J.

of Supercritical Fluids 46 (2008) 285–292

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The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Mathematical modelling of essential oil SFE on the micro-scale—Classification of

plant material
Marko Stamenić a , Irena Zizovic a,∗ , Aleksandar Orlović a , Dejan Skala a,b
a University of Belgrade, Faculty of Technology and Metallurgy, Karnegijeva 4, P.O. Box 3503, 11120 Belgrade, Serbia
b Texas A&M University at Qatar, Education City, PO Box 23874 Doha, Qatar, USA

a r t i c l e i n f o a b s t r a c t

Article history: This article reports the achievements of the micro-scale (secretory-structure-scale) mathematical mod-
Received 15 October 2007 elling of essential oil isolation by supercritical carbon dioxide. Some new experimental and modelling
Received in revised form 7 March 2008 results are presented. The improved model for the supercritical fluid extraction from the glandular tri-
Accepted 7 March 2008
chomes (peltate glands) is introduced. According to the behavior of plant secretory structures during the
extraction as well as according to the modelling results, plant material was classified according to the
Keywords:
dominant resistance to mass transfer during the extraction process. External mass transfer was the rate
Supercritical fluid
limiting step in the extraction from plants with secretory ducts and secretory cavities of citrus family.
Mathematical modelling
Extraction
In the case of extraction from secretory cells, internal diffusion was the rate limiting step. In the extrac-
Essential oil tion from glandular trichomes, external mass transfer, as well as diffusion through the gland membrane
Mass transfer influenced the process.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
During the last decades chemical engineering became strongly
intertwined with other disciplines such as material sciences, bio-
chemistry, medicine (tissue engineering), etc. As a consequence, a
need for team work of scientists from different fields and capability
of chemical engineers to implant the knowledge of other disciplines
arised. The authors of this article, in last four years, tried to apply
plant physiology knowledge to the investigation of supercritical
fluid extraction (SFE) of essential oils from different plant mate-
rial. The aim of the study on the micro-scale [1–8], was to reveal
what was happening within the particle of milled plant material
during the extraction process and to apply chemical engineering
approach to the process simulation and modelling.
Essential oils are complex, volatile mixtures of certain secondary
plant metabolites that mostly include terpenoids and phenyl-
propenes. In plant material, 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 structure is specific to the plant family or species.
Process of the essential oil isolation, either by extraction or dis-
tillation, should be dependant on the oil storage and the type of
secretory structure [9]. Secretory structures on the surface of the
∗ Corresponding author. Tel.: +381 11 3303 795; fax: +381 11 3370 387.
E-mail address: zizovic@tmf.bg.ac.yu (I. Zizovic).
plant are glandular trichomes, which are modified epidermal hairs
that can be found covering leaves, stems and even parts of flow-
ers. Glandular trichomes are characteristic of Lamiaceae family
species. Aromatic herbs members of the family Lamiaceae, such as
basil, rosemary, marjoram, oregano, peppermint, spearmint, sage,
hyssop, lavender and thyme, possess two types of glandular tri-
chomes on surface of their leaves, termed peltate and capitate
glands. Recent plant physiology investigations [10], which included
new techniques of gland isolation, showed that all of the essential
oil content was stored on the surface of leaves in peltate glandular
trichomes (peltate glands). Secretory structures within plant tis-
sue can be secretory cells, secretory cavities or secretory ducts.
Secretory ducts are elongated cavities and they branch to create
network extending from the roots through the stem to the leaves,
flowers and fruits [9]. They can be found in all species of the fam-
ily Apiaceae including angelica, ajowan, celery, parsley, caraway,
cumin, dill, coriander and anise as well as in the largest fam-
ily of plants, Asteraceae comprising approximately 23,000 known
species including chamomile, marigold, yarrow, tarragon, worm-
wood, arnica and mugwort. Secretory ducts are also present in
Hypericaceae, Pinaceae and Coniferae families. Secretory cavities
are spherical structures lined with cells or epithelium that produces
essential oils. Secretory cavities are present in fruits and leaves of
plants in citrus family (Rutaceae), in eucalyptus and buchu leaves,
in flower buds of cloves and in the fruit walls of pimento [9]. Citrus
peel oils are present in secretory cavities that have no walls and
are embedded at different depths in the flavedo (the colored outer

0896-8446/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2008.03.007
286 M. Stamenić et al. / J. of Supercritical Fluids 46 (2008) 285–292

Nomenclature
a specific surface of disrupted peltate gland referred
to SC fluid volume (m2 /m3 )
ac specific surface of secretory structure referred to SC
fluid volume (m2 /m3 )
ad specific surface of open duct ends available for mass
transfer referred to SC fluid volume (m2 /m3 )
and specific surface of non-disrupted peltate gland con-
taining essential oil saturated with CO2 referred to
SC fluid volume (m2 /m3 )
aR specific surface of the oil sphere referred to SC fluid
volume (m2 /m3 )
aw specific surface of wetted particles referred to SC
fluid volume (m2 /m3 )
c essential oil concentration in undisrupted secretory
structure (kmol/m3 )
ce essential oil concentration in SC phase at the duct
end (kmol/m3 )
c* concentration of saturation of the essential oil in SC
CO2 on SC phase-essential oil interface (kmol/m3 )
csf essential oil concentration in supercritical phase
(kmol/m3 )
csat essential oil concentration in disrupted peltate
gland (oil phase saturated with CO2 ) (kmol/m3 )
dc secretory cell or cavity diameter (m)
dp plant particle diameter (m)
D1 axial dispersion coefficient (m2 /s)
Dm diffusivity of the essential oil in the non-disrupted
stretched peltate gland membrane (m2 /s)
D̄m average diffusivity of the essential oil in plant mate-
rial (m2 /s)
k mass transfer coefficient (m/s)
K average value of mass transfer coefficient through
the solid phase (m/s)
L length of the extractor bed (m)
M total number of secretory cavities or cells
N total number of peltate glands
P fraction of cavities or cells disrupted by grinding
R radius of the oil sphere (disrupted peltate gland) (m)
Rnd radius of the non-disrupted peltate gland in which
the essential oil is saturated with CO2 (m)
t time (s)
t̄ residence time in extractor vessel (s)
td time needed for the oil in non-disrupted by pretreat-
ment peltate glands to become saturated with CO2
which equals the time when peltate glands disrup-
tion caused by CO2 dissolving (s)
tw time when the oil that embedded the particles is
extracted (s)
u superficial SC fluid velocity (m/s)
V extractor bed volume (m3 )
x axial coordinate along the extractor bed (m)
Greek letters
˛ integer
ı difference between particle radius and secretory
structure radius (m)
ε void fraction of the bed
 number of degrees of freedom
 parameter of CTD function
 fraction of peltate glands disrupted during the
grinding pretreatment
ϕ fraction of peltate glands non-disrupted during
grinding pretreatment which are disrupted by CO2
dissolving
part of the fruit). Secretory cells are spherical secretion-containing
cells where it is only the actual content that distinguishes them
from adjacent non-secretory cells [9]. Secretory cells can also be
larger and have a thick cuticularized lining. This cell type is found
in many different plant tissues: in the rhizome of ginger, in the
perisperm and embryo of nutmeg, in the root of valerian, in the
leaf of lemongrass, bay, citronella and patchouli and in the seed
coat of cardamom [9].
Simultaneously with the SFE investigations, in last two decades,
mathematical models of these processes were developed. Mathe-
matical model of vegetable oil extraction with supercritical CO2 ,
widely used in the literature, was introduced by Sovova [11]. Plug
flow of supercritical solvent through a fixed bed of milled plant
material was considered. Basic assumption of the model was that a
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 pro-
tected by the cell walls follows. This assumption is very realistic and
meritorious for the success and huge application of the introduced
model. Extraction parameters can be evaluated by comparison of
the extraction curves calculated by the model with experimental
data. Advantages of this model are that it can be applied to any
kind of herbaceous material, and to the SFE of essential as well as
fatty oils.
Several investigations have been made in recent years on essen-
tial oil SFE of Lamiaceae family species, as well as on mathematical
modelling of these processes. Most of the models were based on
the solution of differential material balance for the extractor vessel,
and in general, all of them reported that the limiting stage during
extraction was the intraparticle transport. Bartle et al. [12] intro-
duced a model based on the heat transfer analogy for extraction of
1,8-cineole from rosemary leaves. Similar approach adopted Rever-
chon et al. [13,14]. Model given by Reverchon et al. [13] was applied
on the SFE from rosemary, basil and marjoram leaves. The model
described mass transfer between a single spherical porous parti-
cle and the supercritical solvent. The SFE of essential oil from sage
leaves was also investigated by Reverchon [15]. According to the
model, internal diffusion was the rate limiting step and the exter-
nal mass transfer coefficient was neglected. Goto et al. [16] derived
a model based on the local adsorption equilibrium of essential oil
on the lipid in leaves and mass transfer, which was applied on SFE
of peppermint oil. Goodarznia and Eikani [17] developed a model
that had three parameters including mass transfer, axial disper-
sion and intraparticle diffusion coefficients. All mentioned models
observed mass transfer on the particle-size scale and showed good
agreement with the experimental data.
Glandular trichomes as essential oil reservoirs were first incor-
porated into SFE mathematical modelling by Reis-Vasco et al. [18].
Two models for SFE of pennyroyal were developed. The authors
assumed that part of essential oil was stored in glandular trichomes
and part in internal structures of leaf. They took into account the
desorption of essential oil located near the leaf surface and the
extraction mass transfer resistance regarding the part of essential
oil contained in the internal part of the vegetable structure. The
second model incorporated axial dispersion. Simulations were per-
formed for different partitions of essential oil between the surface
 M. Stamenić et al. / J. of Supercritical Fluids 46 (2008) 285–292 287

and internal cells. Further, Gaspar et al. [19,20] reported a method
for glandular trichome disruption induced by the rapid CO2 expan-
sion as a pretreatment for the SFE. Gaspar et al. [21] also developed
a model which included plate geometry of herbaceous particles.
Although disruption of glandular trichomes due to rapid decom-
pression was studied, behavior of glandular trichomes exposed to
supercritical fluid (without decompression) had not been taken into
account. Therefore, proposed models could not explain S shape of
the extraction yield curve obtained during SFE of essential oils from
Lamiaceae family species [13,18,22], which indicated a change in
the SFE regime. The slope of the extraction yield curve, at pressures
around 10 MPa [13,18,20] in the point of the regime change was
similar to the slope of the curve at the beginning of the extraction
process. This implied that in this stage, the rate of the extraction
was almost the same as at the beginning of the process which
indicated that in the point of regime change some new quantity
of essential oil was released and has become easily available for
supercritical CO2 . All this indicated, that even without decompres-
sion, fraction of glandular trichomes will be disrupted due to the
exposure to supercritical fluid. This assumption was experimentally
verified and the SFE process was modelled by the model which
observed mass transfer on the secretory-structure-scale (micro-
scale) [1]. Peltate gland disruption due to exposure to supercritical
CO2 was confirmed by Scanning Electron Microscopy analysis. Pro-
posed mathematical model [1] simulated the process with very
high accuracy (0.83%). The model also indicated a possibility of
the SFE optimization towards reduction of the supercritical solvent
consumption. The optimal SFE processing should include a grinding
followed by herbaceous matrix exposure to supercritical fluid as a
batch (non-flow) in order to enable peltate glands disruption before
the continuous flow extraction. Experimentally determined reduc-
tions of supercritical CO2 consumption due to optimal processing
[4], for observed extraction yields, in the case of SFE of essential oils
from mint, hyssop and wild thyme on the laboratory scale were in
the range 0.250–0.889 kg CO2 /g of produced essential oil extract,
and the corresponding reductions of energy consumption were in
the range 48–170.7 kJ/g of produced essential oil extract.
Another thing that could not be predicted without taking into
account plant physiology knowledge was the behavior of plant
matrix with secretory ducts as secretory reservoirs, when exposed
to supercritical solvent. Once when the duct is cut, whole oil content
becomes easy accessible to supercritical solvent and further cutting
or milling of plant material to smaller particle size has no influence
on SFE process [5,23,24]. This is valid only for the SFE from secre-
tory ducts as essential oil reservoirs at pressures around 10 MPa
when essential oil content is dominant in the extract. Daukšas
et al. [25] were the first who incorporated the knowledge about
secretory ducts into the method for vegetable oil isolation by SFE
(pressure of 25 MPa) from lovage and celery. It was found that by
applying frequent pressure changes in the extraction vessel it was
possible to increase the rate of isolation of CO2 soluble substances
from lovage seeds and leaves as well as lovage and celery roots. The
proposed method was based on the fact that the transportation of
liquid solutes in capillary matrix could be enhanced by exposure to
very fast pressure alternations.
In this study an improved mathematical model on the secretory-
structure-scale for SFE with carbon dioxide of essential oils from
Lamiaceae family species is presented. The first model [1] included
that all the glands that will undergo disruption due to the exposure
to supercritical fluid would crack at the same time. New model
includes experimentally verified distribution of cracking times.
New modelling results regarding SFE from plants with secretory
cells and ducts are also presented. According to these results and
results from the previous studies on the micro-scale, as well as
according to the behavior of specific secretory structure during the
SFE, plant material was classified according to the dominant resis-
tance to mass transfer during the SFE. The basic hypothesis of the
study on the micro-scale stayed the same—the extraction process
from the particular herb should be dependent on the type of its
secretory structure.
2. Mathematical modelling
Material balance for the supercritical phase in the extractor ves-
sel, for isothermal and isobaric system can be written as:
∂c sf ∂2 c sf ∂c sf
= Dl −u + ST (1)
∂t ∂x2 ∂x
where csf is the essential oil concentration in supercritical phase,
Dl is the axial dispersion coefficient, u is the superficial supercrit-
ical fluid velocity, and ST is the Source and Transfer term which
describes essential oil transfer from specific secretory structure
to supercritical fluid phase. Essential oil is represented by a sin-
gle pseudo component. The corresponding initial and boundary
conditions are:
t = 0, 0 ≤ x ≤ L, c sf = 0 (1a)
t > 0, x = 0, c sf = 0 (1b)
∂c sf
t > 0, x = L, = 0. (1c)
∂x

Table 1
Source and Transfer term for each type of secretory structure

Secretory structure ST

Glandular trichomes (peltate glands) Previously published model [1]:

Nak(c ∗ − c sf ) for t ≤ td
Nak(c ∗ − c sf ) + N(1 − )ϕak(c ∗ − c sf ) + N(1 − )(1 − ϕ)and R3 Dm (c − c sf ) for t > td
nd
4R2 Dm
4R2 k
Additional equations : and = Vε
nd
,a = Vε
, − dR = csat (c ∗ − c sf ) − dc = (c − c sf )
dt dt 4R2
nd
Improved model from this study:
Nak(c ∗ − c sf ) + N(1 − )ϕak(c ∗ − c sf ) + N(1 − )(1 − ϕ)and R3 Dm (c − c sf )
nd
for each value of t and ϕ = const.

Secretory ducts aw k(c ∗ − c sf ) for t ≤ tw

ad k(c e − c sf ) for t > tw

Secretory cavities and cells (model I) aw k(c ∗ − c sf ) for t ≤ tw

for dc ≥ dp Mac D̄ım (c − c sf ) for t > tw

Secretory cavities and cells (model II) for dc < dp aR MPk(c* −csf ) + M(1−P)ac K(c−csf )
288 M. Stamenić et al. / J. of Supercritical Fluids 46 (2008) 285–292

Introducing dimensionless concentration, length and time into the oil phase. Dissolved CO2 increased the peltate glands vol-
respectively: ume thereby inducing peltate membrane stretching, and eventually
membrane disruption and opening for a fraction of peltate glands.
c sf
= (2) The oil inside the disrupted glands became easily available for SC
c∗ CO2 . This model enabled SFE process optimization towards low-
x ering of supercritical carbon dioxide (SC CO2 ) consumption due
z= (3)
L to optimal pretreatment of herbaceous material [1,4]. The optimal
t pretreatment included grinding pretreatment followed by SC CO2

= (4)
t̄
where c* is the saturation concentration of the essential oil in SC
CO2 , L is the length of extractor and t̄ = L/u is an average residence
time in extractor, Eq. (1) in dimensionless form can be written as:
∂ 1 ∂2 ∂ L ST
= − + (5)
∂
Pe ∂z 2 ∂z u c∗
where Peclet number is defined as:
uL
Pe = . (6)
Dl
In Table 1, Source and Transfer term is presented for each specific
type of secretory structure as ST (mol/s m3 ). As can be seen from
Table 1. ST, as well as non-dimensional term ST/c ∗ t̄, are functions of
time and position in the extractor vessel, since they are dependant
on concentration in the extractor vessel (csf ).
Mathematical model on the micro-scale for the SFE from glan-
dular trichomes (peltate glands) was previously published [1].
Experimentally verified phenomenon that a fraction of peltate
glands that stayed untouched by grinding process, would be dis-
rupted during extraction process was introduced into the model.
It was assumed that peltate glands membrane was permeable and
supercritical carbon dioxide (SC CO2 ) penetrated it and dissolved
batch (non-flow) pretreatment before the continuous SFE process
[1,4].
The previously published model [1] included simplification that
cracking of the glands due to the CO2 dissolving was instantaneous
for all the glands and it occurred at the moment of time (td ) defined
as time when the oil inside the glands became saturated with CO2 .
The improved model derived in this study includes Cracking Time
Distribution (CTD) during the extraction process.
Eq. (1) was solved for each specific type of secretory structure
using the explicit finite difference method [26]. Parameter identi-
fication and calculation were previously described [1,5,6].
3. Materials and methods
Extractions from the plant material were carried out at Auto-
clave Engineers SCE Screening System previously described [1,5,7].
Essential oils were extracted from Thyme (Thymus serpullum)
leaves (glandular, trichomes), Celery fruit (secretory ducts) and
Valerian root (secretory cells). In the case of SFE from glandular
trichomes CTD was experimentally determined for the T. serpullum
glands. Whole leaves of T. serpullum were exposed to SC CO2 for
different time intervals. After slow decompression, number of dis-
rupted glands was statistically analyzed using Scanning Electron

Fig. 1. SEM images of plant material: (a) peltate glands on the surface of Thymus serpullum leaf (bar = 700 ␮m); (b) celery fruit (bar = 70 ␮m); (c) nutmeg with visible secretory
cells (bar = 70 ␮m); (d) valerian root (bar = 70 ␮m).
 M. Stamenić et al. / J. of Supercritical Fluids 46 (2008) 285–292 289

Fig. 2. Fraction of glands disrupted due to CO2 dissolving (ϕ), as a function of expo- Fig. 4. Modelling results for the SFE from Thymus serpullum at 40 ◦ C and 10 MPa.
sure time to SC CO2 . (Standard deviation from experimental results 5.7 × 10−4 ).

where gamma function is, by definition:

Microscopy. For each exposure time to supercritical fluid (20, 40,  ∞
60, 80 and 100 min) more than 120 peltate glands were analyzed  (˛) = e−x x˛−1 dx, for ˛ > 0 (8)
in order to determine the fraction of disrupted glands due to CO2 0
dissolving (ϕ). For ␣ an integer (as in our case), it has the property that
For the purpose of modelling on the micro-scale, secretory struc- (˛ + 1) = ˛!. Number of degrees of freedom () is 8. In our
ture dimensions are also necessary. Few of SEM micrographs of the case 2 corresponds to t/4. The CTD obtained is shown in
plant tissues used in this study are presented in Fig. 1. Fig. 3.
The results of the mathematical modelling are shown in Fig. 4
4. Results and discussion and the parameters of the model are given in Table 2. The only
adjustable parameter of the model is diffusivity of the essential
In the case of SFE from glandular trichomes CTD was experimen- oil in the non-disrupted stretched peltate gland membrane (Dm ).
tally determined for the T. serpullum glands. Values of the fraction of Value of the fraction of glands disrupted by grinding process () was
glands disrupted due to CO2 dissolving (ϕ), as a function of exposure previously determined [1]. The S shape of extraction yield curve, as
time to SC CO2 are presented in Fig. 2. it was previously explained [1], is due to the period of low essential
On the basis of these results CTD was determined in a form [11]: oil concentrations in the extractor vessel before the peltate gland
cracking due to supercritical CO2 dissolving.
  Mathematical model on the micro-scale for the SFE from plants
2 1 2 /2−1
f ( ) = exp − (2 ) (7) with secretory ducts was previously published [5]. The model
2/2  (/2) 2

Fig. 5. Modelling results for the SFE from celery fruit at 40 ◦ C and 10 MPa. (Standard
Fig. 3. Cracking Time Distribution (CTD) for the glands of the Thymus serpullum. deviation from experimental results 4.2 × 10−3 ).
290 M. Stamenić et al. / J. of Supercritical Fluids 46 (2008) 285–292

Table 2
Model parameters for the SFE from Thymus serpullum

P (MPa) T (K) qCO2 (kg/h) Rnd (␮m) dp (mm) u (×104 m/s) k (×105 m/s) Dl (×107 m2 /s) Dm (×1011 m2 /s) c* (×103 kmol/m3 ) 

10 313 0.3 28 0.7 1.47 3.21 1.83 5.0 6.0 0.55

Table 3
Model parameters for the SFE from celery fruit

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

10 313 0.3 1.47 × 10−4 0.7 0.47 2.68 × 10−5 30.0 2.43 × 10−7

Table 4
Parameters of the SFE processes and presented model

Sample P (MPa) T (K) qCO2 (kg/h) dp (mm) k (×105 m/s) Dl (×107 m2 /s) c* (×103 m3 /s) K (×1011 m/s)

Nutmeg 15 323 0.54 0.556 0.91 2.78 6 0.1

10 313 0.3 3.84 1.48 7.0 0.61
Valerian 0.40
15 313 0.3 1.10 1.79 6.0 0.69

explained the phenomenon that in some cases (when essential oil
reservoirs are secretory ducts) particle size had no influence on
evolution of extraction yield. In this study modelling results will
be presented for the SFE from celery fruit at 40 ◦ C and 10 MPa.
SEM image of celery fruit with clearly visible secretory duct is pre-
sented in Fig. 1b. The results of the mathematical model and model
parameters are presented in Fig. 5 and Table 3 respectively. The
adjustable parameter of the model, which can be varied in narrow
range of experimentally determined values published in the liter-
diameter. In this study, the second model is applied to the litera-
ture experimental data [27] on SFE from nutmeg as well as to the
experimental data on SFE from valerian root. SEM images are pre-
sented in Fig. 1c and d. The results of the mathematical model and
model parameters are presented in Figs. 6 and 7 and Table 4. The
adjustable parameter of the model is the internal mass transfer
coefficient through the solid phase (K). For each modelling result
 standard deviation from
(Figs. 4–7) experimental results was cal-

m

ature, is the solubility of essential oil in SC CO2 (c* ). 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 relatively fast
and therefore the resulting simulation curve is not smooth, as it
was previously explained [5].
In the case of SFE from secretory cavities and cells two math-
ematical models were derived [2,6]. The first model is for the SFE
from the spherical secretory structures with the average diame-
ter similar to the particle size diameter (Rutaceae – citrus family),
and the second is for the spherical secretory structures with the
average diameter few or more times smaller than the particle size
culated J = (1/m) (Yj − Yj,exp )2 .
1
According to the secretory structure characteristics and its
behavior during the SFE process, plant material can be classified
referred to the dominant resistance to mass transfer in the process
of essential oil isolation. Results of the modelling on the micro-scale
support this classification. The classification (Table 5) was made on
the basis of secretory structure characteristics, its behavior during
the SFE process as well as the model parameters values (external
mass transfer coefficient, diffusivity coefficient of the plant tissue
or internal mass transfer coefficient) which are dependant on the
secretory structure. External mass transfer was the rate limiting

Fig. 6. Modelling results for the SFE from nutmeg at 50 ◦ C and 15 MPa for particle Fig. 7. Modelling results SFE from valerian root at 40 ◦ C (Standard deviation from
size of 0.556 mm (SFE literature data [27], Standard deviation from experimental experimental results 9.9 × 10−4 for experiment at 15 MPa and 2.2 × 10−4 for exper-
results 7.2 × 10−2 ). iment at 10 MPa).
 M. Stamenić et al. / J. of Supercritical Fluids 46 (2008) 285–292
Table 5
Plant material classification
step in the extraction from plants with secretory ducts (all the
essential oil content is easy available to SC CO2 ) and secretory cavi-
ties of citrus family (dimensions up to 0.9 mm and totally destroyed
by the grinding process). In the case of extraction from secretory
cells, internal diffusion through the plant material was the rate
limiting step. In the extraction from glandular trichomes, exter-
nal mass transfer, as well as diffusion through the gland membrane
influenced the process. Previously introduced models [12–17,21]
emphasized diffusion within the particle as dominant resistance
to mass transfer. By peltate glands disruption prior to continuous
SFE (by rapid decompression [19,20], or by the exposure to super-
critical fluid for an hour [1,4]) internal mass transfer resistance
can be minimized. Gaspar et al. [19,20] thoroughly investigated
conditions for disruption of glandular trichomes by rapid decom-
pression, as a pretreatment to SFE. Gaspar showed that by rapid
decompression up to 86% of glandular trichomes can be disrupted.
In this and previous studies [1,4] it was shown that disruption
due to the exposure to supercritical fluid was around 50% (ϕ = 0.5).
Including glands previously disrupted by grinding, disruption effi-
ciency is around 75%. Pretreatments of herbaceous matrix like these
will reduce supercritical fluid consumption and save energy in
SFE process [4]. Another study has been performed [28] in order
to reduce solvent consumption. Sensitivity analysis was applied
in order to find optimal processing which would promote rate
of extraction in the second period of SFE when the tied oil was
extracted and the internal mass transfer resistance was dominant.
The effect of changing some operative conditions was also investi-
gated.
5. Conclusion
The knowledge of secretory structure makes it possible to pre-
dict the herbaceous material behavior during the SFE of essential
oils. The model for the SFE from glandular trichomes indicated
a possibility of the SFE optimization towards reduction of the
supercritical CO2 consumption. The optimal SFE processing should
291
include a grinding followed by supercritical CO2 batch (non-flow)
pretreatment prior to continuous flow extraction [1,4]. In the case
of SFE from species with secretory ducts, it can be expected that
particle size will have no influence on evolution of extraction yield
as it was shown in number of experiments [5]. External mass
transfer should be expected to be the rate limiting step in the
extraction from plants with secretory ducts and secretory cavities
of citrus family. In the case of extraction from secretory cells, dif-
fusion through the particle of milled plant material was the rate
limiting step. In the extraction from glandular trichomes (peltate
glands), external mass transfer, as well as diffusion through the
gland membrane influenced the process. The models presented
on the micro-scale for SFE of essential oils from plant material
described experimental data with high accuracy. Although mod-
elling on the micro-scale is more demanding (secretory structure
dimensions, SEM statistical analysis) it reveals mass transfer phe-
nomena within the particle of milled plant material and provides
valuable information for SFE process optimization.
Acknowledgments
Financial support of this work by the Serbian Ministry of Science
and Environmental Protection (Project No. 142073) is gratefully
acknowledged.
Support of Dr. Katerina Svoboda (Scottish Agricultural College)
and Mr. Andrew Syred (who founded Microscopix photolibrary) is
gratefully acknowledged.
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