Chemical Engineering Science 59 (2004) 2253 2263

www.elsevier.com/locate/ces

A robust iterative method of computing e%ectiveness factors

in porous catalysts
Dong Hyun Kim , Jietae Lee
Department of Chemical Engineering, Kyungpook National University, Daegu 702-701, South Korea
Received 19 August 2003; received in revised form 29 December 2003; accepted 15 January 2004

Abstract

A robust, e0cient numerical method for computing the e%ectiveness factor of a heterogeneous reaction in a catalyst is developed in this
study. The method is based on shooting at the outer surface of the catalyst and is optimized for an accurate estimation of the concentration
gradient at the outer surface. The shooting at the outer surface, however, is inherently unstable for a cylindrical or a spherical catalyst,
and it also can become unstable with an increasing Thiele modulus even for a slab catalyst. From an analysis of the governing equation,
however, three criteria are developed to make the method work e0ciently in the presence of instability. The numerical method is shown
to be e%ective for diverse kinetic expressions, from simple power-law to sophisticated LangmiurHinselwood kinetics, and for isothermal
or non-isothermal catalysts. The method is also shown to be easily applicable to a more complex case of multiple steady states, estimating
all the corresponding e%ectiveness factors. In this method, a simple rule that determines the stability of each steady state is proposed.
? 2004 Elsevier Ltd. All rights reserved.

Keywords: E%ectiveness factor; Shooting method; Intraparticle di%usion; Heterogeneous reaction; Multiple steady states; Stability

1. Introduction can be found in Aris (1975) and in Schneider (1976). Also,

The reaction rate in a porous catalyst is a%ected by in-
traparticle mass and heat transfer in addition to the intrinsic
kinetics. The ratio of the observed reaction rate to the rate
in the absence of intraparticle mass and heat transfer resis-
tances is de:ned as the e%ectiveness factor. The factor can
be directly measured experimentally or rather commonly, to
predict the observed rate, it is estimated from the solution
of the intraparticle mass and heat balance equations which
are formulated as di%erential equations with boundary con-
ditions. Except for an isothermal :rst-order reaction and a
zero-order reaction, the balance equations are non-linear and
are usually solved numerically to calculate the e%ectiveness
factor. Since the numerical solution of the problem is re-
garded as tedious and time consuming, approximation of
the e%ectiveness factor has been extensively investigated in
the past and various simple approximate formulae are avail-
able in textbooks (for example, Froment and Bischo%, 1990;
Fogler, 1999; Hill, 1977). In-depth mathematical theory with
a comprehensive list of references on the e%ectiveness factor
Corresponding author. Tel.: +82-53-950-5617;
fax: +82-53-950-6615.
E-mail address: dhkim@knu.ac.kr (D.H. Kim).
a recent book (Wijnggaarden et al., 1998) gives a summary
on various formulae of di%ering complexities and their ap-
plications.
Approximation formulae relate the e%ectiveness factor
with the Thiele modulus
. For very large or small values of
the modulus, all formulae accurately predict the asymptotic
behavior of the e%ectiveness factor, but at moderate
val-
ues, their predictions often di%er more than 20% from the
exact values. Furthermore, for LangmuirHinselwood ki-
netics and/or non-isothermal catalysts, approximation of the
e%ectiveness factor becomes much di0cult, and often yields
unsatisfactory estimates. As present-day computers become
more powerful, numerically solving the balance equations
can be a viable alternative to the approximations.
The usual numerical methods for the boundary-value
problem are the :nite-di%erence methods, the shooting
methods (Carnahan et al., 1969) and the orthogonal col-
location methods (Villadsen and Michelsen, 1978). When
the problem is non-linear, the methods become necessar-
ily iterative ones, :nding an improved solution based on
the results of the previous iterations with a prospect that
the iterative procedure will lead to the desired solution.
The :nite-di%erence method converts the boundary-value
problem to a system of non-linear algebraic equations, the

0009-2509/$ - see front matter ? 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2004.01.056
2254 D.H. Kim, J. Lee / Chemical Engineering Science 59 (2004) 2253 2263

solution of which can be very di0cult to obtain, especially relation in the catalyst
when many base points are used in the method. For a large i De1
Thiele modulus, the concentration pro:le developed in the Ci Cis = (C1 C1s ); i = 2; : : : ; n (2)
Dei
catalyst is steep and the number of base points can be ex-
cessively large since a very small step size is required to is essentially linear, that is, De1 =Dei does not appreciably de-
represent concentration derivatives accurately by the :nite pend on the concentration pro:le developed inside the cata-
di%erence (Chang, 1982). In many cases the non-linear lyst and may be replaced by the ratio evaluated for the bulk
equations are linearized and solved iteratively but without composition and temperature at the outer surface of the cat-
a good initial guess, the iteration may fail to converge. alyst. The linear relationship among the individual species
Orthogonal collocation methods also have similar di0- allows to express the reaction rate in the catalyst, a function
culties as the methods involve solutions of a system of of the n species concentrations, in terms of the key compo-
non-linear equations. The collocation methods are e0cient nent concentration C1 . When the catalyst is non-isothermal,
when successful, but they are often unstable when many the temperature inside the catalyst can be related to C1 as
collocation points are used and the Thiele modulus is large (IH1 )De1
(Shiraishi et al., 1995). The shooting methods convert the T = Ts + (C1s C1 ): (3)
ke
boundary-value problem into an initial-value problem, in
Using this equation enables us to write the non-isothermal
which the missing boundary condition at the initial point is
reaction rate in terms of the concentration C1 .
assumed. Through an iterative procedure, the methods try
We de:ne the following:
to produce a solution that agrees with all the given bound- 
ary conditions (Miyakawa et al., 1999). When the catalyst C1 R(C1 ; T ) R(C1s ; Ts )
center is chosen as the initial point, the methods can only y= ; f(y) = ;
=L ;
C1s R(C1s ; Ts ) C1s De1
be used with the condition that the dependent variable,
usually the concentration of the key reactant, at the center (4)
is not zero, since zero initial conditions can only generate a where
is the Thiele modulus and L is the radius of the
trivial solution. The concentration of the key reactant can, sphere or cylinder, or the half-thickness of the slab. The
in fact, become zero at the center when the Thiele modulus dimensionless equation describing the mass transport of the
is large and the apparent reaction order is less than one. On key component in a porous catalyst is
the other hand, if the catalyst outer surface is chosen as the
d2 y s dy
initial point, the resulting initial-value problem becomes +
2 f(y) = 0; (5)
inherently unstable due to a singularity at the catalyst center d x2 x dx
unless the catalyst is of a slab shape, and hence generation where s is the shape factor of the catalyst (s=0 for an in:nite
of a solution that matches the boundary condition at the slab, s = 1 for an in:nite cylinder, and s = 2 for a sphere). It
center is very di0cult. is assumed that the concentration and the temperature at the
The purpose of this study is to develop a robust method outer surface of the catalyst are prescribed. The boundary
for computation of the e%ectiveness factor without short- conditions are
comings of the previous methods. In this regard, we exam- dy
ine the problems associated with the shooting method and y=1 at x = 1; =0 at x = 0: (6)
dz
propose an algorithm based on that method, which exploits
the inherent instability of the method and enables e0cient The e%ectiveness factor  is given by

computation. s + 1 dy 
= : (7)

2 d x  x=1

2.1. A remark on f(y)

2. Mass transfer in a porous catalyst
A general reaction involving n chemical species can be
written as
n

numerical results violating the range cannot be accepted as
i Ai = 0; (1)
i=1
where i is the stoichiometric coe0cient of the species Ai .
We choose a key reactant and denote the reactant as A1 .
Using a modi:ed MaxwellStefan equation to formulate
the multicomponent di%usion in the catalyst, Schneider
(1976,1998) has shown that the mutual concentration
The formal range of y is [0,1]. During numerical compu-
tation of Eq. (5), however, the range is not often respected,
particularly when numerical instability occurs. Obviously,
a solution of the equation and are discarded, but the results
can be used to improve the solution in iterative procedures.
Before arriving at an acceptable solution, the computed y
may deviate considerably from the formal range, and thus
we need to make a provision for y 1 and y 0. We may
de:ne f(y) outside the range as
f(y) = 1 for y 1; f(y) = 0 for y 6 0: (8)
 D.H. Kim, J. Lee / Chemical Engineering Science 59 (2004) 2253 2263
The :rst condition for y 1 arbitrarily equates the rate to
the rate at the bulk surrounding the catalyst and may make
f(y) continuous, and the second condition prevents f(y)
becoming negative. This de:nition will simply aid the nu-
merical computation to arrive at the :nal solution which is
within the permitted y range (0 6 y 6 1).
Numerous kinetic studies have reported reaction rates
with negative reaction orders (for an example, see Jiang et
al., 1993). In this case, as y decreases to zero, the reac-
tion rate f(y) increases without bound, which is physically
unrealistic and a source of error such as division by zero
in numerical computations. In reality, every reaction ceases
when there is no reactant, y = 0, and the reaction rate is :-
nite. The negative reaction order should be interpreted as an
approximation of the real reaction rate for y down to some
value near zero, but not to zero itself. In this regard, we
may assume that f(y) is bounded above, that is f(y) 6 K
in 0 6 y 6 1, where K is a su0ciently large number.
3. Shooting method
In the well-known shooting method, the boundary-value
problem becomes an initial-value problem with all the
conditions speci:ed at the initial point. The missing ini-
tial conditions are assumed and the initial-value problem
is solved iteratively until the computed solution agrees
with all the boundary conditions. This approach involves
a trial-and-error procedure. In the given boundary-value
problem, one of the two boundary points, x = 0 or 1, can
be used as the initial point.
3.1. Shooting method at x = 0
When x=0 is chosen as the initial point, dy=d x=0 is given
and y(0) is assumed. The initial-value problem is solved
using a step-by-step procedure from x = 0 to 1, and the com-
puted solution y at x = 1 is compared with the boundary
condition y(1) = 1. This is repeated by adjusting the ini-
tial guess until the computed value agrees with the bound-
ary condition within a speci:ed tolerance. This method can
be successful only when y(0) 0 is assured beforehand,
since with y(0) = 0 the resulting computed solution would
be always a trivial solution, y(x) = 0, and cannot agree with
y(1) = 1. In general, however, y(0) 0 is not guaranteed,
for example, if f(y) = 1, a zero-order reaction, it can be
shown that y(0)=0 when
6 and s=2 (spherical cata-
lyst). For an apparent reaction order less than one and large

, y can be zero at 0 6 x 1. Therefore, the applicability
of this shooting method is limited. We denote this method
as forward shooting to distinguish it from the shooting at
x = 1, discussed next.
3.2. Shooting method at x = 1
The missing initial condition in this case is dy=d x at x = 1
and by suitably adjusting the initial guess for the missing
2255
condition, the method tries to produce a solution which gives
dy=d x = 0 either at x = 0 if y(0) 0 or at some 0 x 1
where y = 0. The resulting initial problem, however, often
becomes inherently unstable, that is, its solution is very sen-
sitive to the initial guess as x moves from 1 to 0. We may
call this method reverse shooting, in contrast to the shoot-
ing at x = 0.
We let z = 1 x and rewrite Eq. (5) in terms of z, then
d2 y s dy
2
= +
2 f(y); 0 z 1: (9)
dz 1 z dz
The boundary conditions are

dy 
y = 1 at z = 0; = 0: (10)
dz  z=1
We let ya (z) be the solution of this boundary-value problem,
Eqs. (9) and (10), and also let the gradient of ya at z = 0 be
a. Then, theoretically, the integration of Eq. (9) from z = 0
with the following initial conditions is expected to give the
correct solution ya (z) of the boundary-value problem

dy 
y = 1 at z = 0; = a: (11)
dz  z=0
In the shooting method, we solve Eq. (9) with an assumed
initial guess for dy=d z at z =0 and the given initial condition
y = 1 at z = 0. We let the assumed initial guess be

dy 
= b: (12)
dz  z=0
The purpose of the method is to improve b through an itera-
tive procedure and to arrive at an approximation of a within
a speci:ed accuracy.
If b is not close to a, the computed y(z) may behave un-
realistically in the z interval: y decreases to negative values
or y decreases initially and increases later. If y(z) 0 at
some point, it can be shown that, after that point, y(z) con-
tinues to grow in negative numbers. Or if y starts to increase
at some point, it continues to grow with an increasing pos-
itive slope after the point. Since the reactant is consumed
everywhere in the catalyst, the concentration must be mono-
tone decreasing with respect to z and, nevertheless, should
be non-negative. Consequently, when dy=d z 0 or y 0
occurs at a step during the course of the computation by a
step-by-step method, the concentration pro:le computed af-
ter the step will be certainly erroneous, and thus the compu-
tation may be terminated at the step. Based on the predicted
behavior of y(z) after the step, the initial guess b can be
accordingly adjusted in the next iteration for an improved
solution. Therefore, using dy=d x 0 and y 0 as the cri-
teria in the iteration can considerably reduce the amount of
calculations.
Next, we examine how the error in the initial guess propa-
gates in the z interval and also the instability associated with
Eq. (9), since the equation is not analytic at z = 1 when s = 1
or 2. Let yb be the solution of the initial-value problem, Eqs.
(9) and (12) with y(0) = 1, and de:ne u(z) = yb (z) ya (z),
2256 D.H. Kim, J. Lee / Chemical Engineering Science 59 (2004) 2253 2263

Table 1 behavior of u(z) revealed by the method is

Solutions of Eqs. (14) and (15) for f(y) = 1 and y and for various
catalyst geometry u(z) z for s = 0; (16)
f(y) = 1 f(y) = y 1
 u(z) ln for s = 1; (17)
s=0 z sinh(
z) 1z


(slab) 1
u(z) for s = 2: (18)
1 I0 (
)K0 (
(1 z)) K0 (
)I0 (
(1 z))
1z
s=1  ln 
1z
[I0 (
)K1 (
) + I1 (
)K0 (
)] This behavior agrees with u(z) listed in Table 1.
(cylinder) Instability or a rapid growth of the error is normally unde-
 sinh(
z) sirable in calculating the concentration pro:le y(z). In our
s=2  
1z
(1 z) case, however, where an accurate estimation of a is sought
(sphere) for, the instability inevitably gives rise to dy=d z 0 or
y(z) 0 in the computed pro:le and, as a result, can make
the initial guess as close as desired to a by simply checking
dy=d z 0 or y(z) 0 in the pro:le.
the error of yb . As yb satis:es Eq. (9), we obtain
In the initial-value problem, information on whether u(z)
d 2 yb s dyb keeps its sign (+ or ) throughout the z range is helpful. If it

2 f(yb )
d z2 1 z dz does not change its sign, the initial guess with a positive error
( 0) generates a concentration pro:le which is always
d 2 ya s dya 2 d2 u greater than the correct solution over the whole interval, and
=
f(y a ) +
d z2 1 z dz d z2 vice versa. This will simplify correction of the initial guess
s du in the iterative procedure for improving b.

2 (f(ya + u) f(ya )) = 0: (13) Table 1 shows that the sign u(z) is the same as the sign of 
1 z dz
in (0,1) for f(y)=1 or y. It is easy to show that when f(y) is
Since ya is the solution, Eq. (13) becomes non-decreasing with respect to y, u(z) and du=d z keep their
d2 u s du signs (the same with each other) throughout the z interval.
= +
2 (f(ya + u) f(ya )): (14) For example, if (=du=d z at z = 0) 0, then u(z) 0 near
d z2 1 z dz
the initial point z =0, and this makes f(ya +u)f(ya ) 0
The initial conditions for u(z) are since f(y) is non-decreasing. Consequently, the right-hand
 side of Eq. (14) is greater than zero, and this in turn keeps
du 
u(0) = yb (0) ya (0) = 0; = b a : (15) du=d z 0 in the next step. The same pattern in the sign of
d z z=0
u(z) and du=d z continues in successive steps until z =1. The
u(z) is the error in the computed solution when the initial opposite is true when  0.
guess for dy=d z at z = 0 (x = 1) is incorrect by . When A negative reaction order gives rise to f(y) mono-
Eq. (9) is unstable, u(z) can grow very rapidly as z goes to 1. tone decreasing with y. In the cases where f(y) is not
The analytic solution of Eqs. (14) and (15) is possible non-decreasing with y, we are unable to theoretically de-
for a few special forms of f(y). Table 1 lists the solution cide the sign of u(z) over the whole z interval. Based on the
for f(y) = 1 and y. In Table 1, except for the case of s = 0, behavior of y(z) afterward dy=d z 0 or y(z) 0, how-
u(z) grows without bound as z 1, indicating instability, ever, it is clear that if u(z) does not change its sign until
and thus it is impossible to compute y(z) which is :nite at dy=d z 0 or y 0, u(z) keeps its sign over the entire z
z = 1, let alone that it agrees with the boundary condition interval (0,1).
dy=d z = 0 at z = 1. Fig. 1 shows the e%ect of
on u(z) for We applied the shooting method for a number of func-
f(y) = y. u(z) increases more rapidly with increasing
for tional forms of f(y) and in all the tested cases except the
all s. Thus, when
 1, Eq. (9) can become unstable well cases of multiple steady states, we found u(z) did not change
before z = 1, whereas for a small
, u(z) is moderate when its sign, i.e. the error grew in positive direction if the error
s = 0 or begins to grow rapidly near z = 1 if s = 1 and 2. in the initial guess dy=d z at z = 0, , was positive or grew in
On the other hand, when f(y) = 1, u(z) is independent of
the negative direction if  0. We demonstrate this with an

and modest if s = 0 or grows rapidly near the singular point example where f(y) = 1= y,
= 2, and s = 1. Fig. 2 shows
z = 1 when s = 1 or 2. the computed pro:les of y(z) for various initial guesses. At
For f(y) other than those in Table 1, Eq. (14) becomes the start, y(z) decreases for all b, but eventually either re-
non-linear and, in general, it is not possible to solve the Oects upward when b is greater than a certain value, 3:08
equation analytically over (0,1), but the behavior of u(z) in the present case, or continues to decrease when b is lower
in the vicinity of z = 1 can be inspected by the method of than the value. The pro:les for b = 3:08 and 3:10 are vir-
perturbation. Details of the method as applied to Eq. (14) tually identical in 0 6 z 0:4, whereas in 0:4 z 6 1, the
are given in Appendix A. In close proximity to z = 1, the pro:les deviate from each other considerably with di%erent
 D.H. Kim, J. Lee / Chemical Engineering Science 59 (2004) 2253 2263 2257

20 20
s=0 s=1

=20
15 15
=10
=20
u(z)/ =10

u(z)/
10 10 =5

=5
5 5 =2
=2
=1
=1
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
(a) z (b) z

20
s=2

15
=20 =10
=5
u(z)/

10
=2
=1
5

0
0.0 0.2 0.4 0.6 0.8 1.0
(c) z

Fig. 1. E%ect of Thiele modulus
on error u(z) for a :rst-order reaction f(y) = y. (a) s = 0, (b) s = 1 and (c) s = 2.

2 correct solution ya (z), whereas a negative error results in

yb (z) ya (z).
1
b= -1 We add a few more examples to show the possible out-
come of y(z) with the reverse shooting method. Fig. 3 shows
-2
-3.08 the computed pro:les for f(y) = y, s = 0, 1 and 2 and
y(z)

0
= 1 and 10. In each case, the pro:les are obtained for two
-4
-1
-5
=2, s=1
-2
0.0 0.2 0.4
z
Fig. 2. Variation of computed concentration pro:le y(z) with respect to
initial guess b. f(y) = 1= y.
signs. In this interval, 3:10 b 3:08, the correct
initial guess of the problem exists, which is calculated as
3:08007 : : : : Due to the instability near z = 1, it is not
possible to obtain the pro:le that agrees with the boundary
condition at the catalyst center however accurate the initial
guess may be, but it is entirely possible to reduce the inter-
val of b arbitrarily small, and yet the pro:les computed with
the end points of the interval have opposite signs near the
catalyst center. By imposing y(z) = 0 for 0:4 z 6 1, one
may consider the pro:le for either b = 3:08 or 3:10 as
the solution ya (z). With thus determined ya (z), it is seen in
Fig. 2 that over the whole z range, a positive error in
the initial guess results in yb (z) always greater than the
-3.1 values of b, which are close to each other but with an op-
posite sign in their errors with respect to the exact b(=a).
When
= 10, the pro:les for all three cases of s are simi-
lar. Each of them drops to zero at a point in the interval and
0.6 0.8 1.0
then moves either upward or downward, depending on the
sign of the error in b. On the other hand, when
= 1, the
characteristics associated with s are visible: s = 0 gives pro-
:les almost identical to the end of the interval without any
appreciable growth of the error in the initial guess; s=1 gen-
erates pro:les with a discernable di%erence at z = 1; while
s = 2 yields one pro:le going to and the other going to
near z = 1. Although, in theory, the pro:le for s = 1 and

= 1 should also be either or at z = 1, it is seen that
computation with a :nite precision and a small dy=d z near
z = 1 fails to show clearly the exact asymptotic behavior of
ln(1=(1 z)) near z = 1. When the error growth is not dra-
matic or in the absence of the instability, it can be shown
that either dy=d z 0 or dy=d z 0 is established near or at
z = 1.
We may conclude that during the reverse shooting with
an initial guess b, one of the three cases occurs, namely,
dy
Case A 0; b = b+ ; (19)
dz
2258 D.H. Kim, J. Lee / Chemical Engineering Science 59 (2004) 2253 2263

2 2

=10, b=-11.54
1 1 =1, b=-0.465
=1, b=-0.84
=10, b=-10.96 =1, b=-0.475
=1, b=-0.85

y(z)
y(z)
0 0
=10, b=-11.55
=10, b=-10.97
-1 -1

s=0 s=1
-2 -2
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0

(a) z (b) z

2
=10, b=-10.39

1 =1, b=-0.322
=1, b=-0.323
y(z)

=10, b=-10.40
-1

s=2
-2
0.0 0.2 0.4 0.6 0.8 1.0
(c) z

Fig. 3. Computed concentration pro:les for
= 1 and 10 with initial guesses close to the exact values f(y) = y. (a) s = 0, (b) s = 1 and (c) s = 2.

Case B y 0; b = b ;
 val (b ; b+ ) su0ciently small, so that any b in the interval
dy 
Case C y(1) 0 and 0; b = b :
d z z=1
In Case A, yb (z) increases after dyb =d z becomes positive,
and then yb (z) ya (z) near z = 1. In Case B, after yb (z)
becomes negative, it continues to be negative to z = 1, and
thus obviously yb (z) ya (z) near z=1. Case C occurs when
the reverse shooting does not encounter either case A or B
until z = 1 and indicates yb (z) ya (z) at z = 1. We may
classify b as either b+ if Case A occurs or b if Case B or C
occurs in the reverse shooting. Then the exact concentration
gradient at z = 0, a, is located at the border between b+ and
b .
It is shown that when f(y) is non-decreasing with respect
to y, then u(z) and du=d z have the same sign, either positive
or negative, and their sign does not change in the entire
z interval. Consequently, for this f(y), b+ has a positive
error ( 0) and b has a negative error, and thus b+ is
always greater than b . As shown in Fig. 2, the relation
b+ b can also be observed even when f(y) is monotone
decreasing with respect to y.
4. An algorithm for the reverse shooting
The proposed algorithm is based on the assumption
b+ b and consists of two stages. The :rst stage is to
:nd two initial guesses, one of which is a b+ and the other
(20) is a b . The second stage is to reduce the size of the inter-
is accurate within a speci:ed tolerance.
(21)
The main part of the algorithm is to determine whether
the b used in the computation is b+ or b . To make the de-
cision, y(z) and dy=d z are computed by a step-by-step pro-
cedure and checked at each z increment whether dy=d z 0
(b = b+ ) or y 0 (b = b ). Once the decision is made, the
computation with the given b may be stopped there. If the
decision cannot be made until z = 1, then dy=d z|z=1 0 and
y(1) 0 and thus b = b . Here we may also check whether
dy=d z|z=1 can be regarded as zero within a speci:ed, toler-
ance.
The remaining part consists of getting a better guess for
b. At the start of the :rst stage, the begining of the algo-
rithm, we do not have any information on where b changes
from b to b+ . Since dya =d z at the surface (=a) always de-
creases (its magnitude increases because of its minus sign.)
with increasing
, we may begin with b =
or any other
reasonable guess and run the main part to determine whether
b = b+ (Case I) or b = b (Case II).
In Case I, we have a b+ and search for a b , which is
less than b+ . We may assign the trial b as 2b+ and run the
main part (2b+ b+ , since b+ 0). If a b is found in
this, then we have an interval (b ; b+ ) and can move to the
second stage below. Otherwise, we have found another new
b+ . Replace the old b+ with this newly found b+ and try
again with b = 2b+ . Repeating these steps will eventually
yield a b and an interval (b ; b+ ).
 D.H. Kim, J. Lee / Chemical Engineering Science 59 (2004) 2253 2263 2259

100 1.2

1.1
10 b+
1.0
1 b- 0.9 b-
-b -b
0.1 0.8
b+
0.7
b+
0.01
0.6

0.001 0.5
0.1 1 1.00 1.05 1.10 1.15 1.20
(a) (a)
10 2.0

1.8

1.6

1.4

1
1.2

1.0
0.1 1 1.00 1.05 1.10 1.15 1.20
(b)
(b)
Fig. 4. (a) Plot of boundary between b+ and b and (b) plot of e%ec-
tiveness factor corresponding to the boundary points, f(y) = 1=y0:9 . The Fig. 5. Magni:ed view of the marked regions in Fig. 4. (a) Plot of
marked regions are magni:ed in Fig. 5. boundary between b+ and b and (b) plot of e%ectiveness factor.

In Case II, we have a b and look for a b+ . In this, the
new trial b should be greater than b and hence may try
with b = b =2. If this new b is determined to be a b+ , then
we move to the second stage. Otherwise, replace the old b
with the new trial b and try again with b = b =2. We repeat
these steps until we obtain (b ; b+ ).
The interval (b ; b+ ) obtained above is equivalent to
(b ; b =2) or (2b+ ; b+ ). In the second stage, we use the
method of interval halving or bisection to reduce the size
of the interval. We solve the initial-value problem, Eq. (9)
with y = 1 at z = 0 and b = (b+ + b )=2, and check whether
the present b is a b+ or a b . We replace b+ or b with the
newly found b+ or b , respectively, and continue interval
halving until the interval becomes su0ciently small, so any
b in the interval has the desired accuracy. In all, 1114 it-
erations are needed to compute the e%ectiveness factor with
0.1% accuracy.
5. Multiple steady states
The initial guess b is in the range (0; ). If b = 0,
then Eq. (9) gives d 2 y=d z 2 0 at z = 0 since
2 f(y) 0.
Hence dy=d z 0 for z 0 and b = 0 belongs to b+ . On
the other hand, it is obvious that b = belongs to b .
Consequently, on decreasing b from 0 to , b changes
its class from b+ to b at least once. Multiple steady states
exist when b changes its class, either from b+ to b or
from b to b+ , more than once on the b-axis for a given

. On decreasing b, if there are two changes of the type
b+ b , there must be a change of the type b b+ in
between the two. In view of this, the number of the steady
states can only be an odd number (2m + 1), among which
m + 1 states occur at b+ b , while m states occur at
b b+ .
Fig. 4(a) shows the regions for b+ and b for f(y) =
1=y0:9 and s = 1. On the line that separates the two regions,
b changes its class and a steady state exists. Normally, upon
decreasing b from 0, b changes from b+ to b once for a
given
. In Fig. 4(a), however, when 0:684
1:175,
b changes its class apparently three times as b decreases
from 0 : b+ b , b b+ , and :nally b+ b . Hence,
three steady states exist in the
range. Fig. 4(b) shows a
plot of the corresponding e%ectiveness factors. Furthermore
Fig. 5(a), a magni:cation of the small marked region in
Fig. 4(a), reveals additional two more such changes in the
region 1:049
1:065, and hence a total of :ve steady
states exist in this small
interval.
2260 D.H. Kim, J. Lee / Chemical Engineering Science 59 (2004) 2253 2263

When there is only a single steady state, it is a sta- Table 2

ble steady state and exists where b+ b , as shown in Methanol steam reforming kinetics and other necessary data used in Fig. 6
Figs. 4(a) and (b). If three steady states are possible, two of Catalyst property: pellet density=2350 kg=m3 , void fraction = 0:47,
these will normally be stable, whereas the third state which mean-pore radius = 8 109 m
normally exists between the two stable states is unstable. Reaction rate (Lim, 2002):

In the
range where three steady states are possible, two kK1 PCH3 OH = PH2
RCH3 OH =

(mol/gcat/h)
steady states are obtained at b+ b and the third state (1 + K1 PCH3 OH = PH2 )(1 + K2 PH2 )
 
located between the two on the b axis, exists at b b+ . 105:3 kJ=mol
k = 1:16 1011 exp
This suggests that the steady states at which b+ b are RT
 
stable, while the states at which b b+ are unstable. In 20:06 J=mol=K 20 kJ=mol
K1 = exp +
view of this, the proposed algorithm based on the assump- R RT
tion that b+ b is e%ective for computation of the e%ec-  
57:18 J=mol=K 50 kJ=mol
K2 = exp +
tiveness factor of the stable steady states. However, if the R RT
algorithm is modi:ed to :nd the position at which b changes Partial pressures are in atm unit
its class, the example in Fig. 4 demonstrates that all the pos-
Reaction temperature: 503 K, total pressure: 1 atm
sible steady states and their stabilities as well as the cor- Bulk composition (mol %):
responding e%ectiveness factors can be easily found by the A: 20% CH3 OH, 30% H2 O, 50% N2 (inert)
reverse shooting method. This is another advantage of the B: 50% H2 , 20% CH3 OH, 30% H2 O
present method when compared to other methods such as
the :nite-di%erence methods and the orthogonal collocation E%ective di%usivities (m2 =s)
Composition A
methods, which by themselves are normally unable to :nd H2 : 1:80 106 , CO2 : 3:87 107 , H2 O : 6:04 107 ,
all the possible steady states and moreover require an initial CH3 OH : 4:49 107
estimate of the concentration pro:le that is close to the cor- Composition B
rect pro:le to compute the pro:le of an unstable steady state. H2 : 1:84 106 , CO2 : 3:96 107 , H2 O : 6:17 107 ,
We may assert that the classi:cation of the initial guess b CH3 OH : 4:60 107
according to the criteria mentioned before is not only useful
in computing the e%ectiveness factors, but also provides a
simple means of making a decision on the stability of the Cu=ZnO=Al2 O3 catalyst
steady states. CH3 OH + H2 O CO2 + 3H2 :
In the previous section, we discussed that when f(y)
is non-decreasing, a positive error in b( 0) always re- The reaction rate reported by Lim (2002) and other data for
sults in yb (z) ya (z) and dyb =d z dya =d z, whereas a computation are listed in Table 2. Methanol was taken as
negative error gives yb (z) ya (z) and dyb =d z dya =d z. the key component and its e%ective di%usivity in the catalyst
If dyb =d z dya =d z, then dyb =d z must become positive at was estimated using the modi:ed MaxwellStefan equation
a point in the z range 0 z 6 1, and thus the initial guess (Schneider, 1976) and the cross-linked pore model (Feng
b belongs to b+ . On the other hand, if yb (z) ya (z) and et al., 1974), recommended by Haugaard and Livbjerg (1998)
dyb =d z dya =d z, then it is evident that either yb (z) 0 based on an experimental comparison of pore-di%usion mod-
at some point in the z range or dyb =d z|z=1 0, giving that els. The catalyst particle diameter varied from 1 105 to
the initial guess belongs to b . This gives that b+ is always 0:1 m, which resulted in
in the range 0.11000 for the
greater than b , and hence, upon decreasing b from zero, composition A and 0.027270 for composition B. Fig. 6
there is only one point on the b-axis (0; ) at which b shows the e%ectiveness factor curves computed by the shoot-
moves from b+ to b . Consequently, the condition that ing method for the two bulk compositions. As it turns out,
f(y) is non-decreasing is a su0cient condition for the the curve also depends on the bulk composition, indicating
uniqueness of the steady state. complexity in the dependence of the e%ectiveness factor on
reaction conditions and kinetics. Fig. 6 also compares the
prediction of an approximation of the e%ectiveness factor,
6. Examples ,
recommended as the best in Wijnggaarden et al. (1998).
The approximation is expressed as an implicit equation:
In the shooting method, a numerical routine for the 1
 =  ;
initial-value problem is needed. Routines based on the 1 + An
1 + (1 )An
0
RungeKutta method or its variants are readily available in
commercial subroutine packages or an internet repository
2
An0 = 1 ;
(www.netlib.org). Any of those will work :ne in the (s + 1)2 [2
f(y) dy]
0
method. 
As a practical example for application of the present !
2 df(y) 
An1 = ; (22)
method, we consider methanol steam reforming over a (s + 1)2 dy y=1
 D.H. Kim, J. Lee / Chemical Engineering Science 59 (2004) 2253 2263
exact
approximation
relative error
B
1 0.3
A -0.1
0.2
0.1 A
0.1
B
0.01 0.0
0.01 0.1 1 10 100 1000
Fig. 6. Comparison of exact e%ectiveness factor and its approximation by
Eq. (22) for methanol steam reforming reaction over a Cu catalyst.
where ! is a geometry factor, which depends only on the
shape of the catalyst like s and the value of which is given
as 23 for slab, 1 for cylinder, and 65 for sphere. The approxi-
mation is seen to predict the e%ectiveness factor of compo-
sition B within 10% error, while relatively poor agreement
is observed for composition A with a maximum of 30% er-
ror. Furthermore, the approximation can be used only when
An1 is positive, that is df(y)=dy|y=1 0. This limits the
applicability of the approximation.
As another example, we consider a non-isothermal spher-
ical catalyst in which a half-order reaction takes place. The
temperature inside the catalyst is related to the concentration
by Eq. (3), enabling to write the reaction rate in terms of
the concentration variable. The dimensionless reaction rate
f(y) is given by
 E 
A exp RT C1
f(y) =  steady states and the corresponding e%ectiveness factors. A
A exp RT E
C1s
s

#$(1 y)
= exp y;
1 + #(1 y)
where # = (IH1 )De1 C1s =ke Ts and $ = E=RTs . For $ = 30
and # = 0:1; 0 and 0.1, the e%ectiveness factors were com-
puted by the reverse shooting method and shown in Fig. 7.
Within a limited Thiele modulus range for a given # and
$, the same e%ectiveness factor can be computed by the
well-known method proposed by Weisz and Hicks (1962),
being similar to the forward shooting method and thus hav-
ing the same limitation that the center concentration must be
greater than zero. For the half-order reaction and for a large
Thiele modulus, however, the concentration can decrease to
zero at some interior location and remains zero thereafter to
the center of the catalyst. In this case the method of Weisz
and Hicks fails. In Fig. 7, the Thiele modulus ranges within
which the method of Weisz and Hicks can be applied suc-
cessfully are marked with arrows.
2261
10
=0.1
1 0
Relative error
0.1
=30
0.01
0.1 1 10 100
Fig. 7. E%ectiveness factor of nonisothermal spherical catalyst for
half-order kinetics.
7. Conclusion
A robust numerical method for computing the e%ective-
ness factor has been developed in this study. The method is
an iterative one and based on the shooting at the outer surface
of the catalyst, denoted as reverse shooting. We have shown
that during the reverse shooting with an initial guess b, one
of three cases occurs in the computed pro:le yb (z): namely,
dyb =d z 0, yb (z) 0, or yb (1) 0 and dyb =d z|z=1 0.
We classi:ed b as either b+ if dyb =d z 0 occurs or b
otherwise. With this classi:cation, a steady state, a solution
of the problem, has been shown to exist at the boundary
between b+ and b . An algorithm useful for locating the
boundary point when there is a unique steady state is pro-
posed. Also in the case of multiple steady states, the method
is shown to be e%ective and e0cient to determine all the
simple rule that b+ b at the boundary point is suggested
for the stability of a steady state.
(23)
Notation
A chemical species involved in reaction
a exact concentration gradient at the catalyst sur-
face
b initial guess of the concentration gradient at the
surface
b+ initial guess b for a concentration pro:le with
dy=d z 0 at a point
b initial guess b for a concentration pro:le with
either y 0 at a point or dy=d z|z=1 0
C concentration, mol=m3
De e%ective di%usivity, m2 =s
f(y) dimensionless reaction rate (=R(C1 ; T )=
R(C1s ; Ts ))
2262 D.H. Kim, J. Lee / Chemical Engineering Science 59 (2004) 2253 2263

ke thermal conductivity of catalyst, W/m/K f(ya + u) can also be expanded as


L radius of a cylindrical or spherical catalyst, or 
2 df 
f(ya + u) = f(ya + u0 ) + & u1 + : (A.6)
half-thickness of a slab catalyst, m dy y=ya +u0
N mole Oux, mol=m2 =s
R(C1 ; T ) reaction rate, a function of C1 and T , mol=m3 =s Substitution of Eqs. (A.5) and (A.6) into Eq. (A.3) and
s shape factor of the catalyst (in:nite slab s = 0; collecting the terms of order &0 , we obtain
in:nite cylinder s = 1; sphere s = 2)
d 2 u0 s du0
T temperature, K 2
= ; (A.7)
d( 1 ( d(
u(z) error in the computed pro:le (=yb (z) ya (z)) 
x dimensionless position variable in the catalyst du0 
u0 (()|(=0 = q1 ; = q2 : (A.8)
(center, x = 0; outer surface, x = 1) d( (=0
y dimensionless concentration of the key compo-
nent (=C1 =C1s ) The terms of order &2 are
ya (z) exact dimensionless concentration pro:le in the
d 2 u1 s du1
catalyst 2
= +
2 (f(ya + u0 ) f(ya )); (A.9)
yb (z) dimensionless concentration pro:le obtained d( 1 ( d(

with b du1 
u1 (()|(=0 = 0; = 0: (A.10)
z dimensionless position variable (=1 x) d( (=0
Greek letters As u0 is the dominant term in Eq. (A.5) as & 0, we solve
 error in the initial guess b (=b a) for only u0 and obtain
 e%ectiveness factor s = 0 (slab)


 stoichiometric number z1
u0 = &q2 ( + q1 = q1 + q2 +1 ; (A.11)

Thiele modulus, de:ned in Eq. (4) &
Subscripts s = 1 (cylinder)
1 key component 1
u0 = q2 ln + q1
i chemical species 1(
s catalyst outer surface 1
= q2 ln + q1 + q2 ln &; (A.12)
1z
Appendix A s = 2 (sphere)
q2
Here we are interested in the behavior of u(z) in the z u0 = + q1
1(
interval (1 &; 1). We assume that the initial-value problem,
&q2
Eqs. (14) and (15), has been computed from z = 0 to 1 &, = + q1 : (A.13)
and the result at z = 1 & is 1z

du 
u(1 &) = q1 ; = q2 =&: (A.1)
d z z=1&
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