-

\'.

Eflgi~urinq

CJrf!mic{l/

Vol.

SciE'nr.e.

Pergnmon

Prin(:::d

No. 5.

SI,

CQPyright
in Grea

633-61;;', J?96

pp.

1996

EI:;c'Iicr

8rilain.

AlJ

'"ti

0009 - 2509 (95)00299-

EFFECT OF INTRAPARTICLE

Scicncc

righl.'.>

OC<)9 -2509j96

Ud

ro::scrvcd

SI S.C;O .;. 0.00

DIFFUSION

ON CATALYST

DECAY
M.

M.e

CHOCRNL\

: Department

RAFFO

N. AMADEO:

CALDERN],

and

M.

LABORDEt

of Chemical
Engineering
(FI) - PINMATE
(FCEyN).
Universily
of Buenos
de Indusrri:ls.
Ciud:ld Universitari:l,
1428 Buenos Aires. Argentina
Depanment
of Chemical
Reactors,
eNEA,
Buenos Aires, Argentina

Aires,

P:lbelJn
.

21 A"guse

1995)

(Firse reccived
Absrract~

14 June

The inrerreiation

1995; revised

between

interna!

manuscripr
diffusion

recei,ed

and acceprqd

and deactiV:ltion

is ex;;mi"ed.

The stud'!

is centered

On the copper cat:llysl used in the warer-gas-shifl

reacrion ('NGSR). This caralys[ is deacti',:ared
by the
presence of chlorine
in the feed. A Langmuir-Hinshelwood
model for the react,on
kinerics is considered.
Wirh a high diffusional
resistance,
the poison is e1iminated inside rhe peilel, and this aplains
he observed
inhomogeneous
deacrivaion
of the industrial
bed. The !ife of the catalyst
increases
when diffusional
resistance
for the poison
cata1ysl decay. is defined.

increases.

A genera!

equation

INTRODCTION

Reactor

models

transport

for catalytic

restriction

deactivation
leve!.

overlaid

They

deactivation:
analysis

(1966) solved

the mass con-

tbe tbree different

of Masamune
to a complex

types of

and paralle!.
and Smith

first-order

(1966) bas
reaction

sys-

tem by Murakami
ei al. (1968) and ro LangmuirHinshelwood
kinetics by Chu (1968). Chu introduced
tbe concept of a reJative effectiveness factor.
Hegedus (1974) studied the general case of combined external and interna] mass transfer resistances
and the effect of the pellet
The concept

of activity,

geometry.
as defined

by Levenspiel

(1972) was introduced

by Krishnaswamy
and Kittrell
(1981) in arder to study the diffusional
effecrs in
a catalyst wirh deactivation.
They developed analytical procedures
for nrh-order irreversible reaclons and
defined a deactivatian
effectiveness factor.
recently,

Grzesik

ei al. (1992a, b) applied

rime-on-stream
rheory (TOST)
tion system to solve a fixed-bed
ering borh the intraparticle
catalyst decay_

lo'

rbe

for a first-order
reacreactor model consid-

diffusion

restriclion

and

internal diffusion in a catalyst pellet in the presence of

a slow decay of the catalyst activiry. The st~dy has
The applied
aim af to
thisa work
analyzeused
tbe in
effects
of the
been
coppris-to
catalysl
he warer-

Crrespoodi!1g

:.luthor.

the

(WGSR):

a Langrnuir-Hinshelwood-type

assumed

to apply.

These

catalysts

kinetics
have good

is

low-

temperature
activity and are tberefore attractive since
the e.quilibrium
is favored at low temperarure.
In
addition to higher activiry, another advantage
claimed for the low-remperature
shift catalysts is higher
seJectivity
and
fewer side reaclions
at elevated
pressures
and

(van Herwijnen

Hakkarainen,

and de long,

1989).

However.

1980; Salmi
copper-based

Iaw-temperature
shif, cataIysts are being irreversibly
poisoned
by even smalJ quantities
of cblorine in the
feed (Young and Clark, 1974).
With

respect

to WGSR,

Elnashaie

and Alhabdan

(1989) analyzed the jEtraparticle

effecls on an industrial reactor
operating
at steady srate. Gonzalez
Velasco

er al. (1992)

a WGS

industrial

disregarding

proposed

reactor

policies
decay

in
but

efects.

MATHE:'vlATICAL

For an isothermal,

optimal

wirh catalyst

the diffusional

MODEL

cyJindrical

catalyst

particle

with

constant
properties
and ignoring the externaI diffusional effects, the mass conservation
equarion ,for the
reacrant

(CO) is

- CIco

r1 dr
d

wirh rhe following

al
t

includes

to a satisfactory

numerically
for a single, isotherwith first-order
reaction and de-

analyzed

which

with simultaneous:catalysr

series, independent

been extended

More

reaction

factor.

with

for which
and Smith

servarion equations
mal cataIyst pellet

The

gas-shifi

reactions

are as yet not develope'd

Masamune

activation.

and

foe the efectiveness

r --

dr
( dCco)

boundary
r

O,

rcoa(r

e)

(1)

conditions:

dCcodr

(2)

1
..

S.!

r-- - -:O;:.-;.-~ -: -.:;::.....,ain ;:::ac~I)n

3.:_

0.3

Kco ia:::> - )
K.!.o atm-,
\

:e!;. tat;-r -

2.2ex~(iOI5/T)

fO.

O." ex;;! 15:3.3,'T)

O (})~ 7 ~:(p(27H.9. T
0.05 ex DI 596.I/T)

IJ

1.0
< OA,

/\.-1;. dL . -:,

1 Yoar

I,

2Year

JYear

0.2

!
CO

H,

Compound

r,0198

The

kinetic

rco

Cl,

O.f)O~J2 O.C03i

expression

given by (.\m,!deo

O.eD5ll

0.003

for the mQ.in reactlon

Fig. 1. .-\cli:;ity

is

kCcoCH,o(l

KcoCeo

KH:OCH,O

+-

f" ..:

~_._.:.> ..

values given in Table

The conc~ntration

ea

by the fo!lowing

reoa(r) d V

where

i
[

expressi,0r.:

C?)

7.,

D"co

CLeo

D::f;

(Cco - C~o)

In eq. (10) the surface

and of the poison

1
-=-+-D""

(see Table

2):

wirh the following

The reaction

rate of the poison

is

Cp

(he caaiyst

The deactivation

the activlty

Q.s

(rco), =

=1

a[

=O

experimental

data

(9)
O

of

::In

(a

= O)

1). Therefore,

and

the

[he anal-

of ea. (8) was evalu::w::d from

industria!

reactor

(he one-dimensional
pscudohomogeneous
(Gonzi!ez
V~!J.seo al., ,9921.

applying
rT',odd

are shown.

Ir can be seen that

the profiles become sharper when k L in~es,

and
(hus for high values of k i the poison will be exhausred
inside the pe1k(.
, The activiry profiles

for all r.

The kineric eoefficient

reproduce
rhe situacion showed in Fig. 1.
In Fig. 2(a)-(c) poison profiles in the pellet for three
values of k (0.2.2000 and 8000 moll-'
h - ') ar differen times of operation

a=---rco
wirh a

(a

T = 2300e and cgo = ~.7 x 10 - 3 moll- 1, the effect

of the poisoning rate on he caralysr decay was investigated in order to obtain he k1 values which can

ra[e is

is d~fined

deactivated

ysis for a pellet placd atehe inl:t of rhe bed wili be (

also valid for al! other pellets in the bed unit shifted in
__ time acco.rriing to the position relative to rhe front.)
Then, for a pelle placed in a zone of the bed where

(8)
where

completely

wirh fresh catalyst

()

. I

ing forward in the bed wi(h rime as indicated in Fig. 1.

The bed is clearly divided into two zones: the first with ,
second

=O
cg

R,

(5)

conditions:

dC;;7dr

O,

In a previous paper, Gonzlez Velasco e al. (1992)

proved that the indumial
catalyric bed is deactivaed
inhomogeneously,
wirh a fronr of de3.ctivation
mov-

for he pOIson

a r
1:::.:,::::;:'

dr /

boundary

at r =

r-

equarion

.(, r dr \

rate, which remains

RESULTS

D. -1 -d ( r -dC,) = r alr )

reaction

in the following.

DK'

The m2.SS conservaion

(chlorine) is given by

(i1)

constant during the operation

time, is affeeted by the
average activity instead of the surface activity, an
intuitively
more attracci'le definition, as wil! be explained

D",,'

a(r)dV
V
.

(4)

The Wheeler equation (Wheeier, 1955) was' used in

order to e'lalu2.te the effecrive diffusion coemcient of

(10)

TCOQ.HV

aM

each component

le!1gth.

re:lCCOr

of the th species is re!aed to he

concentration

(C;-

liS

J:
'7=-----

KH,CHY
(3)

wirh par2.merer

30

The solution of equation sysem [l)-(3)

is de{ailed
in the ";ppendi.~.
is defined as
The effectiveness factOr of

(J)

Kco,Cco,

I
I

.~
I
.:-: ....::.

I
70

eo

(1

I
60

Li:ngrh %

ec ,,1.,1995):

"

I
50

times of operario

for he cO[JcentrJtion.
sh:lrper
J.c[ivicy

for he same values

n are presented

01'

in Fig. ~(a)-(c).

and
As

a ~ given time the pr~files ~

nevenhcless.
he averaae
~hen k 1 inc~ses:
lnCr~:lScS wit~ ~n(r~:.lSlr.g k ~ sinc~ Ihe YJ.lue

I
I
I
I

-_..

------,---_._---~~_._

---

....

-.=_-'~' --~-

Effeet or inlrapartiek
(a)

diffusion on eatalysl decay

4th month
3rd month

\.0??oo
0.99999

t=O

0.9

2nd month

I.0t
(a) 0.3

0.99998

'"
>

0.7
0.6

S( 0.99997

U 099996

0.5

<

685

0.4

O.}

1st month

0.\

2nd month

0.2F---------

0.99995
0.99994
O

0.2

004

0.6

0.8

1.0

0 ..\

0.2

rfR

0.9

1.0

LO'

.8

0.7

0.7

o 0.6
03
S::!

0.4

~
>

0.6

;:
-<

0.3
0.4

0.3

0.3
0.2

0.2
0.1
o

t=O

0.9

0.8

0.2

0.4

0.6

0.8

0.1
1.0

rfR

r/R

(e)

0.8

(b)
1.0

0.6
r/R

(b)

'"

0.4
1.0
0.6
0.3

-<

(e)
>
;:

0.9
0.7
0.8

rfR

rIR

Fig. 2. Dimensionless
poison eonecnlratin
vs dimensionless radius al diferent times of operation: (al k, =
0.2 moll-' h-1: (b) k, = 2ooomoll-'
h-',
(e) k, = 8000
moll-' h-,.

of kz (0.002 h - ') remains the same (slow deactivation

rate)o
The
profiJes are shown in Fig. 4. 1t can be
appreciated that the profiles depart more slowly from
the initial profile (at r = O) when k is increased. This
means that the catalyst deactivates more slowly. if
k, increases.
.
The effect of k on the effectiveness factor for
conversion is indicated in Fig. 5. It approaches 1 at
arge values of time for al! k, values. The fact that the
effectiveness factor, ~s defined in eq. (10), approaches
1 indicates that the catalyst js completel .deactivated.
This situation only arises if the average activity is zero
and not if the surface activity is zero. Thus the definition of effectiveness factor as in eq. (10) is juslified. In
a'ddition, at a given time, Ibe effectiveness fae.ter

eo

ea

fig. 3. Aetivity vs dimensionless radius al diferenl times

ofoperation: (a) k, = 0.2moll- h-l, (b) k, = 1ooomoll-1
h-', (e) k, = 8000 moll-' b-l

increases. when k 1 deereases; it means that the deaetivation rate decrases when th;;-Qise-a-- d1ffusional
resistance increases. Ot.."lerwise, for the highest
k, va!ue seleeted, the effectiveness factor initial!y decreases with the time of operation, but thereafter it
follows the general lrend of r to approach 1 as time
increases. This can be explained by considering
eq. (10) while making a srnultaneous analysis of the
profiJes (Figs 3 and 4). Al srnal!
activity and
values o'f time lhe activity is seen to decrease abruptly
in the externa! zone of tbe pellet while rco rernains
approxirnately constant. On the other hand, in the
center of lhe pellet even though the activity is significant, he
concentration, and consequently rco, are
exuemely srna!!.
It may be noted tba[, :, = O, the diffusional effect

eo

eo

in lhe main reJctioo

i5

signiilcant.

-.

M.

686

CHOeRN el al.

It is proved

1.0

4th month

0,9

0.8

- k,=O.2 mollh
-k,=2000 mol/h

06
0,5

So!

8
U

"k,=8000

04
0.3

mol/h _
4th

0,2
O.,

2nd
month

High values of
eliminared
inside

monlh.

,
0.2

t=O

0.6

0,4

0,8

10

r/R

eo

Fig, 4, DimensionJess
concentration vs dimensionless
radius al different times ofoperation and dierent k, vaJues,

/0---:7-- /+

.
I./

;::

J.5

tlJ.............

+__

10.1

._

I/lh
/.~=o.2mOl/lh
k=2000mo
k=8000mol/lh

Time months

Fig. 5. Effectiveness factor of eo vs operation time 1:, = 0.2,

2000, 8000 moll- I h - 1
rco
p
E
*
component,
12 t-1
D,\(;
krco
r'
a
K;
1:
R
C;
a,lr
kd
DK
Dd';
C~o
kt
1:2
Cp
D<;ip

.-..- ....

..

~.~
~.

~
~
"~

. ~

">
c:

.~

I.j

k,=O.2mol/lh
k=2000mol/lh

UJ

'0-'
+

g
2

).1

,~(8000mOlllh
I O~I

:\"

\\

,\
100

:;

".

./
10'

Thiele modulus*Caverage activity)'~

Fig. 6. Effectiveness factor of eo vs Thiele modulus of CO
k, = 0.2,
modified by"the average activiry (C!>~o:<Dco,a~')
2000, 8000 mol - 1 h - l.

A plot oi the effectiveness

(high values of k

increascs
1)

for the

factor oi CO vs rhe Thiele

modulus
modified
by the average activity (<!>o), is
shown in Fig. 6 ior three different values of 1:t. Each
() during
curve represents
the time oftheoperation.
evolution it ofis both
norewortny
parameters
that

,to values.
a non-deactivated
r lOhw
Final!y,
at a catalystThat
given as that
!ele leastd
mo ufOI
us,
t e
) kt
these plots have
the same
shape
corresponding
effectiveness factor in creases when k, decreases.
SUMlYIARY AND CONCLUSIONS

Diffusional
effects are studied for a catal)'.>t used in
the WGSR which suffers an independent
deactivation
due to chlorine in the feed. -

k"

ior ",hich
the
pellet,

the poison can be

exolains
the
In-

bomogeneous
deaciva[ion
or the ind'ust[ial b~d, such
as il can be observed in Fig. 1. 1t also means lhat lhe
analysis made ror a pe!let placed in a gjven zone or the
bed is valid ror al! the peIlets in [he bed.
Al t = O, a diFfusional resistance ror the main reactant exists (/

<

0.2).

The definirion
or he eFfecti'leness faclor given by
eq, (10) predicls lhal r tends to 1 ror large limes of
operation,
al any Thiele modulus value. This conclusion agrees wilh thal of Grzesik er al. (1992a), who
used irreversible
first-order
knerics and the TOST
lheory,

+
..-/

lhe life of he catalyst

resislance

poison incre:lses. [n his case, lhe average activitYaiSQ

increases. Masamune
and Smi[h (1966) and Grzesik .
el al. (l992a)
arrived e rhe same conclusion
for an
irreversible
firsl-order
reaction.

4th month

0,7
'"

lhat

",hen diffusional

Equajon

(10) is lhe generalized

definition

of

the effectiveness iacwr and it is v:llid for any type of

kinencs. In addition, chis equarion includes rhe deactivation.
Consequently
it may be concluded
that
tends to 1 ior large times oi ogerarion regaLdless_oJ_
the kineiics and [he assumed mechanism oi deactiva-_
tion.

-' i

,i1t

main
reaction
rate,coefficient
moll3reaction
trate
-of
1oi
acrivity
i'lOTATlOi'i'
radius,
effective
average
kinetic
poisoning
coefficienr
activity
diffusion
reaction
coefficient
rateo
deactivation
3rate
i-3eo
I1
dimensionless
concentration
molecular
diffusion
coefficient
coefficient
of
main
dimensionless
reaction
pellet
Knudsen
variable
kinetic
radius,
defined
diffusion
1main
codficient,
eq_
poisoning
(lOA)
tt --rate
adsorption
constant
ai
.\
eFfective
diffusion
component,
i mollcomponent,
of
mo11-3
poison,
concenrration
of
equilibrium
constant
concentration
oi in
poison,
mol
1-12
kpC~,
kdq,
lpoll-3
t-1
t-1
[eq. (7)J, t-1
p
r[eq.
12
r
I
atm-'
!une
radial
coordinate,
1
12 t-1
component,
Y, value
in t-I
the
center
oi tbe pellet'
(8)J,
13
mol-I
(3)J,
moI1-3t-'atm

..

Efoct o intraparticlc

conversion

Y"

of lhe

1'2, Y), auxiliary

difTusion

on cHal}'st

doeay

687
..\PPE"DIX

poison
lo order

variables

1'~

tiai eqs
rJc

to obtain

lhc dimensiQnless

(l). (5) and (8), {he follo'.ving

orm of the difTercn-

definijons must be gi ....en

r/ R,

C, = C~(I - X,l

Greek letrers
'1.,

stoichiometric

lenn of equilibrium
toler~nce

effectiveness
nllmber
Thjele
<Dco'

coefficient

of

i component

in eq. (3)

factor

of

eo

of iteralions
modulus

of

eo

a~;'

Tbiele

modlllus

lt must be nored rhat r20 is only J function of rhe CO

concentration
ir ~q. (-\.)is considered.
Then, (he dimensionless dilTerential eqs (1), (5) and (8) are

of poison

Sl'perscripr
O

iniria!

r"
dr
dX,\
- 1 dr"
- d ('.r' -)
da(r",

REFERENCES
Atnadeo,

N.,

Cerrella,

E., Pennella.

F. and

1995, Kinetics o rhe low-temperature

tion on a copper/zinc
o.~ide/alumina
.
Appl. Res. 25, 21.
Chu, c., 1968, Effect o adsorption
pellets. lEC Fundam. 7, 509.
Elnasahie,
S. S. E. H. and Alhabdan,

Laborde,

water-gas
catalyst.

M.,

shift reacLarin Am.

\Virh lhe following

on the fouliog

F. M., 1989, Mathemalo industrial

:'vfodel/ing 12,

l ..

l.

on-stream
catalyst
decay. Chem. Engng Sci. 47, 2805.
Grzesik,
M., Skrzypek.
1. and Wojciechowski,
B., 1992b,
Time-on-srream
catalysr
decay behavior
in a fixed-bed
catal)'ric
reactor under rhe innuence o inr,aparticle
diffusion: intraparticle
diffusion afects only c:ltal)'tic ,e:lctions.
Chem. Engng Sei. 47, 4049.

L L,

1974, On the poisoning

of porous caralysts
Hegedus,
by an impurit)'
in the feed. lnd. Engng Citem. F,mdam. 13,
190.
Hlavacek,
M. and Kubicek,
V., 1983, Numerical So/ueions o/
Non-linear
Boundary
Val"e Problems
wirh Appliearions.
Prentice-Hall,
EngJewood
Cliffs, N1.
Krishnaswamy,
&-attd Kittrell,
R., 1981, Diffusional
influences on deactiyation
rates. A.LCb.E. 1. 27, 120.
Levenspiel.
O., 1972, Citemica/
Reacror Engineering,
2nd.
Edition. Wiley, New York.

on catalyst

fouling.

5<udv o the

Jow-temperature
water-gas
sbift reaction oyer a u-ZnO
catalyst.
Appl. Cara/. 49, 285.
van Herwijnen,
T. and de long. W.. 1980, Kinetics
and
mechanism
of the CO shifr on Cu/ZnO:
L Kinerics of
the forward and reverse CO shirt reactions.
1. Caca/. 63,
83.
Wheeler,
A., 1955, Caealysis,
Vol. n, Chap 2 (Edited
P. H. Emmer). Reinhold
Pub. Corp., New York.
Young,
P. W and Clark, C. ', 1974. \Vhy
de:lctivJ.t~. CJem. Enqng Prog. 5"2, SlO.

;J

and inirial

a(r", t) =

O,

Taking
considered

al r" = O,

dC20/dr"

at r" = 1,

Co

into account
and
that

la(r'

t)

(A3)

t)

conditions:

for all r'

by

shiit ca'<ll)'sts

= dX ,/dr"

= 1

= O

X, =

and

rhat an independent
rhe deacrivation
is

O.

deacrivarion
is
relarivelv
slow

(k,

-G k,), eqs (2."1) and (3"\) can be solvecI sequentiallY.

Considering a(r') = I ar e = O, a profile of X,(r')
is oblained
from eq. (lA). The nexr step is to eeplace bis prolile in

eq. (3A) and integrate

until a time e + 61. Ihe new activity
profile [a(r*, r + "'e)] is used to evaluate :l new poison proThis
procedure
is repeated
until
file from
eq. (2.A).
a(r', e + /(r) has become negligible.
The activity
profiles seored al intervals
of l month (the
whoJe period considered
\Vas 3 years (Gonzalez
Velasco ee
al .. 1991)) are used to obtain lhe CO profiies from eq. (lA).
Concentrarion
values in the center cith~ pellet were evaluated using he shooting
,echnique
(Hlavacek and Kubichek,
mass
1983). This method.
applied to [he CO and chiorine
balances,
implies
rhal for e:lch of eOs (2,1,.) and (3A) two
ordinary
differential
equations
are obtained.
For instance,
for eq. (2A):

dX, d Y,
-=-=Y,
drdrwith

Y, = S ar r* =

and

Y, =

(A4)

ar r- = l

1966, Performance
of fouled
1. 12, 384.
T., Hanori,
T. and Masuda,
M.

R., 1989, Kioetic

= k,( 1 - X ,)a(r',

l. M.,

diffusion

(A2)

", .
= 'v;(1

boundary

1968, Effect of intraparticle

lEC Fundam. 7,599.
Sal mi, T. and Hakkarainen,

(Al)

ej

,.

o caralysr

Gonzlez
Velasco, 1., Gutirrez
Ortiz, M., Goozlez
Marcos,
Amadeo,
N., Laborde,
M. and Paz, M., 1992, Optimal
inlet temperature
trajectories
oe adiabatic
packed reactors witb catalyst
decay. Chem. Engng Sei. 47, 1495.
Grzesik,
M . Skrzypek,
and Wojciechowski,
B.. 1992a.
Modelling
of inlraparticle
diffusion affecred by [he time-

S. and Smitb,
pellers, A.LCh.E.
Y .. Kobayashi.

<1>corcoa(r',

e)

- -d-e -

ae e =

ieal modelling
and computer
simulation
water-gas
sbifr converters.
vIaeh. Compue.
1017.

Masamune,
catalyst
Murakami,

--,- ---,- r- -r"I dr"

dr"20)
d ( . dC

surface

- ~

Y, - lv;a(r*,

e)(1 -

Y,)
(A5)

wirh Y, = O at r- = O.
The following auxiliar)'
YJ

vari:lbles

r, = d Y,/ds.

= d Y,jds.

Differenrialing
eqs (4A)
crossing derivati ....es:
-

and

-1=-=1"

ds
d(dY,\
dr' /

~('~\=dYJ=y"
dr'"

cs)

are del1.ned:

(5A) wirh

dY,
es

eespect

to s and

(A6)

(A7)

dr"

M.

688

CHOCR6N el al.
whcec

(A8)

o is the tolerancc

admitted.

s'"

with

y"

A value

al r =
SK

at

_~,*

Y.+'D;a('*,i)Y)

is not

(All)
dE(SK)jds

Then,

in function

01 Y 1 and

Y 3:

O.

,* = O is

assumed

and (9A) are integrated

up to r'
following condition
must be satisned:

(7.'1.)

condition

=SK_~.

(A9)

~(dY2)=dY"=
d,' ds
d,

Ir this

In arder
satistjed, a new value 01 s (SK+ ') must be employed.
la estim:lte the new value equation
(lOA) must be expandcd
in Taylor series, rrom which:

and the eqs (4A),

(5.'1.),

1. At chis point

sl(';-

S';

the

(.'1.10)

y! ,.'"L~.

(A12)

Y':\'''l.J" .
The equations
method.

are solved

using

a fourth-order

Runge

Kutta