Modelling the extraction of essential oils with compressed

carbon dioxide
F. Gaspar *, T. Lu, R. Santos, B. Al-Duri
School of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
Received 26 October 2001; received in revised form 9 May 2002; accepted 9 May 2002
Abstract
Three models were used to describe the extraction of essential oils from oregano bracts using compressed carbon
dioxide. They were developed on the basis of a plate-like geometry of the particles and were tested experimentally using
various bract pre-treatments, pressures, temperatures and solvent flow rates. The two particle phase derived models
applied, the Single Plate model (SP model) and the Simple Single Plate model (SSP model), differ only by the allowance
or not for a film coefficient (k
f
) and have as the only adjustable parameter the matrix diffusivity (D
m
). The third model,
the Fluid Phase/Simple Single Plate model (FP/SSP model), considers both the particle mass balance and a detailed
description of the fluid mass balance. In addition to the matrix diffusivity the FP/SSP model may require the
adjustment of the fraction of oil leached by the solvent during the pressurisation procedure (f
0
). All models gave a good
fit to the experimental data though the FP/SSP model gave the best fit. However, the matrix diffusivities found
correlated very poorly with the estimated diffusivity of essential oils in carbon dioxide (D
12
), which indicates a complex
intraparticle transport.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Carbon dioxide; Essential oils; Extraction; Modelling
1. Introduction
The extraction of essential oils with compressed
carbon dioxide is a modern technique that have
shown, in particular applications, significant ad-
vantages over more conventional methods such as
steam distillation and liquid solvent extraction.
The gentle nature of the process allied to the
relatively high solubility of the aromatic com-
pounds in compressed carbon dioxide yields a high
quality extract at a competitive cost. Among the
main process parameters that affect the extraction
are the pre-treatment of the herbaceous matrices,
the extraction pressure and temperature and the
solvent flow rate.
The ability to predict the course of the extrac-
tion process, knowing the process parameters, is a
powerful tool in both design and optimisation of a
carbon dioxide industrial plant. Mathematical
modelling is probably the most challenging and
informative predicting tool. Generally, the extrac-
* Corresponding author. Tel.: '/44-121-414-6965; fax: '/44-
121-414-5234
E-mail address: f.gaspar@bham.ac.uk (F. Gaspar).
J. of Supercritical Fluids 25 (2003) 247/260
www.elsevier.com/locate/supflu
0896-8446/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
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tion models reported in literature belong to three
distinct categories: empirical models, models pri-
marily based on the fluid phase mass balance and
models primarily based on the particle phase mass
balance. (A review of mathematical models is
given by Reverchon [1].) Examples of empirical
models are the two-stage (washing/diffusion)
model from So and MacDonald [2] and the model
proposed by Kandiah and Spiro [3] to describe
kinetics of extraction of essential oils from ginger
rhizomes. The main limitations of these empirical
models are the lack of physical significance and,
consequently, the difficulty in predicting their
fitting parameters. With a stronger physical sig-
nificance are the models based on the fluid and
particle phase mass balances. However an analy-
tical solution of the particle and fluid phase mass
balances is not possible, and many modifications
and approximations were employed in order to
derive the models proposed in the literature. Some
models consider primarily the fluid phase mass
balance and are, consequently, known as plug flow
Nomenclature
A area of the extraction bed (m
2
)
a as defined in Eq. (5) (m
2
s
(1
)
A
p
projected area of the plate like particles (bracts) (m
2
)
b as defined in Eq. (6) (m s
(1
)
C concentration of oil in the fluid phase (kg m
(3
)
C
p
concentration of oil in the particle phase (kg m
(3
)
D
ax
axial dispersion coefficient (m
2
s
(1
)
D
m
diffusion coefficient of the oil within the matrix (m
2
s
(1
)
E extraction degree (%)
F mass flow rate of solvent (kg s
(1
)
f
0
fraction of oil initially dissolved in the fluid phase
g as defined in Eq. (7) (kg s
(1
)
k
f
film coefficient (m s
(1
)
L length of the extraction bed (m)
M mass of oil extracted from the bed (kg)
n integer
t extraction time (s)
u
i
interstitial velocity of the fluid phase (m s
(1
)
u
s
superficial velocity of the fluid phase (m s
(1
)
V
p
volume of particles within the bed (m
3
)
x co-ordinate of the particle (m)
z axial co-ordinate of the bed (m)
Greek letters
b
n
positive roots of the implicit equation
d thickness of the plate like particles (bracts) (m)
o porosity of the bed
Subscripts
0 initial (t 0/0)
after infinite time (t 0/)
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 248
or dispersed models. The main disadvantage of the
approach is that most of the information concern-
ing the intraparticle mass transfer mechanism is
lost. Examples of this approach are the character-
istic time model [4,5], the model applied by
Esqu vel et al. [6] to the extraction of essential
oils from oregano herbs and the model used by
Goto et al. [7] to describe the extraction of oil from
peppermint leaves. In the latter case, a plate
geometry was assumed for the particles and the
fluid phase mass balance was simplified by con-
sidering a uniform extraction along the bed.
In general, the models based primarily on the
particle phase mass balance were found more
adequate for the extraction of essential oils with
compressed carbon dioxide. This is not surprising
since, in many cases, the intraparticle transport
was found to be the limiting factor of the extrac-
tion. Bartle et al. [8] presented a model based on a
spherical geometry for extraction of small quan-
tities of materials (such as essential oils), so that
the extraction rate was limited by a diffusion
mechanism. This model, here referred to as the
Simple Single Sphere model (as opposed to the
Single Sphere model presented latter by Reverchon
et al. [9]), performed reasonably well in spite of the
non-ideal nature of the various samples tested.
However, the model gave little information about
the early stage of extraction, in which the majority
of the material was extracted. Deviations to model
predictions were qualitatively explained in terms of
particle shape, solubility limitation and a non-
homogeneous distribution of the solute within the
particles. Modified versions of the Simple Single
Sphere model were subsequently presented to
account for solubility limitation and also for plate
geometry [10]. Reverchon et al. [9] also proposed a
spherical model (Single Sphere model) for the
extraction of essential oils from matrices such as
rosemary, basil and marjoram leaves. The Single
Sphere model differs from the simpler Simple
Single Sphere model by the inclusion of an
external film resistance. Different material, parti-
cle sizes and experimental scales were fairly
modelled but the advantage of including the film
resistance was limited as intraparticle diffusion
resulted as the controlling stage.
In the present work, modelling of the extraction
of essential oils from an aromatic herb using
compressed carbon dioxide was studied. Oregano
(Origanum virens L.) bracts were used as the
herbaceous matrix. Two analytical models based
on the particle phase mass balance were applied.
Furthermore, a new numerical model using both
the fluid phase and the particle phase mass
balances was developed and tested on experiments
where different pre-treatments, pressures, tem-
peratures and solvent flow rates were used.
2. Experimental work
Extraction tests on oregano bracts were per-
formed over a wide range of experimental condi-
tions. Table 1 summarises the operating conditions
(pressure, temperature and solvent flow rate), the
state of the matrices and respective particle size for
the selected 24 runs. The experimental equipment
and procedure for the extraction of the essential
oils with compressed carbon dioxide were pre-
viously described [11]. In order to evaluate the
geometry of the particles, the projected area (A
p
)
and the thickness (d) of the intact bracts were
measured by microscopy and micromanipulation,
respectively. (Details of the micromanipulation
technique and equipment are described elsewhere
[12].) For untreated bracts the ratio of projected
area diameter to thickness (D
p
/d) ranged from 82
to 391 depending on the size of the bracts. For pre-
treated bracts, the projected area diameter was not
measured but, instead, estimated by assuming that
the reduction in the projected area diameter during
the comminution process was similar to the
reduction in the particle size measured by the
sieving process (d
p
). Table 2 summarises these
results.
For each test, a 30-g sample of comminuted
bracts (or a 15-g sample in the case of intact
bracts) was charged to the extractor. The extractor
diameter and height was 95 and 45 mm, respec-
tively. The porosity of the bed (o ) was 0.85 for
intact bracts (where only 15-g samples were
charged) and 0.70 for comminuted bracts (where
30-g samples were used). In order to measure the
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 249
bed porosity, a glass vessel (with the same dimen-
sions of the extractor) charged with the same mass
of herb was carefully filled with water. Bed
porosity was then calculated as the ratio of water
volume to extractor volume.
3. Basis for mathematical models
Prior to presenting the theoretical section, the
experimental evidence which underlines the devel-
opment and application of the models is presented.
Table 1
Experiments used to model the extraction curves of essential oils
Run # P (bar) T (K) F (kg h
(1
) Matrix state/d
p
(mm)
Effect of pressure and temperature (P and T) 1 70 300 0.5 Comminuted/0.36
2 80 300 0.5 Comminuted/0.36
3 80 310 0.5 Comminuted/0.36
4 100 300 0.5 Comminuted/0.36
5 100 310 0.5 Comminuted/0.36
6 100 320 0.5 Comminuted/0.36
7 150 300 0.5 Comminuted/0.36
8 150 310 0.5 Comminuted/0.36
9 150 320 0.5 Comminuted/0.36
10 200 300 0.5 Comminuted/0.36
11 200 310 0.5 Comminuted/0.36
12 200 320 0.5 Comminuted/0.36
Effect of solvent flow rate (F) 13 70 300 0.3 Comminuted/0.36
14 70 300 0.5 Comminuted/0.36
15 70 300 0.7 Comminuted/0.36
16 70 300 0.9 Comminuted/0.36
17 100 310 0.3 Comminuted/0.36
18 100 310 0.5 Comminuted/0.36
19 100 310 0.7 Comminuted/0.36
20 100 310 0.9 Comminuted/0.36
Effect of particle size (d
p
) 21 70 300 0.3 Intact/1.55
22 70 300 0.3 Comminuted/0.70
23 70 300 0.3 Comminuted/0.36
24 70 300 0.3 Comminuted/0.33
Table 2
Characterisation of the matrix before and after the pre-treatments
Pre-treatment d
p
(mm) A
p
(mm
2
) D
p
(mm) d (mm) D
p
/d
No treatment 1.55 1.2/12 2.5/7.8 0.02/0.03 82/391
Atmospheric comminution
to 0.70 mm 0.70 N.M. 1.1/3.5
a
0.02/0.03
b
37/167
to 0.36 mm 0.36 N.M. 0.6/1.8
a
0.02/0.03
b
19/91
to 0.33 mm 0.33 N.M. 0.5/1.7
a
0.02/0.03
b
18/83
a
Assumed to proportional to the reduction in particle size during the pre-treatment.
b
Assumed equal to intact matrix since the ratio d
p
/d /10.
N.M., not measured.
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 250
3.1. Extraction rates mainly controlled by
intraparticle resistances
In general, literature reported that the limiting
stage when extracting essential oils from aromatic
herbs is the intraparticle transport. This arises
from the relatively high solubility of essential oil
components in compressed CO
2
and from the
relatively low content of essential oils in aromatic
herbs. The experimental results reported in this
paper also support these findings. When using
intact bracts the rate of extraction was extremely
low, indicating a substantial intraparticle resis-
tance. After comminution of the bracts the rates
and yields of extraction dramatically increased: the
first 60/80% of the essential oils were easily and
quickly extracted in the earliest stage, whereas the
last fraction was very slowly extracted in the later
stages. The fraction of the essential oils easily
extracted in the earlier stages should correspond to
oil that had been liberated from the essential oil
glands during the mechanical pre-treatment of the
matrix. On the other hand, the slow extraction of
the last fraction of essential oils indicates that
these oils were still highly retained within the
matrix (either located within glands that survived
the pre-treatment, retained within internal tissues
or adsorbed at the matrix surface). Intraparticle
resistances such as the cuticle or cell walls may
therefore have controlled the extraction of the last
fraction of essential oils. Other evidence of extrac-
tion rates limited by intraparticle resistance arose
when studying the effect of solvent flow rate on the
extraction rates. In this case it was found that the
extraction rate was mostly time dependent, a clear
evidence of extraction rates limited by intraparticle
resistances.
3.2. Particles with plate geometry
Most models proposed in literature were devel-
oped on the basis of spherical particles, the
equivalent diameter being commonly estimated
as the weight mean diameter calculated from a
sieving process. However, in many cases the
particle geometry is closer to a plate. Examples
of plate geometry particles are the leaf material of
aromatic herbs and flaked matrices. It can be seen
from Table 2 that the ratio between the estimated
projected area diameter and the thickness of the
bracts, in all matrices used, ranged from 18 to 391,
which supports the assumption of plate geometry.
Microscopic observations on comminuted bracts
(where the ratio D
p
/A
p
is smaller) also supports the
plate like geometry (see Fig. 1).
3.3. Ultimate extraction yields limited by the
matrix pre-treatment and by the co-extraction of
cuticular waxes
In previous work [13], using the same herbac-
eous matrix, the extraction of the last fraction of
the oils was found to occur in parallel to that of
the higher molecular weight cuticular waxes.
Consequently, the ultimate yields of essential oils
(yields after an infinite period of extraction) are
likely to be limited by the ability of the solvent to
dissolve wax material. If so, the models should use
the ultimate yields upon predicting the maximum
extractable oil (at t0/) rather than the initial
content within the matrix. Moreover, the ultimate
yield is also likely to be dependent on the fraction
of the non-retained oil and, consequently, on the
matrix pre-treatment.
Fig. 1. Scanning electron micrograph ( )/6000): Plate-like
geometry observed in comminuted bracts.
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 251
3.4. Two distinct fractions of essential oils at the
extraction stage
In the experimental extraction curves two frac-
tions of essential oils could be distinguished. The
first fraction, the non-retained oils, was easily
extracted in the earlier stages, whereas the last
fraction, the highly retained oils, was very slowly
extracted at the latter stages of extraction. The
fraction of non-retained oils is likely to be related
to the fraction of disrupted glands (glandular
trichomes) at the extraction stage, whereas the
highly retained oils were presumably located
within the glands that survived the matrix pre-
treatment [11].
3.5. Fluid phase retention
Despite the experimental evidence that intrapar-
ticle resistances primarily limited the extraction
rates, the extraction of the oils out of the extractor
vessel is also dictated by fluid phase retention.
Fluid phase retention is responsible for the dis-
crepancy between the oil extracted from the
particles and the oil removed from the extractor.
The fluid phase mass balance should therefore be
included in the mathematical models if an accurate
description of the extraction process is required.
4. Extraction models
Three models are proposed and applied in the
present work where the particles were described as
plates. The first two models, namely the Simple
Single Plate and the Single Plate models, were
exclusively based on the particle phase mass
balance, and consequently cannot comply with
the experimental evidence given in Sections 3.4 and
3.5. The difference between the two models is the
inclusion or not of the film resistance. The third
model, the Fluid Phase/Simple Single Plate (FP/
SSP), includes a detailed description of the fluid
phase mass balance in addition to the particle mass
balance, and is able to conform with the experi-
mental evidence given in Sections 3.1, 3.2, 3.3, 3.4
and 3.5.
4.1. The Simple Single Plate model (SSP model)
This model, originally proposed by Bartle et al.
[10], was slightly modified to account for the
extractable masses of oil (instead of initial content)
and was rewritten in terms of extraction degree.
The model assumes that:
1) the extractable oil is initially uniformly dis-
tributed within the plate like particles,
2) all particles are, at a given time, at the same
extraction stage,
3) intraparticle transport is described by a diffu-
sional process through the thickness of the
particles,
4) concentration in the fluid phase is negligible
when compared to that in the particle phase,
5) the resistance to mass transport offered by the
stagnant film is negligible and,
6) the mass extracted from the bed equals that
extracted from the particles (fluid phase mass
balance is neglected).
The SSP model equation, rewritten in terms of
extraction degrees, is given below.
E(t)0E

_
1(

0
8
(2n '1)
2
e
((D
m
(2n'1)
2
p
2
t)=d
2
_
(1)
In the above equation E(t) and E

are the
extraction degree after time t and infinite, D
m
is
the matrix diffusivity, d is the thickness of the
particles (plates) and n is an integer.
4.2. The Single Plate model (SP model)
The SP model was derived from the equations
proposed by Wong for the heat loss from an
infinite slab to a surrounding medium [14]. The
equations were translated to mass transfer context
using the heat-mass transfer analogies. The model
was developed on the same assumptions as the SSP
model except in the allowance for an external
resistance. The model equation is given below,
where k
f
is the film coefficient and b
n
are the
positive roots of the implicit equation.
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 252
E(t)0E

_
4

1
sin
2
b
n
2b
2
n
'b
n
sin 2b
n
[1(e
((2b
n
=d)
2
D
m
t
]
_
(2)
b
n
tan b
n
0
k
f
d
2D
m
4.3. Fluid Phase/Simple Single Plate model (FP/
SSP model)
The FP/SSPmodel combines the fluidphase mass
balance with the SSP model. As mentioned pre-
viously, the latter is based on the evidence that
intraparticle diffusion controls the extraction rate.
Furthermore, theFP/SSPmodel alsoaccountsforthe
likelypresenceof essential oilsinthefluidphaseat the
start of the dynamic extraction. Upon system
pressurisation, some of the non-retained oils are
likelytobeleachedbythesolventontothefluidphase.
The FP/SSP model assumes that
1) a fraction f
0
of the extractable oil is initially
uniformly distributed within the fluid phase
and the remaining fraction (1(/f
0
) of the
extractable oil is initially uniformly distributed
within the plate like particles,
2) the intraparticle transport is described by the
SSP model and,
3) axial dispersion, fluid phase density and
porosity of the bed are constant along the
bed and independent of the extraction time.
The modelling equation is given below, where
M(t) and M

are the mass of oil extracted from

the bed after time t and infinite, u
s
is the superficial
velocity of the solvent and A the cross-sectional
area of the bed.
E(t)0
M(t)
M

0
g
t
0
C(z 0L; t)u
s
A dt
M

(3)
The concentration profile in the fluid phase, C,
is obtained from integration of the fluid phase
mass balance expressed in Eq. (4).
@C
@t
0a
@
2
C
@z
2
'b
@C
@z
'g(t) (4)
where
a0D
ax
=o (5)
b0(u
s
=o 0(u
i
(6)
g(t)0
M

ALo

n00
8D
m
d
2
e
(D
m
t[(2n'1)p=d]
2
(7)
In the above equations z is the axial co-ordinate
of the bed, D
ax
is the axial dispersion coefficient, o
is the bed porosity and g(t) is the rate of mass
transfer from the particles. The rate of mass
transfer from the particles, g(t), was obtained by
taking the time derivative of the SSP model
(written in terms of mass).
The leached oil is uniformly distributed in the
fluid phase at the start of the extraction. During
extraction, the solvent is fed at the bottom of the
extractor. These initial and boundary conditions,
applied to Eq. (4), are given by Eqs. (8) and (9).
C0C
0
<t00 (8)
C00<z00 (9)
where
C
0
0
f
0
M

ALo
(10)
C
0
is the initial concentration in the fluid phase
calculated in Eq. (10) from the fraction of oil
initially dissolved in the fluid phase, i.e. f
0
. The
concentration at the exit of the bed, C(z0/L, t),
required to calculate E(t ), was computed by a
numerical method presented in Appendix A.
5. Modelling parameters
In the SSP and SP models the only adjustable
parameter was the diffusivity of the essential oils
within the matrix, D
m
, whereas in the FP/SSP
model D
m
and f
0
were both used as adjustable
parameters. The modelling equations were fitted to
the experimental data using the Golden Section
method. The adjustment criterion was minimisa-
tion of the standard deviation between the experi-
mental and calculated degrees of extraction.
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 253
Other model parameters (non-adjustable para-
meters) were estimated from the experimental
results or by correlations proposed in literature.
The extraction degree after infinite time (E

) was
assumed to be the extraction degree after 200 min
in the cases where an asymptotic value was
obtained from the extraction curves. The average
thickness of the bracts (d), 24 mm, was estimated
from the micromanipulation measurements. The
film coefficient (k
f
) and the binary diffusivity (D
12
)
were calculated using the correlation proposed by
Catchpole et al. [15] and the general equation
suggested by Catchpole and King [16], respec-
tively. Tan and Liou equation [17] was used to
calculate the axial dispersion coefficient (D
ax
). The
porosity of the bed (o ) was determined experimen-
tally, as described in Section 2.
6. Results and discussion
The best-fit parameters of the extraction models
are shown in Table 3. For all models, the standard
deviation between experimental and modelled
extraction degrees was never greater than 7%.
These results are presented in Table 4.
The FP/SSP model was initially applied to the
experimental data with two adjustable parameters
(FP/SSP model with f
0
free in Tables 3 and 4):
matrix diffusivity (D
m
) and the fraction of oil
initially dissolved in the fluid phase (f
0
). The best-
fitting values of f
0
revealed an expected result in
relation to the state of matrix. The adjustable
parameter f
0
was found to range between 0.43 and
0.61 in 86% of the runs where comminuted bracts
were used (see Fig. 2). The only exceptions were
Table 3
Best-t parameters from the extraction models (matrix diffusivity and fraction of oil initially dissolved in the uid phase)
Run # P (bar) T (K) SSP model SP model FP/SSP model (f
0
free) FP/SSP model (f
0
fixed)
D
m
)/10
14
(m
2
s
(1
) D
m
)/10
14
(m
2
s
(1
) D
m
)/10
14
(m
2
s
(1
) f
0
D
m
)/10
14
(m
2
s
(1
) f
0
1 70 300 5.3 5.6 2.8 0.50 2.8 0.51
2 80 300 6.2 6.6 2.6 0.57 3.3 0.51
3 80 310 3.3 3.4 * * * *
4 100 300 6.2 6.5 3.2 0.54 3.5 0.51
5 100 310 3.8 4.0 4.6 0.01 2.1 0.51
6 100 320 4.0 4.2 * * * *
7 150 300 5.5 5.8 2.6 0.54 2.9 0.51
8 150 310 5.4 5.7 3.4 0.48 3.1 0.51
9 150 320 5.5 5.8 3.0 0.51 3.0 0.51
10 200 300 5.8 6.1 2.9 0.56 3.4 0.51
11 200 310 4.5 4.4 2.6 0.47 2.4 0.51
12 200 320 6.3 6.6 3.0 0.61 4.0 0.51
13 70 300 3.1 3.3 3.2 0.21 1.7 0.51
14 70 300 3.9 4.4 2.1 0.45 1.8 0.51
15 70 300 5.0 5.3 2.8 0.45 2.4 0.51
16 70 300 6.2 6.6 2.8 0.56 3.2 0.51
17 100 310 3.8 4.0 3.5 0.29 2.1 0.51
18 100 310 4.8 4.4 2.4 0.49 2.3 0.51
19 100 310 5.1 5.3 2.6 0.48 2.4 0.51
20 100 310 5.4 5.6 2.6 0.50 2.6 0.51
21 70 300 0.3 0.3 0.2 0.09 0.2 0.09
22 70 300 4.2 4.4 2.6 0.49 2.4 0.51
23 70 300 4.5 4.4 2.5 0.52 2.6 0.51
24 70 300 4.3 4.4 3.0 0.47 2.6 0.51
*
Runs 3 and 6 were not modelled due to software limitations (the stability criteria, Eq. (a5) resulted in very small time scale
increments, which in turn led to overflow of the software available).
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 254
found in runs 5, 13 and 17, where the values of f
0
were considerably lower. (A possible reason for the
discrepancy on the f
0
best-fit values on these three
runs is the larger error on the experimental curve
for small extraction degrees and the high sensitiv-
ity of the modelling parameters on the extraction
degree after 20 min. In the three runs, the
extraction degree after 20 min ranged from 52 to
59%, i.e. the lowest values among the modelled
experiments. The experimental error associated
with these values is about 5/6% of the stated
value).
The consistency on the best-fit values of f
0
when
modelling the extractions from comminuted bracts
is expected in view of the following evidence:
1) The fraction of oil initially dissolved in the
fluid phase (f
0
) depends on the fraction of oil
readily accessible to the solvent at the start of
Table 4
Standard deviation of extraction models to experimental data
Run # P (bar) T (K) S.D. (%)
SSP model SP model FP/SSP model (f
0
free) FP/SSP model (f
0
fixed)
1 70 300 3.2 2.7 0.7 0.8
2 80 300 3.4 2.8 0.9 1.2
3 80 310 2.0 1.7 / /
4 100 300 2.9 2.4 0.8 0.8
5 100 310 1.5 1.6 0.8 6.2
6 100 320 1.7 1.3 / /
7 150 300 3.8 3.3 0.8 1.0
8 150 310 2.6 2.2 0.7 0.8
9 150 320 3.0 2.5 0.7 0.7
10 200 300 3.6 3.1 0.9 1.2
11 200 310 3.5 2.9 1.0 1.2
12 200 320 3.5 3.0 1.0 1.7
13 70 300 1.4 1.2 1.3 6.2
14 70 300 4.6 4.0 0.8 1.6
15 70 300 3.0 2.6 0.9 1.2
16 70 300 3.4 2.8 0.7 1.0
17 100 310 1.5 1.2 1.2 4.0
18 100 310 3.8 3.4 0.6 0.6
19 100 310 3.4 2.9 0.9 1.0
20 100 310 3.4 2.9 0.8 0.9
21 70 300 1.3 1.6 0.4 0.4
22 70 300 3.4 2.7 0.7 0.9
23 70 300 3.7 3.0 0.8 0.9
24 70 300 2.6 2.0 0.7 1.1
Average S.D. (%) 2.9 2.5 0.8 1.6
Fig. 2. Best t values of f
0
(fraction of oil initially dissolved in
the uid phase) obtained by the FP/SSP model.
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 255
the pressurisation of the extractor. This frac-
tion is closely related to the state of the matrix
at the extraction stage and consequently to the
matrix pre-treatment.
2) In all experiments on comminuted bracts, the
matrix pre-treatment was similar (atmospheric
comminution in a commercial blender). The
only difference in the pre-treatments occurred
in runs 22 and 24 where the exposure period to
the blender was, instead of 40, 20 and 60 s,
respectively. The effect of particle size (result-
ing from different periods of exposure to the
blender) on the rates and yields of extraction
of essential oils was found negligible. Conse-
quently, the fraction of oil readily available to
the solvent in these matrices was likely to be
similar.
On the basis of this evidence and on the
consistency of the best-fit values of f
0
, a second
simulation with the FP/SSP model was considered
where the value of f
0
was fixed to 0.51 for all the
experiments performed with comminuted bracts
(0.51 was the mean value of the initial best-fit
values of f
0
). In run 21, however, where an intact
matrix was extracted, the value of f
0
was kept
equal to that previously obtained by the two-
parameter FP/SSP model. (The best-fit value of
0.09 or 9% seems reasonable in view of the intact
state of matrix.)
It should be noted that by fixing f
0
for similarly
treated matrices, the FP/SSP model is simplified to
a one-adjustable parameter model. The best-fitting
parameters of the FP/SSP model with f
0
fixed are
also shown in Table 3. When comparing the best-
fit values of the matrix diffusivity (D
m
) from the
models several trends are observed:
a) The higher values of D
m
were obtained from
the models exclusively based on the particle
mass balance (SSP model and SP model). The
decrease on the best-fit values of D
m
in the FP/
SSP models resulted, mostly, from the allow-
ance for a significant fraction of oil initially
dissolved in the fluid phase (f
0
).
b) When comparing the SSP and SP models it
can be seen that the latter presents, in general,
slightly higher values of matrix diffusivity
(D
m
). This arises from the inclusion of the
resistance to mass transport through the
stagnant film on the SP model. (The proximity
of the D
m
values obtained from these two
models is, however, strong evidence that the
film resistance is much smaller than the
intraparticle resistances.)
A sample of the comparison between the models
and the experimental data is shown in Fig. 3. In
Figs. 4/6, the FP/SSP (with f
0
fixed) model is
compared to the experimental data. (Note that the
FP/SSP (with f
0
free) is in most cases indistinguish-
able from the FP/SSP (with f
0
fixed).) It can be
seen in the Figs. 4/6 that a good fit was obtained
from the FP/SSP model. The quality of the fittings
is better illustrated in Table 4, where the standard
deviation of each model to the experimental data is
presented. It can be seen in Table 4 that the
standard deviation of the models to the experi-
mental data ranged, in average, from 0.8 to 2.9%.
The FP/SSP models presented consistently lower
deviations than the SSP and SP models. The
inclusion of the fluid phase mass balance (and in
the case of the FP/SSP with f
0
free, the use of one
more adjustable) had a clear advantage in the
accuracy of the fitting.
It was also noted, that the inclusion of the axial
dispersion coefficient in the FP/SSP model had
little effect on both best-fit parameters and quality Fig. 3. Experimental vs. models: (run 18).
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 256
of the fitting. As a consequence, a first order
differential mass balance may be adequate when
describing the fluid phase mass balance in Eq. (4).
If a successful fit to experimental data is
important when testing the accuracy of a theore-
tical model, the ability to predict its adjustable
parameters is of utmost importance for its valida-
tion and use for simulation purposes. In all models
presented the matrix diffusivity, describing the
intraparticle transport, is the main (or only)
adjustable parameter and needs to be successfully
correlated. It should be noted that a constant ratio
between matrix diffusivity (D
m
) and oil diffusivity
in carbon dioxide (D
12
) would be expected, if the
extraction rate was controlled by diffusion of the
oils within the stagnant fluid phase within the
particle porous network and, in addition, the
porous network remained unchanged during ex-
traction. In Fig. 7, the ratio between the best-fit
values of D
m
and the binary diffusivity of essential
oils in compressed carbon dioxide (D
12
) is pre-
sented. From Fig. 7, it can be seen that the ratio
D
m
/D
12
varies considerable in all models tested,
though a better correlation is found for the FP/
Fig. 4. Experimental vs. FP/SSP model: effect of pressure and temperature on the essential oils extraction curves (runs 1/12).
Fig. 5. Experimental vs. FP/SSP model: effect of ow rate on the essential oils extraction curves (runs 13/20).
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 257
SSP models. This is strong evidence that diffusion
was not the only phenomena responsible for the
intraparticle transport of the oils. The decrease of
the intraparticle resistances during the extraction
process may also have played an important role in
the extraction process. In addition, the intraparti-
cle transport may also be affected by the rate at
which the solvent access the oils and by the
kinetics of desorption of essential oils from the
herbaceous matrices in presence of compressed
CO
2
.
Despite the good fitting to experimental data,
the difficulty to predict the intraparticle transport
of essential oils limits the ability of the models to
predict extraction rates.
Fig. 6. Experimental vs. FP/SSP model: effect of particle size
on the essential oils extraction curves (runs 21/24).
Fig. 7. Relation between best t values of matrix diffusivity (D
m
) and binary diffusivity of essential oils in CO
2
(D
12
).
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 258
7. Conclusions
The models proposed for the extraction of
essential oils were found able to fit closely the
experimental data. However, the main parameter
of these models, namely the diffusivity of the
essential oils within the matrices, is not easily
predictable, which may limit the applicability of
these models. A detailed study on the specific
intraparticle mass-transfer mechanism(s) would
certainly help to the development of a more
versatile model.
Acknowledgements
We express our gratitude to PRAXIS XXI
Program and the European Commission-Directo-
rate-General for Agriculture (Project No AIR-CT-
0818) for their nancial support.
Appendix A: Numerical solution of the FP/SSP
model
Eq. (4) is a partial differential equation and
together with Eqs. (8) and (9) raise a problem of
initial value type. Initial value problems, unlike
boundary value problems, contain at least one
independent variable with an open range of
variation (in this case time). Jensen and Jeffreys
presented two suitable methods for initial value
problems: the step-by-step method and the itera-
tion method [18]. Despite the iteration process
being preferable (all derivatives are replaced by
finite-differences correct to second order), the
simplest step-by-step solution was adopted.
A.1. Step-by-step solution
In order to obtain a stable solution with this
method, the time derivative in Eq. (4) was replaced
by its finite-difference corrected to first order and
the spatial derivatives by their correspondent finite
differences corrected to second order. (The use of a
time finite-difference corrected to second order
leads to an oscillating solution.) Therefore,
C
m;n'1
(C
m;n
Dt
0a
C
m'1;n
(2C
m;n
'C
m(1;n
(Dz)
2
'b

C
m'1;n
(C
m(1;n
2Dz
'g(nDt) (a1)
where suffixes m and n count the z and t
increments. Rearranging Eq. (a1) yields,
C
m;n'1
0Dt(M
1
'M
2
)C
m'1;n
'(1(2M
1
Dt)C
m;n
'Dt(M
1
(M
2
)C
m(1;n
'Dtg(nDt) (a2)
where
M
1
0
a
(Dz)
2
0
D
ax
o(Dz)
2
(a3)
and
M
2
0
b
2Dz
0
(u
i
2Dz
(a4)
For a stable calculation, M
1
and M
2
must be
chosen so that no negative coefficients arise in the
finite-difference equation. This stability criterion is
given below.
Dt(M
1
'M
2
)0
1(2M
1
Dt0
Dt(M
1
(M
2
)0
U
DzB
j
2a
b
j
0
2D
ax
ou
i
DtB
Dz
2
2a
0
oDz
2
2D
ax
universal-condition
_

_
_

_
M
1
0; M
2
B0 (a5)
After choosing suitable values for Dz and Dt ,
the following equations were used to solve the
model.
C
m;n'1
0Dt(M
1
'M
2
)C
m'1;n
'(1(2M
1
Dt)C
m;n
'Dt(M
1
(M
2
)C
m(1;n
'Dtg[(n'1)Dt] (a6)
C
0;n
00 (a7)
C
m;0
0C
0
(a8)
F. Gaspar et al. / J. of Supercritical Fluids 25 (2003) 247/260 259
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