Chemical Engineering Science, Vol. 53, No. 7, pp.

1387—1395, 1998
( 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0009–2509(97)00445–4 0009—2509/98 $19.00#0.00

Supercritical carbon dioxide extraction of

essential oils: Modeling and simulation
Iraj Goodarznia* and Mohammad H. Eikani
Department of Chemical Engineering, Sharif University of Technology, P.O. Box 11365-9465,
Tehran, Iran

(Received 15 November 1996; in revised form 21 October 1997; accepted 16 December 1997)

Abstract—Extraction of essential oils using supercritical CO was studied. A mathematical

2
two-phase model was developed to simulate extraction yield at different operating conditions.
Unsteady-state mass balance for solute in solid and in supercritical phases led to two partial
differential equations that were solved numerically using a linear equilibrium relationship. The
model has three parameters including mass transfer, axial dispersion and intraparticle diffusion
coefficients. The last one was used as the model tuning parameter and the others were predicted
applying existing experimental correlations. The model is able to show the influence of different
process parameters such as particle size and flow rate on the essential oil recovery. ( 1998
Elsevier Science Ltd. All rights reserved.

Keywords: Supercritical extraction; essential oils; modeling and simulation.

INTRODUCTION
Supercritical fluid extraction (SCFE) is a new and
powerful technique in separation processes. Several
investigations have been made in recent years on
probable industrial applications of the SCFE which
offer some preferences over the conventional methods,
such as separation by extractive solvents or by distil-
lation, especially in the areas of the food, pharmaceut-
ical, chemical and oil industries (Bruno and Ely, 1991).
Extraction of the essential or volatile oils using
supercritical CO from herbs and spices has been
2 The second one applied the analogy between the
considered as a possible applied field of the SCFE
because of low operating temperature, no contamina-
tion of product by usual solvents and no need to have
large plant area.
High-pressure equipment is more expensive than
those for the conventional separation processes, how-
ever, the operating cost is usually lower, hence the
total costs are comparable if the process is carried out
at optimum conditions and sufficient extractor vol-
ume (Sovova et al., 1994a).
A dynamic model is necessary to gain access to
optimum operating conditions of the SCFE of the
essential oils. Most of SCFE models have been
proposed for extraction of edible oil from oil seeds
(Brunner, 1984; Bulley et al., 1984; Gangadahra and
Mukhopadyay, 1988; Gil et al., 1988; Lee et al., 1986,
Sovova et al., 1994b; Stastova et al., 1996).
*Corresponding author. Tel.: (#98-21) 6005819; fax:
(#98-21) 6012983.
1387
There are few works about the SCFE of the essen-
tial oils that are characterized by low extraction yield
and variety of final components such as terpenes and
their derivatives, fatty oils, resins and waxes. Three
different approaches for modeling the SCFE of the
essential oils have been proposed (Reverchon, 1996).
The first approach was based on empirical kinetic
equations. Kandiah and Spiro (1990) described ex-
traction kinetics of essential oils from ginger rhizomes
and Nguyen et al. (1991) modeled the CO SCFE of
2
vanilla pods.
heat and mass transfer. Bartle et al. (1990) offered such
a model and based it on the hypothesis that mass
transfer resistance on the fluid side is equal to zero.
Reverchon et al. (1993) modeled the SCFE of herba-
ceous matrices which include internal and film resist-
ances. The model showed that intraparticle mass
transfer was the controlling factor for the extraction
process.
The third one was based on differential mass bal-
ances along the extraction bed. These models require
mass transfer mechanism and an equilibrium relation-
ship. Sovova et al. (1994a) tested SCFE of caraway
seed essential oil. They divided the process in two
parts: the first was dominated by external mass trans-
fer resistance and the second one was dominated by
internal mass transfer resistance. Roy et al. (1996)
analyzed extraction of ginger root with supercritical
CO . They applied the shrinking core model to ana-
2
lyze their experimental results, with the effective
diffusivity and solubility as fitting parameters.
Reverchon (1996) proposed a model for supercritical
1388 I. Goodarznia and M. H. Eikani
extraction of sage oil. His results showed that the t"0, 0)x)1, º"mC (2a)
s0
internal mass transfer was the limiting factor and
proved that the particle shape was a key factor in qz0, m"0, º"0 (2b)
fitting experimental data. Also, he tested the introduc- Lº
tion of particle-size distribution and concluded that qz0, m"1, "(1!Bi)º#BiC .
Lm f
this led to better fitting of the experimental data for
small particles. (2c)
In this work, a model that is based on the differen-
tial mass balance in the solid and SC phases is pro- The governing differential equation for the SC phase
posed. Since, under SC operations, it is believed that is
the transport mechanisms would be similar to those Supercritical phase:
under gaseous and liquid operations; therefore, the LC 1 L2C LC 6(1!e)¸ Bi
axial dispersion may have an important effect in f" f! f# (C !C ).
Lq Pe LZ2 LZ eR Pe fs f
a fixed bed (Tan and Liou,1989). So, the effect of the b p
axial dispersion is included in derivation of the gov- (3)
erning equations. The model can be used for kinetic
studies and evaluating the effects of different operat- The corresponding initial and boundary conditions
ing conditions on the extraction process. are
q"0, C "0
0)Z)1, (3a)
MODEL DESCRIPTION
f
1 LC
A two-phase model comprising solid and super- qz0, Z"0, C ! f"0 (3b)
critical phases was used. Extraction vessel is con- f Pe LZ
b
sidered to be a cylinder filled by mono-sized spherical
LC
solid particles. The major assumptions of the model qz0, Z"1, f"0. (3c)
are as follows: LZ
Equations (2) and (3) may be solved using a linear
f The system is isothermal and isobaric. equilibrium relationship (Reverchon, 1996) between
f The physical properties of supercritical CO are concentrations in the solid phase and SCF phase at
2
constant. the interface, as follows:
f The radial concentration gradients in the extrac-
tor are neglected. C "k C` (4)
fs p ss
f The flow regime is axially dispersed.
where C is the solute concentration in the fluid
f The essential oil is assumed as a single compon- fs
phase at the particle surface, C` is the solute concen-
ent and the effect of other components on the extrac- ss
tration in the solid phase at equilibrium with the fluid
tion process at specified pressure and temperature is phase and k is the volumetric partition coefficient of
negligible. p
the solute between the solid and the fluid phase.
f The concentration of solute in solid particles is
Therefore, there are three eqs (2)—(4) which can be
independent of coordinates h and /. solved, simultaneously, for three unknowns C ,
s
C and C .
The governing partial differential equation for the f fs
solid phase derived from differential mass balance is SOLUTION TECHNIQUE
as follows:
In the proposed model, the bed of solid particles is
Solid phase: divided into n stages in the finite difference form. At
each stage, n, it is considered that all particles are at

C A BD
LC 2 ¸ 1 L LC
s" m2 s . (1) the same extraction conditions and the bulk (or free
Lq Pe R m2 Lm Lm stream) fluid composition (C ) is assumed to be uni-
p f
form. By this method the dispersed plug-flow extrac-
The associated initial and boundary conditions are
tor is approximated by a series of mixed extractors.
t"0, 0)x)1, C "C (1a) Substituting eq. (4) into eqs (2) and (3), the solution
s so
algorithm is as follows:
LC
qz0, m"0, s"0 (1b)
Lm (1) Assume a concentration profile, C (t, z), in the
f
fluid phase. Now, the value of C in Eq. 2(c) at any
LC f
qz0, m"1, ! s"Bi (C !C ). (1c) section of the bed may be obtained from this profile
Lm fs f
and is constant.
Substituting º"mC in eq. (1) (Carslaw and Jaeger, (2) Using eq. (2), concentration profile in solid par-
s ticle is obtained.
1959):
(3) Next, having the concentration of the solute at
Lº 2 ¸ L2º the particle surface, eq. (3) is solved. The solution is
" (2)
Lq Pe R Lm2 a new concentration profile in the fluid phase.
p
 Supercritical carbon dioxide extraction of essential oils 1389
(4) The calculated concentration profile is com- each time step by the Thomas algorithm (Jaluria,
pared with the assumed concentration profile. If the 1988).
difference between these two concentration profiles
is smaller than convergence criteria the procedure PARAMETER IDENTIFICATION AND CORRELATIONS
is performed for the next time step and if not the The parameters involved in the model are mass
assumed concentration profile is replaced by its transfer coefficient to the bulk phase, axial dispersion
calculated value and the aforementioned loop is coefficient in the SC phase, and diffusion coefficient in
repeated. the solid phase.
The mass transfer coefficient in an SC extractor was
In steps (2) and (3) the Crank—Nicolson implicit estimated using the empirical correlation reported by
method, that is unconditionally stable, is used to find Tan et al. (1988)
the concentration profiles in the solid and fluid
phases. The time derivations were substituted by for- Sh"0.38Re0.83Sc1@3 (7)
ward difference approximation with a truncation er- where
ror of O(*q). A central difference approximation was
employed for the spatial derivatives with a truncation ShD
k " e. (8)
error of O [(*Z)2]. In the boundary conditions (2c) f 2R
and (3c) the spatial derivatives were substitued by
backward difference approximation and in the Tan et al. (1988) estimated an external diffusivity of
about 1]10~8 m2/s for the beta-naphthol/CO sys-
boundary condition (3b) forward difference approxi- 2
mation was applied. The finite difference form of the tem in the temperature and pressure ranges of
governing differential equations can be written as 35—50°C and 60—140 bar, respectively. Reverchon
follows: et al. (1993) accepted this value, because of the similar
molecular weight of beta-naphthol and the essential
Solid phase: oils. The same value of external diffusivity is assumed
in this work.
!F º #2(1#F )º !F º The axial dispersion coefficient in the SC phase was
1 k`1,i`1 1 k`1,i 1 k`1,i~1
approximated as follows (Tan and Liou, 1989):
"F º #2(1!F )º #F º ,
1 k,i`1 1 k,i 1 k,i~1
Pe "1.634Re0.265Sc~0.919 (9)
1)i)NR!1 (5) pd
where
k"0, 0)i)NR, º "m C (5a)
0,i i s0 º d
D " 0 p (10)
Kz0, i"0, º "0
k,0
(5b) L Pe e
pd
kz0, i"NR, Viscosity of supercritical CO was estimated using
2
Jossi et al. (1962) empirical correlation
4º !º #2*mBiC
º " k,NR~1 k,NR~2 k,j . (5c)
k,NR (3!2*m#2k Bi*m) [(k!k*)m*#10~4]1@4"0.10230#0.023364o
r
p
#0.058533o2!0.040758o2#0.0093324o4 . (11)
Supercritical phase r r r
In eq. (11) the value of m* for CO is 0.0224. Further-
(!F #F )C #2(1#F )C 2
2 3 k`1,j`1 2 k`1,j more, m* which is the viscosity in the normal pressure
!(F #F )C "(F !F )C (0.1—5 bar) can be calculated as follows:
2 3 k`1,j~1 2 3 k,j`1
k*m*"34.0]10~5 ¹0.94 , ¹ )1.50 (11a)
#[2(1!F )!F ]C #(F #F ) C r r
2 4 k,j 2 3 k,j~1
k*m*"17.78]10~5 (4.58¹ !1.67)5@8, ¹ z1.50.
#F º , 1)j)ML!1 (6) r r
4 k,NR
(11b)
k"0, 0)j)ML, C "0 (6a)
0,j
The experimental values for density of supercritical
4C !C CO at 100 bar/40°C and 90 bar/40°C are 623 and
kz0, j"0, C " k,1 k,2 (6b) 2
k,0 2Pe *Z#3 485 kg/m3, respectively, which were used here.
b
kz0, j"ML, C "4 C !1 C .
k,ML 3 k,ML~1 3 k,ML~2 RESULTS AND DISCUSSION

(6c) It has been proven that the optimum extraction

As seen from eqs (5) and (6), in the two phases, a set
of simultaneous linear algebraic equations must be
solved for implicit method to obtain the concentra-
tion distribution at any time. In both cases, tridiag-
onal systems arise which are conveniently solved at
pressure and temperature for obtaining high yield of
essential oils resulting in negligible solubility of the
other components are in the ranges from 80 to 100 bar
and from 40 to 50°C (Stahl and Gerard, 1985; Rever-
chon et al., 1993; Sovova et al., 1994a). The proposed
model was used to predict, extraction yields vs time
1390 I. Goodarznia and M. H. Eikani
for four natural materials such as rosemary, basil,
marjoram and caraway, in the same ranges of pressure
and temperature. From botanical point of view, the
first three samples are in the form of leaves and the
fourth is a seed. Seeds have higher contents of essen-
tial oils, and it is possible that they do not exactly
represent intraparticle limiting stage in their mass
transfer process. The caraway seeds were selected for
evaluating the model capability for predicting extrac-
tion yields of these natural materials, as well.
Table1 presents the charge, extractor volume, in-
itial concentrations, particle diameters and flow rates
for these processes. Values of k for the leaves (rose-
p
mary, basil and marjoram) and the caraway seeds are
needed to solve the system of mass balance partial
differential equations. According to Reverchon (1996)
and Sovova et al. (1994a) a mean value of k of 0.45 at
p
100 bar/40°C for the leaves was calculated and ap-
plied, and for the caraway seeds, values of k of 1.7 at
p
100 bar/40°C and 0.3 at 90 bar/40°C were obtained.
The void fraction for the bed of leaves and caraway
seeds was 0.514 and 0.4, respectively.
In Figs 1—4, the experimental values of supercritical
extraction yield vs time are compared with the pre-
dicted profiles from the model. Here, yield is defined
as the percent of the amount of essential oil extracted
per initial amount of oil in the solid phase. Using
diffusion coefficient in the solid phase as a model
parameter, the best fit to the given data has been
obtained employing the least-squares method. The
resulting values are given in Figs 1—4. As seen from
this figures, the one-parameter model predicts the
trends of the extraction yield, conveniently. The
values of diffusion coefficients in the solid particles are
in conformity with Nguyen et al. (1991) and Rever-
chon et al. (1993, 1994) reported data.
As shown in Fig. 2, the model overestimates the
essential oil yields for larger particles. This is in

Table 1. The selected samples for verifying the model

Charge Extracter Initial conc. Diameter Flow rate

Sample (g) volume (cm3) (kmol/m3) (mm) (cm3/s) Reference

Reverchon et al.
Rosemary 230 400 0.075 0.23 0.5
(1993)
Basil 220 400 0.063 0.17 0.5
Reverchon et al.
Basil (pilot) 6000 20,000 0.063 0.55 28
Basil (pilot) 6000 20,000 0.063 1.30 28 (1994)
Reverchon et al.
Marjoram 230 400 0.053 0.15 0.5
(1993)

Caraway
90 bar,
400°C 75 150 0.233 0.504 0.06 Sovova et al.
100 bar, 40°C 75 150 0.233 0.504 0.047 (1994a)

Fig. 1. SCFE of rosemary leaves.

 Supercritical carbon dioxide extraction of essential oils 1391

Fig. 2. SCFE of basil leaves.

Fig. 3. SCFE of marjoram leaves.

accordance to the work of Reverchon et al. (1994) and
Reverchon (1996), who indicated that the assumption
of spherical particles is not valid for larger particles.
Larger diffusivities are obtained at 90 and 100 bar
at 40°C for caraway seeds that have higher content of
the essential oils than the leaves, because of the im-
mediate availability of the solute next to the surface in
the first part of the extraction process. Also, at
100 bar, the density of CO is higher than that at
2
90 bar, consequently, solvating power is higher and
the yield is larger. The two different values of cal-
culated diffusivities show dependence of diffusivity on
pressure at fixed temperature.
The effects of the particle size and the flow rate on
extraction yield of basil, are presented in Figs 5 and 6.
Figure 5 shows that smaller particle size leads to
higher extraction of oil. However, in industrial ap-
plications, there are practical limitations due to par-
ticle size.
As shown in Fig. 6, yield increases with flow rate,
but the curves flatten quickly and no appreciable gain
is achieved by increasing the flow rate beyond certain
values.
In Fig. 7, variation of SC phase concentration at
Z"0.5 and 1 for basil are presented. The model
shows at the beginning of the extraction, there exists
a jump in the SC phase concentration at the exit of the
extractor and after a limited time, it gradually de-
creases. This is in accordance to the results of Rever-
chon in analyzing SCFE of sage oil (1996).
1392 I. Goodarznia and M. H. Eikani

Fig. 4. SCFE of caraway seeds.

Fig. 5. Effect of particle size on SCFE of basil.

Fig. 6. Yield of basil extraction vs flow rate at different times.

 Supercritical carbon dioxide extraction of essential oils 1393

Fig. 7. Concentration profile at Z"0.5 and 1 in the SC extractor.

Fig. 8. Concentration profile vs radius along a basil particle (dp"0.17 mm).

Furthermore, the model can be used to determine
the concentration profiles at any time in the bed
during the extraction. Figure 8 shows the dimension-
less concentration profiles of basil vs dimensionless
radius at the entrance and at the exit of the extractor.
There are little differences between these profiles,
which are greater at the beginning of the extraction
process.
from the physical point of view. The model predic-
tions are satisfactory and have reliable trends. Con-
centration profiles in the solid phase and in the SC
phase may be shown at any section of the extraction
bed at any given time. The model indicates dependa-
bility of extraction to the particle size. Hence, the
proper selection of the particle shape is an important
factor to model SCFE for plant materials.

Acknowledgements
CONCLUSION
The support of the Sharif University of Technology and
The simplified model of Reverchon et al. (1993) was the G.T.B. Group (Km. 44 Kashan-Delijan Road, Kashan,
developed by introducing differential mass balances IRAN) is gratefully acknowledged.
using two phase model, and applying a linear equilib-
rium relationship. Because of considering the effect of NOTATION
variation of the concentration profile in the SC phase, a specific surface, m2/m3
it seems that the proposed model is more significant Bi Biot number ("k R/D )
f m
1394 I. Goodarznia and M. H. Eikani
C solute concentration in the SC phase, i space index (in the solid phase)
f
kmol/m3 j space index (in the bed)
C solute concentration in the SC phase at the k time index
fs
particle surface, kmol/m3 ML number of subdivisions in the bed
C solute concentration in the solid phase, NR number of subdivisions in the spherical par-
s
kmol/m3 ticle
Css solute concentration in the solid phase at the 0 time t"0
particle surface, kmol/m3 r reduced form
d particle diameter, m ss surface of the particle
p
D diffusivity in the film surrounding the par-
e
ticle, m2/s
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