Catalyst Decay

Bamrung Sungnoen
Process Technology Center–Process Innovation
 Rate law
(Plus catalyst deactivation)

Separable kinetics: Nonseparable kinetics:

-rA' = a  Past history  × -rA'  Fresh catalyst  -rA' = -rA'  Past history, Fresh catalyst 

the ratio of the rate of reaction on a catalyst that has been used for a time t
a t =
the rate of reaction on a fresh catalyst ( t = 0)
rA'  t 
a t = '
rA (t = 0)

rA' = a  t  k  T  fn  CαA  CβB .... 

 = p a  t   k  T  fn  CαA ×CβB .... 
da 
The rate of catalyst decay: rd = -
dt

Deactivation by Sintering (Aging) Deactivation by Coking or Fouling

Deactivation by Poisoning
Deactivation by Sintering (Aging)
The most commonly used decay laws for sintering is second
order with respect to the present activity:

da
rd = - = kda 2
dt

The sintering decay constant, kd, follows

1 the Arrhenius equation
a  t,T  =
1+k d t
 Ed  1 1 
k d = k d  T0  exp   - 
R  T0 T  
The amount of sintering is usually measured in terms of
the active surface area of the catalyst Sa

Tips:
Sintering is usually negligible at temperatures
below 40% of the melting temperature of the
Sa 0 solid
Sa =
1+k d t
Deactivation by Coking or Fouling
The amount of coke on the surface after a time t (Empirical relationship):

CCoke = At n Ccoke = the concentration of carbon on the surface, g/m2

n, A = fouling parameters"

Commonly used forms:

1 Tips:
a  t,T  = When possible, coking can be reduced by
k Ck CCp +1 running at elevated pressures (2000 to 3000
kPa) and hydrogen-rich streams. A number of
other techniques for minimizing fouling are
1 1
a  t,T  = = discussed by Bartholomew
k Ck A p t np +1 k ' t m +1

Other commonly used forms are:

1
a=e α1CC a= α = A dimensionless fouling correlation (Pacheco and Petersen)
α 2 CC +1
Deactivation by Poisoning
The rate of removal of total active sites (Ct) from the surface:

dC t dCPS
rPS = - = = k d  C t0 - CPS  CP
dt dt CP = the concentration of poison in the gas phase
CP.S = the concentration of poisoned sites
Ct0 = the total number of sites initially available
dCPS 1 1
= k d  C t0 - CPS  CP Ct0 - CP.S = the number of sites that are unpoisoned
dt C t0 C t0 f = the fraction of the total number of sites that have been
poisoned yields
df
= k d 1 - f  C P
dt

da  t 
= a  t  k d CP
dt
Empirical Decay Laws
Empirical decay laws along with the reaction systems to which they apply
Temperature–Time Trajectories
da E  1 1  n
In many large-scale reactors, reaction systems where - = k d0  T0  exp  d  -  a
deactivation by poisoning occurs, the catalyst decay is
dt R  T0 T  
relatively slow. In continuous flow systems, one way to
maintain a constant conversion with a decaying catalyst in da  E 
a packed or fluidized bed is to increase the reaction rate - = k d0  T0  exp   d  lna   a n
by increasing the temperature to the reactor. dt  Ea 

rA,maintain = a  t   rA
Ed
' '
da 
- = k d0  T0  a Ea a n
dt
k  T0  CA = a  t,T  k  T  C A Integrating with a = 1 at t = 0 for the case n ≠
(1 + Ed/Ea )
k  T0  = a  t,T  k  T 
1 - a a
1 - n + E /E
d

t=
 -E    -E   k d0 1 - n + E d /E a 
A 0 exp  a  = a  t,T   A 0exp  a  
 RT0    RT  
 E - nE a + E d  1 1 
 -E  1 1  1 - exp  a  - 
exp  a    = a  R  T T0 
 R  T0 T   t=
k d0 1 - n + E d /E a 

1 R 1
= lna +
T Ea T0