c-ompu,ers them. Engng, Vol. 14, No. 12, pp. 13 17-I 322, I!?90 0098-l 354/90 $3.00 + 0.

00
Printed in Great Britain. All rights reserved Copyright 0 1990 Pergamon Press plc

OPTIMAL CATALYST PELLET ACTIVITY

DISTRIBUTIONS-FIXED-BED REACTOR WITH
CATALYST DEACTIVATION
J. MARK&, A. BRUNOVSK~ and Z. LETKOVA
Department of Organic Technology, Slovak Institute of Technology,
8 12 37 Bratislava, Czechoslovakia

(Received 23 March 1990;final revision received 4 July 1990; received fir publicaiion 18 July 1990)

Abstract-The catalyst pellet activity distribution to maximize fixed-bed reactor performance (profit per
time) is determined for first-order, second-order and consecutive first-order reactions in the presence of
deactivation. An isothermal heterogeneousplug-flow reactor packed with multiple zones of narrow active
region catalystsis considered. The optimal active catalyst location is estimatedby a gradient type method.
The gradient components are computed with the help of adjoint equations. It is found that the best
performance is achieved for one type of catalystsalong the reactor. Significantimprovementsover activity
distributions are obtained.

INTRODUXION The aim of the present paper is to optimize the

catalyst pellet activity distribution in a multiple-zone
The optimal activity distribution in catalyst pellets
fixed-bed reactor (each zone containing one type of
for reacting systems undergoing deactivation has
pellets) for first-order, second-order and consecutive
been estimated recently by Brunovskh et al. (1990).
first-order reactions in the presence of irreversible
In this paper a single catalyst pellet has been analyzed
catalyst poison chemisorption. More precisely, the
and a general optimality criterion has been devel-
optimal narrow active region location in the pellet at
oped. As the objective function, profit per time,
each reactor zone is estimated.
taking into account the price of the product and the
cost of the catalyst replacement or regeneration has
been considered. It has been shown that the optimal OPTIMIZATION PROBLEM
activity distribution is in all cases of the Dirac delta The duration of the reactor operating time and the
type. time dependence of the effectiveness factor depend
Due to the change of the bulk flow conditions upon the active catalyst distribution. The operating
along the fixed-bed reactor, the optimal activity time can be increased by locating the active catalyst
distribution is a function of pellet position. The inside the pellet. The maximum value of the effective-
problem of estimating the active catalyst location that ness factor, at least for positive-order reactions, is
maximizes fixed-bed reactor outlet conversion for a obtained for externally located activity. In order
bimolecular Langmuir-Hinshelwood reaction has to avoid this, the economic criterion chosen is as
been studied by Morbidelli et al. (1986a,b) and Lee follows:
et al. (1987). It was shown that the optimal activity
distribution is again a Dirac delta one. In the work profit
of Lee et al. (1987), a reactor packed in a series of time
zones, each characterized by catalyst pellets having a price of cost of raw
different Dirac delta distribution has been considered.
the produc materials
It has been found that, by using of two or three zones, =
the theoretical optimal reactor performance (i.e. each operating time
pellet having a different activity distribution) is (1)
closely approached.
For both catalytic reactions A + B and A + B + C it
The optimal catalyst activity distribution in
becomes:
a nonisothermal heterogeneous plug-flow reactor
for a first-order catalytic reaction and irreversible profit
catalyst poison chemisorption has been investi-
gated by MarkoS and Brunovskk (1989). In this
study it has been shown that the duration of the
time

at VoCBdt -a2
t*
s0
Vo (C&O - C,)dt -cc,
operating time is significantly increased by a catalyst = f
with narrow region activity distribution inside the t*
pellet. (2)
1317
CACE
14,12--A
1318 J. MARK& et al.

where a,, u2 and CQare costs of product, raw material where R, is the reaction rate and R, is its mean value
and catalyst, t* is the operating time. Introducing given by:
dimensionless variables and dividing by u, we obtain L
the following objective function: R, = (n + 1)
R, cp drp (10)
50
F(&z*)
and R, is the mean rate of deactivation:

K,=(n+l) fbcp* dv. (11)

=
s0
The boundary and initial conditions are:
max. (3)
r = 0: z E (0, l>;
For single reaction A 4 B this criterion can be
simplified: 6((P - @I
a(.& cp. T) = a@,4090)= (n + l)@_
(1W
Vl (I - m,,,,) ds - 1
F(Q,r+)=

where vi is proportional
5
O

portional to a, /as and B = a2/u,.

t*
to (a, - a2)/a3, vz is pro-
= max, (4) (ntl)

T >
s
0

0: z = 0;
a(z,rp,O)cpdv

YA,, = yp., = 1,
= 1, Wb)

The aim of the present work is to determine the z x E (0, l>;

Dirac delta activity location at each reactor zone:
P=o; dY,=dY,=o,
drp drp
subject to the constraint; rp = 1; Y* = m.,> YP = YP,/ (13)
qi, o (0, l>, i=l,...,k, and the deactivation rate expression is of the form:
and the operating time t* for which the maximum da
value of the objective function (3) is obtained. The R,z-_= - Yrc,Q(z,rp,O)P
dz
initial activity distribution has been assumed:
= _ y wrp- 9)
P(n + l>f@nP

Basic equations
(14)
Let us consider an isothermal heterogeneous
plug-flow reactor divided into k zones of the same
Consecutive reaction
volume. Each zone is packed with one type of cata-
lyst pellets. It is assumed, that the gas-to-solid mass The mode1 equations are:
transfer resistance is negligible and that the deacti-
mass balances of the key component A:
vation is slow, so that given any activity distri-
bution, the concentrations have steady state be- dY,/
haviour. In the reactor either single A -P B reaction or A = -Da,R,, (1%
dz
consecutive A -P B-C reactions take place simul-
taneously with irreversible chemisorption of catalyst V2YA=@;R,; (16)
poison. mass balances of component B:
Single reaction dy,,
A = Da,K, - Da,K,, (17)
Under the above assumption the model equations dz
are as follows:
V2 Y, = - @;, R, + @i2 R2. (18)
mass balances of the key component:
Mass balances of catalyst poison are given by
dYA/ equations (8) and (9), mean reaction rates are:
L = -Da,K,,
dz L
K, = (n + 1) R,cpdv> (19)
VY*=@hR,; (7) s0
mass balances of the poison: I

K,=(n + 1) R,cpdv (20)

dY,, s 0
d = DapK,, (8)
dz and mean rate of deactivation is given by equation
V2Yp= -@$Rp; (9) (14).
 Optimal catalyst pellet activity distributions 1319

Initial and boundary conditions (12) and (13) are time derivative of activity and the mass balances
complete by: contains space derivatives of concentrations only.
This is why the model equations have been solved by
5 >o; z=o; Y BJ -0
- 9 the following procedure:
zE<O,l>; p=o, dYa
-=o, -by explicit finite difference scheme for deactiva-
dv tion rate equation the predicted value of activity
9 = 1, ye = Y&J. (13a) fi(z, t + Ar) was obtained from ~(z, r) and Yi
(z -AZ, z + Ar) values,
-using @(z, r + At), Yi(z - AZ, t + At), predicted
SOLUTION OF MODEL EQUATIONS
values of Y(z, r + AT) have been obtained by
Because the catalytic reactions as well as catalyst the explicit finite difference scheme for material
deactivation take place only in a narrow layer at balances,
the point @, the catalyst pellet mass balances can -at the next step average values p and I were
be solved analytically, and the original system of computed from @ and ,u(z, r) or Y and
model equations for single reaction is reduced to Y (z - AZ, T + Ar), respectively,
the system: -the corrected values of activity and concen-
trations were obtained by the implicit finite
dL, -Da,i?,, difference scheme for the model equations using
L=
dz
(21)
the average values computed in the previous
step,
dYr/ (n + 1)
d = -Da, Y,.,p (22) -the last two steps were repeated until satisfactory
dz n+l--ffp
coincidence was achieved.

(23) In such a way activity and concentration profiles were

computed at 7 + AT time step.
This algorithm is described in Ilavsk9 et al. (1983)
(24) in detail.

OPTlMIZATiON TECHNIQUE
(25)
with initial and boundary conditions: The objective function has k + 1 parameters, k
parameters correspond to the activity locations
r =0:zE<0,1>; p = 1, C& at k reactor zones and the remaining
91.....
t > 0: z = 0; YAJ = yP,,= 1 (26) parameter is the operating time T*. The optimization
procedure consists by estimation of activity locations
For consecutive reactions the model equations $,, . . . , r& by gradient type of method. For each
become: vector (9,). . , &) the time dependence of concen-
dy,, trations and activity along the reactor and objective
L = -DaAE,, (27) function have been computed by solution of the
dz
model equations. The time has been increased until
dYa/ the objective function reaches its maximum.
( = Da,K, -Da,&, (28)
dz The gradient is the vector with the components:
xR,+(n+l)(Y,,,-_A)=O, (29)
bxK2+(n+ l)(Ys,,- Y,)=bxwR,, (30)
PAvP,,&)~~ dz dr, (34)
a, = pFA, (31)
for single reaction and for consecutive reactions:
%=CCJfr%, (32)
with initiai and boundary conditions:
r=o:zE<O,l>; /4=1,
aF,
-=-
a9i
v
r* ss
+
o o

Q(YA./- YEN.,,
YP./,

&PA,P,,P,,P,)sx dz dr, (35)

T >O:r = 1; Y a,/-- YP./ = 1,
The catalyst poison balance and deactivation rate is
given by equations (22) and (23).
The systems of model equations (21-26) or (27-33)
with (22) and (23) were solved by the predictor-
corrector method.
Because the model equations are in the pseudo-
steady state form, the deactivation rate contains the
Ya,, = 0. (33)
where pA , pB, pP and p,, are the adjoint variables.
Development of gradient expression P and the system
of adjoint equations is in Appendix A for a single
reaction. In Appendix B, the expression Q and system
of adjoint equations for consecutive reactions are
derived.
Due to the constraint r& E <O, 1> for i = 1, . . _, k
the projected gradient method has been applied.
1320 J. MARK& ef al.

0.8
0.8
5 F
0.6
0.6

0.4 1, 0.1

0.2
/
I 1
0 1 I
10 20 30 40 50
@.p

Fig. 1. Optimal activity location vs poison Thiele modulus Fig. 3. Optimal activity location vs poison Thiele modulus
for several Damkiihler numbers Da,. First-order reaction for several Damkiihler numbers Da,. Consecutive reactions
(v=1,DaA=1,0~=1,n=2). (v = 1, /3 = 0.01, Da, = 1, GA = 1, o = 5, b = 1, n = 2).

The (I + 1) iteration is computed from the Zth one of multiple zones have been achieved. For each case,
by the scheme: 1, 2, 3, 5, 9 zones have been considered. The maxi-
mum of the objective function has been obtained for
Qi = const. for all reactor zones.
where The resulting optimal activity location for
three reaction systems as a function of poison Thiele
cTF/.~Q~for qj 6 (0, 1),
modulus for several Damkiihler numbers are in
Or vi= 1 and aF/L3@i<0, Figs l-3. There is no qualitative difference between
these three examples. For each reaction and for
or Gi=O and aF/dcjSi>O,
a low DomkGhler number (0.1, 1) the optimal
Yi =
0 for 8, = 1 and aF/&jii
> 0, activity location moves from the pellet centre towards
the external surface with the increase of poison
1 or & = 0 and dFfd& -c0. (37)
Thiele modulus. For DamkGhler number 10 and low
The step length A has been determined by Fibonacci value of poison Thiele modulus (the border depends
search technique in the gradient direction (as in the on reaction) the optimal activity location is at the
method of steepest ascent). external surface. On increasing the poison Thiele
modulus, the optimal location jumped into the pellet
interior and later moved slowly towards the pellet
RESULTS AND DISCUSSION
surface.
Three reaction systems have been investigated Finally, it is worthwhile to show the influence of
numerically: first-order, second-order reaction and the activity location on the process profit per time.
two consecutive first-order reactions. In all numeri- In Figs 4 and 5 activity location vs objective function
cally investigated cases no improvement by the use

jr-
0.0
10
T
0.6

a.4

1, 0.1
0.2

01 I I I I IO
0 1 I I I I I
0 0.2 0.4
_ 0.8 0.6
1.0
0 10 20 30 40 50 Q
*P Fig. 4. Objective function (- ) and operating time (----)
Fig. 2. Optimal activitylocation vs poison Thiele modulus vs active catalyst location for consecutive reactions (0 = 5,
for severalDamkiihlernumbersDa,. Second-orderreaction b = 1, Da, = 1, 8, = t, 0, = 5, Da, = 10, Y = 100, n = 2
(vnl,Da,=l.~,=l,n=2). curves parametrimd by p).
 Optimal catalyst pellet activity distributions 1321

0.5
\ 25 R, = Catalyst pellet radius

1 \El

-F
--- r* 20
r*
RP = Dimensionless rate of deactivation
r = Radial pellet coordinate
t = Time
1 = I/(q,,k,) = characteristic deactivation
t* = Operating time
time

15 V, = Volumetric flow rate

u = External fluid phase velocity
x = $,(+)@i = dimensionless parameter
IO x = Axial coordinate
Y = C/CT = dimensionless concentration
z = x/L = dimensionless axial coordinate
0.1 5 Greek
c( = @i/e; = dimensionless parameter
0 0 e, =Cost of product
oLz=Cost of raw material
0 0.2 0.4 0.6 0.8 1.0
5 c+ =Cost of catalyst
p = ur/a, = dimensionless parameter
Fig. 5. Objective function ( -) and operating time (----) 6 = Dirac delta function
vs active catalyst location for consecutive reactions (0 = 5, E= Bed void fraction
b = 1, Da,=l, @,=l, @r=5, Da,= 10, v = 1, n =2 fl =Relative activity
curves parametrized by /?). Y, , v2= Dimensionless parameters, defined in equation (4)
@(cp) =I =; for n = 0, ln(rp) for n = 1 and 1 - I/cp for
and operating time for consecutive reactions are
P,, = Bed density
illustrated. The system exhibited in Fig. 4 corre-
pa = Catalyst density
sponds to the relatively expensive product and non- T= r/r0 = dimensionless time
expensive cataiyst (v2 = 100) and the resulting r* = Dimensionless operating time
optimal location is at the external surface. The value c = Concentration term in reaction rate equation
of the objective function is increasing with the in- @ = Thiele modulus: @: = R:R,/(D Co, ,), S& , =
R~R,l(D,..C~,,), cgB.2 = i$R,liD, . B Cd, . f).
crease of 4. Figure 5 corresponds to the comparable
ep = RiafpJ(D,JC$,,)
prices of product and catalyst, i.e. v2 = 1. There is a 40 = rlRp = dimensionless radial coordinate
significant maximum at the activity location about @ = Dimensionless active catalyst location
0.4. From both cases (Figs 4 and 5) it is evident that w = k.,, l&r
the operating time greatly increases when the activity Subscripts
location is moving into the pellet interior. A, B = Reactants
The results presented illustrate the improvement of P = Poison
the fixed-bed reactor through the use of nonuniform f = Fluid phase
active catalyst distribution. The result that the best 1= First reaction
2= Second (undesirable) reaction
performance corresponds to the reactor packed with
one type of catalyst is not general. For example, with superscript
bimolecular Langmuir-Hinshelwood reaction and 0 = Inlet stream
the high value of poison Thiele modulus [this corre-
sponds to the problem of maximizing reactor outlet
REFERENCES
conversion, Lee et al. (1988)J the performance of
the reactor can be improved by the use of several BrunovskP A., M. Morbidelli and P. Brunovsky, Gem.
zones of catalyst. The optimization technique, which Engag sci. 45, 917 (1990).
was developed in this paper, does not depend on Ilavsky J., A. Brunovska, J. Valtyni and J. Burianek. C/rem.
Papers 37, 433 (1983).
the reaction rate equation and can be successfully Lee C. K., M. Morbidelli and A. Varma, Ind. Engng Chem.
adapted for another case. Res. 26, 167 (1987).
MarkoS J. and A. Brunovska, Collecr. Czech. Chem. Com-
mun. 54, 375 (1989).
NOMENCLATURE Morbidelli M., A. Servida, S. Carra and A. Varma, Ind.
A = Activity Engng Chem. Fundam. 25, 3 13 (1986a).
~8 = Equilibrium amount of adsorbed poison Morbidelli M., A. Servida and A. Varma, Ind. Engng Chem.
dimensionless parameter Fundam. 25, 307 (1986b)
b =Qs.,/@A,r=
C = Concentration
D, = Diffusion coefficient
Da = DamkBhler number, Da, - (1 - c)k,., L/v, APPENDIX A
Da, = (1 --r)k,,,L/y, Da, = (1 - c)p,agk,L/v
k = Number of zones in reactor In this appendix we derive formula (29) for the gradient and
k,. = Catalytic reaction rate constant system of adjoint equations for one reaction problem (tirst-
k, = Deactivation rate constant or second-order). By the derivation the objective function
L = Reactor length (4) we obtain:
n = Integer characteristic of pellet geometry
p = Adjoint variables (Al)
R = Dimensionless reaction rate
1322 J. MARK& er al.

where APPENDIX B
xi=+,.(+)@: i=l,..., k. 642) The formula and system of adjoint equations for consecu-
The mathematical model of the reactor consists of equations tive first-order reactions [rate equations (31), (32)]. which
(21-26) linearizing them we obtain: were developed by the same procedure described in Appen-
dix A, can be written as follows:
day, / _
- -Da*C(Y*)& -D~*P~(Y*)~Y*, gradient components:
---L (A3)
dz P L
da YE-.,= -Da,/% (APA - B,PB + PA+
(A4) IS0 0
dz
+ M,p,)bx dz dr, (Bl)
-=-A, (A5) system of adjoint equations:
dr
O=[z&(Y*)-(n + l)lSY*+(n + 1)6Y*,, dP,
- = APA - BAPB > (W
d.r
+ &(Y*)dx + xC(Y*)&, (A6)
where dps
- =&P,, 033)
dr
A= (n+l)
n + 1 - axp dp,
- = PPPP + %P,, W)
dz
(A7)
dp
p = A,P, - B,P, + P,A+ + M,P, 3 (B5)
and dr
Y* for first-order reaction, with terminal and boundary conditions:
C(Y*) = (Ag)
Pi for second-order reaction.
T =rf:zo<O, l>; p,=o,
From equation (A6) we obtain the expression for 6Y*,
which we can substitute into equation (A3). By Iinter- rE<O,T*>:z=1; pA=-B,PP=O,PB=
changing sides in equations (A3-A5), multiplying by v/r*, where
integrating over (0, s+> and <O, 1> we obtain:
A = Da*@ + 1)~
A
n+l-px

A = Da*@ + 1) Y*.,
+D%K(Y,)Sp +r5(y,)SYA1 p,dzdr r (n+i-_luc)2
>
A = Da,@ + I)Y.wP
+ Da+ ,dr dr x (n+l-p.x)*

1'
B = Da*@ + 1)~ 1 + bw
(A9)

B'=(n+)co
DaA(n
+1)~
* (n+l--xp) C (n+l)w-bbxp

where p*, pp and p,, are adjoint variables. Integrating by

parts we obtain the system of adjoint equations:
-bxp
dp, (n + l)C(Y*)
- = DaAwA (Al3 Y Yis.rb
dr n + 1 -X&(Y,) B, = Da*@ + 1)~
(n + L*~px)r - [(n + 1)~ - bxp]
dp,
_ =- n T 1_ h,, PaPpP + p,] , (All) by,,, [(n + 1)~ - clsxzbl
dz
x
{(n + 1 - p~)[(n + 1)~ - bxc(l}2>
dp
* = Da,p*C(Y*)
dr [I
1+
WC(Y*)
n + 1 - XPC(Y*) 1 Y Y&/W

x(:+?I
yzcj2
Pw++
B,, = Da*(n + 1)
(n + lh.l@X)2 - [(n + 1)~ - bxp]
~~1.
bjuY,,,[2(n + 1)~ - bxp - wxfl]
with terminal and boundary conditions: x {[(n + 1)~ - bxD](n + 1- xpc)}
r=s*:zE<O,1>; p,=o, Pp = Da+,,
rE<O,?*>:z= 1; p*=l,p,=O (Al2) P, = Da,M,,.
and expression for gradient:
P, = Da,M,,
SF,=; Mp= (n+l)r
Flfl-ax/L
x(~+)~.~~~[D~ p*+p] (A13)
(n+l-axp) * * M = YP.fM + 1Y

where * (n + 1 - jmx)*
0 for 2 s (.q-, , q). (n + l)yp,~fiza
bx = i = 1,. . , k. (A14)
1 for z o (.z-, , .q), Mx=(n+l-pax).