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Extraction and Modeling of Lavender Flower Essential Oil Using Supercritical

Carbon Dioxide

Article  in  Industrial & Engineering Chemistry Research · January 2000

DOI: 10.1021/ie9904798

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 Ind. Eng. Chem. Res. 2000, 39, 473-477 473

Extraction and Modeling of Lavender Flower Essential Oil Using

Supercritical Carbon Dioxide
1 n, Nalan A. Akgu
Mesut Akgu 1 n, and Salih Dinçer*
Chemical Engineering Department, Yildiz Technical University, Sisli, 80270 Istanbul, Turkey

Essential oil was extracted from lavender flowers (Lavandula Stoechas subspecies Cariensis
Boiss) in a semicontinuous system by supercritical CO2. Experiments were carried out in the
ranges of 8-14 MPa pressures, 308-323 K temperatures, and 1.092-2.184 × 10-3 kg/min carbon
dioxide flow rates. The extraction process was modeled by a quasi-steady-state model as a function
of extraction time, flow rate, pressure, and temperature. The model contains only one adjustable
parameter, the intraparticle diffusion coefficient (effective diffusivity) De. The model using the
best fit of De correlates the data satisfactorily.

Introduction spike species contains over 70% camphor and fenchone,

Supercritical fluid extraction (SCE) has been demon-
strated as an alternative to conventional separation
processes in the production of essential oils for a long
time. It has been widely accepted by many investigators
that SCE provides a rapid and quantitative method for
extracting essential oils from aromatic plants that
compares favorably with steam distillation.1-5 Analysis
of the SCE products and assessment of their composition
showed that the extracts had higher yield, finer odor,
and longer shelf-life.1-3 Moreover, because supercritical
fluids have liquidlike density and gaslike viscosity and
diffusivity, they have high mass-transfer characteristics
and their effectiveness can be controlled by small
changes in temperature and pressure.6
The majority of experiments in the literature on
supercritical extraction of natural products are compli-
cated by several parameters such as the properties of
plants (e.g., particle size, moisture content, polarity of
the essential oil components, and molecular weight) and
operating conditions (e.g., pressure, temperature, ex-
traction time, raw material/solvent ratio, entrainer,
etc.). However, some or all of these parameters can
affect the extraction rate and the composition of the
extracts. This influence can be explained by different
diffusion times due to structural differences of various
kinds of aromatic plants. Goto et al.7 extracted essential
oils from mint, ginger, and tomato seeds, and they noted
that the extraction behavior of natural materials cannot
be represented by a single mechanism and illustrated
that the extraction behavior for seeds, flowers, and
leaves must be explained by different mechanisms.
Reverchon and Poletto,8 Catchpole et al.,9 and Roy et
al.10 pointed out that the intraparticle diffusion is
dominant in the extraction process when extracting
sage, celery, and ginger, which have woody structure.
Lavender flowers are aromatic plants with three main
species (true lavender, spike lavender, and lavandin)
and numerous subspecies. Although the essential oils
of the true lavender, lavandin, and their subspecies
contain up to 65% linalool and linalyl acetate, which
are used widely in perfumery,11 the essential oil of the
* To whom correspondence should be addressed. Telephone:
+90(212) 224 49 68. Fax: +90(212) 224 49 68. E-mail: dincer@
yildiz.edu.tr.
10.1021/ie9904798 CCC: $19.00 © 2000 American Chemical Society
Published on Web 01/14/2000
which are used as pharmaceutical products.12,13 Ada-
soglu et al.14 optimized the SCE of spike lavender
(Lavandula Stoechas subspecies Cariensis Boiss) by
response surface methodology. True lavender essential
oil was extracted using supercritical CO2 as the solvent,
and the chromatographic analysis of the oil extracted
was studied by Reverchon et al.11
In this work, the extraction of essential oil from
lavender flowers by supercritical CO2 in a semicontinu-
ous system was studied. The extraction rate of essential
oil was investigated as a function of temperature,
pressure, and CO2 flow rate. The extraction process was
modeled for various experimental conditions by applying
mass balance in the packed-bed extractor.15
Mathematical Model
Extraction of a solute from the solid matrix occurs in
three stages of diffusion of fluid to particle pores,
dissolution of extractable matter in the fluid, and
transfer to the bulk fluid. Therefore, several models
have been developed based on empirical kinetic models
or differential mass balances for the fixed bed. Poletto
and Reverchon16 simulated the extraction of seeds and
flowers by differential mass balance, equilibrium, and
lumped parameter models. Goto et al.17 adapted the
shrinking-core model, which has been used in solid-
fluid reactions, adsorption, and ion exchange, to SCE
of natural materials. Roy et al.10 modeled the SCE of
ginger oil successfully by the shrinking-core model.
In this work, the shrinking-core model was applied
to the extraction of lavender flowers. Actually, this
model is called as quasi-steady-state model because of
the assumption of no axial dispersion in the fixed bed.17
Moreover, the following assumptions are also made
during model solution: (1) the extraction is an irrevers-
ible desorption process, (2) the matrix is a porous
material where lavender oil is uniformly distributed
throughout the particle, (3) the system is isothermal,
(4) the physical properties of the fluid are constant
during the extraction. Based on these assumptions, the
material balance in the extractor is described as17
∂C ∂C 1 -  3kf
+ν )- [C - Ci(R)] (1)
∂t ∂z  R
474 Ind. Eng. Chem. Res., Vol. 39, No. 2, 2000

Average solid-phase oil concentration (qj ) variation with

time is equated to the rate of mass transfer of the solute
within the external film surrounding the particle:

j 3kf
∂q
) [C - Ci(R)] (2)
∂t R
The diffusion to the outer region in the particle is Figure 1. Experimental setup: (1) CO2 cylinder; (2) syringe
expressed by pump; (3) extractor; (4) pressure gauge; (5) expansion valve; (6)

( )
collection bottle; (7) wet-test meter; (8) heating bath.
De ∂ 2 ∂Ci
r )0 (3) Experimental Setup and Procedure. Experiments
r2 ∂r ∂r
were performed in a semicontinuous extraction system
schematically shown in Figure 1. The experimental
The average solid-phase oil concentration is described
apparatus consists of a tubular extractor (50 cm length
as a function of the particle diameter:
× 1 cm i.d.; internal volume 38 mL), which is placed

()
rc 3 into a constant-temperature bath, and a syringe pump
j
q
) (4) (ISCO, model 260 D). Carbon dioxide was compressed
q0 R into the extractor by the syringe pump, after the
extractor temperature reached the desired value. The
The initial and boundary conditions are given as follows: flow rates of CO2 were maintained at 1.2, 1.7, and 2.5
mL/min at pump conditions. These flow rates were
rc ) R at t ) 0 (5) converted to the interstitial velocities at the column
conditions by using the appropriate densities and the
C)0 at t ) 0 (6) bed dimensions. The temperature was controlled by an
C)0 at z ) 0 (7) immersion circulator (Lauda GMBH & Co., model
Lauda M/2; controlled to (0.1 °C accuracy). CO2-
∂C/∂z ) 0 at z ) L (8) containing essential oil was passed through the collec-
Ci ) Csat at r ) rc (9) tion bottle containing methanol placed into the ice bath.

( )
∂Ci
De ) kf[C - Ci(R)] (10)
∂r r)R
The equations and the initial and boundary conditions
can be expressed in terms of the following dimensionless
variables:
X ) C/Csat; Xi ) Ci/Csat; ξ ) r/R; Z ) z/L;
a ) νR2/DeL; θ ) (De/R2)t; yj ) q
j /q0;
b ) Csat/q0; Bi ) kfR/De
The numerical integration of eqs 1-4, written in terms
of dimensionless variables, was accomplished by using
MATHCAD (MathSoft, Inc., MathcadPlus6.0).
The yield (cumulative amount of extract up to time
θ) is given as
yield )
ab
1-
∫0θX dθ (11)
Experimental Section
Material. The spike lavender flower (L. Stoechas
subspecies C. Boiss), growing wild in nature and well-
known as Gargan in the Aydin-Çine region in Turkey,
was used in this work. These flowers were harvested
in May, dried in shade, frozen in liquid nitrogen, and
then crushed manually to the desired size. The particle
size was about 1.2 mm. The initial oil content was 1.51
wt %. A total of 10 g of the sample was used in each
experimental run.
The essential oil components were identified by GC
as β-pinene, R-pinene, camphene, DL-limonene, fen-
chone, cis- and trans-linalool oxide, camphor, linalool,
linalyl acetate, R-fenchyl acetate, caryophyllene oxide,
R-cadinol, tert-sobrelol, etc. The major components were
camphor (43.74%) and fenchone (33.14%).
The amount of essential oil trapped in the methanol was
determined by GC for every 30 min.
Analytical Procedure. The Unicam model 610 GC
was used for the analysis of essential oil extracted. The
separation was achieved by using a capillary column
(EC-WAX Carbowax, 30 m × 0.32 mm i.d., film thick-
ness 0.25 µm). Argon was used as the carrier gas. GC
was temperature-programmed as follows: from 60 °C,
1 °C/min to 63 °C, and then 20 °C/min to 210 °C. The
concentration of essential oil components was computed
from GC peak areas using calibration curves.
Results and Discussion
Experimental Results. Figure 2 shows the effect of
CO2 flow rate, where yield is plotted versus extraction
time and the amount of CO2 consumed in parts a and
b, respectively. It is seen that the extraction rate is not
affected significantly by the CO2 flow rate. The extrac-
tion rate increases linearly with time in the early stages
of extraction. This kind of linearity indicates that the
solute concentration in the fluid at the outlet of the
extractor is constant, and hence in the first part of the
extraction, the fluid leaving the system appears to be
at equilibrium conditions. A similar explanation was
given by Reverchon and Poletto,8 Goto et al.,7 and Roy
et al.,18 when extracting various flowers, peppermint,
and tomato seeds, respectively. However, the saturation
solubility values measured by assuming the essential
oil, containing over 75 wt % fenchone and camphor,
consists of fenchone and camphor only were much
higher than the solubilities calculated from the slopes
of curves given in Figures 2b, 3, and 4, implying that
the extraction process is not controlled by solubility but
by intraparticle diffusivity.
The effect of temperature on the extraction yield at
10 MPa is shown in Figure 3. The extraction rate
increases because of the increase in the solute solubility
where the effect of the vapor pressure increase overcame

Figure 2. Effect of CO2 flow rate on the extraction yield of
lavender essential oil (a) versus extraction time at 323 K and 10
MPa and (b) versus amount of CO2 consumed at 323 K and 10
MPa.
Figure 3. Effect of temperature on the extraction yield of lavender
essential oil at 1.456 × 10-3 kg/min of CO2 flow rate and 10 MPa
versus amount of CO2 consumed.
the effect of the solvent density decrease. Roy et al.10
also pointed out that the extraction rate increased with
increasing temperature because of increasing solute
vapor pressure in their studies on ginger oil.
Figure 4 shows the effect of pressure on the extraction
yield at 323 K. Because the essential oils have lower
solubility in CO2 below the solute-solvent mixture
critical pressure which is about 9.6 MPa at 323 K,19 the
extraction rate at 8 MPa was lower than both of those
at 12 and 14 MPa. At 12 and 14 MPa, however, the
extraction rates were close to each other because of the
miscibility of essential oil with the supercritical CO2. A
similar explanation was given by Roy et al.,10 and they
emphasized that solubility is controlled by a balance
between solvent density and solute vapor pressure
changes.
Modeling Results. The physical properties of both
the solvent and solute at the experimental conditions
Ind. Eng. Chem. Res., Vol. 39, No. 2, 2000 475
Figure 4. Effect of pressure on the extraction yield of lavender
essential oil at 1.456 × 10-3 kg/min of CO2 flow rate and 323 K
versus amount of CO2 consumed.
are shown in Table 1. The density of CO2 was extrapo-
lated from IUPAC20 tables. The viscosity of CO2 was
calculated by the residual viscosity correlation of Jossi,
Stiel, and Thodos.21 The binary diffusivity D12 of the
lavender essential oil-CO2 system at the experimental
conditions was estimated by the method of Akgerman
et al.22 They measured the diffusion coefficients of
naphthalene, phenanthrene, and hexachlorobenzene in
supercritical CO2 using the Taylor dispersion technique
and correlated their data. The same correlation was
used here for the lavender flower essential oil compo-
nents in supercritical CO2 which are organic and non-
polar in nature. The external mass-transfer coefficient,
kf, was estimated from the Lee-Holder correlation.23
Lee and Holder23 measured the mass-transfer coefficient
of naphthalene and toluene in a packed-bed column
under supercritical conditions of CO2 by a chromato-
graphic method and developed a generalized mass-
transfer correlation, which considers both the effects of
natural and forced convection. The correlation is valid
for 0.3 < Re < 135, which is in the range of our
application. The bed void fraction, , was calculated as
about 0.9 by compressing 10 g of lavender flower into a
vise. The density of the solid matrix was 688 kg/m3. The
initial average solid matrix essential oil concentration,
j 0, was calculated as about 10.42 kg/m3. Csat is deter-
q
mined as a total concentration of fenchone and camphor
because the lavender essential oil in this study contains
over 75 wt % fenchone and camphor. It is 0.243 kg/m3
at 12-14 MPa and 323 K and 0.0514 kg/m3 at 8 MPa
and 323 K.19
The intraparticle diffusivity (effective diffusivity), De,
is found by fitting model results to experimental results,
and it is different for different kinds of plant material.
For example, De is 2.5 × 10-10 m2/s for ginger oil10 and
5.1 × 10-12, 3.1 × 10-12, and 1.4 × 10-12 m2/s for
coriander, sage, and celery, respectively.9 Reverchon et
al.24 explained that these differences could be related
to the different mass-transfer resistances because of
different types of cell structure and mechanisms of
solute extraction. Roy et al.10 pointed out that this could
also be related to the different diffusion resistances due
to the different solute nature such as molecular size,
hydrophilic property, etc. In this work, the best fit was
obtained as De ) 1.2 × 10-11 m2/s for the lavender flower
used.
The solid lines in Figures 2-4 show the quasi-steady-
state model results. The model using the best fit of De
correlates the experimental data satisfactorily. Although
the initial stages of extraction show a linear relation-
476 Ind. Eng. Chem. Res., Vol. 39, No. 2, 2000

Table 1. Physical Parameters of SC-CO2 at Various Experimental Conditions

pressure temperature Q × 103 u × 104 ν × 104 F × 10-2 D12 × 108 µ × 104 kf × 104
(MPa) (K) (kg/min) (m/s) (m/s) (kg/m3) Re (m2/s) (kg‚m/s) (m/s)
80 323 1.456 12.6 14 2.22 1.52 3.084 2.210 20
100 308 1.456 4.16 4.62 7.10 0.61 1.407 5.792 6.81
313 1.456 4.94 5.50 6.15 0.75 1.594 4.848 8.44
323 1.456 7.4 8.22 4.08 1.13 2.167 3.208 10
323 1.092 5.24 5.82 4.08 0.80 2.167 3.210 13.1
323 2.184 10.9 12.1 4.08 1.66 2.167 3.210 13.5
120 323 1.456 5.8 6.44 5.25 0.89 1.824 4.095 10
140 323 1.456 4.7 5.22 6.42 0.70 1.565 5.160 8.03

ship, the slopes of the curves indicate that the extraction
is not controlled by solubility but by intraparticle
diffusivity. Roy et al.10 state that solutes in the outer
parts of flower particles are extracted much faster than
the solutes in the inner parts of flower particles at the
beginning of extraction. This is attributed to mass-
transfer/diffusion limitations. As the extraction time
increases, the diffusion of solutes from inner parts to
the bulk phase are more difficult because the solid-phase
oil concentration decreases; therefore, the extraction
rate also decreases.
Conclusions
The essential oil of the lavender flower used was
extracted using supercritical carbon dioxide to deter-
mine the effects of solvent flow rate, temperature, and
pressure on the extraction rate. The experimental
results show that the extraction rate is not affected
significantly by the CO2 flow rate. Although the extrac-
tion rate increases linearly with time in the early stages
of extraction, the extraction process is not limited by
the solubility of solute in the supercritical CO2. Thus,
intraparticle mass-transfer/diffusion limitations are
dominant. The extraction rate increases with increasing
temperature because of increasing vapor pressure of the
components. The extraction rate increases with increas-
ing pressure because of the solubility increase of es-
sential oil components. Moreover, the extraction process
was modeled using the quasi-steady-state model with
one adjustable parameter, the intraparticle diffusion
coefficient. The model using the best fit of De correlates
the data satisfactorily.
Nomenclature
a: dimensionless interstitial velocity
b: dimensionless parameter defined as Csat/qo
Bi: biot number
C: bulk fluid phase concentration, kg/m3
Ci: concentration in the particle pores, kg/m3
Csat: saturation concentration of solute in the fluid phase,
kg/m3
D12: binary diffusion coefficient, m2/s
De: intraparticle diffusion coefficient (effective diffusivity),
m2/s
kf: mass-transfer coefficient, m/s
L: extractor length, m
Q: flow rate, kg/min
j : average solid-phase oil concentration, kg/m3
q (12) Vallejo, M. C. G.; Vallejo, I. G.; Negueruela, A. V. Essential
qo: initial solid-phase oil concentration, kg/m3
R: particle radius, m
Re: Reynolds number
r: particle radius variable
rc: critical particle diameter variable
t: time
u: superficial velocity, m/s
X: dimensionless concentration in the bulk fluid phase
Xi: dimensionless concentration in pores
yj: dimensionless average solid-phase concentration
Z: dimensionless bed height variable
z: bed height variable
Greek Letters
: bed void fraction
θ: dimensionless time
µ: viscosity, kg‚m/s
ν: interstitial fluid velocity, m/s
ξ: dimensionless radius
F: density, kg/m3
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Received for review July 1, 1999
Revised manuscript received November 9, 1999
Accepted November 11, 1999
IE9904798