L -17 Catalyst Deactivation

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
What is catalyst deactivation?
Catalysts have only a limited lifetime.

Some lose their activity after a few minutes,
others last for more than ten years.

The maintenance of catalyst activity for as
long as possible is of major economic
importance in industry.
Catalyst loss of activity with time-, i.e.
deactivation.
Also known as Ageing
Catalyst activity is defined as



( )
( )
( )
'
-r t
A
a t =
'
-r t =0
A
Catalyst deactivation is the result of number
of unwanted chemical and physical changes.
Decline in activity is due to
- Blocking of the catalytically active sites
- Loss of catalytically active sites due to
chemical, thermal or mechanical processes
Types of Catalyst Deactivation

Three causes for deactivation:
a. Structural changes in the catalyst itself (SINTERING)
. These changes may result from a migration of
components under the influence of prolonged operation
at high temperatures, so that originally finely dispersed
crystallites tend to grow in size.

Ageing : Temperature fluctuations may cause
stresses in the catalyst particle, which may
then disintegrate into powder with a possible
destruction of its fine structure.

b. Poisoning : Essentially irreversible
chemisorption of some impurity in the feed
stream, which is termed poisoning.

c. FOULING/COKING :Deposition of
carbonaceous residues from a reactant,
product or some intermediate, which is
termed coking.
Cause of Catalyst Deactivation
Causes of Catalyst Deactivation
Poisoning of the catalyst
Deposits on the Catalyst Surface
( Fouling, coking)
Thermal Processes and sintering
Catalyst loss via Gas Phase
Causes of Catalyst Deactivation
Poisoning of a Catalyst
Loss of activity due to strong chemisorptions
on active sites of impurities present in the
feed stream.

In heterogeneous catalysis the poison
molecules are absorbed more strongly to
the catalyst surface than the reactant
molecules, the catalyst becomes inactive.






Modify the nature of active sites
Poisons Classification
Poisons can be Classified as
Selective and Non Selective





- Reversible or Irreversible


Example : Reversible Poisoning is due to Oxygen
Compounds (O
2
,H
2
O,CO,CO
2
) and irreversible
Poisoning is connected with non metals such as
S, Cl, As, Ph
Tailored Reactor and Process Design
Relation between time-scale of deactivation
and reactor type
Time scale Typical reactor/process type
years fixed-bed reactor; no regeneration required,

months fixed-bed reactor;
regeneration while reactor is off-line

weeks fixed-bed reactors in swing mode, moving-
bed reactor

minutes - days fluidised-bed reactor, slurry reactor;
continuous regeneration

seconds entrained-flow reactor with
continuous regeneration
KINETICS
' '
-r =a(past history) -r (fresh catalyst)
A A





' '
-r =-r (past history, fresh catalyst)
A A
non separable kinetics

The adjustment for the decay of the catalysts:
The reactions are divided into two categories
separable kinetics
Rate of Catalyst decay, r
d


First Order Decay , p(a)=a
Second Order Decay, p(a) = a
2






da
r =- =p[a(t)]
d dt
Poisoning
( )


`

)
A+SA . S
Main Reaction A . S B . S+C g
B . S B+S
kC
' A
-r =a(t)
A 1+K C +K C
A A B B
Poisoning Reaction P+S

P.S
da
q
' m
r =- =k C a
p
d d dt
Impurity P in feed Stream
Assume rate of removal of gas stream onto
catalyst sites is proportional to the Number
of sites that are unpoisoned and conc of
poison in gas phase i.e
r =k(C -C )C
to P P.S P.S
dC
P.S
=r =k (C - C )C
d t0 P P.S P.S dt
(C -C )
t0 P.S
(C )
p
Fouling/ COKING of Catalyst
Physical (mechanical) deposition of
species from fluid phase onto the catalyst
surface which results in activity loss due to
blocking of sites and/or pores.
Common to reactions involving
hydrocarbons.

A carbonaceous (coke) material being
deposited on the surface of a catalyst.













Decay by coking
Coke Deposited can be measured
-TGA or DTA
-Monitoring the evolution of CO
2
and H
2
O

Position of Deposited Coke
Catalyst Deactivation
Fouling/Coking
Deposition of carbonaceous material on catalyst surface
Catalyst activity level is a function of the amount of carbon
deposited on the catalyst surface (C
c
):
where A and n are fouling parameters dependent on the type
of gas being processed.
Activity is expressed as f(C
c
) by one of the following:
n
c
At C =
( )
np p p
c
t A 1
1
C 1
1
t a
+
=
+
=
c 1
C
e a
o
=
c 2
C 1
1
a
o +
=
Catalyst Deactivation
Fouling/Coking
Deposition of carbonaceous material on
catalyst surface
Catalyst activity level is a function of the
amount of carbon deposited on the
catalyst surface (C
c
):




( )
1 1
a t = =
p p np
1+C 1+A t
c
1
a =
1+ C
c
2
where A and n are fouling parameters
dependent on the type of gas being
processed.

-Activity is expressed as f(Cc) by one of the
following:
- C
c
1
a=e
n
C =At
c