Catalyst Deactivation

and Regeneration

Advanced Reaction Systems A

Catalyst Deactivation
 Until now, we assumed that catalyst activity remains
constant
 But actually it decreases with time
 The activity of the fresh catalyst is compromised by
deactivation kinetics
 Two situations occur:
 Separable kinetics: It is possible to study kinetics and decay
independently
  r   = rate of  r    a r  
 A  disappearance of A  A   A  fresh
per mass of catalyst a = activity parameter
(mol A/g.s)
 Non-separable kinetics: The kinetics and deactivation are linked,
for example through a mechanism consisting of several
elementary steps or a non-ideal surface. Their effects cannot be
separated.

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 Separable kinetics
 Activity parameter

Rate of reaction on catalyst used for time t  rA t 
at   

Rate of reaction on fresh catalyst  rA t  0 

 Typical deactivation profile, showing activity as

function of time
1.0
a(t)

0
t

Rate of disappearance of reactant A on catalyst used for time t


 rA  a (t )k (T ) fn(C A , CB ,..., CP )
Catalyst activity Rate constant Gas phase concentration of
(time dependent) (temperature dependent) reactants & products

Rate of deactivation

da
 rd    pat kd T hC A , Cb ,...., CP 
dt
P is a h(Ci) is the
kd is the
function of functionality of rd on
decay
the activity the reacting species
specific
constant concentration

 The functionality of the activity term

 p(a) = a This function will vary with the gas catalytic system
 p(a) = a2 being used and the reason or mechanism for the decay.

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 Types of Deactivation
 Sintering
 Coking or Fouling
 Poisoning
We will consider each type of deactivation in turn.

 Deactivation by Sintering

 Sintering is the loss of catalytic activity due to prolonged

exposure to high temperatures
 Loss of surface area occurs by
 Crystal agglomeration
 Closing of pores inside the catalyst
 Recrystallization causing change in surface structure

 Decay by sintering: pore closure

t=0

 Agglomeration of deposited metal sites

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 Deactivation by sintering – commonly represented as Second Order
decay
da a da t
rd  kd a 2    a1  a 2  0 kd dt
dt
 a is the present activity rd = rate of deactivation s-1
a = activity (-)
 Integrating with a = 1 at time t = 0 yields kd = decay constant (s-1)
1
a (t ) 
1  kd t
 Amount of sintering in terms of active surface area of catalyst, Sa
Surface area at time t = 0
S
Sa  a 0 a = Sa/Sa0
1  kd t
 Sintering decay constant follows Arrhenius equation:
Decay activation energy = 70 kcal/mol
Sintering can be for reforming of heptane on Pt/Al2O3
reduced by operating
 E  1 1 
at less than 0.3 – 0.4 Tm kd  k d T0 exp  d   
Tm = melting point  R  T0 T 

 Calculating Conversion with Catalyst

Decay in Batch Reactors
 First order isomerisation reaction A→B
 Batch reactor design equation
NA0 = no of moles at t=0
dX  X = conversion
N A0  rA W t = time
dt
W = mass of catalyst
 Reaction rate law
 k’= rate per unit mass of
 rA  k at C A catalyst

 Decay law: second order decay by sintering

1
a t  
1  kd t
 Stoichiometry
N A0
C A  C A0 1  X   1  X 
V

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 Combing the above equations gives
dX W
 k at (1  X )
dt V
 let k = kW/V, then separating the variables gives
dX
 ka(t ) dt
1 X
 substituting for a and integrating yields
X dX t dt
0 1 X
 k 0
1  kd t
 1  k
ln   ln 1  kd t 
1 X  kd
 Solving for conversion X at any time t, we find that:
1
X 1
1  kd t k / kd

Class Example
 Sketch X vs t for various values of k and kd
 e.g. K = 1.0 h-1, kd = 0.01, 0.1, 0.5. 1 h-1
 Calculate your values for t = 0 – 20 hours.

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Deactivation by Coking or Fouling
 Common in reactions with hydrocarbons
 A layer of carbonaceous material (coke) is deposited
upon the catalyst surface

 Picture of (left) fresh catalyst and (right)

coked catalyst (Engelhard catalysts)

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 Amount of coke on the surface after time t

CC  At n
Amount of
n, A are
carbon on
fouling parameters
the surface (g/m2)

 For cracking of an East Texas light gas oil

% coke  0.47 t(min)

 Effect of coke on activity, a common form of expression:

1
a
kCK CCp  1

 In terms of time

1 1
a 
kCK A t  1 1  k t m
P np

 For Texas light gas oil (at 750 F) the decay law is:
1
a
1  7.6t 1 / 2 Time in seconds
 Other commonly used forms

1
a  e1CC a
1   2CC
 Coking can be reduced by running at elevated pressures (2000 to
3000 KPa) and using hydrogen rich streams. Operating the catalyst
in a supercritical fluid near to the critical point can also reduce
coking.

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 Deactivation by poisoning
 Molecules become irreversibly chemisorbed on active
sites
 The number of sites for the main reaction are reduced.
 The poison can be a reactant, product or impurity.
 The example below applies to an inpurity P in the feed
 S is an active site on the catalyst

 A  S  A.S 
   kC A
 A.S  B.S  C ( g )  rA  at 
 B.S  B  S  1  K AC A  K BCB
 
da 
P  S  P.S rd    kd C pm a q
dt

Change of surface sites with time:

 Rate of removal of poison from gas stream

rP.S  kd Ct 0  CP.S CP

Concentration of Concentration of Concentration of
sites initially poisoned sites poison in the gas
available
phase
 Since every molecule adsorbing on to an active site
poisons that site, removal rate of poison = active site
removal rate

dCt dCP. S
   rP.S  kd Ct 0  CP.S CP
dt dt

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 Divide through by Cf0 and letting f =
fraction of the total number of sites that
have been poisoned
df
 kd 1  f CP
dt

 (1-f)=a(t), the activity

da
  at kd C p
dt