J. Sep. Sci.

2002, 25, 477–489 Al-Jabari 477

Maher Al-Jabari Kinetic models of supercritical fluid extraction

Department of Chemical
Engineering, An-Najah National
University, Nablus,
P.O.Box 7-707, Palestine
The scope of this paper is to review the theoretical basis for modeling various applica-
tions of supercritical fluid extractions (SFE), including industrial processes and analy-
tical tests. Most of the models for SFE are concerned mainly with one stage SFE in
packed beds. However, in SFE tests, an initial static stage (with no flow) is usually
implemented for the purpose of achieving higher yields with pre-extractions. The
importance of accounting for the initial static stage is illustrated and a basis for mode-
ling such a stage is presented.
Theoretically, SFE models are similar to those for conventional transport processes
in that they are based on differential mass balance for solute in both phases and
invoke a rate equation (based on desorption kinetics or mass transfer) as well as a
thermodynamic equation to describe the interactions at the interface. Local equili-
brium theory can be implemented using linear or non-linear isotherms. A conceptual
scheme for developing SFE models from these general equations is suggested.
The similarity between modeling SFE processes and reversible adsorption/desorption
processes is demonstrated and shown to provide a useful basis for developing new
models for the SFE process. The concept of analogy is presented and used to deve-
lop a new model for SFE in packed beds from a previous deposition model.
Recent models for SFE tests with CSTR flow field are presented, including a mass
transfer model with local linear equilibrium and a model based on the Langmuir iso-
therm. A new equilibrium CSTR model is also presented and compared to these two
models.

Key Words: Modeling; Extraction; Supercritical fluid; Industrial processes; Analytical

tests;
Received: November 28, 2001; revised: January 29, 2002; accepted: February 2, 2002

1 Introduction
A fluid is considered to be supercritical when its tempera-
ture is raised above its critical temperature and its pres-
sure raised above its critical pressure. Under these condi-
and HPLC. Then, the interest developed rapidly into appli-
cations in SF separations, and particularly into supercriti-
cal fluid extraction (SFE) [3].
Conventional extraction methods using liquid solvents are

tions, the fluid characteristics combine those for liquids
and for gases. It is considered to be similar to liquids in
having high density and thus high solvent strength for var-
ious solutes, which largely increases with increasing pres-
sure [1]. However, since supercritical fluids (SF) are not
liquefied under pressure, they retain many attractive char-
acteristics of the gases such as low viscosity resulting in
high penetration capabilities and in high associated mass
transfer coefficients. All these factors have given SF great
potential for a wide range of processes [2]. Over the last
20 years, there has been an intense interest in the use of
SF in separation science [3]. SF were first used in chro-
matography as alternative media to gases or liquids in GC
Correspondence: Prof. Maher Al-Jabari, Department of
Chemical Engineering, An-Najah National University, Na-
blus, P.O.Box 7-707, Palestine.
E-mail: aljabari@mail.com
Fax: +972 9-2387982
Review
slow and usually require several hours or sometimes even
days to effect complete extractions. They also result in
dilute extracts, thus necessitating concentration of the
extracted solute in the liquid solvent, and they may not
result in quantitative recovery of target solutes. In certain
cases, solvents are associated with hazardous effects.
Moreover, an ideal extraction method should be rapid,
yield quantitative recovery of target solute without degra-
dation, and the solvent should be easily separated from
the solute. All these facts supported the development of
alternative extraction methods. Supercritical fluid extrac-
tion (SFE) technology offered scientists attractive fea-
tures overcoming many of the limitations of conventional
extractions. Nowadays, SFE is used in many applications
[5 – 21], with the extraction of natural products [4] being of
major economic importance. This includes recovery of
caffeine from coffee beans, extraction of nicotine from
tobacco wastes [6], isolation of essential oils from plants
[7], as well as the extraction of carotene and lipids from

i WILEY-VCH Verlag GmbH, 69469 Weinheim 2002 1615-9306/2002/0806–0477$17.50+.50/0

478 Al-Jabari
pressed palm oil fibers [7], extractions of chemicals from
forest products and wood pulp [8 – 11]. In addition, SFE
has been used as analytical tool to quantify metal content
in liquid and solid samples using in-situ complexation with
a suitable chelating agent [15 – 21]. New developments
include fractionation of products, dyeing of fibers, treat-
ment of contaminated soils [13, 14], production of pow-
ders in micron and sub-micron range, and reactions in or
with supercritical fluid [2]. SFE is established on the indus-
trial scale and as an analytical tool [15 – 17, 22, 23],
although its industrial scale application is still limited due
to the need for high-pressure equipment.
This wide range of applications have motivated research-
ers to develop models that would describe the various pro-
cesses and provide a tool for evaluating the performance
of SFE and optimizing operating conditions. There are
various models available in the literature for SFE [22 – 34].
In general, modeling SFE involves two different theoreti-
cal approaches, viz. kinetic and thermodynamic modeling.
Thermodynamic modeling is concerned with estimating
equilibrium states [13, 16, 31, 32], i. e. determining the
solubility of solutes in SF which is beyond the scope of this
paper. Kinetic models are concerned with following the
progress of extraction with time, or in other words, the
dynamics of SFE process. In this paper, SFE modeling
refers to kinetic models.
The theoretical basis underlying all kinetic SFE models is
established in this paper. The paper illustrates how pre-
vious models can be derived from such a basis and how
new models can be developed. Most of the existing SFE
models are based on the mass transfer approach [23 –
30], while other models are basically empirical [7, 16, 33,
34]. A model based on Langmuir kinetics has recently
been developed by the author [22]. Many of the models
were concerned with operation in packed beds [24 – 30];
the author had developed two models for SFE as an ana-
lytical tool [22, 23].
As a transport process, SFE is similar to conventional
extraction and reversible adsorption/desorption pro-
cesses. This similarity justifies drawing an analogy
between SFE and conventional reversible adsorption pro-
cesses, which would enable researchers to establish new
models for SFE. This approach is demonstrated in this
paper. Previous adsorption models [35 – 41] were based
mainly on mass transfer approaches similar to those of
SFE models. Thus, the analogy between these two pro-
cesses can lead to new SFE models. Such analogy is not
limited to molecular adsorption; the paper also highlights
the analogy with models for particle deposition developed
by the author and co-workers [42 – 44] and by other
researchers [45, 46]. In fact, those previous particle
deposition models were developed, to certain extent, on
J. Sep. Sci. 2002, 25, 477–489
the basis of analogies between particle deposition and
molecular adsorption.
In this paper, the general equations that govern all kinetic
models are first introduced, followed by presentation of a
conceptual scheme for developing particular SFE models.
Then, various kinetic SFE models are presented and dis-
cussed.
2 General equations
The general equations that govern the process of SFE are
similar to those that govern many mass transport opera-
tions involving solids and fluids such as leaching and
adsorption processes. Those equations include two differ-
ential solute mass balances for the solvating phase and
for the treated phase, in addition to a kinetic equation that
describes the rate of solute transfer between the two
phases. At the interface, equilibrium may be assumed to
exist, and thus a thermodynamic equation is needed. In
this section, equations are developed for SFE processes
in general without being applied to a certain system. The
subsequent section illustrates how they can be used for
developing certain models for certain systems. Equations
presented here are restricted to cases where the solid
matrix is inert and non-swelling.
2.1 Solute mass balance for supercritical phase
For an SFE in a continuous contact apparatus, a differen-
tial shell mass balance for solute in the supercritical phase
yields the following partial differential equation (PDE):
qc qc q2 c ð1 ÿ eÞ
þU ÿ Da ¼ÿ aNA ð1Þ
qt qx qx 2 e
Where c is the concentration of solute in the bulk of the
supercritical phase, U is the superficial velocity of SF
through the process vessel, Da is the axial dispersion coef-
ficient, x is the linear position in the vessel measured from
SF inlet, e is the volume fraction of SF in the vessel, t is the
time, a is the specific surface area of the solid, and NA is
the flux of solute from solid towards SF expressed per unit
surface area of the solid. Equation (1) is referred to as the
axial dispersion equation and usually used to describe the
transport of a solute in a fluid flowing through continuous
contact apparatus (like packed beds). This equation is
valid for SFE in industrial processes or their simulations
on the lab scale.
In analytical tests, the extraction vessel is usually small,
having a small tube inlet and a small tube outlet. Such a
design creates flow expansion upon entrance of SF into
the test vessel and contraction upon leaving. Both of these
effects result in considerable flow mixing and hence the
J. Sep. Sci. 2002, 25, 477–489
flow field in the vessel is considered to be similar to that
for a continuous stirred tank reactor (CSTR). The differen-
tial shell mass balance on solute in the supercritical phase
for a CSTR system yields the following simplified ordering
differential equation (ODE):
Q dc ð1 ÿ eÞ
cþ ¼ÿ aNA ð2Þ
eV dt e
Where Q is the volumetric flow rate of SF through an
extraction vessel of volume (V ).
2.2 Solute mass balance for solid phase
For both types of operations, differential mass balance for
solute in the solid phase provides the following equation:
qq
qs ¼ ÿaNA ð3Þ
qt
Where q is the mass fraction of solute in the solid and qs is
the density of the solids. The flux, NA, is a sink term here
whereas in Eqs. (1) and (2) it is a source term. Equation
(3) is valid for the two types of applications, i. e. for indus-
trial and analytical vessels. For analytical tests, exact deri-
vatives are used in Eq. (3) since q and c are only time
dependent. In certain applications, the mass fraction of
solute in the solid phase may vary with the internal posi-
tion inside the solids. In such cases, an internal diffusion
model would have to be solved for the local mass fraction
(q r) within the solid (see Section 2.3.1.2), from which the
average bulk mass fraction of solute in solids (q) is deter-
mined.
2.3 Solute transfer across the interface
(sink-source term)
The rate of transfer of solute across the interface between
the solid and SF phases, i.e. the sink-source term (NA) in
Eqs. (1) – (3), is governed by the physics of the transport
process. There are three steps, which may control such
transport processes. These are
1. Solute diffusion inside the solid particles (internal
mass transfer).
2. Solute dissolution from solid into SF phase at the
solid-SF interface (desorption kinetics).
3. Solute convection in SF from the interface to the bulk
of SF (external mass transfer).
In addition to these, other mechanisms may be involved in
more complicated systems. For example, when the poros-
ity of the solid is pronounced, the rate of outward solute
transport from the solid is governed by osmotic flow in the
pores (fluid mechanics) as well as diffusion in the fluid that
fills the voids in addition to diffusion in the solid phase
Kintic models of supercritical fluid extraction 479
(mass transfer). In such cases, diffusion and/or internal
flow resistance for the fluid in the pores may be encoun-
tered. These effects could be lumped together in one term
accounting for internal solute transport where a modified
internal mass transfer coefficient is used.
Consequently, the type of expression used for such a
sink-source term would depend on what step is the rate
determining one. For certain systems, the rate-limiting
step may be switched from one mechanism into another
as the SFE proceeds with time (as in drying processes).
For example, de Franc et al. [7] demonstrated that SFE
extraction curves of carotene and lipids from pressed
palm oil fibers are described by three steps in analogy to
drying curves: the first linear portion is a period of constant
extraction rate and is characterized by convective mass
transfer between the solid surface and the fluid phase.
The second part of the extraction curve represents the
falling rate period; at this step both convection and diffu-
sion in the solid must be considered. For the third step,
which is a diffusion-controlled rate period, diffusion in the
solid controls the rate of mass transfer. In another publica-
tion [22], the author demonstrated that for some systems,
an SFE model based on a desorption step provides a bet-
ter fit for experimental SFE curves than typical mass
transfer models.
In general, there are two types of approaches for account-
ing for the sink-source term (NA). These include (1) the
mass transfer approach, which can be based on internal,
external, or overall mass transfer resistance, and (2) des-
orption kinetics. All these approaches are applicable for
SFE is both industrial and analytical vessels, depending
on the characteristics of the two phases (SF and solids).
The following sub-sections establish the rate equations
for these various cases.
2.3.1 Mass transfer approach
2.3.1.1 External mass transfer
As in conventional mass transfer operations, the flux of
solute from the interface with a concentration c i into the
bulk of SF with a concentration c is given by
NA ¼ kc ðc i ÿ cÞ ð4Þ
Where k c is the mass transfer coefficient in the SF phase.
Several correlations for mass transfer coefficients for var-
ious types of solid geometries and flow conditions can be
found in books on mass transfer.
2.3.1.2 Internal mass transfer
The rate of solute transfer across the solid particles may
be obtained from internal diffusion models. Such models
are based on mass balance of solute across a differential
480 Al-Jabari
shell within a given single solid particle. The solid particles
may be considered as individual spherical particles [34],
semi-infinite bodies [12, 6] when the diffusion path is
much shorter than the characteristic dimension of the par-
ticles, or as a slab when the solid particles are thin and
wide. The resulting mathematical equations are similar to
those describing conductive heat transfer through similar
geometries for which solutions are available in heat con-
duction literature.
As an example, the general equation for diffusion in sphe-
rical particles is presented. For a bed of homogeneous
spherical particles, a solute mass balance on a differential
shell of thickness (dr) within a single particle leads to the
following PDE:
 2  2.3.2 Desorption kinetics
qqr q qr 2 qqr
¼ Ds þ ð5Þ
qt qr 2 r qr
Where r is the radial position within the sphere, Ds is the
diffusion coefficient in the solid and q r is the local mass
fraction of solute in the solid particle. The solution of
Eq. (5) requires two boundary conditions and one initial
condition (see Section 2.5).
After solving Eq. (5) for q r in the solid, the rate of transfer
of solute outward across the surface of solid particle (with
radius r0) can be obtained from the solution of Eq. (5) and
using Fick’s law. This affords
qq r
aNA ¼ ÿqs Ds ð6Þ
qr
where the derivative is estimated at r0.
As an alternative to this approach, a mass flux expression
may be used for solute transport in the solid phase similar
to that used in conventional leaching processes. The flux
equation is
NA ¼ ks ðq ÿ q i Þ ð7Þ
Where k s is the mass transfer coefficient in the solid phase
(which may account for the various types of internal resis-
tances as mentioned above), q s is the mass fraction of
solute in the solid at the interface with SF (which is in equi-
librium with c i when the desorption kinetics is negligible
according to local equilibrium theory).
2.3.1.3 Overall mass transfer resistance
The mass flux equation using the bulk concentration (c *)
rather than the interfacial concentration may be preferred
for cases when the equilibrium isotherm is considered to
be linear. Using the overall mass transfer coefficient, the
flux is given by
J. Sep. Sci. 2002, 25, 477–489
NA ¼ kco ðc  ÿ cÞ ð8Þ
using the SF variables, or
NA ¼ kso ðq ÿ q  Þ ð9Þ
Using the solid variables, where k co and k so are overall
mass transfer coefficients, c * is the concentration of
solute in the SF that is in equilibrium with the average
(bulk) mass fraction of solute in the solid phase and q * is
the mass fraction of solute in the solid that is in equilibrium
with the average (bulk) solute concentration in the SF
phase.
In most of previous SFE models, desorption kinetics was
assumed to be instantaneous, and thus the local equili-
brium concept was implemented at the interface between
the two phases. However, for some systems where the
interactions between the solute and the solid surface are
considerable, such a step could be the rate-limiting step
and thus there is a need to describe such kinetics by a cer-
tain rate equation based on molecular exchange at the
surface. The mechanism of molecular transport can be
visualized as follows: the molecules are usually attached
to a solid surface by secondary forces like van der Waals
forces. As a result of vibrational energy of the adhered
(adsorbed) molecules, part of these molecules will have
sufficient energy to overcome the bonding energy with the
solid surface and thus will leave the surface. On the other
hand, those molecules that are already in the supercritical
phase are in continuous random motion with rotational,
kinetic, and vibrational energies and thus part of them will
be continually striking the surface and consequently a
fraction of these molecules will adhere back onto the sur-
face. Hence, the process of solute transport is a reversible
process in a fashion similar to conventional molecular
adsorption processes. In such a case, the overall solute
desorption process consists of two elementary processes:
(1) desorption of solute molecules from the solid surface
into the supercritical phase and (2) re-adsorption of solute
molecules onto the surface at the available free sites. An
equation for desorption kinetics consists of two terms for
these two elementary steps.
Langmuir kinetics was used in chemical reaction literature
as the rate equation to describe the adsorption or desorp-
tion processes [48, 49]. In analogy to the molecular
adsorption process, Langmuir kinetics was also used, in
recent studies, to describe the rate of particle deposition/
detachment onto and from solid surfaces [43, 45].
Recently, the author developed an SFE model based on
Langmuir kinetics, which was the first attempt to base
SFE models on desorption kinetics [22].
J. Sep. Sci. 2002, 25, 477–489
According to Langmuir kinetics, the rate of the elementary
molecular desorption is basically proportional to the num-
ber of molecules attached to the solid surface, or their sur-
face concentration expressed as mass fraction, q. The
rate of re-adsorption onto the solid surface is proportional
to the rate of molecular collisions with the surface, which
is proportional to solute concentration in the supercritical
phase, c. The surface capacity for a solute can not exceed
that corresponding to a monomolecular layer (q max) since
the primary attraction forces that attach the molecules to
the surface diminish rapidly with the distance from the sur-
face. Hence, only those molecules colliding with unoccu-
pied sites on the surface will be adsorbed, and thus the
rate of adsorption is also proportional to the fraction of
unoccupied sites. Accordingly, Langmuir kinetics estab-
lishes that the net rate of desorption in SFE is given by the
difference between these two competing rates as follows
 
q
NA ¼ kd q ÿ ka c 1 ÿ ð10Þ
qmax
Where k d and k a are the desorption and adsorption coeffi-
cients, respectively. Both k a and k d are dependent on the
temperature and the molecular energy according to the
Arrhenius equation.
2.3.4 Instantaneous solute transfer
In some practical SFE applications, the two mass transfer
resistances (internal and external) can be negligible and
desorption kinetics can be extremely rapid. In such cases,
the concentration in the SF phase (c) reaches equilibrium
instantaneously. Thus, modeling SFE becomes simpler
since the rate equation (sink-source term) is not needed in
this case, while Eq. (3) is transformed by estimating the
derivative of q from the applicable equilibrium relation
(see Section 2.4 below). Then, Eq. (3) is replaced by
qq dq qc
¼ ð11Þ
qt dc qt
2.4 Local equilibrium concept
When desorption kinetics is not rate-limiting, equilibrium is
achieved instantaneously at the interface. This is the
basis for local equilibrium theory. Thus, the concentration
of solute in an SF at the interface may be governed by its
solubility in the SF, which, in turn, correlates with the den-
sity of the SF. For example, a simple semi-log plot of
solute solubility as a function of SF density can provide an
excellent correlation of experimental equilibrium data over
a relatively wide range of temperature. Modeling of solubi-
lities in SFE has followed the approach based on the
known equations of state. Despite extensive studies,
Kintic models of supercritical fluid extraction 481
state-of-the-art equations of state are still not capable of
adequately and quantitatively predicting SF behavior [25,
14]. Details of such thermodynamic modeling are beyond
the scope of this paper as mentioned earlier.
The equilibrium concentration of solute in SF is equal to
the solubility (S ) when the solute has no affinity to the solid
matrix. In such a case, the concentration in the SF phase
is independent of the mass fraction in the solids:
c ¼ S m f ðqÞ ð12Þ
Solute is attracted to and adsorbed onto the solid phase
through physical forces, and an equilibrium isotherm is
required to describe these interactions. Various types of
equations including linear and non-linear equilibrium iso-
therms can be used to describe the equilibrium distribu-
tion of solute between the solid phase and the SF. The lin-
ear equilibrium isotherm is given by
q ¼ Kc ð13Þ
where K is the equilibrium distribution coefficient. Non-lin-
ear equilibrium isotherms may also be used, such as the
Langmuir isotherm, which can be obtained from Eq. (9) by
setting the rate of desorption to zero (equilibrium). Upon
rearranging, one obtains:
1 1 1 1
¼ þ ð14Þ
q K c qmax
Where K (the equilibrium constant) is defined as the ratio
(k a/k d). The dimensionless equilibrium constant is defined
as follows:
ð1 ÿ eÞ
Ke ¼ qs K ð15Þ
e
2.5 Initial and boundary conditions
Solving various combinations of the above general differ-
ential equations requires various combinations of bound-
ary and initial conditions, which are summarized in this
section.
In both types of applications, the solution of ODE’s for the
static stage, requires the following two initial conditions
referring to fresh initial SF phase and to the initial mass
fraction of solute on the solids, q 0:
at t = 0, c = 0 (16)
at t = 0, q = q 0 (17)
482 Al-Jabari
While the initial conditions for the dynamic stage are
obtained from the solution of the transport equations for
the static stage defined as cs and qs for the concentrations
in SF and solid phase, respectively, and estimated at the
end of the static stage. Consequently, for the dynamic
stage, the initial conditions are:
at t = 0, c = c s (18)
at t = 0, q = q s (19)
In previous models developed for SFE in packed beds,
some researchers [52] have mistakenly replaced the initial
conditions in Eqs. (18) and (19) with those in Eqs. (16)
and (17) although the model was for fitting data from two
stage operations (see static stage below). Equations (16)
and (17) are applicable initial conditions for the dynamic
stage if no static stage is involved.
For models describing analytical vessels, Eqs. (16) – (19)
are the only required conditions for solving the transport
equations (ODE). However, for the industrial type of
operation in packed beds, boundary conditions are also
needed in addition to the above same initial conditions.
For solving the axial dispersion model, two boundary con-
ditions are needed at the bed inlet and outlet. Such bound-
ary conditions, for mass transfer operations in packed
beds in general, have been the subject of numerous
reports in the literature [49]. The Danckwerts’ boundary
conditions are
Da qc
at x ¼ 0; c ¼ ð20Þ
U qx
qc
at x ¼ L; ¼0 ð21Þ
qx
For models that handle internal diffusion equations, other
sets of boundary conditions are needed, together with an
initial condition similar to that in Eq. (17). For example, for
models of internal diffusion in spherical particles, Eq. (5),
the first boundary condition is
qq r
at r ¼ 0; ¼0 ð22Þ
qr
The second boundary condition depends on the relative
importance of various rates of solute transfer as well as
the rate of refreshment of the SF phase (wash out rate).
When the rate of desorption kinetics, external mass trans-
fer, and the rate of SF wash out are all very rapid, the SF
phase can be considered as a perfect sink for the solute,
i. e.
J. Sep. Sci. 2002, 25, 477–489
at r = R, q r = 0 (23)
where R is the radius of the particle. On the other hand,
when the external mass transfer contributes to the solute
transport, a surface balance is required for the solute at
the interface in order to specify the boundary condition.
The surface balance assures that the rate of solute diffu-
sion in the solid according to Fick’s law is equivalent to
that transferred across the SF by convection. In this case
the following boundary condition is used
qqr
at r ¼ R; ð1 ÿ eÞqs Ds ¼ ekc ðci ÿ cÞ ð24Þ
qr
3 Conceptual scheme for developing SFE
models
Combining and arranging the above general equations
required for any considered SFE system leads to specific
models for certain practical systems. This approach is
based on an understanding the constraints of the physical
system, which are then translated into a list of assump-
tions enabling a researcher to specify the equations
required for modeling SFE.
Prior to starting the process of modeling SFE, it is very
important to specify the type of operation, i. e. whether it is
a two-stage operation (dynamic after static) or a one stage
(dynamic) operation in order to determine whether a static
model is needed as well as the dynamic model. In cases
where a static stage is involved, a separate model for no-
flow conditions has to be developed and solved prior to
modeling the dynamic stage. The static model is similar
for both types of processes (packed beds and CSTR).
The solution of the static model would provide the initial
conditions for the dynamic model.
Now the first step in developing a dynamic SFE model is
to identify the type of flow field in the process, which will
determine what type of equation is to be used for the dif-
ferential mass balance (PDE or ODE). As summarized
above, two types of flow fields are usually encountered in
mass transfer operations, viz. those including the axial
dispersion model and the continuous stirred tank reactor
(CSTR) model. The axial dispersion model is chosen
when the concentration of the solute in SF is position and
time dependent as in the packed bed. However, when the
SF is considered to be a well-mixed phase, the CSTR
model is used and the concentration of the solute in the
SF is only time dependent. In addition to this categoriza-
tion, it is also helpful to compare the rate of purging of
solute out of the SFE vessel (fluid displacement) with the
rate of its desorption into the SF. When the fluid displace-
ment rate is faster than solute desorption rate, the con-
J. Sep. Sci. 2002, 25, 477–489 Kintic models of supercritical fluid extraction 483

Table 1. Types of SFE models with sample references.

Rate limiting Mass transfer limiting Desorption Instantaneous

Flow field Internal External Two resistance kinetics solute transfer
Diffusion Flux Eqn. (Langmuir)

Packed beds Rahme et al. Reis-Vasco et al. Rahme et al Montero Fullana Analogy with Reis-Vasco et al.
(1995) [25] (2000) [27], (1995) [25], et al. (2000) [33], Al-Jabari et al. (2000) (27),
Reverchon and Reverchon and Dooley (1995) [12] (1994) [43] Reverchon and
Marrone (1997) [35] Marrone (1997) [35] Marrone (1997) [35]

CSTR Future research Similar to Al-Jabari and Weber Al-Jabari and Al-Jabari Developed in
(1997) [23] Weber (1999) [23] (in press) [22] this paper

Fast SF Solid particles:

flow rate Sphere: Esquivel et al. (1999) [34] and Rincon et al. (1998) [6]
(Zero c-value) Thin plate: Bartle (1990)
Semi infinite slab: Dooley et al. (1995) [12]

centration in the SF is considered to be constant or zero in
some cases [34]. In such a case, the mass fraction of
solute in the solid phase is considered to be dependent on
time and internal position in the solid phase and the non-
steady state diffusion equation (example: Eq. (5)) is
solved for the transfer of the solute across the solid phase.
Models of this type usually express results as percentage
extraction (or average percentage remaining in solid) as a
function of time.
The second step is to identify the rate-limiting step(s) in
the transfer of solute from the solid phase into the SF
phase. The controlling mechanism can be desorption
kinetics or mass transfer which in turn can be internally or
externally controlled, or both phases may have consider-
able resistance. When the mass transfer process is inter-
nal, it is necessary to specify the type of mass transfer
modeling approach, i. e. whether it should be based on
mass transfer flux equations, like Eqs. (4), (7) – (9), or on
solving a diffusion equation and then estimating the flux
from Fick’s law. In addition, it may be necessary for some
systems to consider both desorption kinetics and mass
transfer rates. Such considerations have not been treated
in the literature. For certain systems, all these steps are
extremely rapid and thus there is no need for a flux equa-
tion since equilibrium is approached instantaneously. The
third step, for mass transfer models, is to specify the type
of equilibrium isotherm at the interface.
At the end of the modeling process, one of two types of
model is reached. The model for packed beds may consist
of a single or coupled PDE's while models for CSRT con-
sist of a single or coupled ODE's.
with reversible adsorption or particle deposition models.
The following section provides some examples.
4 Modeling results and discussion
4.1 Static stage
For both types of process vessels (packed beds and
CSTR's), the model for the static stage is the same since it
describes no flow conditions. Setting the third (dispersion)
term and the second (convective) term in Eq. (1) to zero
leads to the same ODE as is obtained after setting the first
(wash out) term in Eq. (2) of CSTR to zero. The resulting
ODE is then solved simultaneously with Eq. (3) after sub-
stituting the proper sink-source term as given by Eqs. (4),
(6) – (10). Closed form solutions are available for the
resulting system of ODE’s for cases with convective mass
transfer and Langmuir kinetics. Such solutions are
obtained using Mathematica software (Wolfram
Research) which provides a useful tool in solving such
models. Figure 1 illustrates the static SFE curves for the
case with mass transfer controlling and linear equilibrium
isotherm with K e = 0.5 The solution is expressed in terms
of dimensionless concentrations where q is non-dimen-
sionalized using q 0 and c using q 0/K. The fractional recov-
ery (Y ) during the static stage is then defined as follows
e c
Y ¼ ð25Þ
ð1 ÿ eÞqs q0
The dimensionless time (s) during the static stage is
defined as follows

Table 1 summarizes these possible modeling ð1 ÿ eÞ

approaches and lists sample references to models that s¼ k i at ð26Þ
e
already exist in the literature. There is still room for the
development of new models. This can be accomplished Where k i is the mass transfer coefficient, the subscript (i)
by adjusting some of the existing models or by analogy is to be replaced with the approriate subscript according
484 Al-Jabari
Figure 1. SFE curves for a static stage with mass transfer
control and linear equilibrium isotherm with K e = 0.5.
to the type of mass flux equation. Similar general curves
are obtained with Langmuir kinetics [22]. The static model
with external mass transfer resistance provided a good fit
with experimental data for static SFE tests, as demon-
strated by Al-Jabari and Weber [23].
As mentioned above, developing a model and obtaining a
solution for the static stage is one important step since it
specifies the type of initial condition that would be needed
for the model of the dynamic stage. Some researchers
omitted this step when they used an invalid initial condi-
tion, and thus obtained misleading results. For example,
Montero et al. [52] implemented a stage with no flow con-
ditions when studying the SFE of hazardous contami-
nants from soils. However, in the model used to describe
the resulting dynamic curves, the mass transfer during
such a static stage was not taken into account and the
initial conditions used were of the type given in Eqs. (16)
and (17).
The first attempt to consider a separate model for the sta-
tic stage was made by Al-Jabari and Weber [23] for SFE
in analytical tests. It is essential to reconsider previous
models of packed beds and resolve the PDE’s with the
resulting initial condition from the proper static stage
model. Such new solutions will provide better fits for
experimental two-stage SFE processes. The solution will
not require any additional mathematical work since closed
form solutions of the static models exist and can be imple-
mented.
However, Reverchon and Marrone [35] had considered
two types of initial conditions for their dynamic model, one
is when the SF phase is free of solute (no static stage) and
the other is for SF that is fully saturated with solute. In their
work, the latter initial condition was used to account for
solute recovery into SF during loading the extraction ves-
sel with CO2 and pressurizing it to the required pressure.
Obviously, they used the two terminal states of the static
curve (Figure 1), i. e. the initial value and the asymptotic
J. Sep. Sci. 2002, 25, 477–489
value. This modification is still insufficient since the actual
initial recovery can be at any value between these two lim-
its as shown in Figure 1 depending on the allowed time
prior to the dynamic stage.
4.2 Fluid displacement models for full SFE static
recovery
The plateau reached by the curve of fractional extraction
during the static stage (Figure 1) is dependent on the
equilibrium constant, which is strongly dependent on the
operating pressure. If the operating pressure is high
enough and if sufficient time is allowed during the static
stage, the fractional recovery during the static stage can
approach a value that is close to full recovery. Conse-
quently, the subsequent dynamic stage is governed by
the fluid displacement process, which is basically charac-
terized by the residence time distribution curves in the pro-
cess vessel used. For CSTR, such a RTD curve can be
obtained by setting the source term in Eq. (2) to zero and
solving the resulting equation with the initial condition in
Eq. (18), noting that c s in this case is equivalent to full
recovery. The author demonstrated experimentally that
the extraction of metal complexes with SF CO2 was well
described by the RTD of CSTR when enough static time
was permitted [51].
Similarly, for packed beds the RTD curve can be obtained
from the solution of the PDE in Eq. (1) after setting the
source term to zero, together with the initial and boundary
conditions in Eq. (18), (20), and (21), respectively. Such a
model was solved by Brenner [50] and used by Al-Jabari
et al. [43] to describe the experimentally obtained RTD of
water flow in packed beds. A simplified solution of the axial
dispersion models is also given by Smith [49].
4.3 SFE models for packed beds
Models for SFE operations in packed beds consist of the
two PDE's of Eqs. (1) and (3) together with the proper
equation for the sink-source term. The required initial and
boundary conditions are given in Eqs. (16) – (21), depend-
ing on the type of operation. The existing models for
packed beds did not account for cases with initial static
stage.
Usually, no closed form solutions are possible for the
PDE’s of SFE in packed beds and thus numerical solu-
tions are obtained using, for example, the Crank-Nicolson
finite difference scheme. In some cases, the axial disper-
sion (third) term in Eq. (1) may be neglected when the
Peclet number estimated on the basis of the axial disper-
sion coefficient is very low. In such a case, plug flow [49]
characteristics are obtained. Reverchon and Marrone [35]
used such an assumption in modeling their SFE work on
the extraction of clove bud essential oil. They also com-
J. Sep. Sci. 2002, 25, 477–489 Kintic models of supercritical fluid extraction 485

pared the results with those obtained from a model includ-

ing the axial dispersion term and found that adding the
axial dispersion term did not improve the fit.
In such an approach, the mass transfer process was con-
sidered to be either internally or externally controlled,
while other models considered the two mass transfer
resistances. In these previous models, desorption kinetics
was not considered to any significant extent, even for
cases where interactions between solid matrix and ana-
lytes were reported to have a substantial effect on the rate
of SFE. In addition to these general mass transfer models,
other simplified models were also developed in the litera-
ture for cases with instantaneous solute transfer step (i. e.
rapid desorption and mass transfer). Such models are
referred to as equilibrium models [35, 27]. The model con-
sists of Eqs. (1) and (11) after substituting the applicable Figure 2. Dynamic SFE curves for analytical tests with mass
equilibrium relation for the derivative of q with respect to c transfer control and linear equilibrium isotherm and with
K e = 1.0.
(Section 2.4). Previous models of this type considered
basically the linear equilibrium isotherm. depressurized and the extracted solute is recovered while
Models of packed beds based on axial dispersion to be gas is bubbled out, referred to as the dynamic stage. Pre-
found in the existing literature include vious characterization of such SFE tests had been per-
formed in the analytical chemical literature based on
– Axial Dispersion models with external mass transfer
experimental observations. For example, Wang and Mar-
resistance and linear equilibrium.
shal [16] described the dynamics of such tests by an
– Axial Dispersion models with external mass transfer
empirical biphasic exponential decay.
resistance and non-linear equilibrium.
– Axial Dispersion models with internal mass transfer As described above, the flow field in such analytical tests
resistance using a flux equation. is of CSTR type due to contraction-expansion at the inlet
– Axial Dispersion models with internal mass transfer and outlet of the test vessel (which is small). Conse-
resistance, where the mass transfer rate is obtained quently, models for such tests usually consist of two
from non-steady internal diffusion equation. ODE’s as given in Eq. (2) and (3) after implementing the
sink-source term according to the controlling mechanism.
– Equilibrium models with linear equilibrium.
A closed form solution for the dynamic SFE with external
Other models that are of future interest and suggested to
mass transfer and linear equilibrium isotherm are
be considered by researchers include:
obtained using Mathematica software (Wolfram
– Axial dispersion models with Langmuir kinetics as the Research). In the case of Langmuir kinetics, however, no
rate equation (see Section 4.6 below). closed form could be obtained for the dynamic stage and
– Resolving the axial dispersion models listed above the system of ODE's was therefore solved numerically by
after developing a static model accounting for the the author [22]. Figure 2 shows the dimensionless curves
initial static stage. for c, q, and Y obtained from the mathematical solution of
– Axial dispersion equilibrium models with a non-linear a mass transfer model with external resistance and linear
equilibrium isotherm. local equilibrium. The dynamic SFE curves shown are for
the case with no static stage. The fractional recovery dur-
ing the dynamic stage is estimated from the solute bal-
4.4 Modeling analytical SFE tests (CSTR)
ance around the test vessel:
The SFE tests are usually performed in three steps:
(1) Pressurizing the test vessel containing the sample to Z t
be extracted with the supercritical fluid. This step is
Kc
Y ¼ dh ð27Þ
usually fast; changes in concentrations between the two 0 q0
phases can be neglected during this stage. (2) Soaking
the sample in the supercritical phase for certain time in The time during the dynamic stage is non-dimensiona-
order to allow the solute desorption into the supercritical lized with respect to the average residence time of the SF
phase, referred to as the static stage. (3) Displacement of in the vessel (i. e. eV/Q) and referred to as h.
the supercritical fluid phase out of the test vessel into a The mass fraction of the solute on the solid surface
collection vessel containing a liquid solvent where it is decreases continuously while the concentration of the
486 Al-Jabari J. Sep. Sci. 2002, 25, 477–489

solute in the SF phase increases and then decreases as a

result of the two competing rates (wash-out of SF in the
vessel and desorption). The fractional recovery, Y,
increases until it approaches the full recovery in a time
period that is dependent on the mass transfer coefficient,
the length of the static stage, and the equilibrium con-
stant.
The solutions obtained for CSRT models provided good
fits to different types of experimental results, including two
stage SFE of metal complexes [23] as well as for SFE of
organics [22].

4.4.1 New equilibrium model for analytical SFE
tests
In this section, a new CSTR model is presented which uti-
lizes a modeling approach similar to that used by
Reverchon and Marrone [35] and Reis-Vasco et al. [27]
for packed beds. In their work, it was assumed that when
the solute is accessible at the solid surface, the kinetics of
the process is governed by equilibrium. This assumption
is not adequate for assuming instantaneous solute trans-
fer between the two bulk phases. It is also essential to
assume that desorption kinetics is instantaneous and that
the external mass transfer resistance is negligible. In this
case, the mass fraction of solute on the solid is in equili-
brium with its concentration in the bulk of the SF phase.
Making such assumptions, combining Eqs. (2) and (3),
and substituting Eq. (11) in the resulting equation after
estimating the derivative of q with respect to c from the lin-
ear equilibrium isotherm in Eq. (13) results in the following
ODE:
Q dc ð1 ÿ eÞ dc
cþ ¼ÿ qs K ð28Þ
eV dt e dt
which requires one initial condition given by Eq. (18), not-
ing that for this case, c s is in equilibrium with q 0, i. e.
Figure 3. Dynamic SFE curves obtained from equilibrium
model, mass transfer model, and Langmuir kinetics without
an initial static stage and all at the same K e = 0.5. Also
shown is the SFE curve from the fluid displacement model.
less time (h). Figure 3 also compares theoretical dynamic
SFE curves obtained from the various models including
cases with fluid displacement, mass transfer, and deso-
rption kinetics at the same dimensionless equilibrium con-
stant (Ke = 0.5).
Obviously, the fastest dynamic SFE process is obtained
with the fluid displacement model since all the solute is
pre-extracted into SF during the static stage. This
response can also be obtained without a static stage but
only if the solvating capacity of the SF phase exceeds the
requirements of all the solute present in solids and all
solute transport steps are instantaneous. The second
fastest dynamic SFE is with the equilibrium model since in
this case the solute transport process is instantaneous,
the delay of the SFE curve relative to that of the fluid dis-
placement model is dependent on the value of the equili-
brium constant. When the solute transport process is sig-
nificant, a further delay is observed due to additional times
required for transport or kinetic processes. The slowest
dynamic SFE is obtained with mass transfer control.

at t = 0, c = q 0/K (29)
4.5 Internal diffusion models
When the rate of refreshment of SF is much faster than
since the solute transfer process is instantaneous, thus
the rate of the solute release from the solid surface and
equilibrium is reached regardless of the length of the initial
the external mass transfer resistance is negligible, internal
(static) stage. The solution of Eq. (28) with the initial con-
diffusion in the solid controls the whole SF process. In
dition given in Eq. (29) is
such a case, there will be no need for a differential mass
balance in the SF phase (i. e. no axial dispersion or CSTR
 
c 1 equations). The solute concentration in the bulk of the SF
¼ Exp ÿ h ð30Þ
ðq0 =K Þ 1 þ ð1 ÿ eÞ=eqs K is usually taken to be negligible (zero) since the SF phase
is considered to be displaced with fresh SF at a rate that is
Where h is the dimensionless time during the dynamic faster than the rate of solute transfer from solids into the
stage. The fractional recovery can be estimated from SF phase. In models of this type, the solid phase is
Eq. (27). The resulting solution for the fractional recovery assumed to be made up of uniform particles and the inter-
(Y ) is plotted in Figure 3 as a function of the dimension- nal non-steady state diffusion equation is solved for one
J. Sep. Sci. 2002, 25, 477–489
particle. The solution is usually expressed as solute resi-
dual on the solid particle (q) as a function of time.
The solid particles may be considered as individual sphe-
rical particles [34], semi-infinite bodies [12] when the diffu-
sion path is much shorter than the characteristic dimen-
sion of the particles, or as a slab when the solid particles
are thin. The resulting PDE’s are similar to those describ-
ing conductive heat transfer through a similar geometry,
for which solutions are available in literature. Each type of
model consists of a single PDE, which is solved with one
initial condition and two boundary conditions.
For example, the spherical particle model is obtained from
the solution of PDE in Eq. (5) together with the initial and
boundary conditions in Eqs. (17), (22), and (23). The solu-
tion of this model is available in the literature and was
used by Esquivel et al. [34] to describe the SFE of olive
husk oil, providing acceptable fit at high SF velocities.
4.6 Establishing new SFE models by analogy
For many transport phenomena, the general transport
equations may have the same mathematical form since
the transport mechanisms are based on similar physical
backgrounds. For example, the mechanism of mass
transfer diffusion is similar to that for heat conduction.
Also, desorption into SF is similar to the conventional
molecular adsorption (or desorption) into liquids. When
the geometry of the systems is also identical, similar
mathematical solutions are obtained for different transport
processes. Thus, existing solutions for conventional pro-
blems similar to those in SFE can be used in new SFE
models. The previous section introduces the concept of
analogy where SFE models were similar to those in pre-
vious conductive heat transfer models. The same mathe-
matical solutions could therefore be used, thus saving
considerable solution time.
Such a concept of analogy can be implemented for obtain-
ing “new” models for SFE. The literature of chemical engi-
neering has a plethora of transport models that describe
the transfer of molecules (or fine particles) from a fluid into
a solid surface and vice versa. By analyzing the physical
behavior of the SFE process and identifying the transport
similarity with conventional transport processes, many of
the previous models can be used for SFE processes.
In this section, it is shown that a previously developed par-
ticle deposition model [43] can be used for SFE in packed
beds after merely changing the initial conditions. The phy-
sical behavior of particle deposition systems is similar to
that of molecular adsorption systems; the Brownian
motion of fine particles resembles molecular diffusion.
The same Langmuir kinetics used for molecular adsorp-
tion onto solid surfaces, Eq. (10), was used in a model to
describe the reversible particle deposition process in
Kintic models of supercritical fluid extraction 487
packed beds developed by Al-Jabari et al. [43] and the
corresponding model for stirred vessels also developed
by Al-Jabari et al. [45]. The solution obtained for particle
deposition in stirred vessel [45] is similar to that for static
SFE after modifying the initial condition [22].
Based on such similarity, a new model for SFE in packed
beds, for the case where solute desorption from the solid
is the rate-limiting step, is derived from the previous
deposition model published by Al-Jabari et al. [43]. The
previous model was developed to describe the particle
deposition in packed beds of collectors using Langmuir
kinetics. The model consisted of two coupled partial differ-
ential equations similar to Eqs. (1), (3), and (10). The axial
dispersion term was neglected compared to the convec-
tion term. This assumption is similar to that used by
Reverchon and Marrone in their mass transfer model in
packed beds (see Section 4.3).
The resulting PDE's were solved numerically using the
Galerkin Finite Element method. The same solution algo-
rithm can be used to describe the SFE. A Fortran program
was developed by the author to solve the resulting PDE's
of deposition in packed beds; the same software is applic-
able after modifying the initial condition to account for de-
sorption rather than adsorption. Results from such a
model are to be presented in a subsequent paper.
5 Concluding remarks
There is a common theoretical basis for modeling SFE
processes. Most of the existing models can be con-
structed on the basis of a group of general equations pre-
sented in this paper. Directions and a scheme for develop-
ing new SFE models are suggested. Previous SFE mod-
els for packed beds have not considered the case with
static stage operation prior to dynamic stage operation;
new models of this type are still needed. A new model is
presented in this paper for analytical tests assuming
instantaneous solute transfer and equilibrium desorption
and compared to other mass transfer, desorption kinetic,
and fluid displacement models. The concept of analogy is
demonstrated for the purpose of developing new models
for SFE based on previously existing models for similar
phenomena.
Nomenclature
a specific surface area of the solid particles
(cm2 N cm – 3)
c concentration of the solute in the bulk supercritical
phase (g cm – 3)
c* concentration of the solute in the bulk of supercritical
phase that is in equilibrium with q (g cm – 3)
488 Al-Jabari J. Sep. Sci. 2002, 25, 477–489

ci concentration of the solute at the interface in the References

supercritical phase (g cm – 3)
cs concentration of the solute in the supercritical phase [1] R.M. Smith, J. Chromatogr. A 1999, 856, 83 – 115.
at the end of the static stage [2] R. Marra, T. Gamse, Chem. Eng. Process. 2000, 39,
Da axial dispersion coefficient (cm2 s – 1) 19 – 28.
Ds diffusion coefficient of solute in solids (cm2 s – 1) [3] K.W. Hutchenson, N.R. Foster, Innovations in Supercri-
K equilibrium constant (cm3 g – 1) tical Fluid Science and Technology, Ch. 1 in: Innovations
Ke dimensionless desorption equilibrium constant in Supercritical Fluids Science and Technology, K.W.
Hutchenson, N.R. Foster, eds., American Chemical
defined in Eq. (15) Society, Washington, DC, 1995.
ka adsorption coefficient (cm s – 1)
[4] M.D. Luque de Castro, M.M. JimØnez-Carmon, V.
kd desorption coefficient (g cm – 2 s – 1) Fernµndez-PØrez, Tr. Anal. Chem. 1999, 18, 708 – 716.
kc mass transfer coefficient in SF phase (cm s – 1)
[5] T.L. Chester, J.D. Pinkston, D.E. Raynie, Anal. Chem.
k co overall mass transfer coefficient in SF phase
1994, 66, 106R-130R.
(cm s – 1)
[6] J. Rincon, A. de Lucas, M.A. Garcia, A. Garcia, A.
ks mass transfer coefficient in solid phase (g cm – 2 s – 1)
Alvarez, A. Carnicer, Sep. Sci. Technol. 1998, 33, 411 –
k so overall mass transfer coefficient in solid phase 423.
(g cm – 2 s – 1)
[7] Luiz F. de Franc, M. Angela, A. Meireles, J. Supercrit.
L bed length (cm) Fluids 2000, 18, 35 – 47.
NA flux of solute from solids into SF phase (g cm – 2 s – 1)
[8] Lixiong Li, Erdogan Kiran, I & EC Research 1988, 27,
Q volumetric flow rate (cm3 s – 1) 1301.
q mass fraction of the solute in the solid sample (g/g)
[9] A.J. Sequeira, L.T. Taylor, J. Chromatogr. Sci. 1992, 30,
q* mass fraction of the solute in the solid sample which 405 – 408.
is in equilibrium with c (g/g)
[10] E.C. McDonald, J. Howard, B. Bennett, Fluid Phase
qmax maximum mass fraction of the solute that can be Equilibria 1983, 10 , 337 – 344.
adsorbing on the solid sample for monolayer cover-
[11] E. Kiran, H. Balkan, J. Supercrit. Fluids 1994, 7, 75 – 86.
age (g/g)
q0 initial mass fraction of the solute in the solid sample [12] K.M. Dooley, D. Launey, J.M. Becnel, T.L. Caines, Mea-
surement and Modeling of Supercritical Fluid Extraction
(g/g)
from Polymeric Matrices, Chapter 18 in: Innovations in
qs mass fraction of the solute in the solid sample at the Supercritical Fluids Science and Technology, K.W.
end of the static stage. Hutchenson, N.R. Foster, eds., American Chemical
qr local mass fraction of solute in solids (g/g) Society, Washington, DC, 1995.
qi mass fraction of solute at the interface in the solid [13] Z.G. Rahme, R.G. Zytner, W.H. Stiver, Kinetic Model for
phase (g/g). the Supercritical Extraction of Contaminants from Soil,
r radial position in a spherical solid particle (cm) Chapter 20 in: Innovations in Supercritical Fluids
Science and Technology, K.W. Hutchenson, N.R. Foster
R radius of the particle (cm). American Chemical Society, Washington, DC, 1995.
S solubility of solute in SF (g cm – 3)
[14] S.J. Macnaughton, P. Alessi, A. Cortesi, I. Kikic, N.R.
t time (s) Foster, Predictive and Experimental Methods for the
V total volume of the extraction vessel (cm3) Choice of Cosolvent in the Supercritical Fluid Extraction
U superficial SF velocity in the extraction vessel of Pesticides, Chapter 8 in: Innovations in Supercritical
(m s – 1) Fluids Science and Technology, K.W. Hutchenson, N.R.
Foster, American Chemical Society, Washington, DC,
x the linear position in the extraction vessel measured
1995.
from SF inlet (m)
Y fraction of the solute recovered [15] K.E. Laintz, C.M. Wai, C.R. Yonker, R.D. Smith, Anal.
Chem. 1992, 64, 2875 – 2878.
[16] Jin Wang, W.D. Marshall, Recovery of Metals from Aqu-
eous Media by Extraction with Supercritical Carbon
Greek symbols Dioxide, Anal. Chem. 1994, 66, 1658–1663.
e volume fraction which is occupied by the supercriti- [17] K. Thurbide, M. Al-Jabari, M. Kowalchuk, Chem. Eng.
cal phase in the extraction vessel. Commun. 2002, 189, 676–684.
qs density of the solid sample (g N cm – 3) [18] C.M. Wai, Anal. Sci. 1995, 11, 165 – 167.
s dimensionless time during the static stage [19] M. Ashraf-Khorassani, M.T. Combs, L.T. Taylor, J.
h dimensionless time during the dynamic stage Chromatogr. A. 1997, 774, 37 – 49.
J. Sep. Sci. 2002, 25, 477–489
[20] K.E. Laintz, C.M. Wai, C.R. Yonker, R.D. Smith, J.
Supercrit. Fluids 1991, 4, 194 – 198.
[21] C.M. Wai, S. Wang, J. Chromatogr. A 1997, 785, 369 –
383.
[22] M. Al-Jabari, Chem. Eng. Commun., in press.
[23] M. Al-Jabari, M.E. Weber, Sep. Sci. Technol. 1999, 34,
2853 – 2863.
[24] E. Björklund, M. Järemo, L. Mathiasson, J.Š. Jönsson,
L. Karlsson, Anal. Chim. Acta 1998, 368, 117 – 128.
[25] Z.G. Rahme, R.G. Zytner, W.H. Stiver, Kinetic Model for
the Supercritical Extraction of Contaminants from Soil,
in: Innovations in Supercritical Fluids Science and Tech-
nology. ACS Symposium Series 608, K.W. Hutchenson,
N. R. Foster, Eds., American Chemical Society,
Washington, DC, 1995, Ch. 20.
[26] M. Goto, B.C. Roy, A. Kodama, T. Hirose, J. Chem. Eng.
Jpn. 1998, 31, 171 – 177 [in Japanese].
[27] E.M.C. Reis-Vasco, J.A.P. Coelho, A.M.F. Palavra, C.
Marrone, E. Reverchonba, Chem. Eng. Sci. 2000, 55,
2917 – 2922.
[28] E. Reverchon, A. Kaziunasb, C. Marrone, Chem. Eng.
Sci. 2000, 55, 2195 – 2201.
[29] I. Goodarzni, M.H. Eikani, Chem. Eng. Sci. 1998, 53,
1387 – 1395.
[30] B. Ramchandran, J.B. Riggs, H.R. Heichelheim, A.F.
Seibert, J.R. Fair, I & EC Research 1992, 31, 281.
[31] N.T. Dunford, M. Goto, F. Temelli, J. Supercrit. Fluids
1998, 13, 303 – 309.
[32] E. Reverchon, G. Lambertia, P. Subraa, Chem. Eng.
Sci. 1998, 53, 3537 – 3544.
[33] M. Fullana, F. Trabelsi, F. Recasens, Chem. Eng. Sci.
2000, 55, 79 – 95.
[34] M.M. Esquivel, M.G. Bernardo-Gil, M.B. King, J. Super-
crit. Fluids 1999, 16, 43 – 58.
[35] E. Reverchon, C. Marrone, Chem. Eng. Sci. 1997, 52,
3421 – 3428.
[36] S. Oiao, X. Hu, Chem. Eng. Sci. 2000, 55, 1533 – 1544.
Kintic models of supercritical fluid extraction 489
[37] S. Oiao, X. Hu, Sep. Purif. Technol. 1999, 16, 261 – 271.
[38] Y. Ding, E. Alpay, Chem. Eng. Sci. 2000, 55, 3461 –
3474.
[39] G. Dünnebier, K.-U. Klatt, Chem. Eng. Sci. 2000, 55,
373 – 380.
[40] D.E. Cherrak, S. Khattabi, G. Guiochon, J. Chromatogr.
A 2000, 877, 109 – 122.
[41] K. Wang, D.D. Do, Sep. Purif. Technol. 1999, 17, 131 –
146.
[42] R. Subramanian, V. Lakshminarayanan, Electrochimica
Acta 2000, 45, 4501 – 4509.
[43] M. Al-Jabari, A.R.P. van Heiningen, T.G.M van de Ven,
J. Pulp Paper Sci. 1994, 20, 249.
[44] H. Mousa, M. Al-Jabari, I. Al-Khateeb, Chem. Eng. J.
2001, 83, 79 – 83.
[45] M. Al-Jabari, H. Mousa, I. Al-Khateeb, J. Sep. Sci. Tech-
nol. 2002, 37, 431 – 449.
[46] M. Kamiti, T.G.M. van de Ven, J. Pulp Pap. Sci. 1994,
20, 199 – 205.
[47] T.G.M. van de Ven, Nordic Pulp Paper Res. J. 1993, 8,
130 – 147.
[48] H.S. Fogler, Elements of Chemical Reaction Engineer-
ing, 2nd Ed. Prentice Hall, New Jersey, USA 1992.
[49] J.M. Smith, Chemical Engineering Kinetics, 3rd Ed.
McGraw-Hill, New York, USA 1981.
[50] H. Brenner, Chem. Eng. Sci. 1962, 17, 229.
[51] M. Al-Jabari, Characterizing Supercritical Fluid Extrac-
tion of Metal Complexes using Spectrophotometric
Technique, Proceedings of First International Chemical
Engineering Conference, University of Jordan, Septem-
ber 2001.
[52] G.A. Montero, T.D. Giorgio, K.B. Schnelle, Jr., Removal
of Hazardous Contaminants from Soils by Supercritical
Fluid Extraction, Ch.19 in: Innovations in Supercritical
Fluids Science and Technology. K.W. Hutchenson, N.R.
Foster, Eds., American Chemical Society, Washington,
DC, 1995.
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