Chemical Engineering Science 61 (2006) 5127 – 5136

www.elsevier.com/locate/ces

An approximation method for the effectiveness factor in porous catalysts

Jietae Lee, Dong Hyun Kim ∗
Department of Chemical Engineering, Kyungpook National University, Daegu 702-701, Republic of Korea

Received 18 November 2005; received in revised form 15 February 2006; accepted 25 February 2006
Available online 6 March 2006

Abstract
An efficient method for computing approximate value of the effectiveness factor is presented. The method is developed for an arbitrary rate
expression and for three representative catalyst shapes, namely, an infinite slab, an infinite cylinder and a sphere. In the method, two new
asymptotic expansions for small and large Thiele moduli are developed and joined together at an intermediate value of the Thiele modulus, which
can be calculated by a simple equation. The approximation is highly accurate for small and large Thiele moduli, and it has small or negligible
errors for intermediate values of the Thiele modulus. As demonstrated with examples, the approximation method is fast, straightforward and
is a dependable alternative to numerical methods for computing exact values of the effectiveness factor.
䉷 2006 Elsevier Ltd. All rights reserved.

Keywords: Effectiveness factor; Approximation; Heterogeneous reaction; Asymptotes of effectiveness factor; Thiele modulus

1. Introduction catalyst (s = 0 for an infinite slab, s = 1 for an infinite cylinder

and s = 2 for a sphere). The dimensionless reaction rate f (y)
The ratio of the observed reaction rate to the rate in the is normalized with respect to the reaction rate at the external
absence of intraparticle mass and heat transfer resistance is surface of the catalyst and hence, at the external surface x = 1,
defined as the effectiveness factor. An accurate estimation of y = 1 and f (1) = 1. The effectiveness factor  is given by
the factor is important in the analysis and design of packed-bed
s + 1 dy(1)
reactors. Formally the estimation involves the solution of the = . (3)
mass balance equation in a porous catalyst (Aris, 1975; Fogler,
2 dx
1999; Kim and Lee, 2004): Except for a few cases such as isothermal first-order and
zero-order reactions, the analytic solution of the boundary-
d2 y s dy value problem, Eqs. (1) and (2), is, in general, not feasible, and
2
+ −
2 f (y) = 0. (1)
dx x dx the problem can only be solved numerically. There have been
available efficient methods for the numerical solution (Kim and
The boundary conditions are Lee, 2004; Lee and Kim, 2005). Nevertheless, when the ef-
fectiveness factor is calculated repeatedly for changing sets of
dy(0) parameters and the desired accuracy of the factor is not ex-
y(1) = 1, = 0. (2) cessively high, computing the factors by numerical methods
dx
can be time consuming. Such is the case in the simulation of
Here y is the dimensionless concentration of the key component packed-bed reactors, where the effectiveness factor has to be
in the reaction, x is the dimensionless space variable in the computed at every point in the reactor. An approximating proce-
catalyst,
is the Thiele modulus and s is the shape factor of the dure for the rapid calculation of the effectiveness factor is thus
needed.
In the literature, various approximation procedures for
∗ Corresponding author. Tel.: +82 53 950 5617; fax: +82 53 950 6615. the effectiveness factor have been proposed. Haynes (1986)
E-mail address: dhkim@mail.knu.ac.kr (D.H. Kim). proposed an approximation using the analytic formula for a
0009-2509/$ - see front matter 䉷 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2006.02.033
5128 J. Lee, D.H. Kim / Chemical Engineering Science 61 (2006) 5127 – 5136

first-order reaction with a modified Thiele modulus: where

⎧ tanh()  y
⎪
⎪ if s = 0, 18 1
⎪  ,
⎪ b2 = − 2 f () ddy,
⎪
⎨ 2I1 () b1 0 0
H N = , if s = 1, (4) ⎧
⎪
⎪ I0 ()  ⎪ −b2 − b22 /b12 + a1 b22
⎪
⎪ ⎪
⎨ 2 , f  (1) 1,
⎪
⎩
3 1
−
1
, if s = 2, b2 /b1 + 3b1 b2 + b13
 tanh()  = (10)
⎪
⎪ −(1.2 + 0.2/f  (1))a1 b1
 ⎩ , f  (1) > 1.
 1 + a1 (b12 + b2 )
1 + s + 0.721

 = 2 2
, 1 = √ , 2 =
f  (1), The approximation is highly accurate for nth order reactions
1 + s + 0.72 2m0
when n > 1. As the order decreases below 1.0, however, large
where deviations arise. Keegan et al. (2003) proposed an approxima-
tion by coupling a first-order Galerkin approximation of the
1
effectiveness factor at low
and an asymptote for large
.
m0 = f (y) dy. (5)
0 Their approximation involves a solution of a nonlinear alge-
braic equation if the reaction rate form is nonlinear.
This approximation can be used only when f  (1)
0. Other- In the present study, we developed a method for approxima-
wise, 2 becomes an imaginary number and the effectiveness tion of the effectiveness factor for any rate expression includ-
factor is incalculable. This is a disadvantage of the approxima- ing the expression with f  (1) < 0. The method involves up to
1
tion since rate expressions with f  (1) < 0, such as power-law d4 f (y)/dy 4 at y = 1 and two simple integrals 0 f (y) dy and
kinetics with a negative order, are not uncommon (see Kim and 1
Lim (2002)). Wijnggaarden et al. (1988) proposed an implicit 0 yf (y) dy. As these can be easily evaluated numerically or,
if possible, analytically, computing an approximate value of the
equation:
effectiveness factor by this method is rapid and straightforward.
1
W I =
, (6) 2. Effectiveness factor approximation for small Thiele
1 − 2a1 W I
2 + (1 − W I )
2 /b12 moduli

where The solution of Eqs. (1) and (2) for small
is determined
 by the method of the regular perturbation (Nayfeh, 1973; Aris,
f  (1)
a1 = − , b1 = (s + 1) 2m0 . (7) 1975). In this method, we seek the solution in the following
(s + 1)(s + 3) form:
For a given
, W I can be found by solving a cubic polynomial y(x) = yL0 (x) +
2 yL1 (x) +
4 yL2(x) + . . . . (11)
in W I which has at least one real root for any f (y). When
f  (1) < 0, however, the only real root of the cubic polynomial Substituting Eq. (11) into Eqs. (1) and (2), we have
often becomes a negative number, which cannot be a solution
d2 (yL0 +
2 yL1 + · · ·) s d(yL0 +
2 yL1 + · · ·)
of Eq. (6) and is unrealistic since  > 0. The approximation by +
Gottifredi and Gonzo (2005) is dx 2 x dx
−
2 f (yL0 +
2 yL1 + · · ·) = 0,
1
GG =
. (8) dy(0) dyL0 (0) dyL1 (0) dyL2 (0)
= +
2 +
4 + · · · = 0,

2 /b12 + exp(−(2a1 + 1/b12 )
2 ) dx dx dx dx

In order to follow the asymptotic behavior of the effectiveness y(1) = yL0 (1) +
2 yL1 (1) +
4 yL2 (1) + · · · = 1 (12)
factor for large Thiele moduli, the coefficient of
2 in the expo- and
nential term in the denominator must be negative, requiring that
f  (1)m0 < (s + 3)/(4(s + 1)). For a power-law rate expression f (yL0 +
2 yL1 +
4 yL2 + · · ·)
and a spherical catalyst (s = 2), the requirement is not satisfied = f (yL0 ) + f  (yL0 )(
2 yL1 +
4 yL2 + · · ·)
unless the reaction order is less than 5/7, thus resulting in a f  (yL0 ) 2
+ (
yL1 +
4 yL2 + · · · )2 + · · · . (13)
misrepresentation of the asymptote at large
. Wedel and Luss 2!
(1980) proposed a rational function in
for approximation of It is obvious in Eq. (12) that yL0 (1) = 1 and yL1 (1) = yL2 (1) =
the effectiveness factor in a spherical catalyst (s = 2), · · · = 0. Collecting the
0 -order terms in Eq. (12) gives
b1  − b12 a1 d2 yL0 s dyL0 dyL0 (0)
1 + 
+
2 2
+ = 0, = 0, yL0 (1) = 1 (14)
b2 + b12 dx x dx dx
W L = (9)
b1  − 2b12 a1 − b2 a1  − b 1 a1 3 The solution of Eq. (14) is
1 + 
+ 2

+

b2 + b12 b2 + b12 yL0 (x) = 1. (15)
 J. Lee, D.H. Kim / Chemical Engineering Science 61 (2006) 5127 – 5136 5129

From Eq. (12), the higher-order equations are The rate of convergence of the infinite series can be acceler-
ated with transformations (Press et al., 1992). Among various
d2 yL1 s dyL1 transformations, the Euler transformation (Appendix A) is very

2 : + − f (1) = 0, effective in accelerating the convergence, particularly when the
dx 2 x dx
signs of the terms alternate. Applying the Euler transformation
and truncating the series after the fifth term,
dyL1 (0)
= 0, yL1 (1) = 0,  
dx s+1 7 4 1
L = 2 4 6 8
q1
+ q 2
+ q 3
+ q 4
+ q 5
10

2 8 8 8
d2 yL2 s dyL2

4 : + − f  (1)yL1 = 0,
dx 2 x dx f  (1) 7 f  (1) + 2(f  (1))2
=1−
2 +
4
dyL2 (0)
= 0, yL2 (1) = 0. (16) (s + 1)(s + 3) 8 (s + 1)2 (s + 3)(s + 5)
dx
(s + 1) (s + 1)
+ q 4
6 + q 5
8 . (21)
Each problem in Eq. (16) is linear and can be solved analyti- 2 8
cally. The solutions are Fig. 1 shows several partial sums of the series Eqs. (20) and
(21), demonstrating an improvement in the partial sum with
x2 − 1 the Euler transformation. When the signs of the terms are not
yL1 (x) = ,
2(s + 1) alternating, the Euler transformation usually does little harm
on the accuracy as well as on the convergence rate. We propose
(s + 1)x 4 − 2(s + 3)x 2 + s + 5 Eq. (21) as the approximation of the effectiveness factor for
yL2 (x) = f  (1) . (17) low
.
8(s + 1)2 (s + 3)
3. Effectiveness factor approximation for large Thiele
With these solutions, we can obtain dy(1)/dx: Moduli

dy(1) dyL0 (1) dyL1 (1) 2 dyL2 (1) 4 We introduce a transformation:

= +
+
+ ···
dx dx dx dx
= q1
2 + q2
4 + q3
6 + · · · , (18) u = x s/2 y (22)

Then Eq. (1) becomes

q1 , q2 , . . . , q5 are listed in Table 1. In evaluating the coeffi-
cients, the derivatives of f (y) at y = 1 are required. For nu- d2 u 2s − s 2 u  u
+ −
2 s/2
x f = 0. (23)
merical derivatives, we recommend the following formulas: dx 2 4 x2 x s/2

3f (1) − 4f (1 − ) + f (1 − 2)
f  (1) ≈ ,
2

2f (1) − 5f (1 − ) + 4f (1 − 2) − f (1 − 3)

f  (1) ≈ ,
2

5f (1) − 18f (1 − ) + 24f (1 − 2) − 14f (1 − 3) + 3f (1 − 4)

f (3) (1) ≈ ,
23

3f (1) − 14f (1 − ) + 26f (1 − 2) − 24f (1 − 3) + 11f (1 − 4) − 2f (1 − 5)

f (4) (1) ≈ . (19)
4

Theoretically, the accuracy of the derivatives improves as  →

The boundary conditions of Eq. (23) are u(0) = 0 since y(0)
0 , but the numerical computation of f (3) (1) or f (4) (1) with
is finite, and u(1) = 1. We let p = du/dx, then d2 u/dx 2 =
a finite precision easily becomes unstable when  is too small.
p dp/du = (1/2) dp 2 /du. Eq. (23) becomes
We found that  = 0.02 was suitable for our purpose.
The effectiveness factor for low
is given as 1 dp 2  u 2s − s 2 u
=
2 x s/2 f − . (24)
2 du x s/2 4 x2
s + 1 dy(1)
= If x can be expressed as a function of u , then the right hand

2 dx side of Eq. (24) depends only on u. When
?1, the reactant is
= 1 + (s + 1)q2
2 + (s + 1)q3
4 + · · · . (20) largely depleted at the catalyst center and its concentration can
5130 J. Lee, D.H. Kim / Chemical Engineering Science 61 (2006) 5127 – 5136

Table 1
Coefficients in the perturbation Eq. (18) for a small Thiele modulus

Eq.(20): 5 terms
Catalyst Coefficient Eq.(20): 3 terms
shape Eq.(21)
1

s=0 q1 = 1

H1
f  (1)


q2 = −
3
H2
f  (1) 2f  (1)2
q3 = +
15 15 : exact
: approx. for φ<<1
: approx. for φ>>1
26f  (1)f  (1) f (3) (1) 17f  (1)3
q4 = − − −
315 105 315 0.1
0.1 1 10
64f  (1)2 f  (1) f  (1)f (3) (1) 62f  (1)4 11f  (1)2 f (4) (1)

q5 = + + + +
945 63 2835 945 945
Fig. 1. Plot of effectiveness factor and approximations for f (y)=y 2 and s =2.
1
s=1 q1 =
2

f  (1) To evaluate Eq. (25), it is necessary to specify x(u), but x(u)

q2 = −
16 is not available in advance because it is not possible to solve
Eq. (23) for an arbitrary rate expression f (y).
f  (1) f  (1)2
q3 = + Here, we use the method of the Picard iteration (Kreyszig,
192 96
1999) to generate a series of approximations for x(u)
17f  (1)f  (1) f (3) (1) 11f  (1)3
(x0 (u), x1 (u), . . . , ). As
→ ∞, the reactant cannot penetrate
q4 = − − − deep into the catalyst due to severe mass transfer limitations,
6144 3072 6144
and the catalytic reaction takes place only in a thin shell at
f  (1)2 f  (1) 29f  (1)f (3) (1) 19f  (1)4 7f  (1)2 f (4) (1) the external surface of the catalyst. This means that x(u) for
q5 = + + + +
1024 122880 61440 40960 61440 0 < u < 1 is close to the external surface, i.e. x(u) ≈ 1.0.
Thus, we may begin the Picard iteration with an initial guess
1
s=2 q1 =
3
x0 (u) = 1. Substituting x0 (u) into Eq. (25), we have

f  (1) 
q2 = − du(1) 1 2s − s 2
45 =
2 f (u)du − 2
≈
2m0 (26)
dx 0 4

f  (1) 2f  (1)2
q3 = +
945 945 and the corresponding approximation of the effectiveness factor
is
2f  (1)f  (1) f (3) (1) f  (1)3
q4 = − − −
s + 1 s + 1
6075 25515 4725
s(s + 1)
H 1 = 2m0 − ≈ 2m0 (27)
32f  (1)2 f  (1) 71f  (1)f (3) (1) 2f  (1)4 17f  (1)2 f (4) (1)
2
2

q5 = + + + +
467775 4209975 93555 1403325 841995
This is the well-known asymptote of the effectiveness factor
for
?1 (Petersen, 1965; Schneider, 1976).
To obtain the next approximation of x(u), x1 (u), we substi-
be approximated as y(0) = 0. This, together with dy(0)/dx = 0, tute x0 (u) = 1 into Eq. (23) and obtain
gives a boundary condition p = 0 at u = 0. Integrating Eq. (24),
we obtain d2 u 2s − s 2
+ u −
2 f (u) = 0. (28)
dx 2 4
du(1)
p(1) =
dx
 The initial conditions are
1 
u

2s − s2 u


=
2 x s/2 (u)f − 2
du. du(1) 2s − s 2
0 x s/2 (u) 4
x 2 (u) u(1) = 1, =
2m0 − . (29)
(25) dx 4
2
 J. Lee, D.H. Kim / Chemical Engineering Science 61 (2006) 5127 – 5136 5131

A power series solution of the initial value problem is The approximation for
?1 by Wedel and Luss (1980)
√
 and Gonzo and Gottifredi (1983),  ≈ (s+1)
2m0 −
2s − s 2

s(s+1)  1 y √
1
1 − u(x) = 2m0 − 2

(1 − x) −
2 (1 − x)2 2 0 f () d dy/ 2m0 , is slightly more accurate
4
2
2 0
 than H 2 but it involves an integral that is more complicated
f  (1) 2s − s 2 3 than m1 . The integral m1 can easily be evaluated simultane-
+ 2m0 −
(1 − x)3 + · · · . (30)
6 4
2 ously with m0 .

In the convergence interval of Eq. (30), we approximate 4. Effectiveness factor approximation for all

√ series by taking only the first term. Thus, 1 − u(x) ≈

the
2m0
(1 − x), and the second approximation x1 (u) is Each approximation presented so far is not valid for all
. It
given by fails to provide an estimate of the effectiveness factor, if
is
1−u considerably different from the values assumed in its derivation.
x1 (u) = 1 − √ . (31) In order to develop a continuous approximation valid for all
,

2m0
it is necessary to connect the approximations for low and high
Substituting x = x1 (u) into Eq. (25), we have
at an intermediate
. For this purpose, we add a term A/
3
 to H 2 , so that
 1   
 
du(1)  u 2s−s 2 u s + 1 s(s + 1) 3m1
=
2 s/2
− A
x1 (u)f du. H = 2m0 + − 2 + 3. (37)
dx 0
s/2
x (u)
1
4
2 x12 (u)
2
2 2m0

(32)
The term A/
3 is introduced since it has little effect on the
It can be shown that accuracy in the
range where H 2 is valid and it allows to


 1       
du(1)  1 − u s/2 1 − u −s/2 2s − s 2 u
=
2 1− √ f u 1− √ − du
dx 0
2m0
2m0 4
2 x12 (u)
     
1 s 1−u s u(1 − u)
=
2 1− √ + O(
−2 ) f u + √ + O(
−2 ) + O(
−2 ) du
0 2
2m0 2
2m0
  
1 s 1
=
2 f (u) + √ (−(1 − u)f (u) + u(1 − u)f (u)) du + O(
−2 )

0 2
2m0
 1
1 s
=
2 f (u)du + √ (−(1 − u)f (u) + u(1 − u)f  (u)) du + O(
−2 )
0
2m0 0
  
s 3m1
=
2m0 + − 1 + O(
−1 ), (33)
2 2m0
connect H to L in a smooth way. We choose an appropriate

where
point, denoted as , at which L ()=H (). Then A is given by
1
  
m1 = yf (y) dy. (34) 3 2 s(s + 1) 3m1
0 A =  L () −  (s + 1) 2m0 −  −2 .
2 2m0
Hence we have (38)
  
dy(1) s 3m1 This gives an approximation of the effectiveness factor for all
≈
2m0 + − 2 + O(
−1 ). (35)
:
dx 2 2m0
The Picard iteration may be continued to improve du(1)/dx but  = L if 0 <
 and  = H if
> . (39)
the iteration becomes increasingly difficult and complicated.
In this approximation,  affects the approximation accuracy and
Neglecting the term of O(
−1 ) in Eq. (35), we obtain
should be within the valid range of L .
 
s + 1 s(s + 1) 3m1 In the convergence interval of the infinite series of  for a
H 2 = 2m0 + −2 . (36) low
, Eq. (21), the high-order term becomes less important

2
2 2m0
as the order increases. Among the terms in L , q5
8 is least
This new approximation is more accurate than the well known significant and would be small or negligible in 0 <
. In
approximation, H 1 . Fig. 1 also shows the approximations, H 1 this respect the magnitude of the term may be used to find the
and H 2 for f (y) = y 2 and s = 2. range (0, ) for L . Since  in 0 <
 is not much different
5132 J. Lee, D.H. Kim / Chemical Engineering Science 61 (2006) 5127 – 5136

Table 2
Proposed approximation of effectiveness factor


L , if 0 <
 
=
H , if
> 

where

f  (1) 7 f  (1) + 2(f  (1))2 (s + 1) (s + 1)

L = 1 −
2 +
6 + q 4
8 + q5
10
(s + 1)(s + 3) 8 (s + 1)2 (s + 3)(s + 5) 2 8

 
s + 1 s(s + 1) 3m1 A
H = 2m0 + −2 + 3

2
2 2m0

 
 s(s + 1) 3m1
A = 3 L () − 2 (s + 1) 2m0 −  −2
2 2m0

1 1
m0 = f (y)dy, m1 = yf (y)dy
0 0

⎧
⎨ (2.8 +s)/2,  if |f  (1)|  0.2
1/8
= 0.02
⎩ min , (s + 2) , otherwise
(s + 1)|q5 |

q4 and q5 are listed in Table 1. Numerical derivatives of f (1) at y = 1 can be obtained by Eq. (19) with  = 0.02.

from 1, it is reasonable to assume that (s + 1)|q5 |8 < , where
 is a small positive number. This, in turn, gives
 1/8
 previous approximations in the literature. The comparisons
= . (40)
(s + 1)|q5 |
If  is excessively small, the interval for L , 0 <
, also
becomes too small. In this case, although L in the interval is
highly accurate, the accuracy of H in
>  can be grossly in-
adequate unless
?1. On the other hand, if  is too large,  can
be outside of the valid range of L , and L as well as H in the
vicinity of  can become unsatisfactory. Numerical results for a
number of rate expressions showed that a satisfactory approxi-
mation was obtained for most reactions if  was determined by
Eq. (40) with  = 0.02. An exception to this is a zero-order re-
action for which q5 = 0, and Eq. (40) does not have a solution
unless  = 0. Numerical tests of the approximation Eq. (39)
showed that estimates of the effectiveness factor with , deter-
mined by Eq. (40) with  = 0.02, also became unsatisfactory
for reactions exhibiting behavior close to the zero-order reac-
tion. In this case, it was found in the tests that  = (2.8 + s)/2
when |f  (1)| 0.2 worked well in producing reasonably accu-
rate estimates. In the case where  calculated by Eq. (40) is
unreasonably large to result in the approximation that is grossly
inaccurate, it is safe to have an upper bound for . For ex-
ample, when f (y) = y 0.24 and s = 2, q5 = 8.18 × 10−9 and
 = 5.48, which is too large for L to be accurate in 0 <
.
Numerical tests have also shown that  = (s + 2) can serve as
an upperbound for . In Table 2, the proposed approximation
of the effectiveness factor is summarized.
5. Numerical examples
Figs. 2–4 compare the approximation of this study and two
are made for three different rate forms: power-law kinet-
ics (Fig. 2), nonisothermal kinetics (Fig. 3) and Langmuir–
Hinselwood rate expressions (Fig. 4). When s = 0, only the
approximation proposed in this study and that of Gottifredi
and Gonzo (2004), GG , are compared with the exact effec-
tiveness factor since the approximation of Wedel and Luss
(1980), W L , was developed for the case of s = 2. As can be
seen in the figures, the proposed approximation shows small or
negligible deviations from the exact values only for interme-
diate
values and becomes highly accurate for small or large

values. On the other hand, the approximation by Gottifredi
and Gonzo often becomes unusable at large
as it misrepre-
sents the asymptotic behavior. When s = 2, the approximation
by Wedel and Luss always follows the correct asymptotes for
small and large
but usually shows less accurate estimates
than the present approximation at intermediate
values.
To examine the approximation accuracy, the following max-
imum error was calculated:
 
 (
) − e (
) 
EMAX = 100 max   , (41)
all
 (
) 
e
where (
) is the approximate value and e (
) is the ex-
act value calculated by the numerical method of Kim and
Lee (2004). Table 3 lists EMAX of the approximations in the
literature and this study for a series of nth order reactions,
non-isothermal first-order reactions and Langmuir–Hinselwood
 J. Lee, D.H. Kim / Chemical Engineering Science 61 (2006) 5127 – 5136 5133

s=0 s=0
1 1



K=4
n=-0.1 K=1
n=2
0.1 0.1

s=2 s=2
1 1
Exact n=-0.2 Exact K=4



Proposed Proposed
WL n=2 WL K=1
GG GG
0.1 0.1
0.2 1 10 20 0.2 1 10 20

Fig. 2. The Effectiveness factor plot for the power law reaction rate functions, Fig. 4. The Effectiveness factor plot for the power law reaction rate functions,
f (y) = y n . Exact, proposed and W L are not distinguishable for s = 2 and f (y) = (1 + K)2 y/(1 + Ky)2 . Exact and proposed are not distinguishable
n = 2. for s = 0 and K = 1, and s = 2 and both K.

s=0
K → ∞. In addition to power-law kinetics with negative or-
1 ders, f (y) = (1 + K)2 y/(1 + Ky)2 also gives f  (1) 0 when
K > 1/2. The Haynes’ approximation did not work for the
kinetic expression. The approximation by Wijnggaarden et al.


b=0.1

b=-0.1 (1988) showed results comparable to those of Haynes and also

did not work when f  (1) 0. The approximation by Gottifredi
0.1 and Gonzo (2004) yielded relatively large maximum errors or
misrepresented the asymptotic behavior at a large
except
s=2
for a few rate expressions and s = 0. The rational approxi-
1
mation by Wedel and Luss (1980) was developed only for a
Exact b=0.1 spherical catalyst (s = 2) and was highly accurate if f  (1)
1,


Proposed
WL b=-0.1 but it showed large maximum errors if f  (1) 0. On the other
GG hand, the approximation by Keegan et al. (2003) worked well
0.1 for the tested rate expressions in the table and gave accurate
0.2 1 10 20
estimates, comparable in most cases and marginally better in


a few rate expressions than those by the present method. The
Fig. 3. The Effectiveness factor plot for the power law reaction rate functions, Keegan et al.’s method, however, involves numerical itera-
f (y) = y exp ((20b(1 − y))/(1 + b(1 − y))). Exact and proposed are not tions in computing the estimates. In comparison, the proposed
distinguishable for s=2 and b=0.1, and exact and W L are not distinguishable method is easier to implement and numerically less expensive
for s = 2 and b = −0.1. than Keegan et al. approximation.
As a realistic example, we simulated an isothermal methanol
steam reformer with the proposed approximation. The reaction
kinetics. For the present approximation, the
values at which
equation is
EMAX was observed were largely in the range 1 <
< 3. Be-
yond this range, the method presented here gave accurate re- CH3 OH + H2 O → CO2 + 3H2 . (42)
sults. In view of the uncertainties in effective diffusivities and
kinetic parameters, an error of 10% in the estimates of the ef- The kinetics of methanol steam reforming over a commercial
fectiveness factor may be regarded as being acceptable. Then, catalyst was recently reported by Lee et al. (2004):
Table 3 indicates that the proposed approximation gives the ef- √
kK 1 (PM / PH )
fectiveness factor estimates which are acceptable in most prac- rM (PM , PH ) = √ √ , (43)
(1 + K1 (PM / PH ))(1 + K2 PH )
tical applications.
As mentioned in the introduction, the approximation by where
Haynes (1986) failed when f  (1)0 and became poorer as  
111 kJ/mol
the apparent reaction order approached zero, even if f  (1) > 0. k = 3.13 × 1010 exp − (mol/kg/s),
RT
This is seen in Table 3 for Langmuir–Hinselwood rate ex-  
pressions f (y) = (1 + K)y/(1 + Ky ), which becomes a first- 20 kJ/mol
K1 = 3.75 × 10−3 exp (kPa−0.5 ),
order reaction when K = 0 and a zero-order reaction when RT
5134 J. Lee, D.H. Kim / Chemical Engineering Science 61 (2006) 5127 – 5136

Table 3
Maximum relative error, EMAX (%)

Catalyst Reaction rate Proposed Keegan et al. Gottifredi and Wijnggaarden et al. Haynes Wedel and
shape expression approximation (2003) Gonzo (2004) (1988) (1986) Luss (1980)

s=0 yn n = −0.1 5.22 9.5 19.7 X X

n=0 1.24 0.0 14.1 X X
n=1 2.98 1.39 0.48 1.55 0.0
n=2 7.30 0.9 0.56 1.33 1.38
 
20b(1 − y)
exp b = −0.1 15.6 1.08 X 2.08 3.0
1 + b(1 − y)
b = 0.1 8.52 1.75 9.0 X X
(1 + K)y
K =1 1.24 0.7 0.63 5.24 4.2
(1 + Ky)
K =5 2.94 0.9 4.4 13.3 20.7
K = 50 3.06 0.4 10.6 28.0 90.2

(1 + K)2 y
K =1 2.82 0.7 3.7 41.6 X
(1 + Ky)2
K =2 4.75 2.21 10.1 X X
K =4 14.6 1.59 22.0 X X

s=1 yn n = −0.1 4.16 1.76 10.9 X X

n=0 2.69 1.15 10.9 X X
n=1 1.65 0.6 4.0 4.03 0.0
n=2 3.88 1.10 X 1.72 2.0
 
20b(1 − y)
exp b = −0.1 4.33 1.71 X 0.08 4.10
1 + b(1 − y)
b = 0.1 3.06 2.06 16.3 X X
(1 + K)y
K =1 3.07 0.3 10.4 10.0 1.7
(1 + Ky)
K =5 1.21 1.00 11.5 21.2 12.2
K = 50 1.80 0.8 11.1 41.9 62.4

(1 + K)2 y
K =1 1.82 1.03 1307 62.3 X
(1 + Ky)2
K =2 5.26 1.60 13.2 X X
K =4 6.54 1.45 13.7 X X

s=2 yn n = −0.2 5.46 2.17 15.6 X X 15.1

n=0 0.98 0.8 15.4 X X 7.44
n=1 1.77 0.8 X 4.00 0.0 0.97
n=2 1.17 1.11 X 1.43 2.36 0.39
 
20b(1 − y)
exp b = −0.1 6.78 1.11 X 0.54 4.78 0.49
1 + b(1 − y)
b = 0.1 3.41 1.43 23.9 X X 12.6
(1 + K)y
K =1 2.67 0.1 12.5 10.5 0.51 3.26
(1 + Ky)
K =5 1.20 0.5 15.5 22.8 8.18 5.65
K = 50 0.99 0.5 15.6 45.7 49.9 7.09

(1 + K)2 y
K =1 1.54 0.8 18.0 69.3 X 5.02
(1 + Ky)2
K =2 5.39 0.8 19.1 X X 9.31
K =4 14.6 1.59 22.0 X X 18.3

Note: X: complex effectiveness factor (Haynes, 1986); negative effectiveness factor (Wijnggaarden et al., 1988); and wrong asymptote at large
(Gottifredi
and Gonzo, 2004).

 
−7 50 kJ/mol the hydrogen partial pressure inside the catalyst is correlated
K2 = 6.34 × 10 exp (kPa−1 ),
RT with the methanol partial pressure in the catalyst by
PM is methanol partial pressure, and PH is hydrogen partial
pressure. We denote the partial pressures at the external surface 3DeM
P H − PH S = (PMS − PM ), (44)
of the catalyst as PMS (methanol) and PH S (hydrogen). Then, DeH
 J. Lee, D.H. Kim / Chemical Engineering Science 61 (2006) 5127 – 5136
1.0
0.8

Conversion, 
0.6
0.4
conversion
0.2
0.0
0 5 10 15
Catalyst weight (g)
Fig. 5. Plot of effectiveness factor and conversion along the methanol reformer
(line: computed with the exact effectiveness factor, circle: computed with the
proposed equation for the effectiveness factor).
where DeM is the methanol effective diffusivity and DeH is
the hydrogen effective diffusivity. The dimensionless reaction
rate is
−rM (PM , PH ) PM
f (y) = where y = . (45)
−rMS (PMS , PH S ) PMS
The effective diffusivities of the participating components and
the catalyst properties are described in detail in Lee et al. (2004).
The reactor is assumed to be a plug-flow packed reactor, which
is described by
dX
FM0 = −rM (PMS , PH S ), X(0) = 0,
dW
where FM0 is the molar feed flow rate of methanol, X is the frac-
tional methanol conversion, and W is the catalyst weight used
as the independent variable with a range from 0 to Wt , the total
weight of the catalyst in the reactor. The feed rate of methanol
vapor and water vapor was 1000 ml (STP)/min and 1500 ml
(STP)/min, respectively, and the total amount of catalyst (di-
ameter: 1 mm) in the reactor was 20 g. The reactor tempera-
ture was fixed at 250 ◦ C. In addition, we redid the simulation
with the exact effectiveness factor numerically computed by the
method of Kim and Lee (2004). In the numerical integration of
the initial value problem, Eq. (46), the effectiveness factor was
affected by the local concentrations and had to be computed at
every point of integration. The computation time was signifi-
cantly dependent on the method used in computing the effec-
tiveness factor. Fig. 5 shows the results of the two simulations.
Along the reactor, the profiles of the effectiveness factor and
the methanol conversion from the two simulations were virtu-
ally identical. The calculated exit conversion was 0.800 (exact)
and 0.802 (approximation). Moreover, the computation time of
the reactor simulation with the approximation was around 1/30
of the time with the numerical method for computing the exact
effectiveness factor, demonstrating a considerable saving in the
computation with the approximation.
5135
6. Conclusion
We developed a straightforward method to rapidly com-
pute approximations of the effectiveness factor. The method
is applicable to any rate expression, and the approximated ef-
fectiveness factor is sufficiently accurate for most practical
applications. In the method, two asymptotes of the effective-
ness factor for small and large
were joined together to cover
all
. The asymptote for small
consisted of terms up to
10 ,
which were obtained from a perturbation analysis of the gov-
erning equation. The Euler transformation was applied to the
series so as to accelerate its convergence and to extend its ap-
plicable
range. The method of the Picard iteration was used
to obtain an asymptote for a large
, in which a new two-term
20
expansion was developed. Thus, the approximation correctly
follows the asymptotes for small and large
and shows small
or negligible errors for intermediate
values.
Notation
A coefficient of
−3 in Eq. (37), defined in Eq. (38)
EMAX maximum relative error in the approximation of the
effectiveness factor, defined in Eq. (41)
f (y) dimensionless reaction rate, normalized with re-
spect to the rate at the external surface of the cata-
lyst
m0 integral of f (y) from y = 0 to 1
m1 integral of yf (y) from y = 0 to 1
P partial pressure, kPa
qi ith coefficient in the expansion, Eq. (21), listed in
(46) Table 1
s shape factor of the catalyst, s = 2 for a sphere, s = 1
for an infinite cylinder, s = 0 for an infinite slab
X methanol conversion
x dimensionless position variable in the catalyst
y dimensionless concentration of the key component
W catalyst weight, kg
Greek letters

value at which L = H , defined in Table 2
 effectiveness factor
GG approximation of the effectiveness factor by
Gottifredi and Gonzo (2005), defined in Eq. (8)
H approximation of the effectiveness factor for large
Thiele moduli, defined in Eq. (37)
H 1 the first asymptote of the effectiveness factor for
large Thiele moduli, defined in Eq. (27)
H 2 the second asymptote of the effectiveness factor for
large Thiele moduli, defined in Eq. (36)
L approximation of the effectiveness factor for small
Thiele moduli, defined in Eq. (21)
W L approximation of the effectiveness factor by Wedel
and Luss (1980), defined in Eq. (9)

Thiele modulus
5136 J. Lee, D.H. Kim / Chemical Engineering Science 61 (2006) 5127 – 5136

Appendix A. Euler Transformation Gottifredi, J.C., Gonzo, E.E., 2005. Approximate expression for the
effectiveness factor estimation and a simple numerical method for
The convergence of series can be accelerated with transfor- concentration profile calculation in porous catalyst. Chemical Engineering
Journal 109, 83–87.
mations (Press et al., 1992). Among various transformations, Haynes, H.W., 1986. An explicit approximation for the effectiveness factor
the Euler transformation is very effective when signs of terms in porous heterogeneous catalysts. Chemical Engineering Science 41,
are alternating. Consider a series whose signs of terms are al- 412–415.
ternating; Keegan, S.D., Mariani, N.J., Bressa, S.P., Mazza, G.D., Barreto, G.F., 2003.
Approximation of the effectiveness factor in catalyst pellets. Chemical
∞
 Engineering Journal 94, 107–112.
u = u 1 − u2 + u3 − u4 + · · · = (−1)k−1 uk , Kim, D.H., Lim, M.S., 2002. Kinetics of selective CO oxidation in hydrogen-
k=1 rich mixtures on Pt/alumina catalysts. Applied Catalysis A: General 224,
27–38.
where each uk is positive. Then a transformed series as Kim, D.H., Lee, J., 2004. A robust iterative method of computing effectiveness
factors in porous catalysts. Chemical Engineering Science 59, 2253–2263.
∞
 (−1)k Kreyszig, E., 1999. Advanced Engineering Mathematics. eight ed. Wiley,
u = u1 − u2 + · · · − un−1 + k u n , New York. pp. 56–58.
2k+1 Lee, J., Kim, D.H., 2005. An improved shooting method for computation of
k=0
effectiveness factors in porous catalysts. Chemical Engineering Science
un = u n ,
0 60, 5569–5573.
Lee, J.K., Ko, J.B., Kim, D.H., 2004. Methanol steam reforming over
1 un = un+1 − un , Cu/ZnO/Al2 O3 catalyst: kinetics and effectiveness factor. Applied
Catalysis A: General 278, 25–35.
2 un = un+2 − 2un+1 + un , Nayfeh, A., 1973. Perturbation Methods. Wiley, New York. pp. 1–18.
Petersen, E.E., 1965. Chemical Reaction Analysis. Prentice-Hall, Englewood
...
Cliffs, NJ. pp. 66–70.
Press, W.H., Teukolsky, S.A., Vetterling, W.T., Flannery, B.P., 1992. Numerical
has a better convergence rate.
Recipes in Fortran. second ed. Cambridge University Press, New York.
pp. 160–163.
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