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Chemical Engineering Science 62 (2007) 2179 2186

www.elsevier.com/locate/ces

Effectiveness factor approximations for multiple steady states in porous


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

Received 8 September 2006; received in revised form 6 December 2006; accepted 11 January 2007
Available online 25 January 2007

Abstract
The effectiveness factor is formally determined by solving a two-point boundary value problem, often numerically. To enhance the com-
putational efciency in simulations of large-scale reactor systems with porous catalysts, a simple approximation formula for the effectiveness
factor is often used. For some reaction rate functions, however, the effectiveness factor as a function of Thiele modulus can show multiple
values or sharp changes for a small change in the modulus. In this case, single-valued approximations of the effectiveness factor may give rise
to large errors. Based on the two well-known asymptotes of the effectiveness factor for small and large Thiele moduli, we proposed equations
for the approximation of the effectiveness factor for up to three multiple steady states and two catalyst geometries of an innite slab and a
sphere. The proposed equations were demonstrated to be useful in estimating the effectiveness factor, particularly for the stable steady states,
and also in quickly estimating the Thiele modulus range where multiple effectiveness factors should be searched.
2007 Elsevier Ltd. All rights reserved.

Keywords: Effectiveness factor; Multiple steady states; Approximation; Reaction engineering; Simulation

1. Introduction et al., 2003; Gottifredi and Gonzo, 2005; Lee and Kim,
2006; Kim and Lee, 2006). All of these approximations are
The effectiveness factor is a correction factor for the reac- single-valued functions of the Thiele modulus, giving a sin-
tion rate in a porous catalyst that accounts for the effects of gle estimate of the effectiveness factor for a given Thiele
internal mass and heat transfer resistances. Formally, the esti- modulus, and therefore, are not applicable to the cases of
mation of the effectiveness factor involves solving a two-point multiple steady states. The effectiveness factor plot by the
boundary value problem which often requires numerical solu- approximations are all continuous and smooth functions of
tions. Efcient numerical methods (Kim and Lee, 2004; Lee the Thiele modulus and can be inaccurate when the effective-
and Kim, 2005) are available to obtain exact effectiveness fac- ness factor changes sharply for a small change in the Thiele
tors. In simulations of packed-bed reactors, however, the ef- modulus. The multiple steady states and a sharp change in
fectiveness factor has to be computed a large number of times the effectiveness factor can occur when the rst derivative of
for changing concentrations and temperature along the reactor. the reaction rate function with respect to the concentration is
This can be time-consuming if the desired accuracy of the sim- negative.
ulation is not excessively high. In this case, it is useful to have In the present study, we developed an approximation proce-
an approximation formula that allows for the rapid calculation dure to calculate easily the approximate values of the effec-
of the effectiveness factor. tiveness factors for up to three multiple steady states. Based
In literature, various approximations for the effectiveness on the well-known asymptotes of the effectiveness factor for
factor have been proposed (Wedel and Luss, 1980; Keegan small and large Thiele moduli, three equations for approximat-
ing the effectiveness factor for small, intermediate and large
Thiele moduli are presented for the catalyst geometries of an
Corresponding author. Tel.: +82 53 950 5617; fax: +82 53 950 6615. innite slab and a sphere. The proposed method can be applied
E-mail address: dhkim@knu.ac.kr (D.H. Kim). not only to estimate the effectiveness factors of the multiple

0009-2509/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2007.01.021
2180 J. Lee, D.H. Kim / Chemical Engineering Science 62 (2007) 2179 2186

steady states but also to quickly estimate the Thiele modulus point (P 1), as shown in Fig. 1. This represents stable solutions
range where multiple solutions should be searched. for a small . The segment L () is the effectiveness factor
between  = 2 and innity, where 2 is the Thiele modulus of
2. Effectiveness factors for multiple steady states the higher turning point (P 2). L () is also a stable solution.
Segment M () is the effectiveness factor between 1 and 2 .
The estimation of effectiveness factor involves the solution For the simulation of a reactor system, computations of S ()
of Eq. (1) in a porous catalyst (Aris, 1975): and L () are important, while computations of M () are
less important because the effectiveness factors correspond to
d2 y s dy unstable steady states which are not realizable. The functions
+ 2 f (y) = 0,
dx 2 x dx of S () and L () are single-valued and can be approximated
by single-valued equations of . To obtain them, we need to
dy(0)
y(1) = 1, = 0. (1) nd three points, P 1, P 2 and P 3, where P 1 and P 2 are the
dx lower and higher turning points, and P 3 is the point that shows
Here, y is the dimensionless concentration of the key component the maximum effectiveness factor, as can be seen in Fig. 1.
in the reaction, x is the dimensionless space variable in the To locate points P 1, P 2 and P 3, we consider a parametric
catalyst,  is the Thiele modulus and s is the shape factor of the description of Eq. (1). We rescaled the independent variable as
catalyst (s = 0 for an innite slab, and s = 2 for a sphere). The (Weisz and Hicks, 1962)
reaction rate function f (y) is normalized with respect to the
reaction rate at the external surface of the catalyst and hence, x = x. (3)
f (1) = 1. The effectiveness factor  is formally given by Then Eq. (1) becomes
s + 1 dy(1)
= . (2) d2 y s dy
2 dx + f (y) = 0, (4)
dx 2 x dx
The effectiveness factor is usually described as a function of dy(0)
the Thiele modulus . For some f (y) with negative f  (1), the = 0, y() = 1. (5)
dx
problem is that Eq. (1) can have multiple solutions and there-
fore, there can be multiple values of the effectiveness factor for For a given initial value y(0), Eq. (4) can be integrated until
a range of , as shown in Fig. 1. Also the effectiveness factor y = 1 to determine  which is x at y = 1 by Eq. (5). The initial
could change sharply as  increases (for example, cases C and value y(0) can be regarded as a new parameter that determines
D in Fig. 1). Such effectiveness factors cannot be described  and  as in the following:
with a single-valued function of .  = h1 (), (6)
In the case of multiple steady states, the effectiveness factor
plot can be divided into three segments, S (), M () and s + 1 dy(1) s + 1 dy()
= = = g1 (), (7)
L (). Segment S () is the effectiveness factor between =0 2 dx  dx
and 1 , where 1 is the Thiele modulus of the lower turning
where

P3  = 1 y(0). (8)

100 P2 A As can be seen in Fig. 2(a), the functions h1 () and g1 () are
B
both single-valued functions. In the case of multiple steady
states, h1 () increases rst, then passes through a local max-
imum and nally increases again as  1. P 1 and P 2 cor-
b=30, s=0 b=30, s=2 respond to the local maximum point and the local minimum
10
point of h1 () in Fig. 2(a), respectively.
C P3
As  increases, y(0) becomes either extremely small or zero.


D
P1
The above approach to locate points, P 2 and P 3, can fail or be-
b=15, s=2 come very difcult. To overcome this problem, a linear approx-
1 imation of f (y) can be adopted (Lee and Kim, 2005). Since
b=15, s=0 the rate expression f (y), other than a rst-order reaction, is in
fact an approximation of the real rate for y down to some value
near zero and the real reaction rate would eventually exhibit a
0.1 rst-order behavior as y 0, it may be reasonable to assume
0.1 1 10 f (y) as a linear function of y when y is small.

f (y) k y, 0 y ,
Fig. 1. Effectiveness factor plots for nonisothermal kinetics f (y) =
0.4b(1y)
(exp 1+0.4(1y) )y. k = f ()/. (9)
J. Lee, D.H. Kim / Chemical Engineering Science 62 (2007) 2179 2186 2181

We may choose  as the largest number such that 3. Effectiveness factor for small and large

   1
  
 1  The asymptotes of the effectiveness factor for small and large
 f (y) dy f ()  < 0.01 f (y) dy. (10)
 0 2  0  are well known. The perturbation equation for a small  (Lee
and Kim, 2006) is
Thus, the approximation by Eq. (9) does not incur errors larger
1
than 1% in terms of the integral 0 f (y) dy. If we assume y =  = 1 + a 1 2 + a 2 4 + ,
at x = , then
f  (1)
a1 = ,
y() = , (s + 1)(s + 3)
   
dy   k tanh( k ), s = 0, 2f  (1)2 + f  (1)
 =   (11) a2 = . (14)
dx x=   k / tanh( k ) /, s = 2. (s + 1)2 (s + 3)(s + 5)

Eq. (4) can be integrated with the initial condition at x = , and, for a large  , (Wedel and Luss, 1980; Kim and Lee, 2006)
Eq. (11), until y = 1 to obtain  and dy/dx at x = . This ap- it is
proach has been found useful in computing exact effectiveness b1 b2
factors, particularly for a large  (Lee and Kim, 2005). The = + 2 + ,
 
solution can be described as

 1
 = h2 (), (12)
b1 = (s + 1) 2 f () d,
0
s + 1 dy(1) s + 1 dy()
= = = g2 (). (13)  
2 dx  dx 
s(s + 1)2 1 y
b2 = 2 f () d dy. (15)
Fig. 2(b) shows the functions where P 2 corresponds to the local b1 0 0
minimum of h2 () and P 3 is the maximum of g2 ().
If we evaluate fully the functions h1 , h2 , g1 and g2 , exact ef- These are valid regardless of the existence of multiple steady
fectiveness factors as well as the turning points can be obtained states and can be utilized to obtain approximate interpolating
by the process. This may be a lengthy, time-consuming com- equations for S () and L ().
putation, particularly if the process has to be repeated many
times such as in the simulation of packed-bed reactors. The 4. Approximation of effectiveness factors
purpose of this study is to estimate the turning points and the
effectiveness factors by a simple procedure without having to 4.1. Estimation of point P1 and S ()
characterize fully those functions.
The perturbation equation for a small  is (Lee and Kim,
a b 2006)
1 1 1 (s + 5)f  (1)
= 2 4
P3 2(s + 1) 8(s + 1)2 (s + 3)
(s 2 + 14s + 61)f  (1)2 + (s 2 + 10s + 33)f  (1) 6
+ 
48(s + 1)3 (s + 3)(s + 5)
+ . (16)
P1
It can be rearranged as (Abramowitz and Stegun, 1972)
g2()/100
0.5 0.5 
h1()  = h1 () = 2(s + 1)(1 + c1  + c2 2 + ),
h2()
(s + 5)f  (1)
c1 = ,
4(s + 3)
P2
P2 (13s 3 + 179s 2 + 751s + 1161)f  (1)2
g1()/100 c2 =
96(s + 3)2 (s + 5)
0 0 (s 2 + 10s + 33)f  (1)
0 0.5
1-
1 0 0.5 1 . (17)
12(s + 3)(s + 5)
 
The series can be truncated as
Fig. 2. Plots of the function h1 (), g1 (), h2 () and g2 () for f (y) = 
12(1y)
(exp 1+0.4(1y) )y and s = 2.  = 2(s + 1)(1 + c1  + c2 2 ). (18)
2182 J. Lee, D.H. Kim / Chemical Engineering Science 62 (2007) 2179 2186

those for s = 2 (B and D in Fig. 1). Methods to nd P 2 and P 3


for the two geometries s = 0 and 2 are developed separately.

P3 4.2.1. An innite slab, s = 0


When s=0, the points P 2 and P 3 are very close and P 2=P 3
is assumed. Moreover they are not far from the asymptote for a
Eq. (18) 1
large , =b1 /=(1/) 2 0 f (y) dy. Since the effectiveness

0.5 1
factor for s = 0 is  = (1/) 2 y(0) f (y) dy, we may locate
g1()/200
2 such that
P1 1 1  12
h1() | 0 f (y) dy 12 f (y) dy| f (y) dy
1 = 0 1 < 2 . (22)
0 f (y) dy 0 f (y) dy
P2
Here, we may set 2 =0.1. The value 2 can be easily determined
1
0 during the integration of 0 f (y) dy to calculate b1 .
1 2
0 0.5 1 With 2 determined by Eq. (22), we integrate Eq. (4) and
 obtain
12(1y)
Fig. 3. Plots of h1 () and g1 () for f (y) = (exp 1+0.4(1y) )y and s = 0. 2 = h1 (2 ),
(23)
2 = g1 (2 ).
Fig. 3 also shows these points. Since b2 = 0 when s = 0, the
Its local maximum will approximate P 1 as most signicant term after the rst term in the series for large
, Eq. (15), is O(3 ). We may include a term of O(3 )

3c 9c12 20c2 to the asymptote  = b1 / to connect it smoothly to the point
1
if (9c12 20c2 ) > 0,
1 = 10c2 (19) (2 , 2 ), as well as to enhance approximation accuracy.

3c1

otherwise. b1 b3
10c2 L () = + 3,
 
By substituting 1 to the truncated series, we have an estimate
of the 1 of P 1 as b3 = (2 b1 /2 )32 , (24)
 for  [2 , ).
1 = 2(s + 1)1 (1 + c1 1 + c2 21 ). (20)

This point is shown in Fig. 3. Even in the absence of multiple 4.2.2. A sphere, s = 2
steady states, Eq. (20) can locate the point where the effective- As shown in Fig. 1, P 2 and P 3 are appreciably different and
ness factor plot changes its slope sharply (for example, case D need to be determined separately. First we nd the asymptote
in Fig. 1). By denition, (=1 y(0)) cannot be greater than 1 for h2 (). As  increases to innity, the problem becomes
and therefore, if 1 from Eq. (19) is greater than 1, it indicates d2 y
an absence of the steady-state multiplicity and that the effec- f (y) = 0,
dx 2
tiveness factor plot with respect to  is smooth. In this case,
recent approximations for the effectiveness factor can be used y() = ,
(Kim and Lee, 2006; Lee and Kim, 2006; Keegan et al., 2003). dy() 
For  [0, 1 ], we propose an approximation for S = f (), (25)
dx
a2 4 where  is determined by Eq. (10).
S () = 1 + a1 2 + . (21) This initial value problem can be integrated from y =  to 1
1 (a2 /a1 ) 2
as (see Appendix)
This can be obtained by applying the Shanks transformation  1
y=1 1
(Bender and Orszag, 1978) to the series, Eq. (14), since the 0 = x|
y= =  dy. (26)
y
transformation enhances the approximation accuracy consider-  dy + f ()
2  f (y)
ably when compared to the simple truncated series, S () =
1 + a1 2 + a2 4 . Since  = x at y = 1 and x =  at y = ,  is given by
 =  + 0 . (27)
4.2. Estimation of point P2, P3 and L ()
This is the asymptote of h2 () as  , shown in Fig. 4.
As shown in Fig. 1, the shape of the effectiveness factors near Before we estimate P 2, rst we estimate P 3 where d/
P 2 and P 3 for s = 0 (A and C in Fig. 1) is quite different from d = 0. From the analytic approximation of  = b1 /+
J. Lee, D.H. Kim / Chemical Engineering Science 62 (2007) 2179 2186 2183

1.5 f(y),s, :given

s=0 s=2
Calculate Calculate
f(1), f(1), f(1), f(1),
1 y
1 f(y)dy, 1 1 ~ ~
2 f(y)dydy
P3 0 f(y)dy, 0 0
g2()/100 0
2(Eq. (22))
h2()  (Eq. (10)), 0 (Eq. (26))

Eq. (31)
Calculate
1 (Eq. (19)), 1 (Eq. (20)) Calculate
0.5 S() (Eq. (21)) a1 (Eq. (19)), 1 (Eq. (20))
S() (Eq. (21))
P2 1<1 Otherwise
2 1<1 Otherwise
Solve the differential Eq.
0 Eq. (27) of Eq. (4) for 2 Calculate 3 (Eq.(28)).
0 Calculate
3 2 and 2 (Eq. (23)), 3>0 Otherwise
0 0.5 1 L(Eq.(24))
 Solve the differential Eq.
of Eq. (4) for =3.
12(1y) Calculate
Fig. 4. Plots of h2 () and g2 () for f (y) = (exp 1+0.4(1y) )y and s = 2.
3 and 3 (Eq. (29)),
L (Eq. (30))
2 (Eq. (32))
b2 /2 for a large ,  of P 3 can be approximated as 3 =
2b2 /b1 , since dd ( b1 + b22 ) = b12 2b32 . Substituting the 3
  
with  in Eq. (27), we have the corresponding 
2b2
3 = 0 . (28)
b1 Calculate
M() (Eq. (33) or Eq. (34)) Calculate () (Eq. (35))
With this , we can calculate the rened estimates of 3 and
3 of P 3.
Stop
3 = h2 (3 ),
Fig. 5. Computation owchart.
3 = g2 (3 ). (29)

To include this point, we add a term of O(3 ) to  = b1 / +


b2 /2 and obtain The point P 2 is shown in Fig. 4. Even in the absence of
multiple steady states, it is the point where the effectiveness
b1 b2 b3
L () = + 2 + 3, factor plot changes its slope sharply (for example, see case D in
   Fig. 1). By denition,  cannot be negative and therefore, if 2 is
negative or complex, it also indicates an absence of the steady-
b3 = (3 b1 /3 b2 /23 )33 . (30) state multiplicity and the effectiveness factor plot with respect
Now we have an additional point (3 , 3 ), calculated by to  becomes smooth. In this case, recent approximations for
Eq. (29), to improve the approximation of h2 (), Eq. (29). A the effectiveness factor can be used (Lee and Kim, 2005; Kim
rened approximation of h2 () is and Lee, 2006; Keegan et al., 2003).

d1
 =  + 0 + , 4.3. Estimation of M ()

d1 = (3 3 0 )3 . (31) When 1 of P 1 is greater than 3 of P 3, P 1 and P 2 are
connected via a linear line as
Eqs. (27) and (31) are compared in Fig. 4. The point P 2 cor-
1 2
responds to the local minimum of h2 () and an approximation M () = 1 + ( 1 ). (33)
of P 2 can 1  2
be obtained from the local minimum of Eq. (31),
2 = 1/ d1 . Substituting 2 into Eq. (31), we have
Otherwise, P 1 and P 3 are connected with a quadratic curve as

2 = 2 d1 + 0 . (32) 1 3
M () = 1 + ( 3 )2 . (34)
We set the valid region for Eq. (32) as  [2 , ). (1 3 )2
2184 J. Lee, D.H. Kim / Chemical Engineering Science 62 (2007) 2179 2186

In the absence of multiple steady states, 3 is greater than 1 r3 = (4a1 + 2r1 + r2 ),


and Eq. (34) is still effective. 
1 + 2r3 2 if r3 0,
2
q( ) = (35)
5. Numerical examples and discussion exp(r3 2 ) otherwise.

Fig. 5 summarizes the computational procedure of the pro- The proposed method was applied to a few nonisothermal
posed method for approximation of the effectiveness factor kinetics and Langmuir Hinselwood kinetics. For selected rate
when f  (1) is negative. Following the procedure, one can expressions, Table 1 lists the exact values and the approxima-
quickly estimate the Thiele modulus range where multiple tions of 1 , 2 and 3 determined by the proposed procedure.
effectiveness factors should be searched. For comparison, we The coefcients of S () and L () are also listed in the table.
use the approximation equation proposed recently by Kim and Figs. 6 and 7 compare plots of the exact effectiveness factor
Lee (2006) in the absence of multiple steady states. and the approximated effectiveness factors by the proposed
method and by Eq. (35) for an innite slab (s = 0). Figs. 8
=
1
, and 9 compare the plots for a sphere (s = 2). It can be seen that
the proposed method can trace the effectiveness factor well and
2
r1  + 2
r2  + q( ) 2
that this method is superior to a single-valued approximation
such as Eq. (35), when there are multiple steady states or when
r1 = 1/b12 , the slope of the effectiveness factor plot is stiff. It is, however,
noted that approximated effectiveness factors can be inaccurate
r2 = 4b22 /b16 , in a close neighbor of 1 and 2 , where a small change in 

Table 1
Computation results

s f (y) 1 2 3 S () L ()


(1 , ER)a (2 , ER)a (3 , ER)a
 
6(1 y)
0 exp y 0.4470 0.5083 0.5083 a1 = 1.6667 b1 = 3.0880
1 + 0.4(1 y)
(0.4556, (0.4507, (0.4889, a2 = 4.6133 b2 = 0
  0.019) 0.128) 0.040) b3 = 0.0407
12(1 y)
exp y 0.3032 0.0927 0.0927 a1 = 3.6666 b1 = 14.818
1 + 0.4(1 y)
(0.2895, (0.0911, (0.0938, a2 = 23.492 b2 = 0
0.047) 0.018) 0.012) b3 = 0.0066
162
y 0.8394 0.7668 0.7668 a1 = 0.2917 b1 = 2.0435
(1 + 15y)2
(0.8209, (0.7664, (0.7718, a2 = 0.2036 b2 = 0
0.023) 0.001) 0.006) b3 = 0.0616
113
y 0.6383 0.4127 0.4127 a1 = 0.5758 b1 = 3.3166
(1 + 11y)3
(0.6374, (0.4110, (0.4113, a2 = 0.6953 b2 = 0
0.001) 0.004) 0.003) b3 = 0.0286
 
6(1 y)
2 exp y 0.8297b 1.0312b 1.1137 a1 = 0.3333 b1 = 9.2640
1 + 0.4(1 y)
(1.1856, a2 = 0.2197 b2 = 4.2842
  0.061) b3 = 0.7574
12(1 y)
exp y 0.5730 0.2150 0.2545 a1 = 0.7333 b1 = 44.454
1 + 0.4(1 y)
(0.5645, (0.2204, (0.3014, a2 = 1.1187 b2 = 4.9413
0.015) 0.025) 0.156) b3 = 0.2804
162
y 1.5931 1.6732 1.7878 a1 = 0.0583 b1 = 6.1305
(1 + 15y)2
(1.5712, (1.5623, (1.9034, a2 = 0.0097 b2 = 4.5378
0.014) 0.071) 0.061) b3 = 1.3110
113
y 1.2199 1.0081 1.1675 a1 = 0.1152 b1 = 9.9499
(1 + 10y)3
(1.2282, (1.0198, (1.3288, a2 = 0.0331 b2 = 5.0174
0.007) 0.011) 0.121) b3 = 1.2424

value, ER = |(Estimate Exact)/Exact|).


a (Exact
bP 1and P 2 do not exist due to the absence of multiple steady states (curve D in Fig. 1). The estimated 1 , 2 , and 3 indicate the  region where the
effectiveness factor changes sharply.
J. Lee, D.H. Kim / Chemical Engineering Science 62 (2007) 2179 2186 2185

1000
Exact Exact
Proposed Proposed
Eq. (35) Eq.(35)
100
100
b=30
b=30

10


10


b=15
1 1
b=15

0.1 0.1
0.01 0.1 1 10 0.01 0.1 1 10
 

Fig. 6. Effectiveness factor plots for nonisothermal kinetics, f (y) = Fig. 8. Effectiveness factor plots for nonisothermal kinetics, f (y) =
0.4b(1y)
0.4b(1y)
(exp 1+0.4(1y) )y and s = 0. (exp 1+0.4(1y) )y and s = 2.

10 10

f(y)=113y/(1+10y)3 f(y)=113y/(1+10y)3

1 1



f(y)=162y/(1+15y)2
f(y)=162y/(1+15y)2
Exact
Exact
Proposed
Proposed
Eq. (35) Eq.(35)

0.1 0.1
0.01 0.1 1 10 0.1 1 10
 

Fig. 7. Effectiveness factor plots for Langmuir Hinselwood kinetics and s =0. Fig. 9. Effectiveness factor plots for Langmuir Hinselwood kinetics and s =2.

can result in a very large variation of . Except for these tiny


regions of , the approximations are highly accurate within a give accurate estimates of the effectiveness factors of the sta-
few percent of the exact values. ble steady states. The formulas also enabled a quick estimation
of the Thiele modulus range, in which multiple values of the
6. Conclusion effectiveness factor should be searched. Compared to the exact
methods, the present method is quick and efcient and is able
For some reaction rate functions with negative derivatives at to reduce signicantly the amount of computations in simula-
the catalyst surface, the effectiveness factor functions in terms tions of packed-bed reactors.
of the Thiele modulus can show sharp changes or multiple val-
ues. In such cases, existing approximation formulas are unable
to provide reasonably accurate estimates of the effectiveness Notation
factor. By extending two asymptotes of the effectiveness fac-
tor for small and large Thiele moduli, we developed approx- a1 , a2 coefcients in a series expansion of  around
imation equations of the effectiveness factor for up to three  = 0 (Eq. (14))
steady states and two catalyst geometries of an innite slab b1 , b2 coefcients in a series expansion of  around an
and a sphere. The proposed formulas were demonstrated to innite  (Eq. (15))
2186 J. Lee, D.H. Kim / Chemical Engineering Science 62 (2007) 2179 2186

c1 , c2 coefcients in Eq. (17) Integrating from y =  to y, we have


d1 coefcient in Eq. (31)  y
f (y) normalized reaction rate function (f (1) = 1) p 2 2 = 2 dy
f (y) (A.3)
g1 () function between effectiveness factor and  = 
1 y(0) and
g2 () function between effectiveness factor and   
h1 () function between Thiele modulus and  = 1 dy y

y(0) p= = 2 dy + 2 .
f (y) (A.4)
dx 
h2 () function between Thiele modulus and 
k f ()/ Hence
p dy/dx   
P 1, turning points where the shape of effectiveness dy  1
 = 2 dy + 2 .
f (y) (A.5)
P 2, factor plot changes dx y=1 
P3
From (A.4), we have
q(2 ) function for Eq. (35)
 
r1 , r2 , r3 coefcients for Eq. (35) dx y
s shape factor (s = 0 for an innite slab, s = 2 =1 2 dy + 2 .
f (y) (A.6)
dy 
for a sphere)
x, x dimensionless space variable and its scaled Integrating from y =  to 1,
one(x = x), respectively  1
y dimensionless concentration of the key com- 1
x|y=1 =  dy. (A.7)
ponent  y
dy + 2
2  f (y)
Greek letters
References
 1 y(0)
1 , 2  at P 1 and P 2, respectively Abramowitz, M., Stegun, I., 1972. Handbook of Mathematical Functions.
2 a small constant Dover Publication, New York.
 effectiveness factor Aris, R., 1975. The Mathematical Theory of Diffusion and Reaction in
S (), effectiveness factor for small, medium and Permeable Catalysts, The Theory of the Steady State, vol. 1. Clarendon,
Oxford.
M (), large values of Thiele modulus, respectively
Bender, C.M., Orszag, S.A., 1978. Advanced Mathematical Methods for
L () Scientists and Engineers. McGraw-Hill, New York.
1 ,  2 ,  3  at P 1, P 2 and P 3, respectively Gottifredi, J.C., Gonzo, E.E., 2005. Approximate expression for the
 a point in x effectiveness factor estimation and a simple numerical method for
 2 , 3  for P 2 and P 3, respectively concentration prole calculation in porous catalyst. Chemical Engineering
Journal 109, 8387.
 Thiele modulus
Keegan, S.D., Mariani, N.J., Bressa, S.P., Mazza, G.D., Bareto, G.F., 2003.
0  given by Eq. (26) Approximation of the effectiveness factor in catalyst pellets. Chemical
1 , 2 , 3  at P 1, P 2 and P 3, respectively Engineering Journal 94, 107112.
 a small constant satisfying Eq. (10) Kim, D.H., Lee, J., 2004. A robust iterative method of computing effectiveness
factors in porous catalysts. Chemical Engineering Science 59, 22532263.
Kim, D.H., Lee, J., 2006. A simple formula for estimation of the effectiveness
factor in porous catalysts. A.I.Ch.E. Journal, accepted for publication.
Appendix A Lee, J., Kim, D.H., 2005. An improved shooting method for computation of
effectiveness factors in porous catalysts. Chemical Engineering Science
60, 55695573.
Consider a differential equation Lee, J., Kim, D.H., 2006. An approximation method of the effectiveness
factor in porous catalysts. Chemical Engineering Science 61, 51275136.
Wedel, S., Luss, D., 1980. A rational approximation of the effectiveness
d2 y
f (y) = 0, factor. Chemical Engineering Communication 7, 245259.
dx Weisz, P.B., Hicks, J.S., 1962. The behavior of porous catalyst particles in
y(0) = , (A.1) view of internal mass and heat diffusion effects. Chemical Engineering
dy(0) Science 17, 265275.
= .
dx

Let p = dy/dx. Then the above differential equation becomes

dp 2
= 2f (y). (A.2)
dy