CLL 222/CHL221, CRE II: L13

cll222_2015-16@googlegroups.com.

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
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.
 Poisons Classification
• Poisons can be Classified as
– Selective and Non Selective
 - Reversible or Irreversible

Example : Reversible Poisoning is due to Oxygen

Compounds (O2,H2O,CO,CO2) and irreversible
Poisoning is connected with non metals such as
S, Cl, As, Ph
 KINETICS
•The adjustment for the decay of the catalysts:
•The reactions are divided into two categories
separable kinetics

-r' =a( past history)×-r' ( fresh catalyst)

A A

• non separable kinetics

-r' =-r' ( past history, fresh catalyst)

A A
Rate of Catalyst decay, rd
da
r =- =p[a( t) ]
d dt
First Order Decay , p(a)=a
Second Order Decay, p(a) = a2
 Preventing 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.
 Decay by sintering : pore closure

Decay by sintering : agglomeration of metal

Sintering of Alumina upon Heating
- Commercial reactors maintain constant
production rate by increasing T (reaction
rate constant increases), as catalyst
decays (catalyst activity a decreases).

•Experimental analysis of the decay rate is as:

da
r = =p  a  ×k d  T  ×h  C 
d dt  i
 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 2nd order process;

1
da a t
at 
r d   k d a2
a 
2
da  k d dt 1  kdt
dt 1 0
•Change in surface structure through
recrystallization or other modes of defect
elimination (active site loss).

-Typically a 2nd order process;

da
r =- =k a 2
d dt d

a -2 t
1 a da =-k  dt
d 0

1
a  t =
1+k t
d
•Sintering measured in active surface area
S
Sa = a0
1+k t
d

•Sintering decay constant follows from

Arrhenius Eqn.

E
 1 1
k =k ( T ) exp[ d  - ]
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 = kd an
Slow decay : Temperature time trajectory
Moderate decay: Moving bed reactors
Rapid Decay: Straight through transport reactors

Coupled differential eqns to be solved are

For and nth order activity decay

and mth order gas phase
Moving bed reactors
Thermofer Catalytic crackin unit (Used for reactions with moderate decay)
Combining activity equation with the mole balance equation:
For a first order Decay
Straight through Transport Reactor
(Circulating fluidized bed reactor)
•Used when deactivation is rapid.
•Used for production of gasoline
•Catalyst pellet and feed enter together and
transported rapidly.
•Bulk density of the catalyst is low compared
to Moving bed.
STTR : Used when coking is rapid.
 Mole balance

r A = ρb r’A

Or

Z= Height ,and U is velocity of catalyst

Reading Assignment: Examples : 10.5 ,10.7, 10.8 Fogler
 Temperature/Time Trajectories
• A control strategy involves maintaining a
constant conversion with catalyst decay by
increasing operating temperature.
• develop a temperature/time trajectory to find T –t
relationship:
• -rA’ (t=0,T0) = -rA’ (t= t,T) = a(t ,T)[-rA’ (t=0,T) ]

k  T  ×a  T, t =k o
(For First order reaction )

E a  
 1 - 1  1  R  1
  

 ln  a  +


R  T
o T 
=
T  E a 
 
k oe   
a =k o  To
 Temperature/Time Trajectories

E   
d   1 - 1 


R   To T 

da 

an
decay law is: r =- =k e

 
d dt d

E

E 
d 
  

- dlna
 
n-
E a 
  
Ea
  
da   

an =k
   
- =k e  
do
a
dt do

1  R  1
=  ln  a  +
T  E a 
 To
 Temperature/Time Trajectories
1  R  1

E a  1 1 
- 


=  ln  a  +
 

R  T To 

T  E a 
 To a =e

  


E a -n E a +E  
d  1 - 1 


1- n+ E E a 
 

R  T T 
 
1-a

 d  


 o


t= 1-e  

k
do 
1-n + E
d
Ea  =
 E 
k  1-n+ d 
do  E 
 a 

E 
-n+ d 



E a  E 

 t  d -n  ≠1
da =-k dt
a  
1 a do 0 E 
 a 
 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 (Cc): Cc  Atn
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:
1 1
at   ae   1C c a
1
1  Cc 1  Ap tnp
p
1   2C c
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:

-α C c C c =Atn
a =e 1