L -18 Catalyst Deactivation

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
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
Catalyst deactivation by site
coverage
Consider reversible isomerization, where C is
a precursor to coke formation that is strongly
absorbed and not found in the gas phase.
| |
|
|
\ .
C
B
k K C C -
sr
t A A
K
r =
A
C
C

S
1+K C +K C +
A A B B
C
S
A + S AS
Neither term
measureable, thus
some empirical
correlation is necessary
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
Preventing of Coking

Optimum catalyst composition

Equilibrium must be in between rate of coke
production and rate of coke removal

Coking can be reduced by running at elevated
pressure and hydrogen-rich streams.
E.g in catalytic reforming processes

Catalyst deactivated by coking can usually be
regenerated by burning off the carbon.

Catalyst Deactivation
Sintering (aging)
Activity loss by loss of active surface
caused by prolonged exposure to
elevated gas-phase reaction
temperatures.
Mechanistically
Crystal agglomeration/growth,
reducing internal surface area
accompanied by narrowing/blocking
of pore cross section.
Sintering of Catalyst
A loss of active surface area resulting from
the prolonged exposure to high gas-phase
temperatures
Occurs in both supported and
unsupported metal catalyst
Two models for crystallite growth due to
sintering
Atomic Migration
Crystallite Migration






Decay by sintering : pore closure
Decay by sintering : agglomeration of metal
Sintering of Alumina upon Heating
( )
( )
| |
|
\ .
da
r = =p a k T h C
d
d i dt
Experimental analysis of the decay rate is as:
- Commercial reactors maintain constant
production rate by increasing T (reaction
rate constant increases), as catalyst
decays (catalyst activity a decreases).
Catalyst Deactivation
Sintering (aging)
Activity loss by loss of active surface caused by prolonged
exposure to elevated gas-phase reaction temperatures.
Mechanistically
Crystal agglomeration/growth, reducing internal surface area
accompanied by narrowing/blocking of pore cross section.
Change in surface structure through recrystallization or other modes of
defect elimination (active site loss).
Typically a 2
nd
order process;
2
d d
a k
dt
da
r = =
} }
=

t
0
d
a
1
2
dt k da a
( )
t k 1
1
t a
d
+
=
da
2
r =- =k a
d d dt
} }
a t
-2
a da=-k dt
1 0
d
( )
1
a t =
1+k t
d
-Typically a 2
nd
order process;
Change in surface structure through
recrystallization or other modes of defect
elimination (active site loss).
Sintering measured in active surface area
S
a0
S =
a
1+k t
d
Sintering decay constant follows from
Arrhenius Eqn.
| |
|
|
\ .
E
1 1
d
k =k (T )exp[ - ]
d d 0
R T T
0
REACTOR DESIGN FOR DEACTIVATING CATALYSTS
Main reaction Kinetics:

Deactivation reaction Kinetics (FIRST ORDER/SECOND ORDER etc.)
da/dt = k
d
a
n
Moving bed reactors
Thermofer Catalytic crackin unit (Used for reactions with moderate decay)
Combining activity equation with the mole balance equation: