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Catalyst Decay PDF
Catalyst Decay PDF
Bamrung Sungnoen
Process Technology Center–Process Innovation
Rate law
(Plus catalyst deactivation)
-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)
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
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):
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
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
rPS = - = = k d C t0 - CPS 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 - CPS 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