Journal of Chromatography A, 1250 (2012) 2–26

Contents lists available at SciVerse ScienceDirect

Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma

Review

Theoretical models for supercritical fluid extraction

Zhen Huang a,b,∗ , Xiao-han Shi b , Wei-juan Jiang b
a
Tianjin Key Laboratory of Refrigeration Technology, Tianjin University of Commerce, Tianjin 300134, China
b
Department of Packaging Engineering, Tianjin University of Commerce, Tianjin 300134, China

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

Article history: For the proper design of supercritical fluid extraction processes, it is essential to have a sound knowledge
Available online 17 April 2012 of the mass transfer mechanism of the extraction process and the appropriate mathematical represen-
tation. In this paper, the advances and applications of kinetic models for describing supercritical fluid
Keywords: extraction from various solid matrices have been presented. The theoretical models overviewed here
Supercritical fluid include the hot ball diffusion, broken and intact cell, shrinking core and some relatively simple models.
Extraction kinetics
Mathematical representations of these models have been in detail interpreted as well as their assump-
Carbon dioxide
tions, parameter identifications and application examples. Extraction process of the analyte solute from
Mathematical model
Mass transfer
the solid matrix by means of supercritical fluid includes the dissolution of the analyte from the solid, the
Diffusion analyte diffusion in the matrix and its transport to the bulk supercritical fluid. Mechanisms involved in
a mass transfer model are discussed in terms of external mass transfer resistance, internal mass transfer
resistance, solute–solid interactions and axial dispersion. The correlations of the external mass trans-
fer coefficient and axial dispersion coefficient with certain dimensionless numbers are also discussed.
Among these models, the broken and intact cell model seems to be the most relevant mathematical model
as it is able to provide realistic description of the plant material structure for better understanding the
mass-transfer kinetics and thus it has been widely employed for modeling supercritical fluid extraction
of natural matters.
© 2012 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. General aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Solid pre-treatment and particle characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Solute–matrix interactions and phase equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Mass transfer and axial dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Relatively simple theoretical models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Diffusion layer theory (DLT) model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Desorption model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3. Partitioning coefficient model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Hot sphere diffusion model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.1. Assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2. Mathematical representation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.3. Parameter identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.4. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5. BIC model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.1. Assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.2. Mathematical representation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5.3. Parameter identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.4. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

∗ Corresponding author at: Tianjin Key Laboratory of Refrigeration Technology, Tianjin University of Commerce, Tianjin 300134, China. Tel.: +86 13752549698;
fax: +86 22 26686529.
E-mail address: huangzhen50@yahoo.com (Z. Huang).

0021-9673/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.chroma.2012.04.032
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26 3

6. Shrinking model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6.1. Assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6.2. Mathematical representation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6.3. Parameter identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
6.4. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

1. Introduction of research have been extensively performed in the community,

namely, (i) operational optimization and scaling–up studies for
Nowadays, supercritical fluid extraction (SFE) has been emerg- high SFE yields and (ii) investigations on solubility measurements
ing as a superior alternative technique for extraction of bioactive in SCCO2 with/without modifiers. In other words, research efforts
species from natural produces, because of its reduction of extrac- have been directed to the measurement and modeling of solubility
tion time, less consumption of organic solvents, being suitable behaviors in SCCO2 , and mass transfer kinetics for analyte extrac-
for thermo-sensitive substance, production of cleaner extracts and tion from solid substrates with SCCO2 . In this work, we have only
environmental benignity [1]. Among various supercritical fluids concerned kinetic SFE process.
used for extraction, supercritical CO2 (SCCO2 ) is the most widely So far, the extraction of substances from natural solid matrices
used since it is nontoxic, non-flammable, non-corrosive, and easy in packed beds has formed the research and development basis of
to handle and allows supercritical operation at low pressures and most present-day SFE processes. Despite this fact, it is still required
near room temperature. In addition, it is cheap and readily avail- to make a full understanding of the whole extraction process of
able in bulk quantities with a high degree of purity. Thus SCCO2 interest, for systemically investigating the influences of various
extraction has become preferably attractive, to replace traditional parameters on the extraction yield, and thus controlling the spe-
industrial extraction techniques, in selective separation of bioac- cific SFE process [36,37]. During the process, a targeted specialty
tive or thermally sensitive components from natural matters for chemical is extracted from a fixed bed loaded into an extraction
various practical purposes [2–4]. More specifically, the increased unit by using a supercritical or near-critical solvent with/without a
use of vegetable extracts by the food, cosmetic, and pharmaceuti- modifier. As the pressurized solvent flows continuously through
cal industries has made the extraction of essential oils using SCCO2 the bed of porous particles, the CO2 molecules will diffuse into
be an attractive technology compared to conventional processes, the pores and adsorb on the particle surface to form an exter-
such as organic solvent extraction and steam distillation, with nal fluid film around the solid particles through the solvent–solid
respect to the product quality [5,6]. For this reason, extraction of matrix interactions. Then the analyte molecules will be dissolved
targeted compounds from a large number of materials by SCCO2 has and convectively transported into the solvent in the pores via
been tremendously investigated as reflected by several thousands solvent–solute interactions. After desorption, the dissolved solute
of published scientific papers. To date, significant progresses and diffuses through the pores and finally transports to the bulk fluid.
achievements of SFE works have been reviewed in several recent At the exit of the extraction unit, the fluid is released to a gaseous
articles [6–17]. Besides selective extraction of desired species from state and the solute precipitates where its amount can be read-
solid matrices, SFE can also be used to remove certain toxic com- ily measured. The process is usually characterized by the overall
ponents or unwanted species from solid matrices and aqueous extraction curve, the plot of the cumulated extract versus the
solutions [18–28]. In fact, supercritical fluid technology is currently extraction time or the amount of solvent consumed during the
no longer a laboratory curiosity as it is successfully commissioned extraction process. Therefore, many SCCO2 extraction studies have
for caffeine, tea, spices, hops and flavor extraction process on large mostly concentrated on the yield of the extract, the influences of
commercial scale in USA and Europe [1]. various parameters such as pressure and temperature on it, and as
In view of engineering processes and applications, there are two well as measuring and modeling the mass transfer rates of extrac-
major factors affecting the development of the SCCO2 extraction tion process. Generally, the extraction yield of a porous solid natural
technologies, and they are the solubility of the extracted solute in substrate depends not only on extraction pressure and temper-
the supercritical fluid and the rate of solute mass transfer out of ature, modifier content, solvent flow rate and analyte solubility,
the material matrices. As we know, the knowledge of the solubil- but also on pre-treatment of solid substrates like drying, milling
ity of solids involving supercritical fluids is essential for evaluating and grinding, physical characteristics of the extraction bed includ-
the feasibility and for establishing optimum SFE operating condi- ing bed porosity, bed height, bed diameter and apparent density of
tions. Even with tunable solvent strength by adjusting pressure solid loaded, and properties of the substrates such as particle size,
or temperature, however, CO2 is not a particularly good solvent particle size distribution, particle geometry, real density of solid
for polar organic compounds as it is a non-polar molecule, and particles, and initial analyte content in the substrate.
then a polar modifier is usually recommended for enhancing its Apart from extensive works on experimental determinations,
solvating power for polar organic compounds. To date, numer- many efforts have also been made to mathematically simulate
ous studies have investigated the influence of polar modifiers on the SFE processes in terms of the time-dependent extraction
the SCCO2 extraction from various matrices as well as solubility curve. Mathematical modeling studies are of great importance
enhancements in SCCO2 [1,2,29–35]. On the other hand, for many as they may enable us generalize the experimental observations
dynamic extractions of solid matrices, the rate of SCCO2 extrac- from the systems studied for optimizing process conditions or
tion is mainly determined by the rate of transfer out of the matrix being extended to new systems other than those researched.
by diffusion [36,37]. Therefore, the whole process of supercritical Subsequently, these modeling works may be quantitatively and
extraction may be controlled either thermodynamically or dynam- qualitatively useful in promoting the development of scaling-up
ically, or both, in terms of solubility control, external mass transfer procedures for any subsequent extraction applications. More-
control or internal mass transfer limitation. Accordingly, two lines over, the knowledge of the mass-transfer mechanism and kinetics
4 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26
parameters along with thermodynamics restrictions could be used
to economically evaluate the extraction process from laboratory
to pilot and industrial scale. In the meantime, the understanding
of various process variables and how they can be connected to a
theoretical model to describe the extraction kinetics may be also
obtainable. For these reasons many mathematical models for SFE
have been proposed and developed, as summarized in two recent
review papers [36,37].
2. General aspects
Mathematical modeling of experimental data is a common task
in the field of engineering and applied sciences. A number of kinetic
extraction models can be found in specialized scientific literatures
that have been proposed for the SFE of packed beds of solid matri-
ces [36,37]. Through fitting experimental data, these models are
attempted to not only provide a quantitative interpretation of the
experimental data, and discover the true values of the parameters
that are physically meaningful, but also complete data at points
where measurements are not carried out. The most important goal
of modeling is the prediction of large scale extraction curves as
functions of the experimental parameters as described above, since
real experiments at large scale are extremely expensive.
Of these models, some are empirically simple in nature and thus
of limited viability as they have no physical meanings correspon-
dent to the materials and the process studied, and sometimes they
may deal with SFE extraction curves very well. However, these
models are not adequate for scaling-up predictions because they
do not provide a description of underlying mass transfer phenom-
ena that occur also in industrial-size extraction units. For examples,
Naik et al. in 1989 [38] proposed a 2-parameter Langmuir-type
model for representing perfume extraction from several vegetable
materials by subcritical CO2 . Barton et al. in 1991 [39] suggested a
2-parameter kinetic model for describing the SFE process of vanilla
oleoresin as a first-order chemical reaction, bearing a form [40]
similar to one-parameter desorption model discussed later. These
empirical models will not be given further consideration in this
review.
Therefore, extraction models should not be a mere mathemat-
ical tool, but should reflect the physical insight arising from the
knowledge of the solid structure and from experimental observa-
tions. From this regards, the most valuable models to represent the
overall fixed bed behavior are those rigorous differential mass bal-
ance models, developed from differential mass balance equations
for the packed bed of solid substrates. By integration of those dif-
ferential equations time-dependent concentration profiles in both
phases can be obtained and the extraction curve could then be cal-
culated from fluid-phase concentration at the extraction unit outlet
[36]. Note that these models contain two differential solute mass
balances for the solute in supercritical phase and in solid phase
respectively, in addition to a solute equilibrium desorption that
describes the interactions between solute and solid matrix.
Arising from different mass transfer mechanisms and equilib-
rium relationships, a varsity of mass balance models have thus
been proposed to characterize the mass transfer kinetics [41–44].
The most important idea involved for developing these models is
the concept of broken and intact cells (BIC), firstly introduced by
Sovová [41]. In the BIC model, the solid phase is considered present
between broken and intact cells and thus the total oil available
within the plant cells are divided by easily accessible oil on the cell
surface and difficultly accessible oil in the intact cell. Shrinking core
(SC) model is the model which describes the situation of irreversible
desorption followed by diffusion in the porous solid through the
pores. This model assumes that the solute inside the particle is
located within a core that shrinks as the solute is extracted [42].
Reverchon et al. [43] developed a hot ball model for SFE process and
treated the solute extraction from a solid matrix as a hot ball cooling
down in a uniform medium. Veress [44] assumed a diffusion-layer
theory (DLT) model to quantify the extraction process of cannabi-
noids from marihuana and hashish by SCCO2 [44]. Tan and Liou [45]
proposed a single parameter desorption model for describing SFE
process as desorption of the analyte from the parent matrix.
In what follows we will review mathematical models for SFE
process classified as: (1) relatively simple models, (2) hot sphere
model, (3) BIC model, and (4) SC model. Here we would like to
highlight those models with analytical solution although they are
valid at strictly limited conditions because they can largely simplify
the estimation of model parameters from the shape of experimental
extraction curve.
In dealing with mathematical modeling of SFE, several general
aspects have to be taken into account [11,46]:
2.1. Solid pre-treatment and particle characteristics
Solid substrates are commonly subjected to mechanical pre-
treatments such as grinding, milling, cutting, chopping, crushing or
other size-reduction methods. These pretreatments have multiple
purposes, including releasing of solutes from cells, facilitating sol-
vent flow through the packed bed, increasing substrate loads into
extraction units, and improving the rate and yield of the subsequent
extraction process. As a consequence, superficial vegetable cells
may be considerably broken, rendering the analyte to be extracted
free on the surface of the solid material. Reverchon et al. [47–49]
used scanning electron microscope (SEM) and found broken cells
on the particle surface. If the broken cells were assumed to form a
single layer, the authors were able to calculate volumetric broken-
to-intact cell ratio and thus reduce the number of model parameters
evaluated from extraction curves. Generally, the content of the
extractable substances oil due to cell breaking is inversely propor-
tional to the final particle diameter and then very small particles
are preferred to improve the extraction rate and yield. But the use
of small particles is not always encouraged since substrate agglom-
erating or channeling may occur in tightly packed beds especially
when particle size is very small or when the extractor diameter
is large, leading to the poor solvent flow and poor performance.
In addition, particles may be spherical, cylinders, slabs, and other
shapes as a result of the grinding process and their shapes may
influence the diffusion of the supercritical solvent in different ways
[36,50–52].
2.2. Solute–matrix interactions and phase equilibrium
Depending on interactions between the solute and the solid
structure, different phase equilibria may be involved. Usually, if
the solute has no interactions with matrix, equilibrium solubility is
readily taken into account. This may be true in the case of vegetable
oil in seeds where the oil content in solid phase is relatively high and
the fluid-phase equilibrium concentration is then independent of
matrix and equal to its solubility in SCCO2 . Consequently, it appar-
ently controls the first period of the SFE process as the fluid phase
leaving the extractor could be reasonably be assumed to be in equi-
librium with solid phase at the extraction unit outlet. Therefore, the
initial part of extraction curve contains information on the type
of equilibrium between the solid and fluid phases. On the other
hand, if the solute–matrix interactions are not negligible, then the
extraction rate should depend on how the analyte is bound to the
solid matrix such as either on the outer surface or inside the solid
structure. Thus the solute desorption from the matrix and its par-
tition equilibrium between the SCCO2 and the solid matrix should
be considered. This case may be possible for essential oils in the
plant where its initial content is only a few percent or less, and the
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26
fluid-phase concentration is much lower than the solubility. For
these considerations, Sovová et al. [53,54] have chosen the equi-
librium solubility (without solute–matrix interaction) in their
modeling works for seed oil extraction while the others has con-
sidered the solute–matrix interactions [55–59].
2.3. Mass transfer and axial dispersion
Besides the analyte phase equilibrium, the rate of SCCO2
extraction strongly depends on mass transfer factors, which are
characterized by the axial dispersion, external mass transfer coef-
ficient, and internal mass transfer coefficient (or solute diffusivity
in the solid matrix) in terms of two dimensionless numbers. One
is Biot number (Bi ) that characterizes the relative importance
of effective intraparticle diffusion (De ) as compared to convec-
tive solid-to-SCCO2 film mass transfer on the particle surface
(Bi = 2kf R/De ). The other is Peclet number (Pe ) that is an index of the
relative importance of axial dispersion (Dl /H) and convective flow
(u) in the displacement of dissolved solute with the SCCO2 along
the bed (Pe = Hu/Dl ). Recasens et al. [60] suggested that if there
is a large effect of particle size, or if kf is significantly less than a
term of 5kf /(Bi + 5) obtained from linear driving force approxima-
tion, the intraparticle diffusion should be included in the model.
Goto et al. [42] found that the intraparticle diffusion may take con-
trol for Bi ≥ 10, and that once Bi is smaller than 10 the external mass
transfer has a large effect on extraction rates, and it is not possible
to get the SCCO2 at the extractor outlet saturated with oil.
With regard to axial dispersion, Recasens et al. [60] indicated
that it can be disregarded when values of Pe are very large, and Goto
et al. [42] further showed that there may be no effect of axial dis-
persion on the whole extraction profiles if Pe ≥ 100. Reverchon and
Marrone [48] thought that axial dispersion might have little effect
on SCCO2 extraction of oil containing seeds because the Pe values
are typically very large. This comes possibly because it is generally
of practical importance to avoid dispersion of the solute along the
bed to keep driving forces for extraction to a maximal level. To avoid
axial dispersion problems during SFE in cylindrical vessels, some
methods may be taken [36,61]: (i) to increase the interstitial solvent
velocity of the SCCO2 , (ii) to produce more than 1 MPa of pressure
drop in the solvent, (iii) to use extraction vessels of small diame-
ter and large length-to-diameter ratio to diminish radial variations
along the bed. According to Rodrigues et al. [61], when the solvent
flow rate is too large, equilibrium conditions are not attained at the
outlet end of the extraction vessel; when too small, solute concen-
tration in the loaded CO2 phase decreases due to axial dispersion
phenomena. Of several solvent flow modules used in the SFE (plug
flow and flow with axial dispersion for longer extraction beds, and
ideal mixer for short extraction beds), Sovová [46] thought that the
plug flow was preferred with respect to extraction performance.
However, axial dispersion does exist in a real extraction process,
and it is more pronounced if the lower is the length-to-diameter
ratio of extraction bed.
3. Relatively simple theoretical models
3.1. Diffusion layer theory (DLT) model
In 1994, Veress proposed a diffusion-layer theory (DLT) model
to quantify the extraction process of cannabinoids from marihuana
and hashish by SCCO2 [44]. More recently, Huang et al. [62] have
employed this model for describing the extraction profiles of amine
removal from freshly synthesized HMS materials. For this model,
the dynamic SFE process may be simply composed of two simulta-
neous processes, i.e., transport of the analyte from the parent matrix
to the bulk of the extraction fluid by dissolution and the flushing out
5
Fig. 1. Schematic of diffusion layer theory for the dissolution of solids in the fluid:
c is the concentration of the dissolving analyte in the bulk solution (g/m3 solvent),
csat is the solute solubility (g/m3 solvent), and z is the distance from the solid–fluid
interface.
of the dissolved analyte from the extraction bed by the extraction
fluid. Based on Fick’s first law, a diffusion-layer mechanism may
take control for the dissolution of a solute in a fluid. Fig. 1 gives the
flowchart of the diffusion lay theory model. Following this theory
[44], the dissolution rate of the solute molecules is controlled by
its diffusion across a diffusion layer of thickness h. Thus the disso-
lution rate (dmt /dt), e.g., the mass of solute dissolved per unit time
(g/t), is given as:
dmt 4R2 De
= (csat − c) (1)
dt h
where mt is the mass of the solute (g), R is the radius of the solid
particles (m), De is the effective solute diffusivity (m2 /s), csat and
c, both in unit of g solute/m3 solvent, are the concentration of the
dissolving solute in equilibrium with a solid surface and in the bulk
solution with extraction time t, respectively.
For the flushing out process of the dissolved analyte, the solute
concentration can be differentially expressed as follows.
dc F
= (c0 − c) (2)
dt V
where F is the volumetric flow rate of the extraction fluid (m3 /s)
and V is the void volume of the extraction chamber (m3 ). The solute
concentration c0 may be assumed at the beginning of the extraction
without mass transfer from the matrix to the fluid.
Derived from Eqs. (1) and (2), the time dependence of the analyte
concentration in dynamic SFE can be given as below:
m0 ˇ
c= (e−Ft/V − e−ˇt ) (3)
ˇV − F
where ˇ is defined by ˇ = 4R2 De /Vh (s−1 ), and m0 is the mass (g)
of solute to be extracted and present in the parent matrix.
Thus the time dependence of the extracted solute mt (g) in
dynamic SFE process can be obtained from the integral of the prod-
uct of c and F by taking into consideration that the full recovery
could only be achieved after an infinite time of extraction, resulting
in
mt ˇF
V 1 −ˇt

=1− e−(F/V )t − e (4)
m0 ˇV − F F ˇ
Apparently, the DLT model is one-parameter model, along with
two measurable process parameters F and V. Based on the ˇ values,
the extraction time required to reach a predefined level of extrac-
tion recovery may be estimated according to the work of Vetess
[44]. This model has been successfully used to simulate the amine
extraction process by methanol modified SCCO2 , and it performs
satisfactorily with the AARD values varying from 1.5 to 6.0%, much
better than the hot ball model [62]. The regressed parameter ˇ
values, ranging from 1.30 to 5.64 min−1 , reflect no dependence on
system temperature but increases with pressure, CO2 flow rate and
6 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

Table 1
Applications of the Tan–Liou model for different SCCO2 extraction systems.

Matrix Solute T (K) P (MPa) kd (×10−4 s−1 ) Reference

Shiitake mushroom Shiitake oil 303–323 15–30 0.190–0.487 Kitzberger et al. [3]
Activated carbon Toluene 308–338 6.08–17.23 2.12–11.1 Tan and Liou, [45]
Turmeric rhizomes Curcumins 343–378 25.0–30.0 3.47–12.2 Chassagnez-Méndez et al. [63]
Pupunha Oil 318–323 25.0–30.0 5.33–6.67 Araújo et al. [64]
Carqueja Oil 303–313 10.0–30.0 3.82–9.28 × 10−2 Silva et al. [66]
Marigold flowers Oleoresin 299–313 12.0–20.0 0.17–0.33 Campos et al. [65]
Croton Oil 288 6.7 0.95–1.01 Sousa et al. [116]
Vetiver roots Volatile oils 313 20.0 1.15–2.33 Talansiera et al. [117]
Fennel seeds Oil 303–313 10.0–25.0 0.93–3.68 Moura et al. [135]

methanol flow rate. More interestingly, the thickness (h) of the dif- Alternatively, some researchers have attempted a so-called one-
fusion layer can be calculated from the ˇ value, along with the De site desorption model to quantitatively evaluate the dissolution and
obtained from the hot ball model. Then the thickness of the diffu- desorption behavior of chemicals under supercritical conditions
sion layer obtained is in the order of 10 nanometers, spanning from [67,68]. If rapid equilibrium between the analyte and the matri-
9.8 to 12.8 nm. ces can be assumed during the extraction process, this model may
be given below to define the extraction curve:
3.2. Desorption model mt
= 1 − Ad · exp(−kd t) (9)
m0
For this kind of desorption models, the SFE process is assumed
where Ad is a dimensionless model coefficient. This model could be
to be desorption of the analyte from the parent matrix. In 1989,
valid for SFE of chemicals freshly added to soils, chemicals with low
Tan and Liou proposed a single parameter desorption model for
hydrophobicity, and soils with low organic carbon content [24].
describing desorption of activated carbon loaded with toluene by
However, for many other systems, nonequilibrium disso-
SCCO2 [45]. This model may be simply derived as follows.
lution/desorption may have been applied. In this case, the
Mass balance for the bulky fluid phase:
nonequilibrium behavior can be represented using a two-site
∂y ∂y 1 − ε s ∂x model in which one fraction of the solute in the matrices is quickly
+u =− · · (5)
∂t ∂z ε f ∂t released and another fraction is slowly released [67–70]. Generally
speaking, the fraction of the total solute that is released quickly
with boundary conditions: t = 0, y = 0 and z = 0. Note that y (g
(Fr ) from the matrices is commonly assumed to be representative
solute/g solvent) and x (g solute/g solute free solid bed) are the
of equilibrium release conditions whereas the remaining fraction
analyte concentration in the SCCO2 fluid phase and the solid phase,
of the total mass that is released slowly (1 − Fr ) is considered to be
respectively; f and s are the density of the SCCO2 fluid and the
kinetically rate-limited. With this model, dissolution/desorption is
solid (g/cm3 ), respectively; ε is the porosity of the extraction bed,
assumed to occur in two different sites in the parent matrices. These
u is the superficial velocity of the SCCO2 solvent (m/s), and z is the
are conceptual “sites” since it is recognized that analyte desorption
axial position (m).
undoubtedly occurs from many actual locations in the matrices.
Mass balance for the solid phase:
The two-site kinetic desorption model can be written, consisting
∂x of two first-order expressions, as follows:
(1 − ε)s = −kd x (6)
∂t mt
= 1 − Fr · exp(−kd1 t) − (1 − Fr ) · exp(−kd2 t) (10)
with t = 0, x = x0 . x0 is the initial solute concentration in the solid m0
phase (g solute/g solute free solid bed), and kd is the desorption where Fr is the fraction of the analyte released quickly, (1 − Fr ) is
rate constant (s−1 ). the fraction of the analyte released slowly; kd1 is the first-order
The time-dependent solute concentration at the exit of the
rate constant describing the quickly released fraction (min−1 ); and
packed bed can then be solved, resulting in
kd2 is the first-order rate constant describing the slowly released
  εk H  
1 − ε s d fraction (min−1 ).
y(z = H, t) = x0 exp − 1 exp(−kd t) (7)
ε f u This model has thus been applied in the extraction SCCO2 extrac-
tion of ginger rhizome [67], Morinda citrifolia roots [68], savory
where H is the height of extraction bed (m). Integration of Eq. (7)
[69], seeds of rosehip, loquat and physic nut [70]. Table 2 presents
from the beginning to time t gives the overall extraction curve:
the regressed results using the two-site kinetic desorption model.
 t
1 − ε s 1 Obviously, the fast desorption rate constant (kd1 ) is at least one
mt (h = H) = QCO2 y (z = H, t)dt = QCO2 · x0 order of magnitude higher than the slow rate constant (kd2 ).
0
ε f kd
 
Note that the kinetic model includes no factor describing extrac-
εHAf tion flow-rate, but relies solely on time. Therefore, doubling the
× 1 − exp [exp(−kd t) − 1] (8) volumetric SCCO2 flow-rate should have little effect on the extrac-
QCO2
tion efficiency per unit time if the extraction efficiency is controlled
where A is the cross-sectional area of the extraction vessel (m2 ), by the kinetics of the initial desorption step and the other extraction
QCO2 is the mass flow rate of the SCCO2 solvent (g/s). parameters remain constant. Thus, in terms of the solvent flow-rate
This model was initially proposed by Tan and Liou in 1989 for effect it would be better to compare this model with the partition-
the removal of toluene from activated carbon with SCCO2 [45], ing coefficient model that will be discussed in the next section.
and has been applied to oil from Shiitake mushroom [3], curcum-
ins from turmeric rhizomes [63], oil from pupunha [64], oleoresin 3.3. Partitioning coefficient model
from marigold [65], and oil from carqueja [66]. Table 1 shows the
regressed results for the Tan–Liou model, and more details on the Partitioning coefficient model, proposed by Kubátová et al. [69],
model can be found in these publications. has been developed on a thermodynamic partitioning coefficient
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26 7

Table 2
Values of Fr , kd1 and kd2 obtained with the two-site kinetic model for different SCCO2 extraction systems.

Matrix Solute T (◦ C) P (MPa) CO2 flow rate Fr kd1 (min−1 ) kd2 (min−1 ) Reference
(ml/min)

Ginger rhisome Oleoresin 50–65 12.7–19.6 – 0.52–0.89 1.75–26.4 × 10−3 1.1–2.2 × 10−4 Kandiah and
Spiro, [67]
Morinda Damnacanthal 150–220 4.0 1.6–4.0 0.76 0.0357–0.090 0.0078–0.029 Anekpankul
citrifolia et al. [68]
roots
Savory Essential oil 50 20.0 0.25–4.0 Kubátová et al.
[69]
Thymol 0.37–0.48 0.09–0.12 0.005–0.006
Carvacrol 0.36–0.48 0.09–0.12 0.005–0.005
Borneol 0.25–0.37 0.07–0.12 0.006–0.007
Thymoquinone 0.20–0.53 0.05–0.15 0.011–0.013
p-Cymene 0.26–0.50 0.06–0.11 0.006–0.007

Sosehip seed Oil 40–80 15–49 3.0 0.75 0.0014–0.1803 1.4 × 10−6 –0.0193 Machmudah
et al. [70]
Loquat seed Oil 3.0 0.75 0.0063–0.0263 0.0007–0.0108
Physic nut seed Oil 3.0 0.75 0.0054–0.0517 1.9 × 10−5 –0.040

Kp , which is defined as the analyte concentration in the solid matrix
phase over that in the SCCO2 fluid phase at equilibrium:
x all other extraction parameters hold the same. Therefore, if the
Kp =
y
This model assumes that the initial desorption step and the
subsequent fluid–matrix partitioning are rapid, and thus do not
significantly affect the extraction rate. For SFE process, this type of
behavior may occur if the initial solute concentration in the plant
matrix is small. Thus, if the size of the solid particles is uniform,
the mass of the solute in each unit mass of extraction fluid and that
remaining in the matrix for particular extraction period can be cal-
culated based on the Kp value determined for the solute. Then, the
extraction curve over the entire extraction process can be obtained
by:
mb 1 − ma /m0 ma
= +
m0 Kp m/[(Vb − Va )f ] + 1 m0
where ma and mb are the cumulative mass (g) of the analyte
extracted after the extraction fluid volume Va and Vb (m3 ), respec-
tively. Thus mb /m0 and ma /m0 are the cumulative fractions of the
analyte extracted by the extraction fluid of the volume Vb and Va ,
respectively. The data points Vb and mb is the next sequential data
point after Va and ma , and m are the mass of the loaded sample
(g).
For this model, the parameter to be regressed against the extrac-
tion data is Kp . Table 3 shows calculated results reported in the
literature [68–70] for using the partitioning coefficient model to
fit with experimental data. It should be noted from the model
that the cumulative amount of solute extracted is described as
a function of SCCO2 volume passed the extractor, and does not
depend on the extraction time. Thus, doubling the extraction fluid
flow-rate should double the extraction rate for the same period
if the extraction is described by thermodynamic partitioning and
(11) cumulative amount of solute extracted is plotted against extrac-
tion time, the curve for the higher flow rate will lie above that for
the lower flow rate. On the other hand, if the same data are plotted
in terms of volume, the curves from all flow rates will overlap com-
pletely. Obviously, this case is different from that for the two-site
desorption model as discussed previously.
4. Hot sphere diffusion model
4.1. Assumptions
The SFE process may be treated analogously as a heat transfer
phenomenon by considering the solid particles as hot balls cooling
(12) down in a uniform surrounding. Then the extracted particles are
assumed to be spherical with initially uniformly distributed solute
diffusing through the matrix analogously to the heat diffusion and
the solute concentration in the solvent is assumed to be close to
zero. Thus, Bartle et al. [71] in 1990 proposed a hot ball diffusion
(HBD) model for describing supercritical fluid extraction processes.
They have insightfully discussed the effect of matrix shape, size
variation, solute distribution and solubility limitations on the hot
ball model for real systems [71,72]. Fig. 2 graphically shows the
particle scheme for the hot ball diffusion (HBD) model. Unlike the
BIC situations where some of the solute is readily accessible to the
solvent on particle surface [41], the hot ball model is suggested
for a matrix which contains small quantities of extractable materi-
als such that the extraction is not limited by solubility. When the
intraparticles or internal diffusion controls the mass transfer pro-
cess, it may be appropriate to start studying mass transfer between

Table 3
Applications of the partitioning coefficient model for different SCCO2 extraction systems.

Matrix Solute T (◦ C) P (MPa) CO2 flow rate (ml/min) Kp Reference

Morinda citrifolia roots Damnacanthal 150–220 4.0 1.6–4.0 43.27–66.46 Anekpankul et al. [68]

Savory Essential oil 50 20.0 0.25–4.0 Kubátová et al. [69]

Thymol 11–12
Carvacrol 9–11
Borneol 7–9
Thymoquinone 3–4
p-Cymene 215–240

Rosehip seed Oil 40–80 15–49 3.0 18.5–337.1 Machmudah et al. [70]
Loquat seed Oil 29.8–233.6
Physic nut seed Oil 29.5–485.9
8 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

The same material flux must fit the transport equation on the

external surface:

M = ke (c|R − c) (13b)

where c|R is the concentration of the solute at the particle surface

(g/m3 ), and ke is the particle-to-supercritical phase mass transfer
coefficient (m/s).
Likewise, it is possible to evaluate the concentration profiles
of the extractable materials along the particle radius at different
extraction times. Then, the differential material balance on the
solute located in a particle may be resulted if the effective solute
diffusivity De does not depends from radius r, the following can be
Fig. 2. Particle scheme for the hot ball diffusion (HBD) model.
obtained:
 

∂ c|R 1 ∂ ∂c|R
= De r2 (14)
∂t r 2 ∂r ∂r
a single particle and the supercritical solvent, and then extend the
results to the whole bed. The extension of the results to the whole This expression is mathematically analogous to the represen-
bed of particles is immediate since all the particles are assumed to tation of the unsteady cooling of a hot sphere suddenly immersed
be at the same extraction conditions. For these reasons, the HDB into a cold fluid. Applying the Fourier transforms and the heat–mass
model has been further elaborated by Reverchon et al. [43] and transfer analogy, it is possible to obtain a general solution for the
Esquível et al. [73], and attempted by a number or researchers to concentration based on the extraction time and the intraparticle
simulate various extraction processes of natural materials [74–81]. position as given below [43,73,79].

4R  sin ˇk − ˇk cos ˇk
More recently, Huang et al. [62] have further extended this model ∞
c|R − c ˇk r
for describing amine extraction from freshly synthesized hexago- = sin
cs0 − c r 2ˇ2 − ˇk sin 2ˇk R
nal mesoporous silica materials by means of methanol-enhanced k k
supercritical CO2 .   2
In this model, the extraction process from a single particle may ˇk
× exp − De t (15)
be described by the following stages in sequence: (1) CO2 diffusion R
in the SCCO2 solution film around the particle; (2) CO2 adsorption
on the particle surface and diffusion into the particle; (3) analyte where the terms ˇk allow the particularization for a given system
dissolving; (4) analyte diffusion out of the solid matrix; (5) analyte and each term of the series is defined by the periodic Eq. (16):
diffusion through the SCCO2 solution film into the bulky solvent.
R
Besides, some assumptions should be included (a) each single ˇk cot ˇk = 1 − kf (16)
De
particle has the same shape and same diameter, (b) extraction of
different analyte components are parallel and non-interacting pro- The mass flux density M may be obtained from the variation
cesses, which is particularly well suited in the SFE of essential oils of the solute concentration at the particle surface with extraction
due to the fact that the essential oil concentration is very low if time, giving [73]
compared with the equilibrium solubility, (c) diffusivities of differ-  t
ent analytes in the parent matrix are independent from the particle ∂c|R
M = −De dt (13c)
radius, and (d) different analytes are treated as a single chemical 0
∂r
compound.
From Eqs. (6) and (8), the general solution can be given as follows
[43,73]:
4.2. Mathematical representation 
∞
(sin ˇk − ˇk cos ˇk )
2
M = 4R(cs0 − c)
The material balance across an internal particle surface of radius 2ˇk4 − ˇk3 sin 2ˇk
k
r (m), according to the first Fick’s law, for a constant density and    2 
diffusivity in the solid and spherical coordinates (r, , ), can be ˇk
· 1 − exp − De t (13d)
given below [43]: R


1 ∂(r 2 xr ) 1 ∂(x sin ) 1 ∂xϕ

The extension of the above single-sphere results to the whole
M = −cs0 De + +
r 2 ∂r r sin  ∂ r sin  ∂ϕ bed can be made on the assumption that all the particles in it behave
(13) in the same way. The number Np of particles that constitute the bed
are
where M is the solute mass flux density per unit of area, in unit
3V (1 − ε)
of g solute/(m2 s), cs0 is the initial solute concentration in the solid Np = (17)
4R3
matrix (g/m3 ), xr , x , and xϕ are the dimensionless concentrations,
functions of the extraction time, along coordinates r, , and ϕ, Then the total cumulative amount mt of the solute extracted is
respectively.
mt = Np · M · 4R2 (18)
Considering that the concentration of the solute is independent
from coordinates  and ϕ, then the solute flux within the particle Eq. (18) holds in the hypothesis that all the particles in the bed
can be reduced as follows: have reached the same extraction stage during the whole process,
thus neglecting the concentration profile that occurs along the bed
1 ∂r 2 xr when supercritical CO2 flows through it. Note that the particles are
M = −c0 De (13a)
r 2 ∂r spherical and are of the same size.
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26 9

Similarly, the total weight of the solute in the fixed bed, m0 , may is the rate controlling mode of the process. However, their two-part
be expressed as models have not led to satisfactory performance as the deviation
4 3 can be higher than 50%.
m0 = Np · R cs0 (19)
3
4.3. Parameter identification
Then, it is possible to obtain the fraction of the solute that is
extracted from the bed against time if the concentration of solute
The extraction calculations obtained either from Eq. (20a) or
in the bulk fluid phase is very small, given by
   2  from Eq. (20) along with Eq. (16) can be thus compared to the exper-
mt  (sin ˇ − ˇ cos ˇ )
∞ 2
ˇk imental data by applying the least-squares method in which the
k k k
= 12 · 1 − exp − De t solute solid diffusivity De used as the model parameter to obtain
m0 ˇ3 (2ˇk − sin 2ˇk ) R
k k the best fit of the experimental data. In order to model the extrac-
(20) tion curve with Eq. (20), ˇk must be calculated from Eq. (16), thus
the external mass transfer coefficient kf has to be evaluated. Usu-
Further, if the solute film resistance is neglected, ke /Dm → ∞, ally, kf can be estimated by using a number of correlations that
then ˇk = n, thus Eq. (20) can be further condensed to the familiar relate this coefficient with dimensionless numbers. These correla-
expression: tions have extensively been used for the solid–fluid transfer case in
a SFE process, as summarized in recent review papers [36,37]. For
  2

6  1
∞
mt n examples, the correlation proposed by Tan et al. [36,37,84] can be
=1− 2 · exp − De t (20a) given as:
m0  n2 R
n=1
1/3
which may also be written in the equivalent form Sh = 0.3Re0.83 Sc (valid for 2 < Re < 40, and 2 < Sc < 20)
  
mt

De t
1/2 1  ∞
nR 3De t
The other expressions commonly used are presented as below.
=6 √ + i erfc  − (20b) King and Catchpole:
m0 R2  De t R2
n=1
1/3
Sh = 0.82Re0.6 Sc (valid for 1 < Re < 70, and 3 < Sc < 11)
For short time, a simplified form for the initial region of the
extraction curve may be obtained by neglecting the higher order Puiggené et al.:
term in Eq. (20b).
1/3
 D t 1/2 Sh = 0.206Re0.8 Sc (valid for 10 < Re < 100, and Sc < 10)
mt 6 e
= √ (20c)
m0  R2 Wakao and Funazkri:
In the long time region, all terms except the first in the series of Sh = 2.0 + 1.1Re0.6 Sc
1/3
(valid for 3 < Re < 10, 000)
exponential terms in Eq. (20a) become negligible and the extraction
yield curve can be recast as: where Sh = dp ke /D12 , Re = f udp /
, Sc =
/f D12 . Sh , Re , and Sc are
 the dimensionless numbers of Reynolds, Sherwood, and Schmidt,
mt 6 2 De t
= 1 − 2 exp − (20d) respectively.
is the viscosity of the supercritical solvent phase
m0  R2 (g/(m s)), and D12 is the external diffusion coefficient (m2 /s) of the
From which it is apparent that a plot of ln(1 − mt /m0 ) versus solute to the supercritical fluid or called the solute–solvent binary
t will approach a straight line with a slope of −2 De /R2 . Ohira diffusivity coefficient as well. More recently, Mongkholkhajornsilp
et al. [80] have treated Eq. (20d) as a one-site kinetic desorption et al. have proposed a new expression of mass transfer coefficient
model with a different form of mt /m0 = 1 − exp(− kt), similar to that in order to improve the correlation performance [85]. In conjunc-
reported by Mehr et al. [74] and Subra et al. [75]. However, some tion with experimental results for nimbin extraction neem seeds,
studies [75,81–83] show that a single line may not properly be the correlation obtained by using non-linear regression analysis is
resulted when ln(1 − mt /m0 ) is plotted against time. In stead, the Sh = 0.135Re0.5 Sc0.33 with Reynolds number from 0.169 to 1.292 and
extraction data points may fall onto two intersecting straight lines, Schmidt number from 6 to 25.
the first with a relatively steep slope and the second with a rela- The values of parameter D12 may be similarly evaluated using
tively shallow one. Therefore, these studies suggest that it may be existing correlations and available data. For example, Reverchon
necessary to consider the presence of two parallel diffusion pro- et al. [43] have assumed a D12 value of 1 × l0−6 m2 /s for describing
cesses inside the solid, with one faster and one slower. It follows SCCO2 extraction of essential oils and waxes from basil, marjo-
that: ram and rosemary leaves. Otherwise, certain correlations should
  
be attempted and these D12 involved correlations have been sum-
mt 6 2 De1 t 2 De2 t marized in recent review [37]. Two of them are exampled here;
=1− 2 f1 exp − + f2 exp (20e)
m0  R2 R2 one is the well-known Stokes–Einstein equation D12 = kB T/(6 
)
where  is the solute molecule radius and kB is Boltzman constant.
where f1 and f2 are the fractions of the solute, which are extracted
The other correction is given below as it is suitable for estimating
with different diffusion coefficients De1 and De2 , respectively.
binary diffusivity of solute in a wide variety of supercritical solvents
Using Eq. (20e) Hojnik et al. [81] have modeled extraction of
[37,52]:
lutein from Marigold flower petals and found that higher De and
lower De values are in the range of 1.45–9.09 × 10−12 m2 /s and c r r −2/3  r
0.9–5.8 × 10−14 m2 /s, respectively. Interestingly, Čretnik et al. [76] D12 = 5.152Dscf Tscf [(scf ) − 0.4510] · , 1 < scf < 2.5

have mathematically modeled separation of parthenolide from
feverfew by dividing the extraction into two continuous parts. The 
c )0.75
Mscf · (Tscf
first part represents the period of constant extraction rate, where c −7
Dscf = 4.30 × 10 ·  2/3 ,
steady state mass transfer prevails and the film resistance controls vscf c
· scf
the rates. The second part represents the period of falling extraction
rate with unsteady state mass transfer where the internal diffusion c
for SCCO2 , Dscf = 4.937 × 10−8 m2 /s
10 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

Table 4
Calculated De values with the HBD models for different SCCO2 extraction systems.

Matrix Solute T (K) P (MPa) De (m2 /s) Reference

Shiitake mushroom Shiitake oil 303–323 15–30 7.35–38.5 × 10−14 Kitzberger et al. [3]
Baizhu herb Extracted 313–333 15–45 1.47–8.13 × 10−13 Huang et al. [40]

Basil leaves Essential oil 313 10 1.5 × 10−13 Reverchon et al. [43]
Cuticular waxes 313 10 1.6 × 10−17

Marjoram leaves Essential oil 313 10 1.4 × 10−13

Cuticular waxes 313 10 3.7 × 10−17

Rosemary leaves Essential oil 313 10 2.8 × 10−13

Cuticular waxes 313 10 9.4 × 10−17

Porous silica material Dodecylamine 323–378 15–25 1.19–6.72 × 10−12 Huang et al. [62]
Oleoresin Marigold flowers 299–313 12.0–20.0 1.30–2.55 × 10−13 Campos et al. [65]
Olive husk Olive husk oil 313 12–18 0.1–25.9 × 10−13 Esquivel et al. [73]
Guaraná seed Caffeine 308–328 13.8–27.6 4.4–4.6 × 10−12 Mehr et al. [74]

Feverfew flower heads Extracted 313–353 20–30 2.74–3.59 × 10−14 Čretnik et al. [76]
Parthenolide 1.28–13.36 × 10−14

Cow brain Cholesterol 323–343 23.0–27.0 1.90–2.80 × 10−13 Vedaraman et al. [77]
Soybeans Oil 313 28 2.2–36 × 10−14 Rochová et al. [78]
Nannochloropsis gaditana Carotenoid 313–333 10–50 0.08–114 × 10−19 Macías-Sánchez et al. [79]
Synechococcus sp. Carotenoid 313–333 10–50 0.02–64 × 10−19
Dunaliella salina Carotenoid 313–333 10–50 0.22–830 × 10−19
Peach almond oil Peach almond 313 15.0–25.0 0.041–2.28 × 10−10 Mezzomo et al. [94]
Guava leaves Extract 308–328 30.0 0.75–0.77 × 10−12 Moura et al. [114]
Vetiver roots Volatile oils 313 20.0 0.7–2.2 × 10−13 Talansier et al. [117]

For cautious cases, temperature and pressure used can be up to

353 K [76] and 50 MPa [79], respectively. In the case of inorganic
c ) 1/3 2
[1 + (Vsc /Vscf ] materials, extraction temperature can be higher to 378 K [62]. As
= 
(1 + Mscf /M0 ) shown in Table 4, the hot ball model performs very well with satis-
factory calculations of extraction yields for various SFE systems, as
 reflected by acceptable correlation deviations for the experimental
0.6640.17 ± 0.1, 2 <  < 10 data.
=
1.0 ± 0.1,  < 2
c is self-diffusion coefficient (m2 /s) of the supercritical
where Dscf
c and V c are the critical molar volume
solvent at critical point, Vscf s reported concerning a vegetable matrix are diversely different by
3
(cm /mol) of the solute and the supercritical solvent, respectively.
 several orders of magnitude. The De values are mostly in order
vscf and Mscf are the molar volume (cm3 /mol) and the molec-
ular weight of supercritical solvent, Tscfr and r are the reduced
scf
temperature and reduced density of supercritical solvent, Tscf c and
c
scf are the critical temperature (K) and critical density (kg/m3 ) of
supercritical solvent.
The size of the particles of interested matters may be measured
using sieves of the Tyler series and determined by the Sauter equa-
tion [40,62,86]:
1 303–323 K and 15–30 MPa [80], respectively. These values are
dp =
k
mi /dpi
i=1
where dp is the averaged particle diameter, i = 1, 2, 3, . . ., k, dpi is
the diameter of the sieve i, and mi is the mass fraction of the
solid retained by the sieve i. Obviously, the diameter obtained is
the weight mean diameter of the measured size distribution. In
addition, the solid density and the bed porosity ε can be mea-
sured by using mercury porosimetry or other gravimetric methods
[40,86–88].
4.4. Applications
The HBD model has been widely employed to model the SCCO2
extraction [43,73–83] and Table 4 summarized some modeled
results using the HBD model. As seen from Table, SCCO2 extrac-
tions of natural matters are mostly performed with temperature
varying from 308 to 333 K and pressure ranging from 10 to 30 MPa.
The HBD model is very useful to estimate the values of solute
diffusion coefficient De since published diffusivity data for the solid
matrix are far lacking. However, it should be noted that the results
of from 10−15 to 10−13 m2 /s, strongly related to system tempera-
ture, pressure, CO2 flow rate and the solute as described previously.
As shown in Table 4, these values are 1.5 × 10−13 , 1.4 × 10−13 and
2.8 × 10−13 m2 /s for essential oils from basil, marjoram and rose-
mary leaves at 313 K and 10 MPa [43], 1.28–13.36 × 10−14 m2 /s
for parthenolide from feverfew flower heads at 313–353 K and
20–30 MPa [77], 0.1–25.9 × 10−13 m2 /s for olive husk oil at 313 K
and 12–18 MPa, and 7.35–38.5 × 10−14 m2 /s for shiitake oil at
(21) higher than those obtained in the extraction of carotenoids from
microalgae [79] or in the extraction of cuticular waxes [43], where
the values obtained by are approximately in the order of 10−19 or
10−17 m2 /s, respectively. The reason for it may be due to the dif-
ference in the material structure, as addressed by Macías-Sánchez
et al. [79]. They state that carotenoids pigments for the microalgae
studied are found in an organelle named the chloroplast or close to
the cellular membrane and the cuticular waxes are found in a thick
film that covers the vegetable matrix, possibly rendering the inter-
nal diffusion coefficients regressed much lower than those reported
for the other systems. For better comparison, they have further
tested extraction of red grape pomace and the values regressed
are in the order of 10−15 m2 /s, similar to those obtained for extrac-
tion of various vegetable matrixes as these matrixes have a similar
structure to red grape pomace. From Table 4 it may be also found
that relatively higher De values of 4.4–4.6 × 10−12 m2 /s are obtained
for caffeine from guaraná seed at 308–328 K and 13.8–27.6 MPa
[75]. Similarly, the values of 1.19–6.72 × 10−12 m2 /s are obtained
at 323–378 K and 15–25 MPa for dodecylamine extraction from
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26
Fig. 3. Particle scheme for the broken and intact cell (BIC) model.
inorganic silica materials. These results may be related to the rela-
tively large-pored structure in the matrix [62].
However, as the extraction proceeds in the extraction bed, the
concentration of the solute in the bulk fluid may not be consid-
ered to be zero, especially if a large amount of accessible solute
is assumed to cover the particle surface. In this sense, the con-
centration of the solute in the fluid cannot be assumed to be zero
any longer. As addressed earlier [72], the hot ball model should be
modified by considering the effect of the solute solubility on the
extraction in terms of ke /De , along with the flow rate, particular
matrix–solute interactions and temperature.
Obviously, Eqs. (13) and (7) may converge to Eq. (14) for high
values of ke /De . But once the value of ke /De is very low, the large sol-
ubility limitation may occur during the extraction process, making
the HBD model not opportune. For this reason, Some researchers
such as Recasens et al. [60], Goto et al. [42], and Macías-Sánchez
et al. [79] have suggested that the choice of the most appropriate
mass transfer model may be properly made by evaluating the values
of the Biot number obtained from the internal diffusion coefficient
De , external mass transfer coefficient ke and particle dimension
Bi = 2kf R/De .
If the Biot number is very high, say, greater than 10, the internal
diffusion may be the controlling factor in the extraction process.
In this case, the application of the HBD model could be appro-
priate. On the other hand, if the Biot number is less than 10, the
controlling factor is the mass transfer in the interstitial fluid. The
HBD model may fail in such a case and other models should be
attempted. Macías-Sánchez et al. [79] have calculated the Biot num-
ber for the extraction of carotenoids from Nannochloropsis gaditana,
Synechococcus sp. and Dunaliella salina studied, and the calculated
results are very high in the order of 107 and 1010 . These values are
greatly higher than 10, indicating that the internal diffusion may
possibly control the extraction process and the calculated diffusion
coefficient could be used in the design of the extraction process.
Vedaraman et al. [77] have drawn from high Biot number values
that the extraction rate cholesterol from cow brain may not be
influenced by the SCCO2 flow rate, however the authors have found
that the increase in the solvent flow rate has led to the increased
cholesterol yield. They have referred it to the concentration driving
force within the solid due to the lower surface concentration of the
solute in the SCCO2 at higher flow rates.
5. BIC model
5.1. Assumptions
For most SCCO2 extraction processes the natural materials to be
extracted like seeds, leaves, kernels, flowers roots, and fruit peels
or pomace, microalgae are usually pretreated like grinding, milling
or crushing before loaded into the extraction bed. For this reason, it
11
is reasonable to bring the concept of broken and intact cells, as pro-
posed by Sovová in [41], to mathematically describe the extraction
process of natural materials. Then Sovová has wisely developed a
broken and intact cell (BIC) model based on Lack’s plug flow model
[41] and many other researchers have applied it for the modeling
of the SCCO2 extraction processes in terms of the overall extraction
curves.
The BIC model is applicable in situations where some of the ana-
lyte is at the outer surfaces of the particles or in ruptured cells due
to the mechanical grinding pretreatment and thus can be readily
accessible to the SFE solvent while the rest is deep down in the
pore structure or in intact cells and then less accessible. Therefore
extraction of easily accessible solute is fast with a rate controlled
by its diffusion and convection in the solvent while the extraction
of the less accessible solute from intact cells is much slower and the
mass transfer resistance is high. Resistance to mass transfer con-
sidered includes both the SFE solvent film around the particles and
the solid phase (i.e., within the particles). The former determines
the rate of extraction of the easily accessible solute while the latter
controls the rate of mass transfer of the less accessible solute.
In this model, the extraction process is apparently in divided
into three periods [41] controlled by different mass transfer mech-
anisms:
(1) Constant extraction rate (CER) period. In this initial period, the
external surface of the particles is covered with easily accessible
solute, extraction proceeds fast at a constant rate determined by
the convective solvent film resistance. At the end of this period
the particles at the bed entrance will have lost all the accessible
solute that they initially contain. But some more deeply embed-
ded solute still remains in the particles so that these particles
are only partly exhausted of solute and extraction of the more
deeply embedded solute from them commences now at the bed
entrance.
(2) Falling extraction rate (FER) period. During the transition
period, the diffusion mechanism starts combined with convec-
tion. The solute in intact cells starts to be extracted and the
readily accessible solute continues to be extracted whereas the
extraction rate drops rapidly during this period. Note that the
particles at the bed inlet lose all the easily accessible solute but
the particles at the bed outlet still have lots of readily accessi-
ble analyte. At the end of this period, all the readily accessible
solute has been removed from the parent matrix.
(3) Diffusion-controlled (DC) period. In the last period, the external
solute in broken cells disappears and only the less accessi-
ble solute in intact cells is slowly extracted. The mass transfer
occurs mainly by slow diffusion in the bed and inside the solid
substrate particles.
In the BIC model, the following assumption should be consid-
ered.
(1) Extraction system is isothermal and isobaric.
(2) Physical properties of the supercritical fluid are constant during
the extraction.
(3) Initial oil concentration and particle size distributions are uni-
form in the packed bed.
(4) Bed void fraction are constant during the extraction in the
packed bed.
(5) Solute accumulation in the solvent is negligible.
(6) SCCO2 is solute free at the bed entrance.
(7) Mass transfer phenomenon of all extract are similar.
(8) Axial dispersion is neglected because of assuming plug flow.
12 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

5.2. Mathematical representation overall extraction curve, e (mass of the extract, g/g solute-free feed),
corresponding to each extraction period, is then determined as
The BIC model describes a situation when a SCF solvent flows  H
axially with superficial velocity u through a bed of pretreated matri- 1
e(t) = x0 − x(z, t) dz (26)
ces in a cylindrical extraction unit. Assuming that the concentration H 0
of the readily accessible solute and that of the less accessible solute
are xb and xi at the beginning of the extraction, respectively, the For evaluation of experimental data, extraction curve should be
total initial concentration of the extractable solute x0 has x0 = xb + xi . expressed in terms of real time or amount of the SCF solvent con-
The fraction, r, of the less accessible solute can be given as r = xi /x0 sumed. Eq. (26) can be analytically solved for each stage, expressing
and sometimes, a term of the grinding efficiency, 1 − r, is used the amount of extract as a function of the specific amount of solvent
instead for expressing the fraction of the readily accessible solute in q, concentrations x0 , xi and y* and parameters Z and W.
the bed. Fig. 3 shows the particle scheme for the broken and intact For stage one q < qCER or t < tCER ,
cell model. It is seen that the easily accessible solute from broken
e = q × y∗ × [1 − exp(−Z)] (27a)
cells is transferred directly to the fluid-phase while the solute from
intact cells diffuses first to broken cells and then to the fluid-phase. For stage two: qCER ≤ q < qFER or tCER ≤ t < tFER
Besides, some researchers suggest that the solute from intact cells
may also diffuse directly to the fluid phase as well [37]. e = y∗ × [q − qm × exp(Zw − Z)] (27b)
Based on differential mass balances, taken both within the solid
For stage three: q ≥ qFER or t ≥ tFER ,
matrix and in the surrounding solvent phase, the BIC model may
be derived as follows [41]. y∗
 x0
   
Solid phase: e = x0 − ln 1 + exp W + ∗ −1
W y
∂x
 xi

−s (1 − ε) = f (x, y) (22) × exp W × (qm − q) × for t ≥ tFER (27c)
∂t x0
Fluid phase: where
∂y ∂y mCO2 q x0 − xi
f u + f ε = f (x, y) (23) q= , q̇ = and qCER = (28a)
∂z ∂t mbed t y∗ · Z
where f(x, y) is the interfacial mass transfer rate. Usually for SFE 
1 xi + (x0 − xi ) · exp(W · x0 /y∗ )
the fluid phase can be treated as a diluted solution, therefore the qFER = qCER + · ln (28b)
W x0
solvent density CO2 can replace the fluid phase density.
The second term in the fluid phase balance Eq. (23) is often
kf a0 f
neglected as plug flow is assumed, giving Z= (28c)
[q̇(1 − ε)s ]
f u
∂y
= f (x, y) (23a) Z · y∗
 x · exp[W · (q − q )] − x 
0 CER i
∂z Zw = · ln (28d)
W · x0 x0 − xi
The boundary conditions are
 W=
ks a0
(28e)
x(z, t = 0) = x0 [q̇(1 − ε)]
y(z = 0, t) = 0
where mCO2 is the mass (g) of SCCO2 solvent consumed and mbed is
To solve Eqs. (22) and (23a), Sovová [41] has defined f(x, y) as a the mass (g) of solute-free feed loaded in the bed. q and q̇ are the
function of the concentration difference using a local mass transfer specific mass (g solvent/g solute-free feed) and specific mass flow
coefficient for both phases. The easily accessible solute which sur- rate (g solvent/g solute-free feed in unit time) of solvent passed
mounts only the diffusion resistance in the solvent is extracted first through the extraction, y* is the equilibrium solubility of the solute
and this part of solute crosses the interfacial boundary fast enough in the SCCO2 solvent (g solute/g solvent), qm is the q value when
to kept the solvent at the boundary saturated, the mass transfer extraction begins inside the particles, qn is the q value when the
rate is easily accessible part of solute is all extracted, Zw is the dimen-
sionless axial co-ordinate between fast and slow extractions, Z is
f (x > xi , y) = kf a0 f (y∗ − y) (24) the dimensionless mass transfer parameter in the fluid phase, W is
But when the solid-phase concentration decreases to xi , the the dimensionless mass transfer parameter in the solid phase, ks
mass transfer is then retarded by the diffusion in the solid phase, is the solid-phase mass transfer coefficient (m/s), kf a0 is the volu-
subsequently resulting in slow extraction process. The mass trans- metric solvent phase mass transfer coefficient (s−1 ), and ks a0 is the
fer rate could thus be expressed as: volumetric solid phase mass transfer coefficient (s−1 ).
If extraction curve were expressed in terms of real time used,
f (x ≤ xi , y) = ks a0 s (x − xf ) (25) two terms of tCER and tFER , i.e., constant extraction rate (CER) and
falling extraction rate (FER) periods, may be used. In other words,
Considering that the solid-phase diffusion resistance is much
tCER is the time at which the extraction of the oil from the inside of
large than the resistance in the supercritical phase, the interfacial
particles starts (min) and tFER is the time at which the extraction of
concentration xf (g solute/g solute-free feed) could be neglected in
easily accessible solute (min) ends. Their quantitative expression
comparison with the concentration inside particles x, and Eq. (25)
may be given as:
becomes
x0 − xi
f (x ≤ xi , y) = ks a0 s x (25a) tCER = (28f)
y∗ · Z · q̇
The concentration profiles in the sold and solvent phases can 
1 xi + (x0 − xi ) · exp(W · x0 /y∗ )
then be calculated by integrating from Eqs. (22) and (23a) after tFER = tCER + · ln (28g)
W · q̇ x0
substituting Eqs. (24) and (25a) for the rate of mass transfer. The
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26 13

5.3. Parameter identification

del Valle et al. [119]

Ivanovic et al. [96]

Ferreira et al. [97]

Huang et al. [40]
Nagy et al. [51]
As an analytical solution to mass balance equations, the extrac-

Jia et al. [93]

tion calculations for the overall extraction curves could be readily

Reference
achieved through from Eqs. (27a)–(27j) with a number of adjustable
parameters regressed against the experimental data. As we can see,
once adjustable parameters include x0 , xi , y*, Z and W are known,
the q-dependent or t-dependent extraction curve can be readily
obtained.
As we know, the time-dependent extraction curve usually

ks (×10−9 m/s)

2
1.8–5.0 × 10

0.038–2.88
exhibits an initial linear extraction period followed a smooth

0.88–2.87
2.36–6.81

0.90–20.7

60.0–90.0
asymptotic plateau for SCCO2 extraction of various plant substrates.

3.49

0.51
Thus there may be two ways to estimate x0 . One common way is to

11
estimate x0 from the exhaustive extraction yield, taking it to be the
maximum yield over all the conditions investigated [40,78,90]. The

7.73–35.0 × 102
other way is to experimentally determine it with organic solvent

3.88–9.28 × 10

0.016–0.059
kf (×10−8 m/s)
[91,92]. The solute solubility y* can be directly measured in SCCO2

4.02–6.14
under low flow rates to ascertain the solute saturation [92]. It can

344–547

291–847
also be evaluated it from the experimental plot of the extraction
yield as a function of the mass of solvent flowed [90]. Since the

466
541

102
initial part of the extraction curves with their linear shape strongly
suggests that equilibrium conditions may have been attained in the
fluid coming out of the extractor and then the initial oil concentra-
tion in the fluid x0 can be approximately by x0 = e/q.

0.598–0.823

0.187–0.918

0.511–0.988

0.587–0.673
0.35–0.62
As for the parameter xi , it is commonly fitted from the exper-
imental data. Instead, it may be replaced by r (r = xi /x0 ) to be

0.123
0.321
0.555

0.335
regressed [92–95]. Note that x0 , xi or r in the modeling should be

r
taken as a constant at different conditions for its resolved phys-
ical meanings, but sometimes they may be adjustably regressed
and then strongly dependent on the extraction conditions (see
Tables 5–7).
y* (×10−3 g/g

24.2–144.4
0.70–11.7

7.35–14.0
The solvent-phase mass transfer coefficient kf and the solid-

2.1–4.69

1.5–25.0
solvent)
phase mass transfer coefficient ks can be regressed from the data

14.47
20.74

17.36
5.05
fitting [51,93,96,97]. In the calculations, parameter a0 must be
solved before using the BIC model and it may be estimated using:
6(1 − ε) 3(1 − ε)
a0 = = (29)
dp R
x0 (×10−2 g/g

10.26–49.01

The porosity ε of the fixed bed can be experimentally deter-

7.27–8.56
2.20–13.1
solute-free

mined by using mercury porosimetry or other gravimetric methods

The kf and ks values obtained with the BIC models for different SCCO2 extraction systems.

7.24

8.18

4.25
feed)

[40,86–88] as ε = 1 − a /s and the apparent density a of the solid

47.8

11.9
12.8

bed may be obtained using the actual mass of feed and the volume
of the extraction unit.
As discussed previously, kf can also be obtained from certain
correlation [36,37]. Table 5 shows calculated kf and ks values
30.0–40.0

for the BIC model. As seen in Table 5, the kf and ks values are
P (MPa)

15–45

15–45

10–20

15–30

4.02–6.14 × 10−8 and 0.88–2.87 × 10−9 m2 /s for Baizhu extract

45.0
45.0
45.0

45.0

[40], 2.91–8.47 × 10−6 and 0.90–20.7 × 10−9 m2 /s for Plumula

nelumbinis oil [93], and 0.038–2.88 × 10−8 , 1.6–5.9 × 10−11 m2 /s
for black pepper essential oil [97], 3.88–9.28 × 10−5 and
313–333

308–338

313–333

303–323
313–323

1.8–5.0 × 10−7 for Helichrysum italicum flower oils [96],

T (K)

313
333
313

323

3.44–4.47 × 10−6 2.6–6.81 × 10−9 m2 /s for corn germ oil [51],

4.66 × 10−6 and 1.1 × 10−8 m2 /s for pumpkin seed oil [51],
5.41 × 10−6 and 3.49 × 10−9 m2 /s for calendula flower oil [51],
1.02 × 10−6 and 5.1 × 10−10 for paprika fruit seed oil [51], respec-
Pumpkin seeds

Rosehip seeds

tively. Obviously, kf is generally 2–4 orders of magnitude larger

Black pepper
Helichrysum
Paprika fruit

nelumbinis
Corn germ

Calendula

than ks , indicating the presence of the easily accessible solute and

Plumula

italicum
flowers

flowers
Baizhu
Matrix

the less accessible solute.

Parameters Z and W are directly proportional to the solvent-
phase mass transfer coefficient and the solid-phase mass transfer
coefficient, respectively but both are inversely proportional to the
specific solvent flow rate. Then these two parameters are some-
Essential oil

times expressed as Z q̇ (s−1 ) and W q̇ (s−1 ) for data fitting. Table 6

Extract

shows regressed Z q̇ and W q̇ values for SCCO2 extraction of celery

Solute
Table 5

seed oil [98], parsley seed oil [99], orange peel oil [88], safflower
Oil
Oil
Oil

Oil
Oil

Oil

Oil

seed oil [100] and Olive husk oil [73]. Similarly, the Z q̇ is much
14 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

higher than W q̇ as the latter is strongly related to the diffusion of

Papamichail et al. [98]

the less accessible solute in the intact particles. Berna et al. [101]

Esquivel et al. [73]

have investigated the influence of the height of the particle bed on

Berna et al. [101]

Han et al. [100]
Louli et al. [99]
Mira et al. [88]
the SFE process of essential oil from two types of orange peel in
terms of Z q̇ and W q̇. They conclude that where there is homoge-
Reference
neous flow the height of the bed has very little effect otherwise a
dragging effect on the particles and the effectiveness of the pro-
cess will be reduced due to the increase in the height of the bed of
particles.
However, the volumetric solvent phase mass transfer coef-
W q̇ (×10−4 s−1 )

ficient kf a0 and the volumetric solid phase mass transfer

0.04–3.79

0.25–6.21

0.42–1.46
2.88–4.33

0.44–2.11
0.15–0.84

0.16–0.66
0.23–1.06
coefficient ks a0 are the most preferably used parameters
instead, to avoid the effect of the different ways for spe-
cific interfacial area calculations, and thus widely reported
in the literatures. Table 7 summarizes calculated results by
using the BIC model for oil extraction of various vegetable
matters [3,29,41,51,53,54,65,66,78,84,87,89–92,94–96,102–119].
Z q̇ (×10−2 s−1 )

0.011–0.068

Obviously, the kf a0 values are generally 2–3 orders of magnitude

3.44–15.2

0.12–5.12
0.64–5.70

0.10–517
1.5–25.7

1.9–14.5

higher than those ks a0 ones, due to the fact the former is strongly
related to the diffusion of the released oil close to the particle sur-
14.5

face while the latter is related to the diffusion of the unreleased

oil in the closed particles. Recently, Özkal et al. [92] have sys-
tematically investigated mass transfer modeling of apricot kernel
0.594–0.913

0.421–0.479

0.511–0.588
0.046–0.479

0.319–0.603
0.072–0.45
0.533–0.60

oil extraction with SCCO2 under various process conditions. The

process parameters include mean particle size, solvent flow rate,
0.771

pressure, temperature and modifier concentration and their effects

r

on the mass transfer coefficients kf a0 and ks a0 are graphically

shown in Fig. 4. As can be seen, both kf a0 and ks a0 are increasing
(i.e., mass transfer resistance is decreasing in both SCCO2 and apri-
cot kernel solid phases), with CO2 flow rate (see Fig. 4a), modifier
y* (×10−3 g/g

2.12–9.55
2.12–9.55

2.30–4.93

content (see Fig. 4b) and extraction temperature (see Fig. 4c), due
2.8–33.0
solvent)

12–110

to the increase in driving force and convection. But they are both
13.2

19.3

decreased with the increase in the particle dimension (see Fig. 4e),
95

due to the decrease in the specific surface area. The increase in the
diffusion path length may also contribute the decrease observed in
ks a0 . However, extraction pressure is seen to influence kf a0 and ks a0
in two opposite trends, as shown in Fig. 4d. The ks a0 increases with
x0 (×10−2 g/g

pressure but the kf a0 decreases with it. The reason for it is due to the
solute-free

fact that the increased oil solubility (i.e., increase in driving force)
24–32

10–15
feed)
The Z q̇ and W q̇ values obtained with the BIC models for different SCCO2 extraction systems.

and decreased oil diffusivity (i.e., increase in mass transfer resis-

6.2

40.8
5.8

12.6
50

10

tance) in SCCO2 both occur as pressure increases. As the decrease

in oil diffusivity is somewhat dominant and then leading to the
kf a0 decrease with the increase in pressure. Similar pressure effect
12–18

22–31

22–28
10–20

20.0

20.0
P (MPa)

has also applied to the ˇ-carotene extraction from apricot bagasse

15

[120] and oil extraction of Plumula nelumbinis [93].

5.4. Applications
318–328

308–318

308–333
T (K)

For realistic description of the plant material structure the con-

313

323

313

313

cept of broken and intact cells has been developed into the BIC
model, which has been verified by Reverchon and Marrone [48].
These researchers have employed SEM analyzer to successfully
identify broken cells on the particle surfaces, and then the volumet-
Naveline cultivar
Satsuma cultivar

ric broken-to-intact cell ratio of different species of seeds could be

Safflower seed
Parsley seed
Orange peel

orange peel

orange peel

readily determined by assuming broken cells to form a single layer

Celery seed
Olive husk

on the particle surfaces. The BIC model has taken into account the
Matrix

solute solubility y* in the solvent phase and the mass transfer coef-
ficient both in the fluid kf and in the solid phases ks , resulting in
an analytical solution for plug flow SFE processes if neglecting the
accumulation of the solute in the fluid phase. Physically speaking,
Safflower seed oil

the BIC model [41,53] has reasonably described the sudden reduc-
Parsley seed oil
Orange peel oil
Celery seed oil

tion in extraction rate after the initial fast extraction period through
Olive husk oil

Essential oil

Essential oil

proposing the broken and intact cell concept. This is actually sup-
ported by many oil-rich examples where the solute concentration
Solute
Table 6

at the outlet from the extraction unit is near constant in the early
stages of the extraction and then falls progressively as extraction
Table 7
The ks a0 and kf a0 values obtained with the BIC models for different SCCO2 extraction systems.

Solute Matrix T (K) P (MPa) x0 (×10−2 g/g y* (×10−3 g/g r kf a (×10−2 s−1 ) ks a (×10−4 s−1 ) Reference
solute-free solvent)
feed)

Shiitake oil Shiitake mushroom 303–323 15.0–30.0 0.55–1.00 2.31–2.52 0.367–0.968 0.010–0.044 0.38–0.87 Kitzberger et al. [3]
Oil Wormwood 313–323 9.0–18.0 3.56 0.25–0.79 0.13 52.0 0.0065–0.108 Martín et al. [29]
Grape oil Grape seeds 313 28 14.4 6.85 0.139–0.681 4.06–9.50 0.065–0.15 Sovová et al. [41,53]
Oil Corn germ 313 45.0 10.26–49.01 14.47 0.123 1.64–2.60 0.124–0.317 Nagy et al. [51]
Oil Pumpkin seeds 333 45.0 47.8 20.74 0.321 1.72 0.406
Oil Calendula flowers 313 45.0 8.18 5.05 0.555 2.3 0.148
Oil Paprika fruit 323 45.0 11.9 17.36 0.335 24.78 0.124
Oleoresin Black pepper 297–333 28 1.3–4.5 1.3–40.0 0.18–0.50 0.27–1.50 0.5–2.0 Sovová et al. [54]
Oleoresin Marigold flowers 299–313 12.0–20.0 3.23–9.98 2.804 0.186–0.510 5.17–76.8 × 10−3 0.83–19.0 × 10−2 Campos et al. [65]
Carqueja oil Carqueja 303–313 10.0–30.0 1.21–2.36 2.83 0.289–0.873 1.46–1.78 17.6–17.8 Silva et al. [66]
Oil Soybeans 20.5 7.00 0.33–0.992 0.03–2.8 0.0058–0.26 Rochová et al. [78]
Essential oil and Chamomile flowers 303–313 10.0–20.0 0.91–4.76 1.15–6.32 0.398–0.522 0.024–0.099 0.126–0.249 Povh et al. [84]
oleoresin
Sea buckthorn oil Sea buckthorn 298–333 17.4–27 0.8–1.34 3.0–8.2 0.33–0.62 0.53–1.20 0.05–0.30 Štastová et al. [87]

Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

Essential oil Aniseed 303 80.0–18.0 3.13–10.67 11.0–27.7 0.250–0.851 1.90–3.27 × 10−2 0.114–0.622 Rodrigues et al. [89]
Rosemarry oil Rosemarry leaves 313 10.0–30.0 5.3 3.3 0.642 0.35 0.3 García-Risco et al. [90]
Oil Sunflower seeds 313 25.0 42.55 3.80 0.0996 18.4–21.9 6.62–14.2 Kiriamiti et al. [91]
Apricot kernel oil Apricot kernel 313–343 30–60 48.4 7.1–23.8 0.02–0.678 1.12–6.20 0.015–0.081 Özkal et al. [92]
Peach almond oil Peach almond 313 15.0–25.0 12.7–19.5 3.0–13.0 0.128–0.580 0.63–2.84 1.00–3.37 Mezzomo et al. [94]
Scaling-up 313 15.0–25.0 13.2 3.0–13.0 0.472–0.75 0.125–1.50 0.248–2.53

Sunflower oil Sunflower seeds 303–333 8.0–25.0 41 2.26–6.0 0.31–0.44 0.41–0.64 0.42–1.12 Nimet et al. [95]
*In subcritical 303–333 8.0–25.0 41 880–1500 0.38–0.45 0.18–0.38 2.33–6.50
propane
Oil Helichrysum 313–333 10–20 4.25 1.5–25.0 0.511–0.988 4.84–6.09 2.01–4.28 Ivanovic et al. [96]
italicum flowers
Fig leaf gourd seeds Fig leaf gourd seeds 308–318 18–20 45.3 2.83–6.86 0.386 2.34–4.57 1.73–4.34 Bernardo-Gil et al. [102]
oil
Hazelnut oil Hazelnut 308–321 18.0–23.4 1960 4.68–9.40 0.332 1.29–3.65 0.897–2.81 Bernardo-Gil and Casquilho [103]
Walnut oil Walnut 308–321 18.0–23.4 2450 7.0 – 15.0 0.419–0.661 1.04–3.07 0.517–1.60
Acorn oil Acorn 308–333 15–21 12.1 6.2–48.2 0.33–0.61 0.134–0.602 0.292–5.22 Bernardo-Gil et al. [104]
Rosemarry oil Rosemarry leaves 313–333 10.0–18.0 3.2 0.238–0.457 0.281–0.625 0.64–2.75 0.837–1.17 Bensebia et al. [105]
Sesame oil Sesame seeds 323–343 25.0–35.0 50.6 6.5–12.6 0.195–0.459 0.11–1.15 2.60–10.33 Döker et al. [106]
Oil Buriti chips 313–328 20–30 8.11 1.74–6.82 0.15 0.195–0.449 0.65–6.5 de França et al. [107]
Essential oil Black pepper 303–323 15–30 2.20–13.1 24.2–144.4 0.35–0.62 0.016–0.059 0.038–2.88 Ferreira & Meireles [108]
Seed oil Grape seeds 313 16.0–20.0 32.9–42.3 1.99–3.41 0.27–0.43 3.52–4.06 0.41–6.27 × 10−2 Passos et al. [109]
Oleoresin Ginger 293–313 15.0–25.0 2.0–3.0 4.12–7.20 – 3.33–4.50 × 10−2 0.98–1.69 Martínez et al. [110]
Carqueja essential Carqueja 313–343 9.0 2.34 6.66–19.1 0.034–0.363 0.82–2.31 2.8–6.9 Vargas et al. [111]
oil
Pigments Bixa orellana seeds 313 20.0 1.2 0.032 – 0.82–1.05 0.5 Nobre et al. [112]
Stevia glycosides Stevia ginger 303 20.0 3.04 2.27 0.23 3.02 × 10−2 0.189 Pasquel et al. [113]
Extract Guava leaves 308–328 30.0 2.8–3.06 3.00 0.51–0.54 0.099–0.0126 0.42–0.44 Moura et al. [114]

Canola seed oil Canola seed 313–333 20.0–25.0 58.7 2.40–5.53 0.587–0.710 0.58–2.78 0.011–0.059 Pederssetti et al. [115]
*In subcritical 303–343 8.0–312.0 58.7 212–360 0.631–0.743 0.037–0.14 0.31–0.72
propane
Oil Croton 288 6.7 3.3 28.3 – 0.013–0.030 0.83–1.11 Sousa et al. [116]
Volatile oils Vetiver roots 313 20.0 2.9–4.7 1.76–10.01 0.172–0.313 0.328–0.515 0.276–0.633 Talansiera et al. [117]
Oleoresin Ginger 298–308 15.0–25.0 2.48–3.46 4.20–8.23 0.355–0.522 0.020–0.034 0.024–0.089 Zancan et al. [118]
Oil Rosehip seeds 313–323 30.0–40.0 7.27–8.56 7.35–14.0 0.587–0.673 2.28–10.1 1.77–2.31 del Valle et al. [119]

15
16 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26
Fig. 4. Influences of various variables on the ks a0 and kf a0 obtained using the BIC model for apricot kernel oil extraction with SCCO2 .
Data from [92].
processes. The analytical model resulted has greatly simplified the
calculations of model parameters from the overall extraction curve.
Thus it is the most widely used models up to now (see Tables 5–7)
and now it seems to be a very convenient tool for scaling-up design
purposes [90,94].
However, the equilibrium relationship, the equilibrium solubil-
ity y*, for free solute has been incorporated into the BIC model
without considering the solute–sold interactions. As discussed pre-
viously, the interactions between the solute and solid matrices
will affect the solute desorption equilibrium in both the fluid and
solid phases. To account for these interactions, several researchers
[41,48,53,57,121–123] have proposed a linear partition relation-
ship in terms of partitioning coefficient between the solid and fluid
phase for modeling the SCCO2 process. Goto et al. [56] have applied
a BET-type adsorption isotherm to simulate a smooth transition
between the equilibrium of free solute at high concentrations and
the equilibrium of solute–matrix interaction at low concentrations.
Besides, Perrut et al. [58] has proposed a discontinuous equilibrium
relationship to cover the solute–sold interactions. Above the point
of discontinuity the fluid-phase concentration is equal to solubility
and below the point it is determined by partition coefficient. The
discontinuous equilibrium curve has been later applied by Wu and
Hou [59] in the simulation of egg yolk oil extraction and by Sajfr-
tová et al. for near-critical extraction of ␤-sitosterol and scopoletin
from stinging nettle roots [124]. Concerning the solute interactions
with the solid matrix, Sovová [46] has later proposed a general
new approach for seed oil and essential oil extraction. The new
feature of the approach is the description of the first extraction
period considering different types of phase equilibria: indepen-
dent on matrix in terms of solubility equilibrium, adsorbed on the
matrix in terms of partition between the two phases, and different
flow patterns such as dispersion. The model has also been veri-
fied on data sets selected from literature for oil extraction from
almond seeds and extraction of essential oils from orange peels and
pennyroyal.
The BIC model has many different versions as different assump-
tions about the mass transfer mechanism within the solid particles
have been employed [75]. Reverchon and Marrone [48] have mod-
ified the BIC model with the SEM analysis of the microstructure
to acquire cell structure data and greatly reduced the number of
parameters that should be regressed from experimental data. They
have retained only the internal mass transfer coefficient as one
adjustable parameter while the film mass transfer coefficient can
be estimated from dimensionless correlations. A fair good fitting of
all the available experimental results has been obtained for SCCO2
extraction process of sunflower, coriander, grape, tomato peanut,
and almond fennel seeds. However, this modification requires SEM
expertise to avoid any confusion between the oil bearing cells and
biological cells and it could not give the accurate results for the
seeds having very low initial oil contents. Besides, in this work
the authors had applied a size reduction pretreatment, which may
be of limited practical significance for oilseed extraction. Later
on, Fiori [125] has applied the Reverchon and Marrone version
of the BIC model and a new version for grape seed oil extrac-
tion, resulting in a value of the effective diffusivity in the range
of 10−12 –10−10 m2 /s and that of the internal transport coefficient
in the range of 10−8 –10−7 m/s, respectively. The modeled results
have also shown that the choice of the value of the maximum
extractable oil yield seems to be of great importance for determin-
ing model parameter and using the maximum experimental value
is preferable. Sovová has recast the original BIC model by fully con-
sidering the solute–solid interactions. The modified version seems
to be versatile for the SFE simulation as it includes flexible rela-
tionships both for phase equilibrium and flow pattern. Thus it can
be advantageously used to simulate different types of extraction
curves involving mass transfer coefficients and equilibrium con-
stants. However, the new model has no more analytical solution but
numerically solved. Furthermore, the number of model parameters
becomes more and varies in accordance with varying complex-
ity of simulated extraction processes in the range 1–3 for phase
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26 17

and Martínez [128] invoked a global optimization method for pre-

dicting supercritical fluid extraction with the BIC model and their
works show that caution should be taken to render the parameters
still physically meaningful.
On the other hand, simplifying the BIC model with less complex
computation or fewer model parameters has also been made. Patel
et al. [129] have reformulated the above-mentioned three-stage
BIC model as a new simple two-stage model, by incorporating the
transition stage into the diffusion-controlled stage:
 ks a0

e = x0 − exp (q − qm ) × [x0 − qm · y∗ (1 − e−Z )]
q̇(1 − ε)
× for q ≥ qm (27d)

Fig. 5. Influences of CO2 flow rates on the kf and Dl obtained with the BIC model for
SCCO2 processing of pretreated rosehip seed.
Data from [119].
equilibrium, 2–3 for mass transfer, and 0–1 for flow pattern.
Recently, Sovová et al. [126] have attempted this new model involv-
ing solute–solid interactions for describing multi-component
extraction of vegetable substrates. But this model still presents a
limit in the case of essential oils extraction, when the extractable
material is located only inside the matrix: the concept of broken
and intact cells is no more applicable and the first part of extraction
controlled by equilibrium does not apply [11].
If the solute accumulation in the fluid phase is taken into account
along with the other same assumptions, Eq. (25a) may be given [99]
 y

f (x ≤ xi , y) = ks a0 s x 1 −
y∗
Therefore the system of differential Eqs. (22) and (23a), coupled
with the expressions (Eqs. (24) and (25b)) for f(x, y) proposed by
Sovová [41], can be solved numerically by employing a fourth order
Runge–Kutta method and assuming that the solid bed is divided
into a number of 10 stages where the solute concentration can be
considered uniform in each stages. Following this treatment, Louli
et al. [99] have attempted the modeling of SCCO2 extraction of pars-
ley seed oil but found that the fitted parameters are consequently
same with those of the analytical BIC model, which means that
the accumulation term has not affected the description of process
significantly.
del Valle et al. [119] have modified the BIC model by considering
the axial dispersion and then Eq. (23) may be given as follows.
The authors [129] then have applied the proposed model with
two adjustable parameters to supercritical extraction of different
biomass. Results for cashew nut shells and black pepper oil show
that the model agrees well with the experimental results for the
seeds having both high as well as low initial oil contents. The com-
parison of the proposed model results with the BIC model [41,53]
results indicate that the accuracy of proposed model is of same
order although the proposed model is simplified by considering
two-section kinetics as against three section kinetics in the origi-
nal one. Likewise, rather similar two-stage modifications have also
been reported in the literatures [29,98,130–134].
Similarly, Martínez et al. have developed another simple modi-
fication of the BIC model, which is taken as the logistic model (LM)
here for better description. The LM model has neglected the accu-
mulation and dispersion in the fluid phase as these phenomena
have no significant influence on the process while compared to the
effect of convection. Following this model, the mass balance Eq.
(23a) for the fluid phase may be rearranged as [110]
(25b)
∂y
uε = F(x, y) (23b)
∂z
The interfacial mass-transfer term, represented as F(x,y), can be
interpreted as a function Si (t) that depends on the composition of
the extract along the process. The extract composition may be pos-
sibly divided into a few groups of chemically similar compounds,
whose composition could be measured along the SFE process. The
logistic equation, usually applied to model time-dependent popu-
lation growth, is then chosen to describe the variation of the extract
composition, giving:

n
n
Ai bi exp(bi tmi − bi t)
F(x, y) = Si (t) = (30)
[1 − exp(bi tmi − bi t)]
2
i=1 i=1

where Ai and bi are two characteristic parameters of the logistic

∂y ∂y ∂2 y
f u + f ε − f εDl 2 = f (x, y) (23a) equation. After integration of Eq. (23b) in z with the boundary con-
∂z ∂t ∂z dition of y(z = 0, t) = 0, the equation for the solute concentration, y,
They have performed SCCO2 processing of pretreated rosehip of extract in the fluid phase at the bed outlet can be obtained:
seeds and investigated the effects of extraction conditions on mass
H
n
transfer coefficient (kf ) and the axial dispersion coefficient (Dl ). y(z = H, t) = Si (31)
Fig. 5 shows the dependence of the kf and Dl on CO2 mass flow rate. uε
i=1
The values of kf and Dl are both increasing with increase in CO2
flow rate but these values are not the same in the case of scaling- Finally, the equation for the overall extraction curve was
up as the extraction becomes slower due to flow heterogeneity and obtained by integration of Eq. (31) in time with the initial condition
increased axial dispersion as well. of m(z = H, t = 0) = 0. For a single group of compounds, say compound
The modified versions of the BIC model, once having no analyti- i, the correspondent extraction curve can be integrated as:
cal solution like the cases of considering either solute accumulation  
QCO2 H 
t n t
[99] or axial dispersion [119], must be numerically resolved for mi (z = H, t) = y(z = H, t)QCO2 dt = Si dt
capturing the overall extraction curves. For instances, Franca and 0
uε 0
i=1
Meireles [127] and Povh et al. [84] used a spline fitting of exper- 

imental CER period values to get model parameters. Ferreira and QCO2 H 1 1
= − (32)
Meireles [89] obtained the mass transfer coefficient from the CER uε 1+ exp(bi tmi − bi t) 1+ exp(bi tmi )
period using a logarithmical solute mass ratio difference. Martínez
18 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

As it can be further derived that when time tends to infinity, the
mass of the extracted component i tends to a fixed value, asymp-
totically. This value can be considered as the total extractable mass
of this compound at the given process conditions. Taking this into
account and with rearrangement of Eq. (32), a new equation for the
extraction curve of a single group of compounds was defined:

solute concentration in pores at the particle surface. ε is noted here
to be the porosity of bed including the intrinsic particle porosity.
Time dependence of the solid-phase concentration, i.e., average
solute concentration in a particle, is assumed to be equal to the rate
of mass transfer of the solute within external film surrounding in
the particle, giving

mi0 1 + exp(bi tmi ) ∂c̄s 3kf

mi (z = H, t) = −1 (32a) = [c − ci (R)] (34)
exp(bi tmi ) 1 + exp(bi tmi − bi t) ∂t R
where c̄s is the averaged solute concentration in the solid phase.
where mi0 is the total extractable mass of the single group i of The diffusion in out region is given by:
compounds (i.e., component i) and it can be determined experi- 
mentally if the total extractable mass and the total composition of De ∂ ∂yi
r2 =0 (35)
the extract are known. In this sense, the LM model can be reduced r 2 ∂r ∂r
to two adjustable parameters per group of compounds: bi (s−1 ) and
The solid phase solute exists within the core, the average value
tmi (s). If the extract is taken as only one compound then the model
of solid phase concentration, can be readily given as
equation may be written as
  c̄s
 r 3
c
m0 1 + exp(btm ) = (36)
m(z = H, t) = −1 (32b) cs0 R
exp(btm ) 1 + exp[b(tm − t)]
At the core boundary, the solute concentration in the fluid phase
where b (s−1 ) and tm (s)are two adjustable parameters.
is at its saturation value, i.e., its equilibrium solubility csat :
The simple LM model has also received much more attention in
modeling a variety of extraction system. Table 8 examples modeled ci = csat at r = rc (37)
results reported in the literatures [3,40,65,94,110,116,135].
Diffusion flux at the outer surface of a particle is equal to the
mass transfer through external film:
6. Shrinking model 
∂c
De i = kf [c − ci (R)] (38)
6.1. Assumptions ∂r
r=R

Initial conditions are given below:

The shrinking core (SC) model describes the situation of the
irreversible desorption followed by diffusion in the porous solid at t = 0, rc = Rcs = cs0 and c = 0 (39)
through the pores. When the mass transfer rate of the solute in the
non-extracted inner part is much slower than that in outer part The two Danckwerts conditions at the inlet and out let of extrac-
where most of the solute has been extracted, or solute concentra- tion unit are given below:
tion is much higher than the solubility of the solute in the solvent ∂c
uc − Dl = 0 at z = 0 (40)
phase, a shape boundary may exit between outer and inner region. ∂z
A schematic drawing of a fixed bed extractor and solid particle is ∂c
shown in Fig. 6. Note that the core of inner region shrinks with = 0 at z = H (41)
∂z
the progress of the extraction and the model then envisages SCCO2
extraction of a particle as sharp inward-moving front separating a For simpler description, the following dimensionless groups are
completely non-extracted core ahead of the front from a completely defined to drive dimensionless formulae of the SC model:
cs c c z r rc
extracted shell behind the front. = , C= , Ci = i , Z = ,  = , c = ,
The following assumptions are used to develop the extraction cs0 csat csat H R R
model: csat De uR2
ω= , = t, =
cs0 R2 De H
(1) The extraction system is both isothermal and isobaric.
(2) The matrix is a porous material where the solute is uniformly With these dimensionless groups, Eqs. (33)–(41) can be reduced
distributed throughout the solid particle. to:
(3) The physical properties of the supercritical fluid are constant
during the extraction. ∂C ∂C  ∂2 C 1−ε
+ = − 3Bi [C − Ci ( = 1)] (33a)
(4) The mobile supercritical fluid phase flows axially through the ∂ ∂Z Pe ∂Z 2 ε
bed from bottom and the solute concentration in the bulk fluid ¯
∂
phase depends on time and the axial coordinate. = 3Biω[C − Ci ( = 1)] (34a)
∂
(5) Axial dispersion is considered and the radial dispersion may be 
neglected because of small extraction unit diameter. 1 ∂ ∂Ci
2 =0 (35a)
(6) The extraction is irreversible desorption.  2 ∂ ∂

Ci = 1 at  = c (36a)
6.2. Mathematical representation 
∂Ci
= Bi[C − Ci ( = 1)] (37a)
Considering axial dispersion, the mass balance of the solute in ∂
=1
the bulk fluid phase is described by [42]
¯ = 3
(38a)
c
∂c ∂c ∂2 c 1 − ε 3kf
+u = Dl 2 − [c − ci (R)] (33)
∂t ∂z ∂z ε R at  = 0, c = 1, = 1 and C = 0 (39a)

where Dl is the solute axial dispersion coefficient (m2 /s), ci is the 1 ∂C

C− = 0 at Z = 0 (40a)
solute concentration in pores within particles (g/m3 ), ci (R) is the Pe ∂Z
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26 19

Table 8
Applications of the LM model for different SCCO2 extraction systems.

Matrix Solute T (K) P (MPa) tm (min) b (×10−4 s−1 ) Reference

Shiitake mushroom Shiitake oil 303–323 15.0–30.0 −5037.9 to 63.4 1.35–3.18 Kitzberger et al. [3]
Baizhu herb Extract 313–333 15.0–45.0 −114.2 to −31.7 0.80–2.88 Huang et al. [40]
Marigold flowers Oleoresin 299–313 12.0–20.0 −500.2 to 508.2 0.45–0.82 Campos et al. [65]
Peach almond Oil 313 15.0–25.0 −2522.0 to 56.0 1.23–6.23 Mezzomo et al. [94]

Ginger Oleoresin 293–313 15.0–25.0 80.6–119.3 2.63–5.12 Martínez et al. [110]

Monotherpenes 313 20.0–25.0 140.9–150.9 2.20–3.85
Sesquitherpenes 313 20.0–25.0 133.2–155.5 2.37–2.77
Hydrocarbons and others 313 20.0–25.0 7932–8214 2.65–4.78

Croton Oil 288 6.7 −1042.6 to −25.6 1.55–2.75 Sousa et al. [116]
Guava leaves Extract 308–328 30.0 −1600 1.37 Moura et al. [135]

Fig. 6. Particle scheme for the shrinking core (SC) model.

∂C By substitution of C into Eq. (44) and integration

= 0 at Z = 1 (41a)
∂Z  c
Z 1 c2 [1 − Bi (1 − 1/c )]
When the boundary conditions, Eqs. (36a) and (37a), are substi- = +1 −
 ωBi 1
exp{[(ε − 1)/ε] · 3BiZ/[1 − Bi (1 − 1/c )]}
tuted into Eq. (35a), the result is
×dc (47)
C −1
C − Ci ( = 1) = (42)
1 − Bi (1 − 1/c )
If  c is further assumed to be constant, the final solution may be
The following equations were derived from Eqs. (33a)–(42) given:

3ωBi ( − Z/) 1−ε

 
∂C ∂C  ∂2 C 1−ε C −1 3Bi Z
+ = − 3Bi · (43) c3 = 1 − exp − · (47a)
∂ ∂Z Pe ∂Z 2 ε 1 − Bi (1 − 1/c ) 1 − Bi (1 − 1/c ) ε 1 − Bi (1 − 1/c )

∂c ωBi (C − 1) The time, te or  e , required for complete equilibrium extraction,

= 2 (44) if the rate process does not interfere with the extraction, is then
∂ c [1 − Bi (1 − 1/c )]
given
The cumulative fraction of solute extracted up to dimensionless
(1 − ε)Hcs0
time  is then given by te = (48a)
εucsat
 
cs0 − cs ωε 1−ε
= C d (45) e = (48b)
cs0 1−ε 0 ωε

If axial dispersion is negligible, a quasi-steady state solution may When the solute–solid interaction may not be negligible, the
be obtained by assuming that changes in  c during the residence solute equilibrium in the solid phase and within the pores should be
time ( = 1/ = De H/uR2 ) of solvent in the column are negligible and taken into account in the SC model. The initial solute in the porous
that changes in the axial direction of the column at any time are solid may be either adsorbed on solid sites, ca0 (g/m3 ), or being free
very small. Then integration of Eq. (43) gives within the pores, ci0 (g/m3 ). The total initial solute concentration
 1−ε  in a particle, cs0 (g/m3 ), is composed of two parts:
3Bi Z
C = 1 − exp − · (46)
ε 1 − Bi (1 − 1/c ) cs0 = (1 − εp )ca0 + εp ci0 (49)
 20
Table 9
The De , kf and Dl values obtained with the SC model for different SCCO2 extraction systems.

Solute Matrix T (K) P (MPa) Csat (×10−3 g/g solvent) De (m2 /s) kf ( m/s) Dl (m2 /s) Reference
−9 −4
Nutmeg oil Nutmeg 313–323 10.0–20.0 9.0–82.0 1.90–76.9 × 10 2.65–21.4 × 10 5.49–69.9 × 10−5 Machmudah
et al. [70]
Sesame oil Sesame seeds 323–343 25.0–35.0 6.5–12.6 4.43–5.57 × 10−10 5.11–6.05 × 10−6 2.69–3.06 × 10−11 Döker et al.
[106]
ˇ-Carotene Apricot bagasse 313–333 30.4–50.7 4.99–32.13 × 10−3 4.66–8.66 × 10−11 0.97–1.70 × 10−11 3.87–13.01 × 10−11 Döker et al.,

Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

[120]
Sunflower oil Sunflower seeds 323–353 20.0–60.0 1.04–28.23 4.73–8.21 × 10−10 3.68–6.39 × 10−6 1.75–3.76 × 10−12 Salgın et al.
[137]
Rapeseed oil Rapeseed 313 30 7.9 5.2 × 10−10 3.30 × 10−5 1.9 × 10−4 Núñez et al.
[138]
Nimbin Neem seeds 308–333 10.0–26.0 0.034–39.4 1.84–4.74 × 10−10 1.56–5.37 × 10−6 3.95–53.5 × 10−8 Ajchariyapagorn
et al. [139]
Isoflavones Soybean meal 313–343 30.0–60.0 68.6–91.8 4.32–12.23 × 10−9 3.67–7.85 × 10−5 7.03–25.11 × 10−6 Kumhom et al.
[143]
Nimbin Neem seeds 308–333 10.0–26.0 – 7.7–28.6 × 10−10 1.41–4.35 × 10−6 – Tonthubthimthong
et al. [35]
Oil Olive husk 313 30.0 12.0 7.71 × 10−10 1.49 × 10−5 – del Valle et al.
[52]
Oil Canola seed 328 36.0 12.0 1.02 × 10−10 2.27 × 10−6 –
Oil Corn germ 305–323 32.0–90.0 8.97–55.0 1.71–2.62 × 10−10 5.98–10.8 × 10−6 –
Oil Rapeseeds 313–353 20.5–75.0 4.06–44.3 0.77–8.57 × 10−10 5.00–22.9 × 10−6 –
Oil Rosehip seeds 313–353 30.0–50.0 7.39–37.7 1.85–29.9 × 10−11 1.31–2.27 × 10−5 –
Oil Peppermint 313–353 8.83–19.6 0.75–21.5 1.70–14.6 × 10−9 1.16–11.6 × 10−4 – Goto et al. [55]
Nimbin Neem seeds 308–333 10.0–26.0 – 1.29–5.34 × 10−10 0.32–16.4 × 10−6 – Mongkholkhajornsilp
et al. [85]
Triglycerides Grape seed 313 28.0 6.85 1.77 × 10−10 0.255–27.6 × 10−6 – Germain et al.
[141]
−9 −6
Triglycerides Rapeseed 313 30.0 7.53 1.78 × 10 2.04–19.1 × 10 –
Essential oil Caraway seed 313 9.0–10.0 5.62–21.0 5.28–7.41 × 10−12 8.14–11.4 × 10−8 –
Oleoresin Ginger 313 16.0 3.92–6.54 0.44–6.4 × 10−12 6.0 × 10−5 – Balachandran
et al. [142]
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26 21

where εp is the porosity of the solid particle. Then, the mass balance binary diffusion coefficient (D12 ), and the effective solute diffu-
of the solute in the solid phase may be written as [55,56,106] sivity in the particles (De ). These parameters are evaluated using
 existing correlations and available data. The methods for obtain-
∂ci ∂cs De ∂ ∂ci
εp + (1 − εp ) = 2 r2 (34a) ing the values of kf and D12 have been outlined in previous section.
∂t ∂t r ∂r ∂r As for De , it may be directly taken as an adjustable parameter and
Likewise, Eq. (44) may be expressed as regressed from the experimental extraction data. Alternatively, it
can be readily estimated as a function of D12 for vegetable oils in
∂c Bi (1 − C) SCCO2 and the value of the particle porosity that is determined by
= (44a)
∂ εp Bi (Ci − 1) + (1 − εp )ωc [c + Bi (1 − c )] using mercury porosimetry assay:
If the interaction of solute with the fluid and solid phase is De = ε2p D12 (56)
assumed to be fast adsorption/desorption equilibrium, a linear
expression can be given by [55]: Similarly, the solute axial dispersion coefficient in the super-
critical phase in packed beds, Dl , can be estimated with several
cs = Kci (50) correlations that are summarized in this review [36,37]. The corre-
lation proposed by Funazukuri et al. [136] may be written in terms
where K is the equilibrium coefficient between the solute in the
of dimensionless Reynolds number and dimensionless Schmidt
fluid and solid phases.
number, giving
The linear driving force approximation may be used to combine
internal and external processed and defined by [55] εDL
= 1.317(ε Re Sc)1.392 for ε Re Sc > 0.3 (57)
kf 1 − ε 15De D12
[c − ci (R)] = (1 − ε)[ci (R) − ci ] (51)
R ε R2 These researchers have measured the Dl values of several
Then, Eqs. (33) and (34a) can be further reduced without con- species in SCCO2 under pressures from 11 to 35 MPa, using the
sidering axial dispersion as follows chromatographic method in a packed bed (ε = 0.38) with particles
c  of 0.05–0.15 mm diameter. The proposed correlation is found to fit
∂c c 3kp s the experimental data quite well and the reported average abso-
ε + = (1 − ε) −c (33a)
∂t  R K lute deviation is 25% over 280 data points with Schmidt numbers
ε  ∂c 3kp
 cs
 ranging from 3.9 to 665. del Valle and de la Fuente [36] have also
p i
+ (1 − εp ) = c− (34b) addressed that this correlation may provide consistent values for
K ∂t R K
the dispersion of solutes in SC–CO2 in a packed bed for a wide range
where kp is the overall mass transfer coefficient for a spherical of values for Reynolds number.
particle, given by To evaluate the importance of axial dispersion, a dimension-
kf less Peclet number can be introduced and evaluated through the
kp = (52) following expression:
1 + Bi /5
The exact solution of Eqs. (33a) and (34b) is Hu
Pe = (58)
Dl
(1 − ε)cs0
c= (em1 t − em2 t ) (53) As discussed previously, several studies [42,48,60,61] have
ε[εp (1 − εp )K](m1 − m2 )
shown that the axial dispersion may have little effect on SCCO2
where extraction as if Pe or Pe /ε is generally larger than 100, due to the
 fact that the size of solid particles typically loaded in the bed is
− +  2 − 4˚
m1 = (54a) very small as compared to the diameter of the extraction unit
2 with a ratio of the former over the latter less than 0.1 and then

− −  2 − 4˚ the axial dispersion problem may have been avoided during SFE
m2 = (54b) process.
2
= kp ap  (54c)
6.4. Applications
1 (1 − ε)
 = + + (54d)
ε ε εp + (1 − εp )K The SC model has been extensively used for simulating SFE
processes of herbaceous matrices such as sesame seeds [106],
˚= (54e) sunflower seeds [137], rapeseed [138], neem seeds [35,85,139],
ε[εp + (1 − εp )K] nutmeg seeds [140], grape seed [141], caraway seed [141], canola
The cumulative fraction of solute extracted is analytically given seed [52], rosehip seeds [52], corn germ [52], olive husk [52], ginger
by [142], soybean meal [143], apricot bagasse [120], and peppermint
 t
[55]. Tezel et al. [144] have further developed a multi-component
cs0 − cs 1 (1 − ε) SC model for seed and essential oil extractions and Machmudah
= c dt =
cs0 (1 − ε)cs0 0
ε[εp + (1 − εp )K](m1 − m2 ) et al. [140] have used it for modeling extraction of two compo-

nents from nutmeg seeds. In their work [140], the SC model has
em1 t −1 em2 t − 1 been used twice for the lighter components and heavier compo-
× − (55)
m1 m2 nents, resulting in the De values in the range of from 4.33 × 10−9 to
7.69 × 10−8 m2 /s and from 1.90 × 10−9 to 3.20 × 10−8 m2 /s, respec-
tively.
6.3. Parameter identification Tables 9 and 10 summarized the correlated results reported
in the literatures [3,35,52,70,85,106,116,117,120,135,137–143].
The mass transfer parameters involved in the shrinking core Among these works, several researchers have systematically inves-
model are the mass transfer coefficient to the bulk phase (kf ), axial tigated the influences of various process parameters such as
dispersion coefficient in the fluid phase (Dl ), the solute–solvent extraction pressure, temperature, particle size and CO2 flow rate on
22 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

Table 10
The calculated and K values with the SC model for different SCCO2 extraction systems.

Solute Matrix T (K) P (MPa) K Reference

Shiitake oil Shiitake mushroom 303–323 15–30 0.15–0.39 1.15–1.77 Kitzberger et al. [3]
Nimbin Neem seeds 308–333 10.0–26.0 7.7–97.4 0.132–0.596 Tonthubthimthong et al. [35]
Volatile oils Croton 288 6.7 0.42–6.96 0.42–0.50 Sousa et al. [116]
Volatile oils Vetiver roots 313 20.0 0.196–1.964 0.735–0.854 Talansier et al. [117]
Oil Fennel seeds 303–313 10.0–25.0 0.088–0.202 0.400–0.476 Moura et al. [135]

Fig. 7. Influences of various variables on the kf and Dl obtained using the SC model for extraction of sunflower oil with SCCO2 .
Data from [137].

Fig. 8. Influences of various variables on the kf and Dl obtained using the SC model for nimbin from neem seeds with SCCO2 .
Data from [139].

the mass transfer rates [35,137,139]. Fig. 7 shows modeled results
for extraction of sunflower oil with SCCO2 [137]. As we can see
from Fig. 7a–c, the kf , De and Dl are all increasing with the extrac-
tion pressure and increase in temperature has also promote the
increase of kf and De . Fig. 7d shows the increases in CO2 flow rate
can result in increased mass transfer rate but render the axial dis-
persion reduce. Similar observations have applied to the case of
increase in particle size, as shown in Figs. 7e and f. However, in
the studies of Tonthubthimthong et al. [35] and Ajchariyapagorn
et al. [139] for SCCO2 extraction of nimbin from neem seeds,
different trends have been obtained and their calculations are
shown in Fig. 8. Their results show that (1) the increase in
particle size has led to the reduction of the kf values but the
increase in the Dl , (2) the increase in CO2 flow rate has made
kf and the Dl both being increased, (3) the increase in pres-
sure has resulted in the decrease in the kf and De as well.
The reason for it may be due to the different assumptions
involved and further exploiting is needed. Furthermore, in the
study of Machmudah et al. [140], the calculations show that the
Bi value thus obtained varies from 14.9 to 107 and is larger
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26
than 10, seemingly indicating that the internal mass transfer
resistance is much greater than the external mass transfer resis-
tance. In addition, the Pe estimated spans from 7.5 to 26.3 and far
smaller than 100, indicative pronounced axial dispersion on the
mass transfer rate.
Apart from the above-mentioned process parameters, the other
factors, based on the SC model calculations, may also influence the
extraction process as well, like the microstructure, drying and flow
type. del Valle et al. [52] have researched microstructural effects on
internal mass transfer of vegetable oil from seeds subjected to vari-
ous high-shear pretreatments using the SC model and explored the
application of microstructure–extractability relationships for mod-
eling SCCO2 extractions. The authors have quantitatively related
the effective diffusivity (De ) inside the porous particles with the
oil diffusivity (D12 ) in SCCO2 through a microstructural correction
factor, which is estimated as the ratio between the porosity and
tortuosity of the particle itself. Besides, Balachandran et al. [142]
have investigated supercritical extraction of oleoresin from fresh,
oven-dried and freeze-dried ginger samples. They have found that
water-rich fresh ginger rhizomes lead to higher extraction yields
and a more pungent and naturally flavored extract relative to the
other two dried samples. The modeled results with the SC model
confirm that this yield enhancement may have resulted principally
from an enhancement in the effective diffusivity within the gin-
ger particle and that the mass transfer rate would decline once
dried ginger samples was used. Germain et al. [141] have investi-
gated SCCO2 extraction of essential oils and lipids from grape seeds,
caraway seeds and rapeseeds under solvent flow conditions (down-
flow and up-flow) and low superficial velocities. Their works show
that there are no differences in mass-transfer rates between solvent
down-flow and up-flow for at a high Reynolds number (Re = 14.1).
But kf at lower Re of 1.57 was 3.6 times smaller when using solvent
up-flow than solvent down-flow condition. That is to say that, the
extraction is slower for solvent up-flow rather than solvent down-
flow condition when using a superficial solvent velocity below a
threshold value between 0.17 and 1.53 mm/s. The reduction in
the extraction rates is probably related to the negative influence
of natural convection phenomena as the loaded SCCO2 phase when
flowing slowly from the bottom of the vertically positioned extrac-
tion unit can be affected negatively by gravity. Thus the interstitial
solvent velocities should be set to values high enough to make the
effect of natural convection on the mass-transfer rates negligible.
However, at higher velocities, the unsteady extraction may be pro-
duced by solvent flow asymmetries or channeling phenomena due
to agglomeration and deformation of particles, increase bed poros-
ity or fluidized or float particles under up-flow conditions.Recently,
Machmudah et al. [140] have compared the performances of the
BIC and SC models for SCCO2 extraction of nutmeg oil at pressures
of 15–20 MPa and temperatures of 313–323 K. Their work shows
that the BIC model with discontinuous phase equilibrium between
fluid and solid phases [58] could only describe the data at lower
extraction yields well whereas the SC model could describe the
experimental data well for all extraction conditions. Then, Fiori
et al. [145] have attempted to bridge the BIC model and SC model
for a better evaluation and proposed a new model. This model
has plausibly taken into account the inner structure of the seeds
consisting of the vegetable cells bearing the oil, and schematized
ground seed particles as spherical particles composed of concen-
tric shells each one consisting of an oil-bearing cell layer. As the
extraction process advances, each shell is irreversibly depleted of
its oil, from the outer shell consisting of broken cells to the inner
shells consisting of intact cells. These considerations have incorpo-
rated the ‘shrinking-core’ concept with the ‘broken and intact cell’
one for describing the supercritical extraction kinetics of seed oils.
This model has been verified by modeling extraction of grape seeds
[145] and later evaluated for supercritical extraction of sunflower
23
seed oil [125]. But these results show the model performance is
dependent on the real granulometric size distribution other than
the weight-averaged particle dimension.
7. Conclusions
This paper has summarized representative developments of
theoretical models for supercritical fluid extraction of solutes from
various solid matrices. These models thoroughly discussed here
include the hot ball diffusion, broken and intact cell, shrinking core
and some relatively simple models. These models are physically
meaningful and valuable to represent the overall extraction pro-
files as they are developed from differential mass balance equations
for the packed solid bed. Due to different assumptions adopted for
mass transfer kinetics, these models thus bear different mathe-
matical expressions. Special emphasis is given to the models with
analytical solutions as they can readily be used for simulating
experimental data. The interactions between the solute and solid
matrices and the possible axial dispersion are also discussed. Of
these models, the broken and intact cell model is probably the
most appropriate one as it seems to capture the solid structure and
the extraction process kinetics and may enable us to develop the
scale-up of laboratory data for industrial design purposes.
Despite great achievements made so far, further efforts and
developments in modeling and scaling-up of SCCO2 extraction pro-
cesses for various solid matrices are still required. These works
may include elaborating the relationship among effective solute
diffusivity, microstructural features of vegetable substrates and
sample treatment, developing convenient and reliable optimiza-
tion methods for theoretical mass transfer models involved with
axial dispersion and solute–solid matrix interactions.
Nomenclature
a0 specific surface area of a solid substrate particle (m−1 )
A cross sectional area of the extraction vessel (m2 )
Ad a dimensionless model coefficient (Eq. (9))
Ai characteristic parameters of the logistic model (Eq. (30))
b characteristic parameter of the logistic model (Eq. (32b))
(s−1 )
bi characteristic parameter of the logistic model (Eq. (30))
(s−1 )
Bi dimensionless Biot number defined as Bi = 2kf R/De
c concentration of solute in the bulk SC CO2 phase (g/m3 )
C (=c/csat ) dimensionless solute concentration in the bulk SC CO2
phase
c0 the solute concentration c at t = 0, usually assumed to be
0
ca0 initial solute concentration adsorbed on solid sites (g/m3 )
c|R concentration of the solute at the particle surface (Eqs.
(13)–(15)) (g/m3 )
ci solute concentration in pores within particles (g/m3 )
ci (R) the solute concentration in pores at the particle surface
(g/m3 )
Ci (=ci /csat ) dimensionless solute concentration in pores within
particles
ci0 initial solute concentration within the pores of the parti-
cles (g/m3 )
cs solute concentration in the solid phase (g/m3 )
c̄s averaged solute concentration in the solid phase (Eq. (34))
(g/m3 )
cs0 initial concentration of solute in the solid or adsorbed
onto the solid (g/m3 )
24 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26

csat concentration of solute that is in equilibrium with a solid Si (t) population growth function defined in Eq. (30) (s−1 )
surface (g/m3 ) t extraction time (s)
D12 binary diffusion coefficient of solute and SCF (m2 /s) T extraction temperature (K)
De effective diffusion coefficient in a solid substrate (m2 /s) tCER time for constant extraction rate (Eq. (28f)) (s)
De1 , De2 different effective diffusion coefficient (Eq. (20e)) (m2 /s) te time required for complete equilibrium extraction (Eq.
Dl solute axial dispersion coefficient in the SCCO2 solvent (48a)) (s)
(m2 /s) tFER time used till the extraction of easily accessible solute
dp particle diameter (m) ends (Eq. (28g)) (s)
dpi the diameter of the sieve i (Eq. (21)) (m) tm characteristic parameter of the logistic model (Eq. (32b))
e time-dependent extraction yield, (g solute/g solute-free (s)
feed) tmi characteristic parameter of the logistic model (Eq. (32))
F volumetric flow rate of the SCCO2 solvent (m3 /s) (s)
Fr the fraction of the analyte released quickly (Eq. (10)) u the superficial velocity of the SCCO2 solvent (m/s)
H height of the packed bed (m) V void volume of the extraction chamber (m3 )
h thickness of the diffusion layer assumed in the DLT model Va , Vb volume of the SCCO2 solvent consumed (Eq. (12)) (m3 )
K equilibrium coefficient in Eq. (50) W dimensionless mass transfer parameter in the solid phase
kB Boltzman constant (J/K) (Eq. (28e))
kd desorption rate constant (s−1 ) x concentration of solute in the solid phase (g solute/g
kd1 the first-order rate constant describing the quickly solute free solid bed)
released fraction (Eq. (10)) (min−1 ) x0 the initial analyte concentration in the solid phase (g
kd2 the first-order rate constant describing the slowly solute/g solute free solid bed)
released fraction (Eq. (10)) (min−1 ) xb initial concentration of the readily accessible solute (g
kf film mass transfer coefficient (m/s) solute/g solute free solid bed)
kf a0 volumetric mass transfer coefficient in the solvent phase xf interfacial solute concentration (g solute/g solute-free
(s−1 ) feed) (Eq. (25))
ks solute mass transfer coefficient in the solid phase (m/s) xi initial concentration of the less accessible solute (g
ks a0 volumetric mass transfer coefficient in the solid phase solute/g solute free solid bed)
(s−1 ) xr , x , xϕ the dimensionless concentrations along coordinates r, 
kp overall mass transfer coefficient for a spherical particle and ϕ (Eq. (13))
(Eq. (52)) (m/s) y (=c/f ) concentration of solute in the SCCO2 fluid phase (g
Kp partition coefficient between tied solute in the solid and solute/g solvent)
dissolved solute in the SCCO2 solvent (Eq. (11)) y (z = H, t) time-dependent solute concentration at the exit of the
m0 mass of solute to be extracted and present in the parent packed bed (g solute/g solvent)
matrix (g) y* (=csat /f ) solubility of solute in the SCCO2 fluid phase (g solute/g
m1 , m2 dimensionless term defined in Eqs. (54a) and (54b) solvent)
ma , mb the cumulative mass (g) of the analyte extracted after z axial position along the bed (m)
consuming Va , Vb of the SCCO2 solvent (Eq. (12)) Z (=z/H) dimensionless axial position used in the SC model
mbed mass of solute-free feed loaded in the bed (Eq. (28a)) (g) Z dimensionless mass transfer parameter in the fluid phase
mCO2 mass of SCCO2 solvent consumed (Eq. (28a)) (g) (Eq. (28c))
mi (z = H, t) extracted mass of the group i of compounds (Eq. (32)) Zw dimensionless axial co-ordinate between fast and slow
(g) extractions (Eq. (28d))
mi0 total extractable mass of the group i of compounds (Eq.
(32a)) (g) Greek letters
mt time dependence of the mass of the extracted solute (g) ˇ characteristic parameter of the DLT model ˇ = 4R2 De /Vh
mt (z = H) time dependence of the mass of the extracted solute (g) (s−1 )
Np number of particles loaded in the bed defined by Eq. (17) ˇk kth term of the series solution defined by the periodic
P extraction pressure (MPa) equation (16)
Pe dimensionless Peclet number defined as Pe = Hu/Dl m the mass of the loaded sample (Eq. (12)) (g)
q specific mass of solvent consumed (g solvent/g solute-free mi the mass fraction of the solid retained by the sieve i (Eq.
feed) (21))
q̇ (=q/t) specific mass flow rate of solvent used (g solvent/g solute- ε porosity of the packed bed
free feed/s) εp porosity of the solid particle
QCO2 (=F × f ) the mass flow rate of the SCCO2 solvent (g/s) ϕ one of the coordinates
qm q value when extraction begins inside the particles (g sol-
viscosity of the SCCO2 solvent (Pa s)
vent/g solute-free feed)  one of the coordinates
qn q value when the easily accessible part of solute is all  (=De t/R2 ) dimensionless time used in the SC model
extracted (g solvent/g solute-free feed) e dimensionless time required for complete equilibrium
r radial position within the particle (m) extraction (Eq. (48b))
r (=xi /x0 ) fraction of the less accessible solute a apparent density of the solid loaded in the extraction bed
R radius of spherical solid particles (m) (g/m3 )
 solute molecule radius (m) s density of solid substrate particle (g/m3 )
rc radius of a shrinking core (m) f density of the SCCO2 fluid (g/m3 )
Re (=udp /
) dimensionless Reynolds number M the solute mass flux density per unit of area (Eq. (13)) (g
Sc (=
/f D12 ) dimensionless Schmidt number solute/m2 s)
Sh (=dp kf /D12 ) dimensionless Sherwood number  (=r/R) dimensionless axial coordinate within a particle
 (=rc /R) dimensionless axial position within a particle
 Z. Huang et al. / J. Chromatogr. A 1250 (2012) 2–26 25

 (=uR2 /De H) dimensionless term used in the SC model [45] C.S. Tan, D.C. Liou, AIChE J. 35 (1989) 1029.
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 dimensionless term defined in Eq. (54d)
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