J.

of Supercritical Fluids 39 (2007) 338–346

Supercritical carbon dioxide extraction of essential oils from plants with

secretory ducts: Mathematical modelling on the micro-scale
Irena Zizovic ∗ , Marko Stamenić, Aleksandar Orlović, Dejan Skala
University of Belgrade, Faculty of Technology and Metallurgy, Karnegijeva 4, P.O. Box 3503, 11120 Belgrade, Serbia and Montenegro
Received 20 September 2005; received in revised form 20 January 2006; accepted 16 March 2006

Abstract
In this study, the supercritical carbon dioxide extraction of essential oils from plants which contain secretory ducts as essential oil reservoirs
was investigated and modelled. Supercritical carbon dioxide extraction of essential oils from Asteraceae family species, marigold and chamomile,
indicated that particle size had no significant influence on the extraction rate in two outermost cases: fine milled plant material and plant material
cut to particle length of 5 mm. This confirmed previously reported phenomenon that in some cases particle size had no influence on the rate
of supercritical extraction process. In order to explain this behavior, the mathematical model which took into consideration the phenomena
occurring on the secretory duct scale, was developed and applied to simulate experimental data of marigold and chamomile supercritical carbon
dioxide extraction. Proposed model was also applied to the literature experimental data of fennel fruit supercritical fluid extraction where the
same phenomenon had been observed. To obtain information regarding secretory structure, scanning electron microscopy investigation of the plant
material was performed. Very good agreement of the model results and experimental data in the case of different plant species, extraction conditions
and particle sizes, confirmed the basic hypothesis of the model.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Supercritical fluid; Mathematical modelling; Extraction; Essential oil; Natural products

1. Introduction Secretory ducts are also present in Hypericaceae, Pinaceae and

Essential oils with or without resins and gums are found in
special secretory structures located within plant tissues or on
the surface of the plant (trichomes). The type of secretory struc-
ture is specific to the plant family or species [1]. Process of
the essential oil isolation, either by extraction or distillation,
should be dependent on the oil storage and the type of secre-
tory structure. Secretory structures within plant tissue can be
secretory cells, secretory cavities or secretory ducts. Secretory
ducts are elongated cavities and they often branch to create net-
work extending from the roots through the stem to the leaves,
flowers and fruits [1]. They can be found in all species of the fam-
ily Apiaceae (Umbelliferae) including angelica, ajowan, celery,
parsley, caraway, cumin, dill, coriander and anise as well as in
the largest family of plants Asteraceae (Compositae) compris-
ing approximately 23,000 known species including chamomile,
marigold, yarrow, tarragon, wormwood, arnica and mugwort.
∗ Corresponding author. Tel.: +381 11 3303 795; fax: +381 11 3370 387.
E-mail address: zizovic@tmf.bg.ac.yu (I. Zizovic).
Coniferae families. In fruits they are called vittae (fennel, car-
away, parsely, cumin, celery). Recently, techniques involving
nuclear magnetic resonance (NMR) and magnetic resonance
imaging (MRI) have been used increasingly to study plant phys-
iology and metabolism including localization of triglyceride
and essential oil accumulation in Apiaceae family fruits [2,3].
Results of these investigations showed that the fruit was shizo-
carp with two single-seeded mericarps (units of structure of the
female portion of flower). The mericarps had six oil canals (vit-
tae), which were associated with essential oil accumulation in
Apiaceae. Reserve oil (triglycerides) was located in the seeds.
Therefore, it was observed that the essential oil and triglycerides
were located in separate, well-defined compartments, mericarp
channels and seed endosperm. This is the fact of interest from
the point of both, essential and fatty oil extraction.
Supercritical fluid extraction (SFE) of essential oils with
carbon dioxide has certain advantages over steam distillation.
Steam distillation can lead to thermal degradation and partial
hydrolysis of some essential oil compounds. SFE with carbon
dioxide can be performed at temperatures around 313 K, thereby
preserving original oil composition and properties. Along with

0896-8446/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2006.03.009
 I. Zizovic et al. / J. of Supercritical Fluids 39 (2007) 338–346
SFE investigations, mathematical models of these processes
were developed. Mathematical model widely used in the lit-
erature, was introduced by Sovová [4]. Basic assumption of the
model is that part of the cells (the hypothetical oil containing
units) was opened by milling. The easily accessible solute from
the cells opened by milling is extracted first, and the slower
extraction of the solute protected by the cell walls follows.
Advantages of this model are that it can be applied on any type of
herbaceous material, and on the SFE of both, essential and fatty
oils. Significant contribution to the modelling of essential oil
SFE was given by Reverchon et al. [5–8] who introduced models
based on the differential mass balance for the extractor vessel and
heat transfer analogy. Essential oil SFE processes were modelled
on the macro-scale by many authors, and experimental results
were described well by the proposed models [4–14]. Recently,
Sovová [14] has introduced new model for SFE of natural prod-
ucts, also based on the concept of broken and intact cells with two
extraction periods, the first one governed by phase equilibrium
and the second one governed by internal diffusion in particles.
A detailed description of the first period was given where dif-
ferent types of phase equilibrium and solvent flow patterns were
taken into account. The number of model parameters was from
four to seven depending on the process complexity. Zizovic et al.
[15–17] introduced micro-scale mathematical models of essen-
tial oil SFE process based on the hypothesis that essential oil
extraction process should be dependent on the type of secretory
structure. The aim of these studies was to verify the phenomena
on the micro-scale and to optimize the SFE process according
to the behavior of specific secretory structure during the extrac-
tion. In the case of Lamiaceae family species, it was found that
peltate glands (essential oil reservoirs) underwent break-up due
to the influence of supercritical carbon dioxide (SC CO2 ) on the
gland membrane. The model was successful in simulating liter-
ature experimental data and it enabled SFE process optimization
of Lamiaceae family species (mint, basil, rosemary, marjoram,
sage, oregano, lavender, thyme) [16]. Mathematical modelling
on the micro-scale of the essential oil SFE processes should
therefore take into account the type of secretory structure (oil
reservoir), the phenomena occurring on the micro-scale and the
impact of these phenomena on the macro-scale process.
In this study, the previously reported phenomenon [18,19]
that in certain cases particle size had no influence on the SFE
process is investigated on the micro-scale. Coelho et al. [18]
studied SFE of essential oil from fennel fruits (Apiaceae) and
reported that for different particle sizes, no significant change in
evolution of extraction yield was observed, in fact the extraction
yield curves overlapped for different particle sizes as a func-
tion of the extraction time at a fixed flow rate. Bocevska and
Sovová [19] studied the SFE of essential oil from yarrow flower
(Asteraceae) and reported that the pretreatment of yarrow flow-
ers (fine milled or cut with scissors) did not affect the extraction
rate. These results can be explained by the consideration of the
phenomena taking place on the secretory structure scale, which
is in both cases a secretory duct. The influence of particle size on
the SFE yield was observed only during the SFE of seed oils from
parsley fruits (Apiaceae) [20]. The authors reported the effect
of particle size on the evolution of extraction yield at 10 MPa,
339
318 K and at SC CO2 flow rate of 1.1 kg/h. For the particle size
of 495 ␮m reported yield at the end of extraction process was
5.5 wt.%, and for the particle size of 293 ␮m reported yield at the
end of the extraction process was 8 wt.%. However, the essential
oil content determined by hydrodistillation was 4.5 wt.%. This
indicates that, especially in the case of SFE from very small
particles of 293 ␮m, some compounds from the damaged seed
endosperm were probably extracted as well.
In order to investigate SFE from secretory ducts and the influ-
ence of particle size on the evolution of extraction yield, two
herbs from Asteraceae family, marigold and chamomile, have
been chosen. The proposed mathematical model was applied
to simulate SFE processes from marigold and chamomile. The
model was also applied to the previously published data [18] in
order to simulate SFE from fennel fruits.
2. Materials and methods
2.1. Materials and equipment
Dried flowers of marigold (Calendula officinalis) and
chamomile (Matricaria recutita) grown in central Serbia were
used for SFE experimental studies. Conventional method of
marigold essential oil production is the extraction with organic
solvents. Therefore, as a characterization of plant material
extraction of the dry marigold flowers with n-hexane in Soxlet
apparatus was performed and 6.11 wt.% of extract was obtained.
Hydrodistillation of marigold flowers yielded 0.11 wt.% of
volatile oil while hydrodistillation of chamomile flowers yielded
0.7 wt.% of deep blue oil. Moisture contents were determined on
a Metrohm 737 Karl Fischer Coulometer equipped with 832 KF
Thermo trap. Samples of plant material were treated at 378 K
for 1 h. Determined moisture values were 10.62 and 10.25 wt.%
for marigold and chamomile flowers, respectively. For the pur-
pose of secretory structure analysis and mathematical modelling,
dried fruits of fennel (Foenicum vulgare) grown in northern Ser-
bia were used.
Extractions with SC CO2 were carried out in an Autoclave
Engineers Screening System shown in Fig. 1. The Supercrit-
ical Extraction Screening System is designed for small batch
research runs using CO2 as the supercritical medium with
Fig. 1. Schematic presentation of the autoclave engineers screening system—T:
CO2 storage tank; C: cryostat; LP: high pressure liquid pump; E: extractor vessel;
S: separator vessel.
340 I. Zizovic et al. / J. of Supercritical Fluids 39 (2007) 338–346
maximum allowable working pressure of 41.3 MPa at 511 K.
Liquid CO2 is supplied from CO2 cylinder by a siphon tube.
The liquid CO2 is cooled in cryostat between the cylinder out-
let and the pump to prevent vaporization. The pump is liquid
metering pump with a maximum output pressure of 41.3 MPa
and an adjustable flow rate from 38 to 380 ml/h. The CO2 is
pumped into the system until the required pressure is obtained.
Back pressure regulators are used to set the system pressure (in
extractor and separator). The extractor vessel (150 ml) is filled
with the plant material from which a substance is to be extracted.
Heaters are supplied on the extractor vessel for temperature ele-
vation. The SC CO2 flows through the extractor and enters the
separator vessel (500 ml). Samples of the extracted substance
can be taken by opening the ball valve located at the bottom
of the vessel. A flowmeter is provided to indicate the flow rate
of CO2 being passed through the system and the flow can be
adjusted by micrometering valve. The CO2 continues to flow
out of the separator through the flowmeter/totalizer and out to
atmosphere.
Plant tissue images were obtained on a scanning electron
microscope (SEM) JSM-T20 (Japan).
2.2. Methods
Flowers of marigold and chamomile were fine milled and
sieved to particle diameter of 0.7 mm or cut to an average particle
length of 5 mm for the determination of the influence of particle
size on the SFE process. In order to suppress co-extraction of
undesired higher molecular-weight compounds, Reverchon [21]
recommends to carry out SFE of essential oils at SC CO2 den-
sities which correspond to temperatures from 313 to 323 K and
pressures from 7.8 to 10 MPa. The influence of SFE conditions
on obtained yield was investigated for marigold and extractions
of milled and cut material were performed at temperatures of
313 and 323 K and pressures of 9 and 10 MPa. In the case of
chamomile, extractions of milled and cut material were carried
out at 313 K and 10 MPa. The amount of total extract was mea-
sured during the extraction. SC CO2 flow rate was 0.3 kg/h in
all the experiments and the mass of marigold and chamomile
samples was 19 and 30 g, respectively.
SEM analysis was performed in order to investigate marigold,
chamomile and fennel fruit secretory ducts. The samples were
mounted onto metal cylinders using collodial silver paste (Dell
Pena, Inc.). The tissue samples were gold coated with alloy
Au–Pd (85:15).
2.3. Mathematical modelling
To simulate SFE from caraway fruits secretory ducts, Zizovic
et al. [17] developed mathematical model without fitting param-
eters. In this study, the proposed model was applied to sim-
ulate SFE from marigold and chamomile flowers as well as
from the fennel fruits [18]. The following assumptions describ-
ing the secretory ducts behavior during SFE process and the
process itself, were used to derive the essential oil extraction
model:
- The system is isothermal and isobaric and the properties of
supercritical CO2 are constant.
- The axial mixing of SC CO2 exists in the extractor and the
flow rate of SC CO2 is constant during extraction process.
- The essential oil is represented by a single pseudo compo-
nent and it is stored in the secretory ducts as essential oil
reservoirs. Pseudo components are ␣-bisabolol, methylhex-
adecanoate and anethole, for chamomile, marigold and fennel,
respectively.
- An average duct diameter is adopted according to SEM images
and the duct length is equal to an average particle diameter.
- The ducts are opened on both sides by grinding pretreat-
ment and SC CO2 dissolves in the oil causing the oil volume
increase, which leads to the essential oil (oil phase contain-
ing dissolved CO2 ) pouring out from the ducts and external
wetting of the particle.
- All particles are spherical and equally wetted and in the case
of 5 mm particles (cut plant material) volume-average particle
diameter was used.
- SC CO2 penetrating and dissolving into the oil phase inside
the duct are instantaneous processes that occurred during pres-
surization of the system prior to the extraction.
- SFE of the oil that embeds the particles takes place first, and
diffusion through the film around the oil phase controls the
extraction process during this period of SFE.
- Subsequent to the extraction of the essential oil embedding
the particles, the SFE of the oil from secretory ducts starts. As
the essential oil contained in the duct is discharged due to the
extraction process, the oil front is moving towards the centre
of the duct and diffusion of the oil through the supercritical
phase inside the duct is present. Diffusion through the film
around the particle is present as well.
- Diffusion through the duct is not obstructed by the duct diam-
eter and it is represented by the molecular diffusion of the
essential oil through SC CO2 .
Material balance for the supercritical phase in the extractor
vessel, for isothermal and isobaric system can be written as:
∂csf ∂2 csf ∂csf
= Dl 2
−u + ST (1)
∂t ∂x ∂x
Where csf is the essential oil concentration in supercritical phase,
t the extraction time, x the axial coordinate along the extractor,
Dl the axial dispersion coefficient, u the superficial supercriti-
cal fluid velocity and ST the is Source and Transfer term which
describes essential oil transfer from specific secretory structure
to supercritical fluid phase. The corresponding initial and bound-
ary conditions are:
t = 0, 0 ≤ x ≤ L, csf = 0 (1a)
t > 0, x = 0, csf = 0 (1b)
∂csf
t > 0, x = L, = 0, (1c)
∂x
where L is the extractor length.
 I. Zizovic et al. / J. of Supercritical Fluids 39 (2007) 338–346 341

According to the basic hypothesis of the model, the following
mathematical equations describing the secretory duct Source and
Transfer term (ST) can be written as:
ST = aw k(c∗ − csf ), for t ≤ tw (2a)
ST = ad k(ce − csf ), for t > tw (2b)
where tw is the time when the oil that embedded the particles is
extracted, c* the equilibrium concentration of the essential oil in
SC CO2 on SC phase–essential oil interface, ce the essential oil
concentration in SC phase at the duct end, aw the specific surface
of wetted particles referred to SC fluid volume and it is dependant
on time, position in the extractor and the quantity of oil that
surrounds the particles, ad the specific surface of open duct ends
available for mass transfer referred to SC fluid volume and k is
the mass transfer coefficient through the SC film surrounding the
particles. Eq. (1) was solved using the finite difference method
in explicit form [22]. For this purpose the extractor was divided
into twenty space increments. Specific surface for SFE from the
ducts was calculated from:
2
2N(dd /2) π
ad = (3)
VE ε
where N is the number of secretory ducts, dd the secretory duct
diameter, ε the void fraction of the bed and VE is the volume of
extractor vessel. Specific surface of wetted particles was calcu-
lated from:
where D is the binary diffusion coefficient of the oil in SC CO2
phase, cd the oil concentration in the SC CO2 phase inside the
duct and z is the axial coordinate of the secretory duct and cd
(z = 0) = ce . Initial condition of Eq. (8) for each space increment
was:
ce = c∗ (9)
for t = tw when duct discharging starts.
2.4. Parameter identification and correlations
Total number of secretory ducts (N) was calculated on the
basis of the essential oil quantity in plant tissue and the average
volume of secretory duct. Volume of the essential oil from secre-
tory duct after saturation with CO2 and the quantity of dispensed
oil was calculated using Peng Robinson Equation of State [23].
Solubility of SC CO2 in the essential oil phase was calculated
from the empirical correlation given by Gaspar et al. [24]:
oil
cCO 2
= k1 P 6 + k2 P 5 + k3 P 4 + k4 P 3 + k5 P 2 + k6 P (10)
where P is pressure and constants k1 –k6 are empirical coeffi-
cients. On the basis of this solubility value the concentration of
the oil phase saturated with SC CO2 (csat ) in the oil film around
the particles can be calculated. Mass transfer coefficient (k) in
the SC film around the particles was estimated using empirical
correlation given by Tan et al. [25]:

3(1 − ε) Sh = 0.38Re0.83 Sc1/3 (11)

aw = (4)
Rw ε where Re, Sc and Sh are Reynolds, Schmidt and Sherwood num-
where Rw is the radius of wetted particle which is a function of bers, respectively, defined as follows:
time, position in the extractor and the quantity of oil that sur-
ρdp u
rounded the particle. All particles are equally wetted and the Re = , (12)
oil film thickness around each particle is the same at the begin- μ
ning of SFE. Decrease of the wetted particle volume due to the μ
Sc = (13)
extraction from the oil film can be defined as: ρD
d(csat Vw ) and
− = 4πR2w k(c∗ − csf ) (5)
dt ShD
where csat is the essential oil concentration in the oil film around k= (14)
dp
particle which is constant and equal to the concentration of the
oil in liquid phase saturated with CO2 and Vw is the wetted where dp is the particle diameter, ρ the density of SC CO2 , μ
particle volume. The volume of the wetted particle is: the viscosity of SC CO2 and D is the binary diffusion coefficient
of essential oil in SC CO2 phase. The viscosity of SC CO2 was
4 3 estimated using empirical correlation [26]. The binary diffusion
Vw = πR (6)
3 w coefficient for essential oil/SC CO2 system in SC film around
According to Eqs. (5) and (6), for each time and space increment the particle was calculated from the equation given by Catchpole
Rw can be obtained from: and King [27]. The axial dispersion coefficient in SC phase was
calculated using correlation given by Tan and Liou [28]:
dRW k ∗
− = (c − csf ) (7) Pe = 1.634Re0.265 Sc−0.919 (15)
dt csat
The essential oil concentration in SC phase at the duct end was where Pe is Peclet number, and
calculated from the equal fluxes on the duct end–SC phase inter- udp
face for each time and space increment: Dl = (16)
Pe
dcd The solubility of essential oil in SC CO2 phase was estimated on
−D = k(ce − csf ) (8)
dz the basis of literature data on solubility of pseudo-components
342 I. Zizovic et al. / J. of Supercritical Fluids 39 (2007) 338–346
in SC CO2 [5,6,29–31]. The void fraction of the bed was esti-
mated on the basis of its dependence on the particle diameter to
extractor tube diameter ratio [32]. For the purpose of mathemat-
ical modelling of SFE from non-spherical particles of cut plant
material the volume-average particle diameter was calculated
[33] and its value was adopted as particle diameter:
 1/3
6V
dp = (17)
π
where V is the mean particle volume.
3. Results and discussion
Experimental data of the SFE from fine milled and cut
marigold flowers at different pressures (9 and 10 MPa) and tem-
peratures (313 and 323 K) are presented in Figs. 2 and 3. Results
of the SFE from fine milled and cut chamomile flowers at 313 K
Fig. 2. Yield of total extract as a function of the specific amount of solvent
mCO2 /msolid (kg CO2 /kg herbaceous material) for SFE from marigold flowers
at 9 MPa and 313 and 323 K.
Fig. 3. Yield of total extract as a function of the specific amount of solvent
mCO2 /msolid (kg CO2 /kg herbaceous material) for SFE from marigold flowers
at 10 MPa and 313 and 323 K.
Fig. 4. Yield of total extract as a function of the specific amount of solvent
mCO2 /msolid (kg CO2 /kg herbaceous material) for SFE from chamomile flowers
at 10 MPa and 313 K.
and 10 MPa are shown in Fig. 4. As can be seen, no signifi-
cant change in the evolution of extraction yield can be observed
besides the reasonable scatter of experimental data. Particle size
had no influence on the extraction rate in two outermost cases:
fine milled material and cut material to particle length of 5 mm.
Results of SFE of marigold flowers indicate that the same phe-
nomenon was observed at different SFE conditions (313–323 K
and 9–10 MPa).
SEM images of marigold and chamomile flowers and fen-
nel fruits are shown in Fig. 5. On the basis of SEM images
of marigold and chamomile samples and on the basis of an
investigation of secretory structures in Asteraceae performed
by Lotocka and Geszprych [34], the values of secretory duct
diameters were estimated as follows: 2.3 ␮m for marigold and
2 ␮m for chamomile. According to the published micrographs
[34] secretory duct diameter in sepals, petals and leaves varied
from 1.3 to 12 ␮m. Secretory ducts as essential oil reservoirs
in Apiaceae fruits are clearly visible and their position in fruit
is well known [2,3]. SEM images of fennel fruits are shown
in Fig. 5c and d. where fennel fruit secretory ducts (vittae) are
clearly visible. In Fig. 5c, the cross-section of fennel fruit with
six oil channels is shown. In Fig. 5d, the longitudinal section of
secretory duct is visible. On the basis of statistical analysis of 20
scanned secretory ducts, an average value of 70 ␮m for the duct
diameter was determined. These estimated values of secretory
duct diameters are large enough to enable unobstructed essen-
tial oil extraction from the oil channels (effects of tortuosity and
diameter constriction can be neglected) regardless of the duct
length, which is by the model equal to the particle size. This is,
also, in accordance with the basic hypothesis of the model by
which diffusion through the duct is not significant resistance to
the mass transfer and is represented by the molecular diffusivity
through the SC CO2 .
Calculated parameters of the model are presented in Table 1
and the results of mathematical modelling and simulation
 I. Zizovic et al. / J. of Supercritical Fluids 39 (2007) 338–346 343

Fig. 5. SEM images of plant tissue: (a) cross-section of marigold petal, bar = 70 ␮m; (b) cross-section of chamomile petal, bar = 70 ␮m; (c) cross-section of fennel
fruit, six oil channels are visible, bar = 700 ␮m; (d) longitudinal section of fennel fruit, one oil channel is visible, bar = 700 ␮m.

are shown in Figs. 6–9. As can be seen, the presented model
simulates experimental data of SFE from secretory ducts with
high accuracy. Change of the extraction mechanism from the
first period, in which the oil is being extracted from the film
embedding the particles, to the second one, in which the oil
is being extracted form the ducts, is clearly visible on the
simulated curves (curve bending in Figs. 6–9). This mechanism
transition is relatively fast and therefore the resulting simulation
curve is not smooth. The normalized oil concentration in SC
CO2 phase (NOC) calculated by the model, defined as the
essential oil concentration in SC CO2 divided by the solubility
of the oil in SC CO2 at SFE conditions, along the dimensionless
extractor length during the SFE of grinded chamomile is shown
in Fig. 10. As can be seen from Fig. 10, the first extraction
period (t < tw ) is characterized by relatively fast mass transfer
resulting in significant increase of the oil concentration in SC
CO2 over narrow extractor axial distance. This step increase of
csf is “moving” along the extractor length with extraction time,
as the oil embedding the particles is being extracted (NOC
profiles for 1, 5 and 8 min). As the film surrounding the particles
is being extracted from consecutive cross-sections of the vessel,
the second mechanism of the extraction from externally dried

Table 1
Parameters of the SFE processes and calculated parameters of the model

Herb P (MPa) T (K) qCO2 (kg/h) dp (mm) u × 104 (m/s) k × 105 (m/s) Dl × 107 (m2 /s) c* × 103 (kmol/m3 ) ε

Marigold 9 313 0.3 0.70 1.73 3.35 2.40 5.7 0.47

Marigold 9 323 0.3 0.70 1.73 2.34 2.34 3.9 0.47
Marigold 10 313 0.3 0.70 1.73 2.58 2.91 12.0 0.47
Marigold 10 323 0.3 0.70 1.73 3.63 2.26 6.0 0.47
Chamomile 10 313 0.3 0.70 1.73 2.94 2.91 15.0 0.47
Chamomilea 10 313 0.3 1.68b 1.73 4.97 5.20 15.0 0.53
Fennel 9 313 2.3 0.55 7.76 16.0 4.22 6.0 0.43
a Cut chamomile.
b Volume-average particle diameter.
344 I. Zizovic et al. / J. of Supercritical Fluids 39 (2007) 338–346
Fig. 6. Comparison of the experimental data and model simulation for grinded
marigold SFE at 9 MPa and temperatures of 313 and 323 K.
particles commences (extraction from the ducts). This start of
the second mechanism can be seen on the NOC profiles for 1,
5 and 8 min, as the low slope monotonous increase of NOC
preceeding the step increase that is due to the first extraction
mechanism (extraction from the embedding film). During this
period of SFE both of the extraction mechanisms, from the
surrounding film as well as from the ducts, are present in the
extraction vessel. After certain time of extraction, the films of
surrounding oil are extracted along entire vessel length, and the
extraction is now proceeding by the second mechanism in the
entire vessel (extraction from the ducts). NOC profiles shown
in Fig. 10 indicate that the extraction from the embedding
film is a much faster process than the extraction from ducts.
Since the fraction of essential oil embedding the particles is
small compared to the fraction remaining within the ducts, the
extraction mechanism transition occurs in relatively short time.
Fig. 7. Comparison of the experimental data and model simulation for grinded
marigold SFE at 10 MPa and temperatures of 313 and 323 K.
Fig. 8. Comparison of the experimental data and model simulation for
chamomile SFE at 313 K and 10 MPa for grinded () and cut () plant material.
This fast mechanism transition results in the bended form of the
simulated integral extraction yield curves. For example, in the
case of grinded chamomile this curve bending occurs around 9th
minute of the SFE (Fig. 8) and this mechanism transition is also
visible in Fig. 10. (NOC profiles for 8th and 9th minute of SFE.)
The mathematical model was also used to simulate SFE from
cut chamomile (average particle length around 5 mm) and the
simulation curve for the cut plant material is presented in Fig. 8.
The simulation results depicted in Fig. 8 confirmed the negligi-
ble effect of grinding on the yield evolution during SFE. Slightly
increased rate of extraction for the fine milled material can be
observed during the extraction period corresponding to approxi-
mately 60% of recovered overall yield. In this period of SFE the
overall process is governed by the oil extraction from the secre-
tory ducts. The recession of the oil front deeper in the ducts dur-
ing this period is in the case of longer ducts accompanied by the
decrease of ce (concentration at the duct end) and consequently
Fig. 9. Comparison of the experimental data [18] and model simulation for
fennel fruit SFE at 313 K and 9 MPa.
 I. Zizovic et al. / J. of Supercritical Fluids 39 (2007) 338–346
Fig. 10. Normalized oil concentration (NOC) in SC CO2 along the dimension-
less extractor length as a function of time for SFE from grinded chamomile at
313 K and 10 MPa according to the proposed model.
by the decrease of mass transfer rate and SFE yield. Negligi-
ble difference of the extraction yield for the fine milled and cut
material verifies the basic assumptions of the developed model.
4. Conclusion
Marigold and chamomile essential oil SC CO2 extraction
confirmed previously reported phenomenon that particle size
does not affect the evolution of extraction yield of some Aster-
aceae and Apiaceae family species. These species are char-
acterized by the specific type of essential oil secretory struc-
ture known as secretory duct. SFE from marigold flowers at
different pressure and temperature conditions confirmed the
same phenomenon. Suggested micro-scale mathematical model
was applied to simulate essential oil SFE from marigold and
chamomile flowers as well as from the fennel fruits for which
the same phenomenon was previously reported in the literature.
Secretory duct diameters were determined by statistical analysis
of SEM micrographs and from published investigations referred
to Asteraceae family species. The determined values were large
enough to allow unobstructed extraction from secretory ducts
disregarding the duct length and the model described experimen-
tal data with high accuracy for the investigated species, different
extraction conditions and particle sizes.
The knowledge of secretory structure makes possible predic-
tion of herbaceous material behavior during the SFE of essential
oils. In the case of SFE of species with secretory ducts, it can be
expected that particle size will have no influence on evolution
of extraction yield, which is the fact of interest from the point
of industrial scale SFE of essential oils.
Acknowledgement
Financial support of this work by the Serbian Ministry of
Science and Environmental Protection (Project No. 142073) is
gratefully acknowledged.
345
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