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Types of deactivation
Reaction models
Kinetics
Mass transfer phenomena pellet
Effect on selectivity
conversion i
stoichiometric coefficient i
deactivation function
dx i
= i r
d (W Fi )
rate expression
space time
catalyst effectiveness
Coupled with:
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
Catalysis Engineering - Deactivation
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
Deactivation of catalysts
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)
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
Catalysis Engineering - Deactivation
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
Fouling
Sintering
Catalysis Engineering - Deactivation
Poisoning
Sintering
loss surface area
gradual or catastrophic
irreversible - nonregenerable
process conditions
kobs
feed conditions
Poisoning
chemisorption on active
sites
reversible or irreversible
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
Catalysis Engineering - Deactivation
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)
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
Mechanisms of sintering
monomer dispersion
2-D cluster
3-D cluster
vapor
particles migrate
surface
coalesce
interparticle transport
migrating
metastable
Secondary
effects
stable
Catalysis Engineering - Deactivation
Deactivation of catalysts
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
uniform or homogeneous
poisoning
diffusion limited
poisoning
pore mouth
poisoning
center
poisoning
series poisoning
Catalysis Engineering - Deactivation
Particle deactivation
modelling slab
rpoisoned
runpoisoned
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'
Catalysis Engineering - Deactivation
0.1
0.1
10
Particle deactivation
uniform poisoning
antiselective
nonselective
J poisoned
F=
J unpoisoned
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 )
Particle deactivation
modelling slab
Pore-mouth poisoning (sharp interface)
c0
L
(1-)L
Deff (c0 c1 )
L
Particle deactivation
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
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
Catalysis Engineering - Deactivation
Particle deactivation
more complex: self-poisoning
Series poisoning:
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)
Catalysis Engineering - Deactivation
Particle deactivation
Doraiswamy & Sharma
ln F
Parallel fouling:
Low values Thiele modulus:
inc
re
as
ing
ln t
Coke formation
Nature:
Kinetic aspects
Voorhies (1945):
cC = t
NT [C *]
NT
= f (cC ),
f (c P )
most convenient
or f (t )
Reaction kinetics:
unaffected
C = 1 t
C = exp( t )
1
C =
1+ t
C =
t
C = (1 + t )
rC =
dC
1 dcC
=
Nt dt
dt
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
rC =
dC
1 dcC
=
Nt dt
dt
t kC0 NT K B pB
C = exp
dt
0 1 + K A pA + K B pB