 9.920 2.27 3.23 3.76
811 0.400 0.37 9.370 2.83 4.13 5.54
AARD (%) 5.53 6.83 1.82

Fig. 4. Correlation of experimental data for supercritical CO2 extraction of theobromine from cocoa seed shells at laboratory scale. Proposed model 1 (AARD = 5.53%), proposed
model 2 (AARD = 6.83%), Sovovs (AARD = 1.82%) and VTII models (AARD = 6.03%). Experimental data at 30 MPa and 353 K [2].

Fig. 5. Correlation of data for supercritical CO2 extraction of theobromine from cocoa seed shells at laboratory scale. Proposed model 1 (AARD = 1.97%), Sovovs (AARD = 1.82%)
and VTII models (AARD = 6.03%). Experimental data at 30 MPa and 353 K [2]. Proposed model 1 when K is not constant.
 C. Pardo-Castano et al. / J. of Supercritical Fluids 97 (2015) 165173 171

Fig. 6. Predictions and data obtained at pilot-plant scale for the supercritical CO2 extraction of theobromine from cocoa seed shells [2] by the proposed and VT-II models.

Fig. 7. Correlation of data for supercritical CO2 extraction of corn germ oil [14] by the proposed model 1. AARD = 3.89%.

Table 3
Parameters obtained for the proposed model 1 in correlation of data for supercritical CO2 extraction of three natural materials.

Natural material Operating conditions Adjustable parameters AARD (%)

Temperature ( C) Pressure (MPa) CO2 velocity 105 (m/s) CO2 ow rate 104 (kg/s) xm K y* 103

30.0 27.8 0.36 21.13 11.61

Corn germ [13] 80.0 45.5 26.4 0.37 10.13 36.66 3.89
52.5 16.7 0.36 6.25 68.73
0.66 0.53 8.36
Striped weaksh [14] 30.0 20 4.87 3.93
1.65 0.49 8.56
15 1.0 1.06 1.33 0.06
18 1.0 0.67 2.00 0.08
Olive husk [15] 39.9 7.28
12 67.0 0.87 1.99 0.01
15 59.0 1.10 1.33 0.02
172 C. Pardo-Castano et al. / J. of Supercritical Fluids 97 (2015) 165173

Fig. 8. Correlation of data for supercritical CO2 extraction of Striped Weaksh oil [15] by the proposed model 1. AARD = 3.93%.

such as VT-II take into account parameters that can be affected
during scaling, we believe that as long as ow conditions such as
Reynolds number are maintained the proposed models should be
as good (or bad) as more rigorous models for scaling purposes.
For the purpose of showing the performance of the proposed
model 1, which showed the highest accuracy in correlating the data
discussed above, we selected additional experimental data from the
literature and tted them with this model. Some of them are dis-
cussed here. Fig. 7 shows the correlation of experimental data for
supercritical CO2 extraction of corn germ oil at 80 C and different
extraction pressures [14]. Fig. 8 shows the correlation of experi-
mental data for pressurized CO2 extraction of striped weaksh oil
at 20 MPa, 30 C and two solvent mass ow rates [15]. Fig. 9 shows
the correlation of data for supercritical CO2 extraction of olive husk
oil at 39.9 C and different pressures and solvent velocities [16].
Table 3 shows the parameters obtained for the proposed model 1
in correlation of data for these three systems.
Figs. 79 show that the performance of the proposed model 1 is
remarkable. This model is capable of correlating experimental data
for pressurized and supercritical extraction of natural matter to a
high accuracy, including not only vegetable matrices but also an
animal matrix such as milled weaksh.
Information presented in this paper illustrate the capability
that proposed model 1 has to correlate experimental data for

Fig. 9. Correlation of data for supercritical CO2 extraction of olive husk oil [16] at constant temperature of 40 C, by the proposed model 1. AARD = 7.28%.
 C. Pardo-Castano et al. / J. of Supercritical Fluids 97 (2015) 165173
pressurized and supercritical extraction processes that experience
changes in temperature (Fig. 2), pressure (Figs. 2, 7 and 9), and
Reynolds number (Figs. 4, 8 and 9).
The proposed models are a close representation of the
phenomena that occur in a SCF extraction process within the frame-
work of the assumptions made, which are: (1) negligible axial
dispersion, a condition that is obtained when the Reynolds number
is greater than 10 and the length/diameter ratio of the extractor is
larger than 50; (2) the accumulation of solute in the SCF during the
extraction is negligible when compared to the amount of the solute
in the solid, which is attained at low values of the solubility of the
solute in the SCF, a usual situation for extraction of natural prod-
ucts; (3) the concentration of the solute in the solid does not change
signicantly in the axial or radial directions, which is typically what
occurs in an industrial extractor, but not in a larger separator such
as a chromatographic extractor; (4) a valid representation of the
solutematrix interaction as an adsorption situation, which in an
extreme case might be attained when the extraction rate is not
limited by solubility, e.g., when the solute is located mainly intra-
cellularly or the porosity of the solid matrix is small enough to limit
the extraction; and (5) only one solute is extracted by the SCF, or,
if several solutes are extracted, the difference in their solubilities is
negligible or no interaction between the solutes is present (i.e., the
solubility of one solute in the SCF is not affected by the concentra-
tion of another one in the same phase). We believe that many cases
in SCF extraction of natural matter correspond to these approxima-
tions. Clearly, as the characteristics of the system move away from
these assumptions, the models should be considered as a useful
semiempirical approximation to the process.
Adsorption-based models for supercritical extraction of natu-
ral matter have been in the literature for some time. In particular,
several models are known that use the BET approach to model
adsorption equilibrium together with rigorous balances [10,17] to
take into account diffusion in micropores, mass transfer to the
supercritical uid, and radial and axial dispersion in the extrac-
tor. Simple models such as those presented in this work capture
essential elements of the extraction. For example, in addition to the
adequate correlation of data that was shown, the models correctly
predict that the apparent solubility (i.e., the slope of the extraction
yield vs. time curve) is a function of the amount of solute initially
present in the bed, an observation that has been presented in the
literature using more elaborated analyses [18]. The models can thus
be useful in studies on supercritical extraction of natural matter.
4. Conclusions
Two simple mathematical models that adequately correlate
information on the kinetics of supercritical uid extraction were
presented. The models integrate modications of the BET adsorp-
tion equilibrium equation with a simplied material balance of
a supercritical extractor. The new models have three and two
adjustable parameters, respectively, each one with a clear physi-
cal meaning. These models produce an average deviation similar
to that obtained with rigorous models such as Sovovs and the
so-called VT-II models. In particular, the performance of proposed
model 1 is in several cases better than those of the VT-II model, a
remarkable result given that it is only constituted by one equation,
as compared to three conditional equations of Sovovs model and
the system of differential equations of VT-II. The proposed model 1
173
is capable of representing the extraction periods as Sovovs model
does, in some cases with higher accuracy. In addition, the proposed
model 2 has a remarkably good performance considering that only
has one simple equation and two adjustable parameters. This model
might be used as a rst approximation and can be used for gener-
ating rst estimates of the parameters for data correlation with the
proposed model 1. The presented results indicate that the models
proposed in this paper are simple and useful tools for correlat-
ing experimental data on supercritical uid extraction of natural
matter.
Acknowledgments
The authors express their gratitude to Departamento Admin-
istrativo de ciencia, tecnologa e innovacin de Colombia
(COLCIENCIAS) for nancial support of this research (Grant 1106-
454-21918).
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