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of Chemical Engineering, University of Southern California, 925 West 37th Street, Los Angeles, CA 90089-1211, USA
& Environmental Sciences Division (EES-5) MS F-649, Los Alamos National Laboratory, Los Alamos, NM 87545, USA
Received 27 October 2000; received in revised form 17 July 2001; accepted 12 December 2001
Abstract
We show that for reaction-transport processes with fast kinetics (in the limit of thermodynamic equilibrium), conventional volume
averaging for determining e6ective kinetic parameters applies only when the macroscopic variable approaches its equilibrium value. Even
under such conditions, computing the e6ective mass transfer coe7cient requires solving an eigenvalue problem, which couples the local
microstructure with the global. Two examples, one involving a simple advectiondissolution problem and another a drying problem in
a pore network, illustrate the theoretical predictions. Similar considerations apply for the case of #nite kinetics, when the macroscale
concentration approaches an equilibrium value. In that case, the e6ective kinetic parameter is not equal to the local, as typically assumed,
but it becomes a function of the local Thiele modulus. ? 2002 Published by Elsevier Science Ltd.
Keywords: Porous media; Mass transfer; Dissolution; Kinetics; Scale-up; Drying
1. Introduction
Mass transport with heterogeneous chemical reaction in
porous media is important in a variety of applications in the
physical, chemical, and engineering sciences. Transport is
typically by advection and di6usion, with reaction occurring at the (usually) disordered pore surface. As a result of
reaction, the pore morphology may also evolve, with examples ranging from gassolid reactions (Dogu, 1980) to
the acidizing of carbonate rocks (Hoefner & Fogler, 1988;
Daccord, Lenormand, & Lietard, 1993). A speci#c class of
problems of interest to this paper involves heterogeneous reactions with #nite or fast kinetics. A limiting case are problems, where thermodynamic equilibrium applies at the pore
surface (Lichtner, 1996).
The latter type of problem arises in various contexts,
for example in the solubilization of trapped non-aqueous
phase liquids (NAPLs) in soils (Imho6, Ja6e, & Pinder,
1993; Jia, Shing, & Yortsos, 1999), or in the drying of a
porous medium (Laurindo & Prat, 1998; Tsimpanogiannis,
Yortsos, Poulou, Kanellopoulos, & Stubos, 1999), where
Corresponding author. Tel.: +1-213-74-00-317;
fax: +01-213-740-8053.
E-mail address: yortsos@euclid.usc.edu (Y. C. Yortsos).
the concentration at the source=sink interface can be considered as constant. In many applications, mass transfer is
driven by the Fow of a liquid in a porous medium. For example, this is the case in the remediation by solvent injection of
ground-water aquifers contaminated by organic chemicals
(NAPLs). The NAPLs are trapped by capillarity in the pore
interstices, forming immobile, disconnected ganglia, which
act as contaminant sources of a generally disordered geometry. A similar situation arises in dissolution or precipitation
and involve mass transport between the pore surface and the
injected Fuid. If, in such problems, the kinetics at the interface are fast, and one can proceed with the assumption of
local thermodynamic equilibrium (for example, the use of
Henrys law at the source interface).
In view of the complexity of the pore space and=or the
source-sink geometry, and the need for workable models, an
important topic pursued for several years has been the development of e6ective models to scale-up the process from
the micro- (pore) scale to the macro- (continuum) scale.
While the upscaling of conventional di6usionreaction systems has been researched for some time (Whitaker, 1999),
the upscaling of dissolution-type processes has been rather
recent. Of particular relevance in this context is the work
of Quintard and Whitaker (1994), to be hereafter referred
2566
to as QW, who applied volume averaging to derive e6ective mass transfer coe7cients for the dissolution of trapped
NAPLs in a porous medium with a periodic microstructure.
Implicit to their approach are two important assumptions,
scale separation at the microscale, and small gradients of the
volume-averaged variable at the pore-network scale. Under
conditions of fast kinetics, however, this requires that the
volume-averaged concentration must be close to its thermodynamic value. It will be shown in this paper that in this
case, the unit-cell problem for calculating e6ective coef#cients involves information both from the microstructure
and the from the gradients of the macroscopic concentration,
thereby resulting in the coupling of micro and macroscale
problems.
Volume averaging is one of two main methods for upscaling. It is closely related to homogenization (Bensoussan, Lions, & Papanicolaou, 1978), with which it shares the same
foundation. Pioneering work in volume averaging in porous
media has been done by Whitaker (1999). An alternative approach involving ensemble averages is based on the method
of moments, applied for example in Edwards, Shapiro, and
Brenner (1993) to derive Darcy-scale di6usionreaction coe7cients. Stochastic theories for reactive transport in various contexts (Hu, Cushman, & Deng, 1997; Cvetkovic &
Dagan, 1994) have also been developed, where the emphasis is on the (macroscopic) permeability heterogeneity, thus
representing upscaling over a larger scale. In this paper, we
will restrict our interest to volume averaging as particularly
applied in the above-cited work of QW.
For volume averaging to be meaningful, the averages
should not depend on the averaging volume itself. In general, this requirement can be translated into two conditions:
that the length scale of the averaging volume (macroscopic
length L) be su7ciently larger than the correlation length of
the microstructure, ,
1 1
(1)
L
and that the upscaled variable vary slowly at the small scale
2 |CD |1;
(2)
interest to this paper, however, the condition of local thermodynamic equilibrium precludes the existence of a small
dimensionless parameter, to ensure the validity of Eqs. (1)
and (2) (in such cases, the local Thiele modulus is in#nite).
It follows that Eq. (2) is satis#ed only in the limit when
the upscaled concentration approaches its thermodynamic
equilibrium value, in all other cases the upscaling being inherently non-local. We will show that even under the #rst
condition, however, micro and macroscale problems still remain coupled. A similar situation exists for conventional
advectionreaction processes, when the kinetics are #nite
and the process approaches an equilibrium state. In the latter
limit, constraint (2) is satis#ed, even though the local Thiele
modulus is not necessarily small. It will be shown that in
this case as well, the e6ective parameter arises from the solution of a problem coupling both local and global scales.
The paper is organized as follows: First, we provide a
brief review of the upscaling constraints of the type (2) for
typical transport-reaction systems. In this we will also draw
an analogy with two-phase Fow in porous media. Then, we
provide simple 1-D examples which illustrate the problem
and provide the motivation for the subsequent development.
Using the methodology of QW we will derive a problem for
the computation of the e6ective mass transfer coe7cient, in
processes where thermodynamic equilibrium applies, with
particular application to a dissolution problem. The closure
problem is found to be di6erent than in QW, as it depends
also on the gradients of the macroscale variable, and can
be cast in terms of an eigenvalue problem. We demonstrate
the theory with two examples, one involving advection
dissolution and another involving drying in a pore network.
Similar ideas apply to reactiondi6usion systems with #nite
kinetics, when an equilibrium state is approached.
2. A brief background
Problems involving transport, reaction or other physicochemical processes in porous media are controlled by two
competing processes, one local and one non-local. The local process does not involve spatial gradients, and although
involving Fuctuating (possibly random) phenomena, such
as chemical reaction at disordered surfaces, it is generally
a stationary process. The non-local process involves spatial
gradients.
Consider, #rst, the example of di6usion with heterogeneous reaction. Here, the local process is the chemical reaction, while the non-local process is di6usion. The ratio in
the magnitude between local and non-local forces is expressed by a dimensionless parameter, which in a reaction
di6usion system is the microscale Thiele modulus
ke
l =
:
(3)
aV D
Here, ke is the heterogeneous reaction kinetic parameter,
aV is the pore surface area per unit volume and D is the
di6usion coe7cient. Recognizing that for relatively homogeneous media the speci#c surface area scales inversely with
the microscale length, aV 1=l, Eq. (3) expresses the ratio
in the speed of reaction to that of di6usion in the microscale.
For negligible microscale gradients in the upscaled variable,
which is the volume-average concentration, di6usion must
be fast at the small scale, compared to reaction. Then, the
homogenization constraint (2) becomes
l 1:
(4)
A measure of the competition between reaction and di6usion, but at the macroscale, is the conventional Thiele modulus
ke L
L
=
l
:
(5)
D
l
This classical reaction engineering parameter is, thus, the
product of two terms, one of which must be small, according
to Eq. (4), and the other large, according to Eq. (1), for
conventional upscaling to apply.
As l increases, it becomes increasingly di7cult to satisfy Eq. (2). Then, an explicit coupling between the two
scales arises, leading in general, to a non-local description.
Nonetheless, gradients of the macroscale variable can be
small, regardless of the value of l , if the process approaches
an asymptotic equilibrium state (where reaction will cease).
For example, this is the case in dissolution processes, where
the solution eventually approaches thermodynamic equilibrium. Even then, it will be shown that the e6ective mass
transfer coe7cient is determined from a problem coupling
the two scales.
Before we proceed, it is instructive to draw a comparison
with immiscible, two-phase displacements in porous media,
also a well-studied topic (e.g. see Lake, 1989). Here, the
local force is capillarity, which controls FuidFuid interfaces at the pore scale, while the non-local forces are viscous. The ratio between viscous and capillary forces at the
microscale is expressed through the capillary number
ql l
q
Ca = 2
=
;
(6)
l
where q is a typical Fow velocity, denotes viscosity and
is the interfacial tension. Capillarity dominates at the small
scale and conventional upscaling is valid if
Ca1:
(7)
This is the immiscible Fow counterpart of (4). As in the corresponding reactiondi6usion example, a macroscopic capillary number can also be de#ned (Dullien, 1979)
L
L
;
(8)
Ca
CaL = Ca
l
k
where k l2 is the permeability of the porous medium, thus
providing the analog of the macroscopic Thiele modulus (5).
Porescale models, as well as experimental results from
two-phase displacements, indicate that viscous e6ects can
2567
2568
Fig. 1. The variation of the residual (trapped) saturation, Sor , in two-phase displacements in porous media vs. the capillary number of the displacement.
The value is normalized with its limiting value at low Ca (reprinted from Lake, 1989). Below a value of the order of 105 ; Sor is independent of Ca,
indicating that local equilibrium applies. It is in this region, where classical upscaling approaches are valid.
Fig. 2. The e6ectiveness factor, , vs. the macroscale Thiele modulus, , corresponding to a #rst-order reaction. The dots represent values for pellets of
various shapes (reprinted from Lapidus & Amundson, 1977). Conventional upscaling is rigorous valid in the region where is constant.
In the sections to follow, we will show how one can modify the volume-averaging methodology to derive rigorously
valid closure problems, even for #nite or fast kinetics, in the
limit where scale separation exists. The new unit-cell problem di6ers from that of QW, in that it involves macroscale
gradients of the upscaled variable and will be shown to
lead to an eigenvalue problem coupling both scales. For
an illustration, we will proceed #rst, with a simple 2-D
example.
3. An illustrative example
Consider a structureless, two-dimensional porous
medium, consisting of the strip (0; ) and (0; l) in the coordinate directions X and Y , respectively (Fig. 3). In this
example, the microstructure consists of the line 0 Y l,
hence volume averaging means integrating over Y in (0; l).
A Fuid phase is assumed to Fow at a constant velocity
vX = U . The solid interface is impermeable and located at
equation
2569
Y=l
aqueous
phase,
dissolving interface,
Y=0
X=0
(9)
ke "
@c
=
c;
(15)
@x
U
where "(!) = c|y=0 =c. Given the analytical expression for
c, one can determine the e6ective kinetic coe7cient, ke6 ,
hence the e6ective DamkQohler number, Da(!) ke6 =U =
ke "(!)=U . We are speci#cally
interested
on the e6ective
(17)
(18)
ke6 = ke :
(10)
@c
=0
@y
(11)
at y = 1
and
@c
= 2l c
@y
at y = 0;
(12)
4
2
2 ( + a )cos(an (1 y)) sin an
n
c=2
ean ! l
;
(13)
an
(4l + a2n ) + 2l
n=1
where ! = x=Pe and an is the nth positive root of the transcendental equation
a tan a = 2l :
(14)
(19)
2570
0.95
2
= 1
l
0.9
0.85
0.8
2= 0.7
l
0.75
0.7
2= 0.5
l
0.65
0.1
0.2
0.3
0.4
0.5
0.6
Fig. 4. The variation of the e6ective Thiele modulus with distance and for di6erent values of the local Thiele modulus, for the advectionreaction
problem of Fig. 3. The (non-local) e6ective Thiele modulus eventually saturates to a l -dependent value.
3.2. Advectiondissolution
1.6
1.4
c(y; !) = 1 2
n=0
a2n !
an
sin(an y);
(21)
1
0.8
0.6
0.4
0.2
where an = (2n + 1)#=2. The corresponding transverselyaveraged macroscopic equation is similar to the previous
@c "l
= (1 c)
@x
U
1.2
(22)
the e6ective mass transfer coe7cient of which can be evaluated using the analytical solution. We #nd
a2 !
e n
"l2
"D (!)
(23)
= n=0 a2 ! 2 :
n =a
D
n
n=0 e
The result is plotted in Fig. 6. As before, the e6ective mass
transfer coe7cient is in general non-local, depending on the
distance from the point of injection, !. At large !, which, depending on Pe can be equal to several microstructure lengths,
10
15
2571
10
9
D()
D,=2/4
3
2
0.1
0.2
0.3
0.4
0.5
0.6
Fig. 6. The variation of the dimensionless e6ective mass transfer coe7cient with distance, for the geometry of Fig. 3 and the advectiondissolution problem. The (non-local) coe7cient eventually saturates
to an asymptotic value.
equilibrium value. Even then, the result is obtained by solving a problem coupling both scales, as will be demonstrated
below. By contrast, by following the conventional closure
problem, the e6ective mass transfer coe7cient is di6erent
and found to be equal to "D; = 3 (see below), a value
which is larger than the actual by about 25%.
In the sections to follow, we will present a general approach for the upscaling of such problems. For convenience
in presentation, we will describe #rst the problem of dissolution (with in#nitely fast kinetics) followed by the problem
involving reaction with #nite kinetics.
4. Dissolution
on A$ ;
(26)
on A$% ;
(27)
where n$% is the unit normal vector directed from the $-phase
toward the %-phase.
De#ne, next, intrinsic and super#cial volume averages
1
1
C$ $ =
C$ dV and C$ =
C$ dV;
V$ V $
V V$
(28)
where V$ is the $-phase averaging volume and V is the averaging volume. Standard upscaling proceeds by decomposing the point concentration into its intrinsic average, which
is the macroscale quantity of interest, and a Fuctuation
C$ = C$ $ + C$
We brieFy summarize the problem of dissolution of a stationary phase in porous media using the volume-averaging
approach. We follow closely the procedure outlined in QW.
Denote by subscript $ a Fowing aqueous phase, by the
trapped hydrocarbon (NAPL) phase, and by % the solid
porous matrix (Fig. 7). Under the assumption of slow dissolution rates, phases and % are of #xed and stationary geometry. The pore-scale boundary value problem is described
by an advectiondi6usion equation
@C$
+ (vC$ ) = D2 C$ ;
@t
(25)
(29)
and likewise
v = v$ + v :
(30)
Following QW, and based on assumptions of isotropy, uniform porosity and constant volume fractions, the governing
equations for the average and the spatial deviation concentration eventually become as follows:
$
@C$ $
+ v C$ $ + v C$
@t
D
=$ D2 C$ $ +
n$ C$ dA
V
A$
+
A$%
+
A$%
n$% C$
dA
+
A$
n$ C$ dA
n$% C$ dA
(31)
2572
and
$
@C$
@t
Introducing Eq. (37) into Eq. (32) and noting that the transient term is small, we then obtain to #rst order the following
problem for the closure variable s$ :
C$ $
s$
v + 2D
(Ceq C$ $ )
2 C$ $
C$ $
D
s$
v
(Ceq C$ $ )
(Ceq C$ $ )
=$ D
C$
+
A$%
+
D
n$ C$ dA
V
A$
A$%
n$% C$
dA
+
A$
n$ C$ dA
n$% C$ dA ;
(32)
where $ is the volume fraction of the $-phase. The respective boundary conditions for the Fuctuation become
C$ = Ceq C$ $
on A$
(33)
and
n$% C$ = n$% C$ $
on A$% :
(34)
(35)
(36)
where x is the coordinate aligned with the main Fow direction. Here, A is a positive constant, and a 0 is the non-zero
positive root of a quadratic, involving among other parameters, the e6ective mass-transfer coe7cient ", the determination of which is sought in the #rst place. Eq. (36) shows
that in the limit where homogenization is expected to apply,
the ratios |C$ $ |=(Ceq C$ $ ), |2 C$ $ |=(Ceq C$ $ ),
etc. are non-negligible constants, indicating that the variables are not independent.
In view of this observation, we will proceed with the
di6erent substitution
C$ = s$ (Ceq C$ $ ):
(37)
C$ $
;
(Ceq C$ $ )
(38)
+
(Ceq C$ $ )
A$%
n$% s$ dA :
(39)
Note the term for the interfacial transport between the dissolving ()-phase and the Fowing aqueous ($)-phase. In deriving the above expressions we assumed constant volume
fractions, isotropy and took account of the following boundary conditions:
s$ = 1
on A$ ;
n$% s$ + n$%
(40)
C$ $
(1 s$ ) = 0
Ceq C$ $
on A$% : (41)
(42)
Both the boundary value problem (38) and boundary condition (41) di6er from those presented in QW. In their corresponding closure problem for s$ , QW neglect all terms associated with the gradients of C$ $ , as being small within
the microstructure. For this to be true, however, requires the
condition
2
$
C$ $
1 and C$ 1:
(43)
Ceq C$ $
Ceq C$ $
A comparison with Eq. (36) shows that Eq. (43) does not in
general apply, when macroscopic equilibrium is approached,
even though this is the very limit where volume averaging
in the conventional sense is to be valid.
In this limit, the steady-state averaged equation is expressed in terms of the following expression:
v C$ $ = $ D2 C$ $ (s$ v (Ceq C$ $ ))
+ "(Ceq C$ $ ):
(44)
With the exception of the second term on the RHS, the other
three terms are conventional. The term containing sv is the
(45)
D$
where
is the e6ective macroscopic dispersion coe7cient
for a passive tracer, which can be obtained independently
(for example using QW). In this formulation, however, the
e6ective reaction rate coe7cient "e6 is di6erent
"e6 = " s$ v
+
(46)
In the particular case of the absence of a Fow #eld, where
the dispersion tensor is a scalar, we #nd, from this approach
D$ "
"e6 =
:
(47)
$ D
In general, it is apparent that the closure problem (38)
(42) couples local and global scales, as the evaluation of
" requires the simultaneous solution of the global problem.
In general, the closure problem (38) (45) is an eigenvalue
problem for ". In the absence of the new terms identi#ed here
the problem can be directly solved using the transformation
s$ = 1 + "
(48)
(49)
= 0 on A$
and
n$% n$%
C$ $
Ceq C$ $
= 0 on A$% :
(51)
2573
@c=@!
@2 s
s = 2 "D :
(1 c)
@y
(52)
at y = 0;
@s
=0
@y
(54)
at y = 1:
(55)
= "D
(56)
and
= 0 at y = 1;
(57)
n = 0; 1; 2; : : : :
(58)
(2n + 1)2 #2
4
2574
(59)
=1
(60)
(65)
(66)
2575
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
Sl
Fig. 8. The variation of the dimensionless e6ective mass transfer coe7cient as a function of the liquid saturation Sl , for a model problem of drying in
a pore-network. Values of "D obtained from the present theory are denoted by dots, those from QW by open circles. The scatter reFects the di6erent
realizations taken and the small size of the network (40 40).
2576
(67)
= D s$ +
$1 "
C$ $
v
:
C$ $
(68)
n$% s$ dA + 2
n$% s$ dA
"=
V
C$ $
A$%
A$%
+
A$%
n$% s$ dA :
(69)
(71)
the equation
@2 s
@ lnc
s = 2 + "D ;
@!
@y
(72)
where we dropped subscript $ for simplicity. The dimensionless mass transfer coe7cient "D is also equal to 2 , obtained from the macroscale equation, @c=@!=2 c. The
corresponding boundary conditions are
@s
(73)
+ 2l (1 + s) = 0 at y = 0;
@y
@s
= 0 at y = 1:
(74)
@y
Taking into account the macroscale relation and using the
substitution s=1+"D , we obtain the eigenvalue problem
= "D
(75)
= 2l
at y = 0
and
= 0 at y = 1:
(76)
(77)
saturating at large values of the latter. Similar results are expected for more complex microstructures. The limiting behavior mimics that of a simple advectionreaction problem,
where di6usion is across a constant boundary layer. While
qualitatively similar, however, the precise dependence requires the solution of an eigenvalue problem, which was
derived above.
Given that the process under consideration is very near
equilibrium, the utility of the above results can be questioned. In response we claim that these do yield the correct results for the case when homogenization is expected to
apply. For tackling the more general problem, where the
process is far from equilibrium and the homogenization constraints do not apply, di6erent, non-local approaches are
needed. Some have already appeared in the literature involving integro-di6erential equations, moment expansions
and=or non-local parameters. An alternative approach of
some promise is to use transverse averaging across the main
direction where the macroscale variable changes. This alternative is currently under consideration.
Acknowledgements
This work was partly supported by Los Alamos National
Laboratory in the form of a student scholarship to the #rst
author. The research of the second and third authors was
partly supported by DOE Contract DE-AC2699BC15211.
Both contributions are gratefully acknowledged.
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solute by steady random velocity in heterogeneous porous formation.
Journal of Fluid Mechanics, 256, 189.
Daccord, G., Lenormand, R., & Lietard, O. (1993). Chemical dissolution
of a porous medium by a reactive Fuid. Chemical Engineering Science,
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Dagan, G. (1989). Flow and transport in porous formations. Berlin:
Springer.
2577