Chemical Engineering Science 57 (2002) 1451 1457

www.elsevier.com/locate/ces

An approximate model for di#usion and reaction in a porous pellet

Miros law K. Szukiewicz
Department of Chemical Engineering and Process Control, Rzeszow University of Technology, Al. Powstancow Warszawy 6,
35-959 Rzeszow, Poland
Received 23 September 2000; received in revised form 9 November 2001; accepted 20 November 2001

Abstract

A method of derivation of linear driving force approximation for di#usion and reaction processes in porous catalysts based on Laplace
Carson transform has been presented. The approximate model for any type of kinetic expression has been derived. Accuracy of developed
model is good, especially in the range of small and intermediate Thiele modulus values that is used most often in cases of practice.
This approximation yields a substantial simpli4cation of analysis and computations and does not require any iterative and trial-and-error
calculations. ? 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Modelling; Porous media; Di#usion; Linear driving-force approximation

1. Introduction equations that approximate a mass balance in the porous

particle has been found (Kim, 1989; Goto & Hirose, 1993;
Fixed-bed reactors are commonly used in industrial Szukiewicz, 2000). Models reported so far in the literature
practice for heterogeneous catalysis processes. A transient concern only 4rst-order reactions. Many catalytic reactions
heterogeneous model of 4xed-bed reactor is described by are not in this category and it is the reason why some e#orts
partial di#erential equation (PDE) both for :uid and for have been made in order to obtain an approximate formula
catalyst pellet. The real di;culty in a solution is the reason with broader validity range. Accuracy of developed model
why this model, despite its quite good accuracy, is not will- is good, especially in the range of small and intermediate
ingly used for modelling. The widely reported way to avoid Thiele modulus values. The resulting model is much more
this drawback is to use an e#ectiveness factor concept. It tractable for analysis and analytical or numerical solution
reduces equations set of the model and makes the solution than the former PDE.
easier to obtain. Unfortunately, for most cases, 4nding the
proper value of the mentioned factor is di;cult and=or
lengthy task (see also Szukiewicz, Kaczmarski, & Petrus, 2. Theory
1998), and this limits its application.
Another way for simpli4cation of a model is replacing of Presented here is the derivation of approximate model of
PDE for mass balance in the pellet by a proper ordinary dif- reaction and di#usion process based on the method used
ferential equation (ODE). The ODE based on average con- for linear type of kinetic equation described in detail by
centration in the pellet is usually called an approximate Szukiewicz (2000).
model. Various approximate models have been reported Transient di#usion and reaction in a porous spherical par-
for di#usion and adsorption processes. They di#er from one ticle can be described by:
another with respect to accuracy and validity range. One
2 
@c @ c 2 @c
can 4nd more information e.g., in the papers by Goto and = +  2 RA ; (1)
@ @x2 x @x
Hirose (1993), and Zhang and Ritter (1997). To make use
of approximate models idea for di#usion and chemical re- IC:
action processes other models should be developed. In dif-
 = 0; c(x; 0) = cin ; (2)
fusion and reaction process 4elds, only a small number of

BC:
Tel.: +48-17-865-1216.
E-mail address: ichms@prz.rzeszow.pl (M. K. Szukiewicz).  0; c(0; ) = extremum; (3)

0009-2509/02/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 2 ) 0 0 0 5 5 - 6
1452 M. K. Szukiewicz / Chemical Engineering Science 57 (2002) 14511457

c(1; ) = cs : (4) The LaplaceCarson transform converts this model into

The model is in dimensionless form; de4nitions of dimen- @2 Q

pQ pxcin = x2 RA; s + 2 RA; c (xcs Q); (15)
sionless variables and parameters are presented in notation. @x2
Note that all concentrations and other dimensionless param- BC:
eters are referred to the largest concentration in the pellet
(not surface concentration). It is a convenient convention if  0; Q(0; p) = 0; (16)
a surface concentration can vary with time.
This model and further the method of approximate for- Q(1; p) = cs ; (17)
mula derivation presented here are valid for any type of ki-
netic rate equation, moreover, here the attention will be fo- where
cused on two most important points from practical point of 
view of kinetics: Q=p qep d: (18)
0
power-law type All complex functions corresponding to real functions in
RA = c :n
(5) LaplaceCarson transform will be de4ned analogously and
marked by capital letter.
LangmuirHinshelwood type The solution of Eq. (15) with corresponding boundary
(1 + X )n c condition is
RA = : (6)

(1 + Xc)n 2 RA; s 2 RA; c cs pcin
Q = cs +
2 RA; c + p
For the latter equation, multiple steady-state solutions can 
exist for n 1 and su;ciently large X (Aris, 1975). In the sinh(x 2 RA; c + p)
following, the study will limit to the range in which multiple 
sinh( 2 RA; c + p)
steady-state solutions cannot exist.
To derive linear driving force (LDF) formula a kinetic rate 2 RA; s 2 RA; c cs pcin
x : (19)
should be linearized, e.g. using Taylors series expansion 2 RA; c + p
limited to the 4rst derivatives only.
 To simplify the notation in the following text, a parameter
@RA  
RA = RA; s + (c cs ): (7)
@c  c=cs  = 2 RA; c + p (20)
Substitution of Eq. (7) in Eq. (1) gives will be used. The average concentration can be evaluated as

2   1
@c @ c 2 @c
= + 2 RA; s + 2 RA; c (cs c); (8) cav = 3 cx2 d x: (21)
@ @x2 x @x
0
where Substitution of Eqs. (10) and (19) in Eq. (21) gives

@RA 

RA; c = (9) 2 RA; s 2 RA; c cs pcin
@c c=cs Cav = 3 cs +
2
IC and BC are the same.
 cosh  sinh  2 RA; s 2 cs pcin
It is advantageous to substitute : (22)
2 sinh  2
q = xc (10)
Eq. (22) can be rearranged into
in Eqs. (8) and (2) (4) to get

pcin 2 RA; s 2 RA; c cs
Cav 2 +
@q @2 q  2
= 2 x2 RA; s + 2 RA; c (xcs q); (11)
@ @x
2 sinh  2 RA; s 2 RA; c cs
IC:
3( cosh  sinh ) 2
 = 0; q(x; 0) = xcin ; (12) pcin
+ = cs : (23)
BC: 2
Successively rearranging both sides of the latter equation by:
 0; q(0; ) = 0; (13)
subtracting Cav ,
q(1; ) = cs : (14) multiplying by 3  cosh sinh 
2 sinh  ,
 M. K. Szukiewicz / Chemical Engineering Science 57 (2002) 14511457 1453

multiplying by 2 (1 3  cosh sinh  1

2 sinh  ) , and The 4rst of approximate models (given by Eqs. (29) and
2
subtracting  Cav (30)) is linear in contrast to the second (described by Eqs.
(32) and (30)). For linear kinetic rate (RA = c) both mod-
gives els give LDF formula for linear kinetic rate presented by
pCav pcin = 3p (cs Cav ) 2 RA; s Szukiewicz (2000). Moreover, if RA; c 0, then the term 
+ 2 RA; c (cs Cav ); (24) is analogously expressed for linearand non-linear rate, but
Thiele modulus  is replaced by 2 RA; c . Analyzing the
where approximate models we conclude: (i) the 4rst model is sim-
( cosh  sinh )2 pler for solving as linear (even analytical solution is easy to
p = : (25) obtain), (ii) the second, non-linear model, generally, can be
2 sinh  3( cosh  sinh )
solved only numerically, (iii) all individual terms of the sec-
Eq. (24) should be treated as complex domain form of ond model have physical meaning (i.e. accumulation, rate
searched LDF formula. The analysis leads to the conclusion of mass transfer, reaction rate), (iv) accuracy of non-linear
that de4ning of real domain LDF approximation on the ba- LDF model will be in all likelihood higher, because the for-
sis of Eq. (24) is easy for constant value of p . Constant mer model (1) (4) is also non-linear.
value of p is expected as  approaches in4nity (or p ap-
proaches 0). Until now the reasoning was the same as for
the linear model presented by Szukiewicz (2000). But for 3. Results and discussion
considered kinetic rates, a value of the derivative RA; c can
be positive, equal to 0, or even negative. It is of no signif- The exact model was reduced to a set of ODEs by apply-
icance for complex domain equation (24) but real domain ing orthogonal collocation method and the resulting set of
approximate models will di#er: equations is solved using procedure LSODA (more infor-
mation on the procedure: www.netlib.org). Approximate
for RA; c 0
  
2 RA; c cosh 2 RA; c sinh 2 RA; c )(2 RA; c )
(
=     ; (26)
(2 RA; c ) sinh 2 RA; c 3( 2 RA; c cosh 2 RA; c sinh 2 RA; c )
for RA; c = 0
models were solved using the procedure LSODA, as
 = 5; (27) well.
for RA; c 0
  
2 RA; c cos 2 RA; c sin 2 RA; c )(2 RA; c )
(
=     ; (28)
(2 RA; c ) sin 2 RA; c 3( 2 RA; c cos 2 RA; c sin 2 RA; c )
provided that p is constant, the inverse transform of eq.
The accuracy of proposed LDF formulas was tested in
(24) gives
two steps for wide range of Thiele modulus values:
@cav
= 3(cs cav ) 2 RA; s unit step change in surface concentration
@
+ 2 RA; c (cs cav ); (29) cs = 1; (33)
IC: time-dependent surface concentration
 = 0; cav = cin : (30) cs = c0 + A sin(!): (34)

It is easy to show that initial condition (30) corresponds to The 4rst of the mentioned tests is standard test for approxi-
initial condition (2). mate equations.
Eq. (29) is LDF approximation of transient di#usion and Tests have been made for following values of kinetic rate
reaction in a porous spherical particle, but referring to Eqs. parameters:
(7) and (9), we conclude that
1. n = [0:5; 0:7; 1:3; 1:5; 2:0] for power-law type,
2 RA; s 2 RA; c (cs cav )
=  2 RA (31) 2. n = [0:5; 1:0; 1:5; 2:0] and X = [0:1; 0:5; 0:7; 1:0; 2:0; 5:0]
for LangmuirHinshelwood type.
and LDF formula can be written as
Errors have been calculated as
@cav
= 3(cs cav ) 2 RA (32)  = (cex capp )=cex : (35)
@
with the same IC (Eq. (30)). Additionally, cin = 0 was assumed.
1454 M. K. Szukiewicz / Chemical Engineering Science 57 (2002) 14511457

1.0

= 1.0
0.8 = 2.0

average concentration, cav

= 3.0
0.6
= 5.0

0.4

exact solution
0.2 non-linear LDF
linear LDF

0.0
0.0 0.1 0.2 0.3 0.4 0.5
time,

Fig. 1. Exact solution vs. LDF formulas for unit step change in surface concentration for power-law kinetic type, n = 1:5.

1.0

= 1.0
0.8
average concentration, c

= 2.0
0.6

= 3.0
0.4

exact solution
0.2 non-linear LDF = 5.0
linear LDF

0.0
0.0 0.1 0.2 0.3 0.4 0.5
time,

Fig. 2. Exact solution vs. LDF formulas for unit step change in surface concentration for LangmuirHinshelwood kinetic, n = 1:5; X = 1:0.

In derivation of the approximate model, linearized ver-
sion of a kinetic rate equation has been used. It is the reason,
why LDF formula di#erently approximates an exact model.
The results obtained for point #1 show that in all cases,
for small values of  di#erences between exact solution and
LDF formulas are relatively large and they decrease as time
passes. Furthermore, the non-linear LDF formula (Eq. (32))
approximates better the former model than linear LDF one
(Eq. (29)). Because of that in the following text 4rst and
foremost non-linear approximate model will be considered.
Such results could be expectedsee the previous section.
Moreover higher the value of Thiele modulus, lower is the
accuracy of both approximate methods, but accuracy falls
unexpectedly in various ways for di#erent values of parame-
ters of kinetic rates. However, in all cases the non-linear LDF
model up to  = 3:0 and linear one up to  = 2:5 show very
good compatibility (maximum error at steady state insigni4-
cantly exceeds 6% and in most circumstances is below 3%).
Especially for the non-linear LDF model, good accuracy is
preserved in many cases for signi4cantly higher values of .
To illustrate these observations, some results of calculations
are presented in Fig. 1 (power-law kinetic rate expression)
and in Fig. 2 (LangmuirHinshelwood type kinetic rate ex-
pression). For example, in Fig. 1 errors at steady state for
 = 3:0 are about 1.4% and 2.5% for non-linear LDF for-
mula and linear LDF one, respectively; in Fig. 2, errors for
the same value of Thiele modulus are about 8% and 15%, re-
spectively. Error for linear LDF model for =5:0 in the 4rst
case is about 10%, in the second case is so large (more than
100%) that an appropriate curve was removed from Fig. 2.
 M. K. Szukiewicz / Chemical Engineering Science 57 (2002) 14511457 1455

Table 1
Deviations among the non-linear approximate solution and exact solution 10
at steady state for  = 2:5 for power-law and LangmuirHinshelwood
kinetic rates
8
n X @RA =@c|c=1  (%)

0.5 0.5 1.0 6

m
0.7 0.7 0.6
1.0 1.0 0.0
1.3 1.3 0.5 4

1.5 1.5 0.7

2.0 2.0 1.2
2

0.5 0.1 0.954 0.1

0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
0.5 0.5 0.833 0.5
0.5 0.7 0.794 0.6
ll
0.5 1.0 0.750 0.7
0.5 2.0 0.666 0.9 Fig. 3. Values of Thiele modulus for which the error does exceed 6%
0.5 5.0 0.583 1.1 vs. .

1.0 0.1 0.909 0.3

1.0 0.5 0.666 1.0
Fig. 3. The curve de4nes Thiele modulus values for which
1.0 0.7 0.588 1.3
1.0 1.0 0.500 1.7 the error is about 6%. For di#erent kinetic rates, deviations
1.0 2.0 0.333 2.5 in the value of m was about some tenths. These di#erences
1.0 5.0 0.167 3.1 decreased with increase in ||. For || 6 0:1 value of m
always exceeds 10, but its value depends on kinetic rate in
1.5 0.1 0.864 0.4
a signi4cant way.
1.5 0.5 0.500 1.8
1.5 0.7 0.382 2.4 As was observed previously, derived LDF formulas are
1.5 1.0 0.250 3.2 long time approximations that approximate well the ex-
1.5 2.0 0.000 5.5 act solution for su;ciently long times. In already cited
1.5 5.0 0.250 10.5 Szukiewicz (2000), following inequality has been proposed
to determine the time for which the approximate model and
2.0 0.1 0.818 0.6
2.0 0.5 0.333 2.8 the exact one give practically the same results:
2.0 0.7 0.176 4.0
2.0 1.0 0.000 5.8
5
 : (37)
2.0 2.0 0.333 13.8 3 + 2
2.0 5.0 0.667 67.0
In my opinion, this inequality is valid also for kinetic rates
considered here, with one reservation, the accuracy should
be su;cient.
For practical purposes it is important to de4ne a criterion
Finally, in Fig. 4 results for time-dependent surface
of evaluation whether LDF formula can be used with su;-
concentration (point #2 of tests) are presented. Proposed
ciently small error for speci4c kinetic rate and reactant con-
non-linear LDF approximation gives the average concentra-
centration. In Table 1 deviations between approximate and
tion changes with high accuracy for this case also. Even for
exact solutions for the same  value and di#erent kinetic
the highest tested frequency (! = 20), the results are satis-
rates are given. The clear relationship between @RA =@c|c=1
factory. The only shortcoming is the small shift in time for
and accuracy is observed for all cases. The larger the value
this case. For other values of parameters and types of kinetic
of  (de4ned below), the larger is the error in calculations.
equation, no signi4cant di#erences have been observed.
Moreover, the sign of  is the same as the sign of the error:
 It is not of any signi4cance that application of LDF for-
@RA  mula accelerates calculation over 20 times (on average).
=1 : (36)
@c c=1 The above discussion concerns also linear LDF model,
but the range of validity is, of course, narrower.
Thus  determines degree of non-linearity of speci4ed ki-
netic rate and smaller the value of , the broader is the
range of validity of approximate model. Furthermore, on
the basis of parameter  it is easy to predict a closeness 4. Conclusions
of approximate solution. For || 0:1, regardless of kinetic
equation type and kinetic parameter values, one can de4ne The non-linear LDF approximation of di#usion with the
maximal value of Thiele modulus for which the deviation at chemical reaction processes (e.g. heterogeneous catalysis)
steady state does not exceed the assumed level, as shown in can be recommended for various non-linear kinetic rates
1456 M. K. Szukiewicz / Chemical Engineering Science 57 (2002) 14511457

0.6

0.5 = 1

average concentration, cav

0.4

= 20
0.3

exact solution
0.2
non-linear LDF
n=1.5, X=0.1, =2.0
0.1 cs=0.5+0.5sin

0.0
0.0 0.4 0.8 1.2 1.6 2.0
time,

Fig. 4. Exact solution vs. non-linear LDF formula for sinusoidal changes in the surface concentration for LangmuirHinshelwood kinetic rate.

and for broad range of parameters values. In derivation of cs surface concentration of

approximate model, linearized version of a kinetic rate equa- component A
tion has been used. It is the reason, why LDF formula better Def ; A e#ective di#usity of
or di#erently approximates an exact model. The good com- component A
patibility of results has been observed for any concerned n parameter in Eqs. (5)
kinetic equation for small and intermediate Thiele modulus and (6)
values. For larger , accuracy in many cases is satisfac- p complex variable
tory. The proposed simple criterion can be used to evaluate q function de4ned by Eq.
chances on successful application of LDF model. (10)
The formula has been derived as a long time ap- r position in a pellet
proximation and, its accuracy rises for longer times. The rA reaction rate
inequality that de4nes validity range of the formula is R radius of a pellet, m
proposed. RA reaction rate, dimen-
And 4nally, the application of approximate formula sim- sionless
pli4es greatly the model solution and greatly accelerates RA; s reaction rate on pellet
calculations, too. surface, dimensionless
RA; c parameter de4ned by
Eq. (9)
t time, s
Notation x = r=R position in a pellet, di-
mensionless
A coe;cient in Eq. (32) X parameter in Eq. (6)
c concentration of com-  coe;cient in Eq. (10)
ponent A  relative error
cA; max largest concentration of  degree of non-linearity
component A of kinetic rate, Eq. (34)
capp ; cex general notation for re-  parameter de4ned by
sults obtained from ap- Eq. (20)
proximate and exact  = tDef ; A =R2 time, dimensionless
model, respectively  variable
cav volume averaged con- ! coe;cient in Eq. (32)
centration of compo- = Thiele modulus
nent A R rA (cA; max )=(Def ; A cA; max )
cin initial concentration of m Thiele modulus values
component A for which the error is
c0 coe;cient in Eq. (32) about 6%
 M. K. Szukiewicz / Chemical Engineering Science 57 (2002) 14511457 1457

 coe;cient de4ned by Goto, M., & Hirose, T. (1993). Approximate rate equation for intraparticle
Eqs. (26) (28) di#usion with or without reaction. Chemical Engineering Science,
48(10), 19121915.
p coe;cient de4ned by
Kim, D. H. (1989). Linear driving force formulas for di#usion and reaction
Eq. (25) in porous catalysts. A.I.Ch.E. Journal, 35, 343346.
Szukiewicz, M. K. (2000). New approximate model for di#usion and
The complex functions corresponding to the real functions reaction in a porous catalyst. A.I.Ch.E. Journal, 46, 661665.
in the LaplaceCarson transform are described by capital Szukiewicz, M. K., Kaczmarski, K., & Petrus, R. (1998). Modelling
of 4xed-bed reactor: Two models of industrial reactor for selective
letters.
hydrogenation of acetylene. Chemical Engineering Science, 53(1),
149155.
Zhang, R., & Ritter, J. A. (1997). New approximate model for nonlinear
References adsorption and di#usion in a single particle. Chemical Engineering
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Aris, R. (1975). The mathematical theory of di5usion and reaction in
permeable catalysts, Vol. 1. Oxford: Clarendon Press.