Proposed Models For Subcritical Water Extraction of Essential Oils
Proposed Models For Subcritical Water Extraction of Essential Oils
Proposed Models For Subcritical Water Extraction of Essential Oils
|
\ .
= +
(
+
(
(1)
where S
a
is the cumulative mass of the analyte extracted
after certain amount of volume V
a
(mgg
1
based on
dry sample), S
b
the cumulative mass of the analyte
extracted after certain amount of volume V
b
(mgg
1
,
based on dry sample), S
0
the total initial mass of ana-
lyte in the matrix (mgg
1
, based on sample), S
b
/S
0
and
S
a
/S
0
are the cumulative fraction of the analyte extracted
by the fluid of the volume V
b
and V
a
(ml), respectively,
K
D
is the distribution coefficient, concentration in
matrix/concentration in fluid, is the density of ex-
traction fluid under given condition (mgml
1
), and m
is the mass of the extracted sample (mg dry sample).
5.2 Kinetic mode
5.2.1 One-site kinetic desorption model
One-site kinetic desorption model describes the
extractions that are controlled by intra-particle diffu-
sion. This occurs when the flow of fluid is fast enough
for the concentration of a particular solute to be well
below its thermodynamically controlled limit. The
one-site kinetic model was derived based on the mass
transfer model that is analogous to the hot ball heat
transfer model [10, 11]. The assumptions are that the
compound is initially uniformly distributed within the
matrix and that, as soon as extraction begins, the con-
centration of compound at the matrix surfaces is zero
(corresponding to no solubility limitation). For a
spherical matrix of uniform size, the solution for the
ratio of the mass, S
r
, of the compound that remains in
the matrix sphere after extraction time, t, to that of the
initial mass of extractable compound, S
0
, is given as:
( )
r 2 2 2
e 2 2
1 0
6 1
exp /
n
S
D n t r
S n
=
= t
t
(2)
Chin. J. Chem. Eng., Vol. 17, No. 3, June 2009 362
in which n is an integer and D
e
is the effective diffu-
sion coefficient of the compound in the material of the
sphere (m
2
s
1
).
The curve for the above solution tends to become
linear at longer time (generally after t0.5t
c
), and ln
(S
r
/S
0
) is given approximately by
( )
r 0 0
ln / 0.4977 / S S t t = (3)
where t
0
is the initial time and t
c
is a characteristic
time (min), defined as:
2 2
c e
/ t r D = t (4)
An alternative form of Eq. (3), or so called a
one-site kinetic desorption model, can be written for
the ratio of mass of analyte removed after time t to the
initial mass S
0
, as given by:
0
1 e
kt t
S
S
= (5)
in which S
t
is the mass of the analyte removed by the
extraction fluid after time t (mgg
1
dry sample), S
0
is
the total initial mass of analyte in the matrix (mgg
1
dry sample), S
t
/S
0
is the fraction of the solute extracted
after time t, and k is a first order rate constant de-
scribing the extraction (min
1
).
5.2.2 Two-site kinetic desorption model
Two-site kinetic model is a simple modification
of the one-site kinetic desorption model, which de-
scribes the extraction occurring from the fast and
slow part [5]. In such case, a certain fraction (F) of
the analyte desorbs at a fast rate defined by k
1
, and the
remaining fraction (1 F) desorbs at a slower rate
defined by k
2
. The model has the following form:
( ) ( )
2
1
0
1
e
e 1
t k t
k t
S
F F
S
= (
(6)
The two site kinetic model does not include sol-
vent volume, but relies solely on extraction time.
Therefore, doubling the extractant flow rate should
have little effect on the extraction efficiency when
plotted as a function of time. On the contrary, the
thermodynamic model is only dependent on the vol-
ume of extractant used. Therefore, the extraction rate
can be varied by changing the flow rate. Hence, the
mechanism of thermodynamic elution and diffusion
kinetics can be compared simply by changing the flow
rate in SCWE. If the concentration of bioactive com-
pounds in the extract increases proportionally with the
flow rate at given extraction time when the solute
concentration is plotted versus extraction time, the
extraction mechanism can be explained by the ther-
modynamic model. However, if an increase in flow
rate has no significant effect on the extraction of the
bioactive compounds, with the other extraction parame-
ters being kept constant, the extraction mechanism can
be modeled by the two site kinetic model [12, 5]. The
mechanism of control and hence the model valid for
SCWE may be different depending on the raw mate-
rial, the target analyte and extraction conditions.
5.3 Thermodynamic partition with external mass
transfer resistance model
This model describes the extraction controlled by
external mass transfer, whose rate is described by re-
sistance type model of the following form:
( )
s
e p s D
/
C
k a C K C
t
c
( =
c
(7)
in which C is the fluid phase concentration (molm
3
),
C
s
is the solid phase concentration (molm
3
), k
e
is the
external mass transfer coefficient (mmin
1
), and a
p
is
the specific surface area of particles (m
2
m
3
) [13]. If
the concentration of the solute in the bulk fluid is as-
sumed small and the ratio of solute concentration in
the liquid to that at the surface of solid matrix is de-
scribed by partitioning equilibrium, K
D
, the solution of
Eq. (7) for the solute concentration in the solid matrix,
C
s
, becomes:
( ) e p D s 0
/ exp k a t K C C = (8)
Equation (8) can be rewritten as the ratio of the
mass of diffusing solute leaving the sample to the ini-
tial mass of solute in the sample, S
t
/S
0
, as given by the
following equation.
( ) e p D 0
/ 1 exp
t
k a t K S S = (9)
Because a
p
is difficult to be measured accurately,
a
p
and k
e
are usually determined together as k
e
a
p
,
which is called overall volumetric mass transfer coef-
ficient. The factors that influence the value of k
e
a
p
include the water flow rate through the extractor and
the size and shape of plant sample.
6 RESULTS AND DISCUSSION
Figure 2 shows extraction curves generated from
SCWE of thymol and carvacrol compounds of Z. mul-
tiflora (at a flow rate of 2 mlmin
1
). While it is
tempting, based on these plots, to assign the thermo-
dynamic K
D
model to the SCWE, we cannot make the
interpretation based only on the results in Fig. 2. The
reason is that, without knowledge of the effect of flow
rate, the relative importance of the desorption kinetics
Figure 2 Comparison of SCWE profiles for major repre-
sentative essential oil compounds from Z. multiflora
(flow rate of 2 mlmin
1
, temperature 150C, mean particle
sizes 0.5 mm, pressure 2 MPa)
thymol;carvacrol
Chin. J. Chem. Eng., Vol. 17, No. 3, June 2009 363
and the extraction curves for SCWE could be de-
scribed by a single site kinetic model, as well as the
single K
D
model proposed above.
6.1 Effect of flow rate
Based on the discussion above, the importance of
K
D
and desorption kinetics was determined by com-
paring the effects of changing flow rate on the extrac-
tion rate of the same samples (Fig. 3). As can be seen,
the rate of essential oil extraction was faster at the
higher flow rate. It is in accordance with the previous
work. It means that the mass transfer of essential oil
components from the surface of the solid phase into
the water phase regulated most of the extraction proc-
ess. Increase of flow rate resulted in increase of super-
ficial velocity and thus, quicker mass transfer [12]. In
practice, the best flow rate must be chosen with two
important factors, extraction time and final extract
concentration. Shorter extraction time and more con-
centrated final extract will be preferable.
(a) Thymol
(b) Carvacrol
Figure 3 Effect of extraction fluid flow rate on SCWE of
thymol and carvacrol from Z. multiflora
(temperature 150C, mean particle sizes 0.5 mm, pressure 2 MPa)
Q/mlmin
1
:1;2;3;4
6.2 Partitioning coefficient (K
D
) model
The model Eq. (1) and the experimental data
from all volumetric flow rate plots were used to de-
termine the K
D
value by minimizing the errors be-
tween the measured data and the K
D
model using
Matlab curve fitting solver. The values of K
D
are
shown in Table 1 for different flow rates. It was dem-
onstrated that individual essential oil compounds have
a range of K
D
values from4 to250 [5]. The K
D
model agreed reasonably with the experimental data
(the average error 8%9%). Nevertheless, if the ex-
traction is strictly controlled by partitioning equilib-
rium, K
D
values for all flow rates must be equal. The
deviation found was possibly due to the existence of
external film transfer resistance, whose model would
be discussed later.
In addition, when the K
D
model was applied to
the SCWE of thymol and carvacrol from Z. multiflora,
the calculated extraction curves and the experimental
curves also show good agreement in Fig. 4. Also K
D
values of thymol and carvacrol were nearly similar,
because they were structural isomer and had similar
behaviour in extraction.
(a) Thymol
exp, Q= 4 mlmin
1
, K
D
= 2;exp, Q= 2 mlmin
1
,
K
D
= 80;exp, Q= 1 mlmin
1
, K
D
= 80
(b) Carvacrol
exp, Q= 4 mlmin
1
, K
D
= 2;exp, Q= 2 mlmin
1
,
K
D
= 70;exp, Q= 1 mlmin
1
, K
D
= 70
Figure 4 Experimental data and K
D
model for different
flow rates of SCWE of thymol and carvacrol from Z. multi-
flora
(temperature 150C, mean particle sizes 0.5 mm, pressure 2 MPa)
The effect of different values of the thermody-
namic distribution coefficient (K
D
) on extraction rates
(with a constant flow rate of 2 mlmin
1
) for thymol
extraction is shown in Fig. 5. As expected, a higher K
D
(stronger competition of the matrix versus the fluid for
the solute) yields slower extraction rates. Based on a
comparison of Fig. 5 with the experimental data shown
Table 1 K
D
values of partitioning coefficient model for
different volumetric flow rates
K
D Flow rate/
mlmin
1
Thymol Carvacrol
1 80 70
2 80 70
4 2 2
Chin. J. Chem. Eng., Vol. 17, No. 3, June 2009 364
in Figs. 3 and 4, it appears that the K
D
model shows a
general extraction curve shape which is the typical
behavior of SCWE.
6.3 One-site kinetic desorption model
Matlab curve fitting solver was used to determine
the desorption rate constant, k, from the data for all
flow rates. The values are show in Table 2. As men-
tioned, the kinetic desorption model does not include a
factor describing extraction flow rate, k should be the
same value for all flow rates if the model is said to fit
the experimental data. However, this was not the case
(Table 2, the average error 3%17%). The kinetic de-
sorption rate increased for the volumetric flow rate of
1 to 4 mlmin
1
. This indicated that the kinetic de-
sorption model may not be suitable for describing the
data at different flow rates of Z. multiflora.
Table 2 Values of k for one-site kinetic desorption model
for different volumetric flow rates
k/min
1
Flow rate/
mlmin
1
Thymol Carvacrol
1 0.0025 0.0028
2 0.0042 0.0039
4 0.0157 0.0157
6.4 Two-site kinetic desorption model
For the two-site kinetic desorption model, the
values of k
1
and k
2
were determined by fitting the ex-
perimental data with the two-site kinetic desorption
models by minimizing the errors between the data and
the model results. In the two-site model, the extraction
rate should not be dependent on the flow rate. The k
1
and k
2
values shown in Tables 3 and 4 demonstrated
that the extraction rates were not completely inde-
pendent of flow rate (the average error 11%20%).
Table 3 k
1
and k
2
values of two-site kinetic desorption
model for thymol at different flow rates
Flow rate/mlmin
1
k
1
/min
1
k
2
/min
1
Mole fraction F
1 0.0088 0.0015 0.21
2 0.0152 0.0026 0.28
4 0.0770 0.0083 0.27
Table 4 k
1
and k
2
values of two-site kinetic desorption
model for carvacrol at different flow rates
Flow rate/mlmin
1
k
1
/min
1
k
2
/min
1
Mole fraction F
1 0.0101 0.0017 0.21
2 0.0747 0.0088 0.42
4 0.0469 0.0082 0.27
6.5 Thermodynamic partition with external mass
transfer model
The values for the model parameters, K
D
and k
e
a
p
in Eq. (9) determined by Matlab curve fitting solver
from the experimental data obtained at 150C are
summarized in Tables 5 and 6 for different mass flow
rates (Q
m
, mgmin
1
). Linear regression of the plot
between ln(k
e
a
p
) and lnQ gives the following correla-
tion for k
e
a
p
and Q:
for thymol
0.2078
e p m
6.5748 k a Q = (10)
for carvacrol
0.6017
e p m
0.1605 k a Q = . (11)
Table 5 Parameters K
D
and k
e
a
p
for external mass transfer
model of SCWE of thymol
Flow rate/
mlmin
1
Mass flow rate
Q
m
/mgmin
1
Parameter K
D
Parameter
k
e
a
p
/min
1
1 938 80 26.700
2 1876 80 32.7975
4 3752 2 1.300
Table 6 Parameters K
D
and k
e
a
p
for external mass transfer
model of SCWE of carvacrol
Flow rate/
mlmin
1
Mass flow
rate/mgmin
1
Parameter K
D
Parameter
k
e
a
p
/min
1
1 938 70 8.92
2 1876 70 62.013
4 3752 2 20.54
7 COMPARISON OF EXTRACTION MODELS
To quantitatively compare the extraction models,
the mean percentage errors between the experimental
data and the models were considered. Based on the
result in fitting from experimental data, the K
D
model
was generally suitable for the description of extraction
over all the volumetric flow rates tested. On the other
Figure 5 Theoretical curves calculated using Eq. (1) for
thymol extractions from Z. multiflora, controlled by ther-
modynamic partitioning
(flow rate of 2 mlmin
1
, temperature 150C, mean particle
sizes 0.5 mm, pressure 2 MPa)
K
D
= 2; K
D
= 20; K
D
= 50; K
D
= 75;
K
D
= 100; K
D
= 150; + exp, Q= 2 mlmin
1
Chin. J. Chem. Eng., Vol. 17, No. 3, June 2009 365
hand, one-site and two-site kinetic desorption models
describe the extraction data reasonably at lower volu-
metric flow rates. Of all the models considered, however,
the thermodynamic partition with external mass trans-
fer model could best describe the experimental data.
8 CONCLUSIONS
In summary, subcritical water provides a promis-
ing alternative for extraction of the thymol and car-
vacrol from Z. multiflora. Extraction mechanisms
were investigated at 150C, 14 mlmin
1
flow rate
and 0.50 mm mean particle size for 150 min extraction
time. Overall by considering mean average errors of
models, a mathematical model base on the combina-
tion of partition coefficient (K
D
) and external mass
transfer gave a good description of subcritical water
extraction of Z. multiflora, while the kinetic model
reasonably described the extraction behavior at lower
flow rates.
ACKNOWLEDGEMENTS
Financial and technical support is gratefully ac-
knowledged to the Semnan University and the Iranian
Research Organization for Science and Technology
(IROST).
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