Deactivation Modelling

Deactivation of catalysts
w
w
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Types of deactivation
Reaction models
Kinetics
Mass transfer phenomena pellet
Effect on selectivity
Catalysis Engineering - Deactivation
Catalytic reactor design equation

steady state
conversion i
stoichiometric coefficient i
deactivation function
dx i
= i r
d (W Fi )
rate expression
space time
catalyst effectiveness
Coupled with:
Heat balance - T-profile

Momentum balance - p-profile
Timescale catalyst deactivation

10 -1 10 0
10 1
10 2
10 3
10 4
10 5
10 6
10 7
10 8
HDS
Hydrocracking
Reforming
FCC
EO
Fat hardening
MA
Aldehydes
Hydrogenations
Acetylene
Oxychlorination
SCR
Formaldehyde
C3 dehydrogenation
101
1 hour
Batch
processes
hrs-days
NH 3 oxidation
TWC
Time / seconds
10-1 10 0
Most bulk
processes
0.1-10 year
102
103
104
105
106
1 day
10 7
10 8
1 year
irreversible loss of activity
Types of deactivation:
Fouling: secondary reactions of reactants or products,
coke formation
Poisoning: strong chemisorption of impurity in feed
Aging:
structural changes or sintering (loss of surface
area, high temperature)
(Inhibition: competitive adsorption, reversible)
Fouling or self-poisoning often cause of deactivation
Deactivation types
Poisoning surface
S
Selective poisoning
S
Fouling
active site
Cl
Cl
Cl Cl
Cl Cl
Cl
Cl
Redispersion
&
evaporation
Sintering
Cl Cl
Cl Cl
Carbonfilament growth
Carbon filament growth

Ni/CaO
H2
CnHm
H H
Formation of nanotubes
May be reversible
Possible destruction of partices
Preparation of carbon supports
Deactivation
conversion
or
kobs
initial level
process time
k obs = k intr NT
constant
variable
variable
blocking pores
loss surface area
Fouling
loss active sites
Sintering
Poisoning
Deactivation - depends on?

heat
Fouling
physical blocking surface
by carbon or dust
usually regenerable
Sintering
loss surface area
gradual or catastrophic
irreversible - nonregenerable
feed & process conditions
process conditions
kobs
feed conditions
Poisoning
chemisorption on active
sites
reversible or irreversible
feed & process conditions

Selectivity poisons Modifiers
block side reactions
inhibit consecutive reactions
(kinetics)
kept as secret !
usually found by accident
What are poisons?

Examples
Surface active
metal or ion
Cu in Ni
Ni in Pt
Pb or Ca in Co3O4
Pb in Fe3O4
High M.W.
product
producer
Strong
chemisorber
Fe on Cu
Fe on Si-Al
from pipes
Bases
acetylenes
dienes
Toxic compounds
(free electron pair)
H2S on Ni
NH3 on Si-Al
Sintering
accelerator
H2 O (Al2O 3)
Cl2 (Cu)
from feed
or product
Sintering...
Loss of active surface due to crystallite growth
support
active phase
Local heating during
preparation (calcination)
reduction (fresh or passivated catalyst)
reaction (hot spots, maldistribution)
regeneration (burn-off coke)
Dependency:
time
temperature
atmosphere
promoters
melting point
da
= kam
dt
E
k = k 0 exp a
RT
affects m and Ea
affects Ea
determines Ea
m often 2 (-6)
Example sintering: n-Heptane reforming
m2/g Pt
dp Pt /nm
300
60
50
hydrocracking
50
40
dehydrocyclization
40
200
30
30
20
100
10
0
10 20 30 40 50 60 70 80
time @780 C / h
isomerization
20
10
n-C7
0
10
15
20
time @780 C / h
not 1:1 relation reactivity and metal surface

structure sensitive reactions
edge sites / steps
surface sites
Mechanisms of sintering
monomer dispersion
2-D cluster
3-D cluster
vapor
particles migrate
surface
coalesce
interparticle transport
migrating
metastable
Secondary
effects
stable
Fouling or self-poisoning
w Parallel reaction
B
A
C
w Series self-poisoning
(FCC, HDM)
w Triangular reaction
(FCC)
Poisoning
w Impurity poisoning
(TWC)
B
A
C
A
P
B
blocking
Deactivation: global view

Concentration profiles over reactor and in particles:
poisoning versus reaction kinetics
types of reactions
mass transport phenomena
increasing poisoning rate
uniform or homogeneous
poisoning
diffusion limited
poisoning
pore mouth
poisoning
center
poisoning
series poisoning
Particle deactivation
modelling slab
Homogenous poisoning: Fraction poisoned

Apparent activity:
F=
rpoisoned
runpoisoned
Diffusion model (first order irrev.):

d 2cA
De
= (1 )k B c A
2
dx
Concentration profile:
cosh( (1 )0 x / L)
c A = c A0
cosh( (1 )0 )
unpoisoned Thiele modulus
Catalyst effectiveness
1st order, irreversible, slab:
1.0
C*
0.8
Effectiveness factor:
0.1
1.0
tanh
0.6
0.4
cylinder
2.0
0.2
0.0
0.0
10.0
0.2
0.4
0.6
0.8
sphere
1.0
z*
Thiele modulus:
=L
slab
kv
Deff
V
1
L= p =
Ap a'
0.1
0.1
10
uniform poisoning
Fraction F of initial activity:
antiselective
nonselective
J poisoned
F=
J unpoisoned
Fraction of initial activity
1.0
0.8
0 =
0.6
large
(1 ) tanh (1 )0
tanh(0 )
=
x =L
Limiting cases:
1
0.4
1. 0 small
small
0.2
0.0
0.0
F (1 )
0.2
0.4
0.6
0.8
Fraction poisoned
1.0
2. 0 large
F
(1 )
modelling slab
Pore-mouth poisoning (sharp interface)
high value Thiele modulus poison

Fraction poisoned
c1
c0
Diffusion model (first order irrev.):

diffusion through completely
deactivated layer L
followed by reaction and diffusion
in the (1-)L layer
L
(1-)L
Deff (c0 c1 )
L
{A (1 )L} k v c1 tanh {(1 )0 }

(1 )0
pore mouth poisoning
Fraction of initial activity:
F=
J poisoned
J unpoisoned
tanh (1 ) 0
1
tanh( 0 )
1 + 0 tanh (1 ) 0
x =L
Fraction of initial activity
1.0
Limiting cases:
0 =
0.8
1. small
0.01
0.6
F (1 )
3
0.4
10
2. large
0.2
100
0.0
0.0
0.2
0.4
0.6
0.8
Fraction poisoned
1.0
1
1 + 0
selective poisoning
more complex: self-poisoning
Series poisoning:
Simultaneous solution diffusion/reaction equations
CA
core poisoning
higher concentration B in center
more coke formation in center
CB
L
Concentration profiles
shell poisoning
high Thiele moduli A and B
Profiles will depend on reactor coordinate (e.g. HDM results J.P. Janssens)
Doraiswamy & Sharma
ln F
Parallel fouling:
Low values Thiele modulus:
inc
re
as
ing
highest residual activity

decreases continuously
But after certain time residual activities for higher Thiele
values are higher
Sometimes one might prefer diffusion limitation conditions
or catalyst activity concentration profiles (TWC)
ln t
Becker & Wei, J. Catal. 46(1977) 372

Series fouling:
Extent of fouling increases continuously with Thiele modulus
Catalyst with least diffusion resistance preferred
Coke deposition effect on diffusivities generally negligible
Coke formation
Nature:
often aromatic precursors that give deposits of highly condensed

aromatic structures of low hydrogen content (H/C<1)
polymerised and dehydrogenated acetylenes, olefins
Kinetic aspects
Voorhies (1945):
cC = t
with: 0.5 (0.3 - 1)
Define catalyst activity decay function:

=
NT [C *]
NT
= f (cC ),
f (c P )
most convenient
or f (t )
Separate time dependent behaviour and reaction kinetics

(not always possible)
Kinetic aspects coke deposition

r = C r 0
Reaction kinetics:
unaffected
Examples of catalyst decay functions (see Froment & Bischoff)
C = 1 t
C = exp( t )
1
C =
1+ t
C =
t
C = (1 + t )
Note: use of time instead

of Coke concentration !
Only process time needed
So, for coking kinetics:
rC =
dC
1 dcC
=
Nt dt
dt
Holds for independent coking rates, how self-poisoning?

Kinetic aspects coke deposition

self poisoning
LHHW kinetics for A->B and coking:
k A0 NT KA C p A
rA =
1 + K A p A + KB p B
Parallel coking A->C
0
k AC
NT KA C p A
rc =
1 + KA p A + KB p B
Series coking B->C

0
kBC
NT K B C p B
rc =
1 + KA p A + KB p B
Relate time to coke concentration and find C
rC =
dC
1 dcC
=
Nt dt
dt
Coke deactivation function

Deactivation function
t kC0 NT K B pB
C = exp
dt
0 1 + K A pA + K B pB
function of time, concentration and reactor coordinate!
Only time dependent function approach assumes:

uniform deactivation in pellet or reactor
independent of local concentration
lumped parameter valid for determination conditions only
may give serious errors in prediction (Froment & Bischoff)
but most convenient to apply

Deactivation Modelling

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Deactivation Modelling

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Deactivation of catalysts

Catalysis Engineering - Deactivation

Catalytic reactor design equation

Catalysis Engineering - Deactivation

Heat balance - T-profile

Timescale catalyst deactivation

Fouling or self-poisoning often cause of deactivation

Catalysis Engineering - Deactivation

Carbon filament growth

Catalysis Engineering - Deactivation

loss surface area

loss active sites

Deactivation - depends on?

feed & process conditions

feed & process conditions

Catalysis Engineering - Deactivation

What are poisons?

Catalysis Engineering - Deactivation

Example sintering: n-Heptane reforming

not 1:1 relation reactivity and metal surface

Catalysis Engineering - Deactivation

Deactivation: global view

Homogenous poisoning: Fraction poisoned

Diffusion model (first order irrev.):

Catalysis Engineering - Deactivation

Fraction F of initial activity:

Fraction of initial activity

Catalysis Engineering - Deactivation

high value Thiele modulus poison

Diffusion model (first order irrev.):

Catalysis Engineering - Deactivation

{A (1 )L} k v c1 tanh {(1 )0 }

Fraction of initial activity

Simultaneous solution diffusion/reaction equations

highest residual activity

Becker & Wei, J. Catal. 46(1977) 372

Catalysis Engineering - Deactivation

often aromatic precursors that give deposits of highly condensed

with: 0.5 (0.3 - 1)

Define catalyst activity decay function:

Separate time dependent behaviour and reaction kinetics

Kinetic aspects coke deposition

Examples of catalyst decay functions (see Froment & Bischoff)

Note: use of time instead

So, for coking kinetics:

Holds for independent coking rates, how self-poisoning?

Kinetic aspects coke deposition

Series coking B->C

Relate time to coke concentration and find C

Catalysis Engineering - Deactivation

Coke deactivation function

function of time, concentration and reactor coordinate!

Only time dependent function approach assumes:

Catalysis Engineering - Deactivation

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