CHEMICAL AND PROCESS ENGINEERING

29, 883–893 (2008)

ROMAN PETRUS, MIROSŁAW K. SZUKIEWICZ*

RELATIVE IMPORTANCE OF HEAT RESISTANCES IN PARTIALLY

IMPREGNATED OR DEACTIVATED SOLID CATALYSTS

Rzeszów University of Technology, Department of Chemical and Process Engineering

al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland

Criteria for isothermal conditions of a reaction with deactivation processes for catalyst pellets have
been derived using approximate concentrations of reagents and temperature profiles. The procedure of
their obtaining is presented for the reaction νAA → νRR and for a power-law type of the kinetic equation.
The method can be easily adapted to other type of kinetic rate equation and/or more complicated reaction
schemes.

Sformułowano kryteria izotermiczności procesów reakcyjnych z dezaktywacją ziaren katalizatora.

Skorzystano w tym celu z przybliżonych profili stężenia i temperatury. Sposób postępowania przedsta-
wiono na przykładzie reakcji typu νAA → νRR dla równania kinetycznego typu potęgowego. Przedsta-
wioną procedurę można łatwo zaadaptować do innego typu równania kinetycznego lub bardziej skompli-
kowanego schematu reakcji.

1. INTRODUCTION

Theoretical and experimental investigations of most of processes of heterogeneous

catalysis are very complex. Deactivation of the catalyst complicates the matter even
more. Diagnostic criteria give quick estimates to questions concerning the importance
of transport limitation, temperature gradients, etc. They improve understanding of
a chemical process at little expense and focus researcher’s attention on the most im-
portant problems. It should be pointed out that the diagnostic criteria – the well-known
“old” method of analysis harmonize well with the new ones such as mathematical
analysis, modelling, simulations, etc. All of these methods require model developing.
The set of equation that comprise the model is only an approximation of a real proc-
ess. “Good” model should be simple, accurate and easy-to-solve. Hardly ever models
meet all these requirements. The researcher normally must seek a compromise involv-
___________
*
Corresponding author, e-mail: ichms@prz.edu.pl
884 R. PETRUS, M. K. SZUKIEWICZ

ing the cost of obtaining the model. Costs of the model include the time and effort
required to derive it, costs of an experiment (e.g., determining values of some model
parameters), cost of verification and, finally, cost of calculations. These important
considerations should be related to the level of physical and chemical details given in
the model and the expected benefits to be derived from its use. Simplification of the
models results in reduction of expenses. This is, in fact, obvious that simplification
can dramatically drop down accuracy of the model (the well-known example in ca-
talysis is a pseudohomogeneous model of a heterogeneous reactor). Criteria can be
utilized as the safe method of simplification (without significant dropping down the
accuracy). This paper deals with criteria concerning partially deactivated catalyst pel-
lets or pellets with a non-active outer shell. These cases, often recognized in practice,
have been investigated both theoretically and experimentally. In the paper given by
Morbidelli and Servida [1] which deals with optimal catalyst activity profiles one can
find the review of relevant papers. Although the catalyst deactivation process often
appears in practice, the criteria concerning deactivated processes have not been pub-
lished. The only exception is the criterion of isothermality of deactivated cylindrical
pellet given by Lee [2]. To fill this gap, in this paper an assembled kit of criteria in-
cluding isothermal conditions and/or absence of diffusion resistances in catalytic reac-
tion with deactivation for planar, cylindrical and sphere catalyst pellet is presented.
Derivation of the criteria is based on the method presented by Petrus and Szukiewicz [3].

2. THEORY

Consider a case, when an active material is supported under a non-active shell or

the outer shell of a catalyst pellet was deactivated in the process. The steady state mass
and heat balances for one-component single non-isothermal reaction
ν AA →ν R R (1)
can be expressed in a dimensionless form as follows
1 d ⎛ m dc A ⎞
⎟ − Φ R( cA ,ϕ ) = 0
2
m ⎜X (2)
X dX ⎝ dX ⎠

1 d ⎛ m dϕ ⎞
⎟ + β 0Φ R( cA ,ϕ ) = 0
2
m ⎜X (3)
X dX ⎝ dX ⎠
with boundary conditions
dcA dϕ
= 0, =0 at X =0 (4)
dX dX
 Heat resistances in partially impregnated or deactivated solid catalysts 885

dc A dc A dϕ dϕ
D = , L = (5)
dX X =S − dX X =S + dX X =S − dX X =S +

dcA dϕ
= Sh∗ (1 − cAs ) , = Nu ∗ (1 − ϕs ) at x =1 (6)
dX dX
R(cA ,ϕ ) is the kinetic expression and it is equal to 0 for the non-active outer shell, D is
the ratio of the effective diffusion coefficients of a component A in an active layer and
in a non-active one, L is the ratio of effective heat conductivities in these layers, S is
dimensionless location of a non-active shell. It has been previously discussed in de-
tails [3] that the aim of this work can be achieved without finding an exact solution of
the model but by assuming parabolic profiles of the reagent and/or temperature. The
profiles for small and intermediate diffusion resistances, i.e. for 0 < X < S are given
by:
• for m ≠ 1
Ψ 0A ⎡ 1 D 1 ⎤
C (Y ) = 1 − ⎢ +
m + 1 ⎣ Sh m − 1
*
S 1−m − 1 +
2S
(
1− Y 2 ⎥
⎦
) ( ) (7)

Ψ 0A ⎡ 1 L 1 ⎤
ϕ (Y ) = 1 + β 0 A ⎢ +
m + 1 ⎣ Nu a − 1
*
S 1−m − 1 +
2S
(
1− Y 2 ⎥
⎦
) ( ) (8)

• for m = 1
Ψ 0A ⎡ 1 1 ⎤
C (Y ) = 1 − ⎢
2 ⎣ Sh *
− D ln S +
2S
1− Y 2 ⎥
⎦
( ) (9)

Ψ 0A ⎡ 1 1 ⎤
ϕ (Y ) = 1 + β0 A ⎢
2 ⎣ Nu *
− L ln S +
2S
1−Y 2 ⎥
⎦
( ) (10)

where Y = X/S. The profiles (7)–(10) are valid if the reaction zone is the same as the
active zone of the pellet, i.e.:

2 ( m + 1)( m − 1) Sh* S 2
Ψ 0 A <Ψ 0 Acrit = for m ≠ 1 (11)
2S 2 ⎡⎣( m − 1) + DSh* S 1−m − DSh* ⎤⎦ + Sh* ( m − 1) S

4 Sh* S 2
Ψ 0 A <Ψ 0 Acrit = for m = 1 (12)
(
2 S 2 1 − DSh* ln S + Sh* S )
For some resistances, the reaction zone becomes narrow and the profiles have to
be described by other equations, namely:
886 R. PETRUS, M. K. SZUKIEWICZ

• for m ≠ 1

Ψ 0A ⎡ 1 D S − (1 − V ) ⎤
C (Z ) = 1− ⎢ *+
m + 1 ⎣ Sh m − 1
(
S 1−m − 1 +
2S 2 )
1− Z 2 ⎥ ( ) (13)
⎦

Ψ 0A ⎡ 1 L S − (1 − V ) ⎤
ϕ ( Z ) = 1 + β0 A ⎢ *+
m + 1 ⎣ Nu m − 1
S 1−m − 1 + (2S 2 )
1− Z 2 ⎥ ( ) (14)
⎦
• for m = 1

Ψ 0A ⎡ 1 S − (1 − V ) ⎤
C (Z ) = 1− ⎢
2 ⎣ Sh*
− D ln S +
2S 2 (1 − Z )⎥
2
(15)
⎦

Ψ 0A ⎡ 1 S − (1 − V ) ⎤
ϕ ( Z ) = 1 + β0 A ⎢
2 ⎣ Nu *
− L ln S +
2S 2 (1 − Z )⎥ 2
(16)
⎦
where
X − (1 − V )
Z=
S − (1 − V )

⎡ 2 ( m + 1) 2 ⎤ 2 D
V = S2 ⎢
Ψ
− *⎥−
Sh m − 1
(
S 3−m − S 2 − S + 1 ) for m ≠ 1 (17)
⎣ 0A ⎦

⎡ 4 2 ⎤
V = S2 ⎢ − * ⎥ + 2 S 2 D ln S − S + 1 for m = 1 (18)
⎣Ψ 0 A Sh ⎦
It should be noted that the value of the Weisz modulus is restricted by physical
reasons so that in this extreme case V approaches 0 which leads to the following equa-
tions

Ψ 0 Abound =
( m + 1) Sh* for m ≠ 1 (19)
Sh* D 1−m
1+
m −1
(
S −1 )
2 Sh*
Ψ 0 Abound = for m = 1 (20)
1 − Sh* D ln S
The equations describing the profiles derived similarly to those presented previ-
ously [3] were described in details by Petrus [4, 5].
An evaluation of the importance of temperature or concentration gradients is
based on the effectiveness factor concept. It is common knowledge that an overall
 Heat resistances in partially impregnated or deactivated solid catalysts 887

effectiveness factor is a reflection of mass and heat resistances both outside and inside
the catalyst pellet. Here it can be presented as a product of three factors:
S
η0 = ( m + 1) ∫ X m R( c ,ϕ ) dX = ηexη shηc (21)
0

The first factor (ηex) is a reflection of interphase transport intrusions; the second
one (ηsh) is a reflection of internal transport intrusions within the inactive shell and
finally ηc is a reflection of intraparticle temperature and gradients of concentrations
within the active layer
η ex = R( cs ,ϕ s ) (22)
R( cc ,ϕc )
η sh = (23)
R( cs ,ϕ s )
S
(m + 1)∫ X m R(c ,ϕ )dX
ηc = 0
(24)
R(cc ,ϕc )
cs, ϕs, cc and ϕc denote concentrations and temperature on the catalyst surface and on
the boundary between the inactive shell and active core, respectively. They are de-
scribed by
Ψ 0A
cs = 1 − (25)
( m + 1) Sh*
Ψ 0A
ϕs = 1 + β0 A (26)
( m + 1) Nu*
Ψ 0A ⎡ 1 D ⎤
cc = 1 − +
m + 1 ⎢⎣ Sh* m − 1
S 1−m − 1 ⎥
⎦
( ) (27)

Ψ 0A ⎡ 1 L ⎤
ϕc = 1 + β 0 A ⎢ +
2 ⎣ Nu m − 1
*
⎦
(
S 1−m − 1 ⎥ for m ≠ 1 ) (28)

and
Ψ 0A ⎛ 1 ⎞
cc = 1 − ⎜ * − D ln S ⎟ (29)
2 ⎝ Sh ⎠
Ψ 0A ⎛ 1 ⎞
ϕc = 1 − β 0 A ⎜ − L ln S ⎟ for m = 1 (30)
2 ⎝ Nu * ⎠
888 R. PETRUS, M. K. SZUKIEWICZ

These results come from steady-state mass and heat fluxes (cf. Eqs. (15) and (17))
[3]. cc, and ϕc were obtained by substituting Z = 1 to Eqs. (14) or (16) and (15) or (17),
respectively. Note that the product ηshηc gives the well-known local effectiveness
factor. And thus, in order to derive the criteria we assume that the influence of overall
transport limitation can be neglected if maximal deviation of η0 does not exceed 5%.
By analogy, an influence of external transport resistances, internal temperature and
concentration gradients in the inactive shell and internal temperature and concentra-
tion gradients in the active layer can also be ignored if maximal deviation of ηex, ηsh or
ηc, respectively, does not exceed 5%. This approach is in many instances sufficiently
exact and permits the criteria obtained to be shown as closed mathematical formulas.
To derive the criteria for reactions (1) with power-law kinetics, we may write
⎡ ⎛ 1 ⎞⎤
R( c ,ϕ ) = c n exp ⎢γ 0 ⎜ 1 − ⎟ ⎥ (31)
⎣ ⎝ ϕ ⎠⎦
In the next section a way and results of derivation of the criteria and mathematical
manipulations will be presented.

3. RESULTS AND DISCUSSION

3.1. OVERALL HEAT TRANSFER RESISTANCES

Considering the most general case, it is enough to take into account the parameter
η0. Its value should be found in the range
0.95 < η0 < 1.05 (32)
Substituting Eq. (21) into Eq. (32) and combining with Eq. (31) leads to
1 ⎧⎪ ⎡ 1 ⎤ ⎫⎪ m
0.95 < ( m + 1) ∫ C (Y ) exp ⎨γ 0 A ⎢1 −
n
⎥ ⎬ Y dY < 1.05 (33)
0 ⎪⎩ ⎢⎣ ϕ (Y ) ⎥⎦ ⎪⎭
Substituting temperature and concentration profiles (Eq. (7) and (8) or Eq. (9) and
(10)) into Eq. (33), power-series expansion of concentration and temperature terms (with
truncating non-linear terms) and, finally, integration gives the following inequality

( m + 1) 0.05 > γ 0 A β 0 AΨ 0 A ⎡⎢ ⎤
1 L 1
+
⎣ Nu m − 1
* (
S 1−m − 1 +
m+3 ⎦
)
S −1 ⎥ for m ≠ 1 (34)

⎛ 1 ⎞
0.1 > γ 0 A β 0 AΨ 0 A ⎜ * − L ln S + 0.25S −1 ⎟ for m = 1 (35)
⎝ Nu ⎠
 Heat resistances in partially impregnated or deactivated solid catalysts 889

This outcome simplifies more for insignificant external heat transfer resistances.
The catalyst pellet can be also isothermal if the reaction zone is narrow, i.e. V → (1 – S);
(cf. [3]). In this case, the following inequality should be considered

1 ⎡ϕ ( 0) − ϕs ⎤
0.05 > γ 0 A ⎢ ⎥ (36)
ϕ s ⎣⎢ ϕ ( 0 ) ⎦⎥

ϕ(0) is temperature at the end of reaction zone (for which the concentration is equal
to 0) and can be expressed by

⎧ Ψ 0A ⎡ 1
ϕ ( 0 ) = 1 + β0 A ⎨1 + ⎢
m + 1 ⎣ Nu *
1
− *+
Sh
L − D 1−m
m −1
S −1 ( )⎤⎦⎥ ⎫⎬ for m ≠ 1 (37)
⎩ ⎭

⎧ Ψ 0A ⎡ 1 1 ⎤⎫
ϕ ( 0 ) = 1 + β 0 A ⎨1 + ⎢ *
− * + ( D − L ) ln S ⎥ ⎬ for m = 1 (38)
⎩ 2 ⎣ Nu Sh ⎦⎭

This inequality leads to the following outcomes

⎧ Ψ 0A ⎡ 1 L − D 1−m ⎤⎫
γ 0 A β 0 A ⎨1 − ⎢ − (
S −1 ⎥⎬ )
⎩ m + 1 ⎣ Sh m −1
*
⎦⎭
0.05 > for m ≠ 1 (39)
⎛ Ψ 0A ⎞⎧ Ψ 0A ⎡ 1 L ⎤⎫
⎜1 + β 0 A
⎝
⎟ ⎨1 + β 0 A
m +1⎠ ⎩ ⎢ +
m + 1 ⎣ Nu m − 1
* (
S 1−m − 1 ⎥ ⎬
⎦⎭
)

⎧ Ψ 0A ⎡ 1 ⎤⎫
γ 0 A β 0 A ⎨1 −
⎢ *
− ( D − L ) ln S ⎥ ⎬
⎩ 2 ⎣ Sh ⎦⎭
0.05 > for m = 1 (40)
⎛ Ψ 0A ⎞ ⎧ Ψ 0A ⎡ 1 ⎤⎫
⎜1 + β0 A ⎟ ⎨1 + β 0 A ⎢ *
− L ln S ⎥ ⎬
⎝ 2 ⎠⎩ 2 ⎣ Nu ⎦⎭

3.2. HEAT TRANSFER RESISTANCES FOR THE ACTIVE CORE

Criteria concerning internal mass and heat transfer resistances in the active core
can be derived in the same way as described in the preceding section. The only differ-
ence is the use of the Eq. (41) instead of Eq. (32)
0.95 < η c < 1.05 (41)
As a result, the heat transfer resistances can be omitted if
890 R. PETRUS, M. K. SZUKIEWICZ

Ψ 0A
γ 0 Aβ0 A
0.05 ( m + 1)( m + 3) > S for m ≠ 1 (42)
2
⎧ Ψ 0A ⎡ 1 L ⎤⎫
⎨1 + β 0 A +
m + 1 ⎢⎣ Nu * m − 1
1− m
S −1 ⎥⎬
⎦⎭
( )
⎩

Ψ 0A
γ 0 Aβ0 A
0.4 > S for m = 1 (43)
2
⎧ Ψ 0A ⎡ 1 ⎤⎫
⎨1 + β 0 A ⎢ *
− L ln S ⎥ ⎬
⎩ 2 ⎣ Nu ⎦⎭
If the thickness of an inactive shell (1 – S) is not large and/or external heat transfer
resistances are insignificant, these outcomes simplifie more.
The active core can be also isothermal if the reaction zone is narrow, i.e.
V → (1 – S) [3]. In this case, the following inequality should be considered

1 ⎡ ϕ ( 0 ) − ϕc ⎤
0.05 > γ 0 A ⎢ ⎥ (44)
ϕc ⎢⎣ ϕ ( 0 ) ⎥⎦

The resulting criteria are given by

⎧ Ψ 0A ⎡ 1
γ 0 A β 0 A ⎨1 − ⎢ +
D
m + 1 ⎣ Sh m − 1
*
S 1−m − 1 ( )⎤⎥⎦ ⎫⎬
0.05 > ⎩ ⎭ for m ≠ 1 (45)
2
⎧ Ψ 0A ⎡ 1 L ⎤⎫
⎨1 + β 0 A ⎢
m + 1 ⎣ Nu *
+
m −1
S 1−m − 1 ( ) ⎥⎬
⎦⎭
⎩

⎧ Ψ 0A ⎡ 1 ⎤⎫
γ 0 A β 0 A ⎨1 − ⎢ *
− D ln S ⎥ ⎬
⎩ 2 ⎣ Sh ⎦⎭
0.05 > 2
for m = 1 (46)
⎧ Ψ 0A ⎡ 1 ⎤⎫
⎨1 + β 0 A ⎢ Nu * − L ln S ⎥ ⎬
⎩ 2 ⎣ ⎦⎭

3.3. DISCUSSION

The criteria presented here are rather difficult to be verified, because experimental
data are not available. Therefore we present some reasons for confirming our ideas.
Firstly, the presented model is often used in catalytic processes. Secondly, the method
of derivation of criteria was previously successfully used and verified for catalytic
processes without deactivation [3]. The method is based on a parabolic approximation
 Heat resistances in partially impregnated or deactivated solid catalysts 891

of concentration and temperature profiles in a pellet and deviations of effectiveness of

the concept of factor values. And, finally, the criterion presented and verified by Lee
[2] (incidentally he has also verified his criterion indirectly) can be derived using the
method presented here. The criterion concerns cylindrical pellets.
According to Lee [2], the inner core of a deactivated catalyst is at least as isother-
mal as the fresh catalyst so long as
⎛ 1 ⎞
a ⎜ Sh* ln + 1⎟ > 1 (47)
⎝ S ⎠
This outcome can also be derived based on the concentration and temperature pro-
files (Eqs. (15) and (16)). Following the derivation scheme given by Lee, the deacti-
vated pellet will be at least as isothermal as the fresh catalyst if
Δϕ c < Δ ϕ c , f (48)

Both temperature differences can be obtained combining Eqs. (16), (18) and (38):

⎡ Ψ 0A ⎛ Ψ 0 A, f ⎞
β 0 A ⎢1 −
⎣ 2Sh * (1 − Sh D ln S )⎤⎥⎦ < β
*
0A ⎜1 −
2Sh* ⎠
⎟ (49)
⎝
Equation (49) can be easily transformed to the following form (taking into account
that a = Ψ0A/Ψ0A,f)

⎛ 1 ⎞
a⎜ DSh * ln + 1⎟ > 1 (50)
⎝ S ⎠
Equation (50) differs from Eq. (47) in one point. In Eq. (50) occurs a parameter D
being the ratio of the mass transfer coefficients in a non-deactivated core and non-
active shell of the pellet. In Lee’s model, D equals 1 because mass and heat transport
conditions are the same in the core and in the shell of the pellet. It should be noted that
above limitations of criterion (47), not being presented in the Lee paper, are directly
shown. The criterion is valid for Ψ0A > Ψ0A,crit. The model presented here is more gen-
eral because it enables considering different values of mass and heat transfer coeffi-
cients in non-deactivated core and non-active shell of the pellet.

4. SUMMARY

• The derived criteria of relative importance of heat transfer concern an important

case when the outer shell of a catalyst pellet was deactivated in the process or an ac-
tive material was supported under a non-active shell. They have been obtained in
a relatively simple way by determining the concentration of the reagent and tempera-
892 R. PETRUS, M. K. SZUKIEWICZ

ture parabolic profiles and, afterwards, by utilizing the deviation of effectiveness fac-
tor concept. The concept allows to derive the criteria for other reaction schemes.
• The criteria are straightforward and their use should not cause difficulties even
though somewhat complex formulas were introduced.

ACKNOWLEDGEMENTS

The work was performed under grant No. 3T09C 024 28 of the Ministry of Education and Science.

SYMBOLS

a – activity
c,ϕ – dimensionless concentration/temperature (related to the bulk)
D – ratio of effective diffusion coefficients in the active core and in the non-active shell
L – ratio of effective heat conductivity coefficients in the active core and in the non-active shell
m – coefficient (equal to 0, 1, 2 for planar, cylindrical and spherical geometry of the pellet,
respectively)
n – order of reaction
Nu*, Sh* – modified Nusselt/ Sherwood number
Rc – hypothetical reaction interface
Rnc – dimensionless radius of a non-active core
S – active shell
V – reaction zone
X, Y, Z – dimensionless coordinates
β0 – Prater parameter
γ0 – dimensionless activation energy
η0 – overall effectiveness factor
η – effectiveness factor
Ψ0A – Weisz modulus
SUBSCRIPTS AND SUPERSCRIPTS

c – boundary between inactive shell and active core

f – fresh catalyst
s – surface
crit – critical

REFERENCES

[1] MORBIDELLI M., SERVIDA A., Ind. Eng. Chem. Fundam., 1982, 21, 278.
[2] LEE H.H., Chem. Eng. Sci., 1980, 35, 905.
[3] PETRUS R., SZUKIEWICZ M.K., AIChE J., 2003, 49, 2419.
[4] PETRUS R., Inż. Chem. Proc., 1991, 12, 187.
[5] PETRUS R., Inż. Chem. Proc., 1991, 12, 365.
 Heat resistances in partially impregnated or deactivated solid catalysts 893

ROMAN PETRUS, MIROSŁAW K. SZUKIEWICZ

KRYTERIA IZOTERMICZNOŚCI DLA REAKCJI KATALITYCZNYCH

W ZIARNACH WARSTWOWYCH LUB CZĘŚCIOWO ZDEZAKTYWOWANYCH

Podjęto próbę opracowania kryteriów izotermiczności dla reakcji katalitycznych w ziarnach war-
stwowych lub częściowo zdezaktywowanych. Te, stosunkowo często spotykane w praktyce przypadki
były badane zarówno teoretycznie, jak i eksperymentalnie – obszerny przegląd literatury dotyczącej tego
problemu można znaleźć w pracy Morbidellego i in. [1], w której określano optymalny rozkład aktywno-
ści katalizatora. Natomiast prawie całkowicie brak jest opracowanych kryteriów izotermiczności – jedy-
nym wyjątkiem jest praca Lee [2], w której autor zajmuje się jedynie znaczeniem wewnętrznego gradien-
tu temperatury w cylindrycznym ziarnie katalizatora. Dla innych przypadków w ogólnodostępnej
literaturze brak jest podobnych opracowań. W niniejszej pracy wyprowadzenie kryteriów oparto na meto-
dzie opublikowanej w pracy Petrusa i in. [3]. Rozważmy przypadek, w którym materiał aktywny jest
osadzony w środku ziarna katalizatora, zewnętrzna powłoka zaś jest nieaktywna lub uległa dezaktywacji.
Dla reakcji opisanej równaniem (1) otrzymuje się dla małych i średnich oporów dyfuzyjnych w ziarnie
przybliżone profile stężenia i temperatury opisane odpowiednio równaniami (7)–(10), dla dużych oporów
dyfuzyjnych zaś równaniami (13)–(16). Oszacowanie istotności wewnętrznych bądź zewnętrznych gra-
dientów temperatury oparto albo na koncepcji ogólnego współczynnika efektywności ziarna (równanie
(21)), zależnego, jak wiadomo, od oporów transportu ciepła i masy wewnątrz i w otoczeniu ziarna, bądź
też na koncepcji wartości współczynników efektywności opisanych równaniami (22)–(24), dotyczącymi
odpowiednich stref w ziarnie katalizatora. Przyjęto zasadę, że odchylenia wartości współczynnika efek-
tywności mniejsze niż 5% świadczą o izotermiczności procesu. W większości przypadków takie założe-
nie jest wystarczające i pozwala uzyskać odpowiednie równania matematyczne w zwartej formie. Do
wyprowadzenia kryteriów przyjęto potęgową postać równania kinetycznego (31). W razie uwzględnienia
zarówno zewnętrznych, jak i wewnętrznych oporów wnikania izotermiczność ziarna jest zapewniona, gdy
spełniony jest warunek (32). Podstawienie równań (21) i (31) prowadzi do zależności (33). Podstawiając
do niej równania (7) i (8) lub (9) i (10), rozwijając otrzymaną zależność w szereg potęgowy (ograniczony
do członów liniowych) po scałkowaniu otrzymujemy równania kryterialne (34) i (35). Ziarno katalizato-
ra ma również stałą temperaturę, gdy spełniony jest warunek (36). Przekształcenie tego równania prowa-
dzi do równań kryterialnych (39) i (40). Określenie warunku izotermiczności dla aktywnego rdzenia
ziarna wymaga rozważenia warunku (41). Postępując podobnie jak poprzednio, otrzymujemy równania
kryterialne (42) i (43). Spełnienie nierówności (44) świadczy również o stałej temperaturze ziarna. Prze-
kształcenie tego równania prowadzi do kryteriów (45) i (46). Ze względu na brak danych doświadczal-
nych weryfikacja przedstawionych kryteriów jest dość kłopotliwa. Pośrednim dowodem ich poprawności
jest wykorzystanie metod matematycznych sprawdzonych i zweryfikowanych dla procesów bez dezakty-
wacji (zob. [3]). Kolejny dowód uzyskali autorzy niniejszej pracy, otrzymując na podstawie przybliżo-
nych profili stężenia i temperatury kryterium izotermiczności ziarna, ktore wcześniej podał i zweryfiko-
wał Lee dla ziarna w kształcie walca (równ. (47)). Identyczne równanie (równ. (50)) otrzymuje się
metodami zastosowanymi w niniejszej pracy. Lee nie uwzględnia współczynnika D, przyjmując D = 1.
Otrzymane kryteria są proste w użyciu i obejmują ważny z praktycznych względów proces dezaktywacji
ziarna. Są one stosunkowo dokładne i otrzymane w prosty, choć niekiedy żmudny, sposób. Ten sposób
może być bez większych trudności zastosowany do innego schematu reakcji i innego typu równania
kinetycznego.

Received 27 November, 2008