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Y.H.

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Chemical Reaction Engineering II
6. Catalyst Deactivation
Todays Topics
Non-elementary
Reaction Kinetics
Heterogeneous
Reactions
External
Diffusion Effects
Diffusion &
Reaction in
Porous Catalyst
Design of Reactor
Data Analysis for
Reactor Design
Catalyst
Deactivation
G/L Reaction on
Solid Catalyst
1. Introduction
Mechanisms of catalyst deactivation
How to model decay
Summary
Catalyst
Deactivation
Determine the order of decay
Catalyst decay in CSTR
Mitigation
Reactor Design for catalyst decay
Text 1. Introduction
Fogler
Chapter 10.7: Catalyst Deactivation
Fluidized catalytic
cracking unit
To convert high-boiling
point, high molecular
weight fractions of
crude oil to more
valuable gasoline and
gases
Better than thermal
cracking because it can
generate higher octane
fuel
1. Introduction
Silica-Alumina Cat-Cracking Catalyst (100X)
fresh spent
Silica-Alumina Cat-Cracking Catalyst (400X)
fresh spent
Silica-Alumina Cat-Cracking Catalyst (800X)
fresh spent
Fresh Silica-Alumina Cat-Cracking Catalyst (1700 & 3000X)
fresh spent
Silica-Alumina Cat-Cracking Catalyst (5000X)
fresh spent
So far, we have always assumed that the activity of
catalysts remained unchanged with time
Usually the activity decreases as catalysts is used
Catalysts are mortal
The decrease (in active sites) can be:
Rapid
Over a period of time
For deactivated catalysts, regeneration or
replacement is necessary from time to time
Catalysts deactivation could be:
Uniform
Selective
But they are probably partially preventable
1. Introduction
Catalytic deactivation adds another level of
complexity to sorting out the reaction rate law
parameters and pathways
When modelling the reactions over decaying
catalysts, we can divide into:
Separable kinetics
Separate rate law and activity
When activity and kinetics are separable, it is possible to
study catalyst decay and reaction kinetics independently
1. Introduction
( ) ( ) catalyst fresh ' history past '
A A
r a r =
Modeling deactivation
And also divide into:
Nonseparable kinetics
We only consider separable kinetics
We define activity as:
1. Introduction
( ) catalyst fresh history, past ' '
A A
r r =
Modeling deactivation
( )
( )
( ) 0 '
'
=

=
t r
t r
t a
A
A
Catalyst used for some time
Rate of fresh catalyst
Activity is a function of history
( ) ( ) catalyst fresh ' history past '
A A
r a r =
The rate of disappearance of reactant A on catalyst
that has been used for some time
The rate of catalyst decay can be expressed by:
1. Introduction Modeling deactivation
( ) | | ( ) ( )
P B A d d
C C C h T k t a p
dt
da
r ,...., , = =
Specific decay constant
Functionality of rate on
reacting species
concentrations, usually
independent or linear
( ) ( ) ( ) ,... , fn '
B A A
C C T k t a r =
Functionality on activity
The functionality of activity term take a variety of
forms:
First order decay
Second order decay
1. Introduction Modeling deactivation
( ) a a p =
( )
2
a a p =
( )
t k
d
e t a

=
a k
dt
da
d
=
2
a k
dt
da
d
= ( )
t k
t a
d
+
=
1
1
2. Mechanisms
Six types:
Mechanism How
Poisoning Chemical
Fouling / coking Mechanical
Sintering / Aging Thermal
Vapourized Chemical / Thermal
Form inactive phase Chemical / Thermal
Crush / grind / erode Mechanical
Although there are six mechanisms, there are only three causes
2. Mechanisms
Sintering (aging):
Loss of activity due to loss of active surface area
resulting from prolonged exposure to high gas-
phase temperatures. Can be lost by:
Crystal agglomeration (recrystallization) and growth
of metals (atomic migration)
Narrowing or closing of pores inside the catalyst
pellet
Sintering
2. Mechanisms
Sintering (aging):
Crystal agglomeration (recrystallization) and growth
of metals (atomic migration)
Sintering
A. Atomic migration
B. Crystallite migration
2. Mechanisms
Sintering (aging):
Is usually negligible at temperatures below 40% of
the melting temperature of the solid
Most common decay rate law:
Integrating with a = 1, t = 0:
Usually measured in terms of active surface area
Sintering
2
a k
dt
da
r
d d
= =
( )
t k
t a
d
+
=
1
1
t k
S S
d
a a
+
=
1
1
0
2. Mechanisms
Sintering (aging):
The sintering decay constant follows the Arrhenius
equation
Example: calculating conversion with catalyst decay
in batch reactors
Reaction is first order
Decay is second order
Sintering
( )
(

|
|
.
|

\
|
=
T T R
E
T k k
d
d d
1 1
exp
0
0
B A
2. Mechanisms
Sintering (aging):
Example: calculating conversion with catalyst decay
in batch reactors
Design equation
Reaction rate law
Decay law (for second-order decay)
Sintering
W r
dt
dX
N
A A
'
0
=
( )
A A
C t a k r ' ' =
( )
t k
t a
d
+
=
1
1
Example
2
a k
dt
da
r
d d
= =
Integrating, with a = 1, t = 0,
2. Mechanisms
Sintering (aging):
Example: calculating conversion with catalyst decay
in batch reactors
Stoichiometry
Combining:
Sintering
( ) ( ) X
V
N
X C C
A
A A
= = 1 1
0
0
( )( ) X t a k
V
W
dt
dX
= 1 '
Example
( )dt t ka
X
dX
=
1
Let k = kW/V
2. Mechanisms
Sintering (aging):
Example: calculating conversion with catalyst decay
in batch reactors
Integrating:
Sintering Example
} }
+
=

t
d
X
t k
dt
k
X
dX
0 0
1 1
( ) t k
k
k
X
d
d
+ =
|
.
|

\
|

1 ln
1
1
ln
( )
d
k k
d
t k
X
/
1
1
1
+
=
You can use the steps for other
type of deactivation
2. Mechanisms
Coking / Fouling:
Common to reactions involving hydrocarbons:
Results from carbonaceous (coke) material being
deposited on the surface of the catalyst
Or it could be through blocking of pores
Coking / Fouling
Carbon on 14% Ni/Al
2
O
3
2. Mechanisms
Coking / Fouling:
Removal of the deposits is called regeneration
The amount of coke on the surface after time t
follows an empirical relationship:
Coking / Fouling
n
coke
At C =
For East Texas
light gas oil
(min) 47 . 0 t C
coke
=
10 22 5 12 4 10 on catalyst
C H C H + C H + C +
2. Mechanisms
Coking / Fouling:
Functionalities between the activity and amount of
coke can be in the form of:
Or:
Catalysts deactivated by coking can usually be
regenerated by burning off the carbon
Coking / Fouling
1
1
+
=
p
C
C
a
For East Texas
light gas oil
1
1
+
=
np p
t A
a
1 6 . 7
1
2 / 1
+
=
t
a
c
C
e a
1
o
=
( )
t k
t a
d
+
=
1
1
2. Mechanisms
Poisoning:
Occurs when poisoning molecules become
irreversibly chemisorbed to active sites, thereby
reducing the number of sites available for the main
reaction.
The poisoning molecule may be reactant, product
or impurity in the feedstream
Example:
Lead, which is used as antiknock component in
gasoline, poisons the catalytic converter
Consequently, lead has been removed
Poisoning
1 mm
Pt / Al
2
O
3
on cordierite
2. Mechanisms Poisoning
2. Mechanisms
Poisoning:
depends on strength of adsorption of some species
relative to another species
e.g. Oxygen may be a partial reactant for partial
oxidation but act as poison in ammonia
synthesis
Poisoning
Sulfur
poisoning of
ethylene
hydrogenation
on a metal
2. Mechanisms
Poisoning:
We consider poisoning:
In the form of impurities in the feed
In packed bed
By reactants or products
Poisoning
2. Mechanisms
Poisoning:
Poison in the feed (impurities):
Main reaction:
Poisoning reaction:
S A S A - +
( ) g C S B S A + - -
S B S B + -
( )
B B A A
A
A
C K C K
kC
t a r
+ +
=
1
'
S P S P - +
q m
p d d
a C k
dt
da
r ' = =
Poisoning
Why there is an extra concentration term?
2. Mechanisms
Poisoning:
Poison in the feed (impurities):
Progressive decay by poisoning
Rate of formation of poisoned sites
( )
P S P T d S P
C C C k r
. .
=
Unpoisoned
sites
Concentration
of poison in the
gas phase
Poisoning
2. Mechanisms
Poisoning:
Poison in the feed (impurities):
This is equal to rate of removal of total active
sites
Dividing by C
T
( )
P S P T d
T
C C C k
dt
dC
.
=
( )
P d
C f k
dt
df
= 1
T
S P
C
C
f
.
=
( )
P d d
C k t a
dt
da
r = =
Activity depends on the fraction of sites
available for adsorption (1-f) !!!
Poisoning
2. Mechanisms
Poisoning:
Poisoning in packed bed reactor:
Poisoning
Initially, only those sites near the entrance will be
deactivated because poison usually present in trace
amounts
As time continues, the sites near the entrance are
saturated and poison must travel farther
downstream before being adsorbed
Deactivation move through the packed bed as a
wave front
2. Mechanisms
Poisoning:
Poisoning in packed bed reactor:
Poisoning
2. Mechanisms
Poisoning:
Poison by either reactants or products:
Main reaction:
Poisoning reaction:
S B S A + +
n
A A A
C k r = '
S A S A - +
q m
A d d
a C k r ' =
Poisoning
reactant
poison
2. Mechanisms
Poisoning:
Restoration of activity is called reactivation
If adsorption is reversible, a change of operating
conditions might be sufficient
Just like regeneration in the fluidized bed
If not, that is called permanent poisoning, can be
mitigated by:
Chemical retreatment of surface
Replacement of spent catalysts
Poisoning
2. Mechanisms
Vapourization:
Metal loss through direct vaporization is generally
an insignificant route to catalyst deactivation
even at high reaction temperatures.
Metal loss through formation of volatile
compounds can be significant over a wide range
of reaction conditions including mild, low-
temperature conditions.
Deactivation is almost always irreversible; loss
of noble metals is very expensive.
Most common types are carbonyls, oxides,
sulfides and halides
Vapourization
2. Mechanisms
Vapourization:
Vapourization
Formation of volatile nickel tetracarbonyl at the
surface of a nickel crystallite in CO atmosphere.
2. Mechanisms
Vapourization (examples):
Vapourization
Catalyt ic Process Catalyt ic
Solid
Vapor
Formed
Comments on
Deactivation Process
Ref.
Automotive
converter
Pd-
Ru/Al
2
O
3
RuO
4
50% loss of Ru during 100 h test in
reducing automotive exhaust.
Barthol ., 1975.
Methanation of CO Ni/Al
2
O
3
Ni(CO)
4
P
CO
> 20 kPa and T < 425 e to
Ni(CO)
4
formation, diffusion and
decomposition on the support as large
cryst allites.
Shen et al., 1981.
CO chemisorption Ni catalysts Ni(CO)
4
P
CO
> 0.4 kPa and T > ue to
Ni(CO)
4
formation; catalyz ed by s ulfur
compounds.
Pannell et al., 1977.
Fischer-Tropsch
Synthesis
Ru/NaY
zeolite
Ru/Al
2
O
3
,
Ru/TiO
2
Ru(CO)
5
,
Ru
3
(CO)
12
Loss of Ru during FTS (H
2
/CO = 1, 200-
250 C, 1 atm) on Ru/NaY zeolite and
Ru/Al
2
O
3
; Up to 40% loss while flowing
CO at 175-2 C over Ru/Al
2
O
3
for 24 h.
Rate of Ru loss less on titania-supported
Ru and for catalysts c ontaining 3 nm
relative to 1.3 nm. Surface carbon lowers
loss.
Qamar and Goodwi n, 1983;
Goodwin et al., 1986.
Ammonia oxi dation Pt-Rh
gauze
PtO
2
Loss: 0.05 0.3 g Pt/ ton HNO
3
;
recovered with Pd gauze; loss of Pt leads
to surface enrichment with inactive Rh.
Sperner and Hohmann,
1976.
HCN synthesis Pt-Rh
gauze
PtO
2
Ext ensive restructuring and loss of
mechanical strength.
Hessa nd Phil lips, 1992.
2. Mechanisms
Formation of inactive phase:
Vapor-solid reactions are similar to but not the same
as poisoning; the distinction is the formation of a new
phase altogether in the former process.
These include:
Reactions of vapor phase with the catalyst surface
to produce inactive surface and bulk phases
reaction of CO with Fe to produce iron carbides (some
inactive) during Fischer-Tropsch synthesis;
reaction of metallic Fe to FeO at > 50 ppmO
2
in
ammonia synthesis;
H
2
O-induced Al migration from the zeolite frame-work
during regeneration of zeolites.
Inactive phase
2. Mechanisms
Formation of inactive phase:
These include:
Catalytic solid-support or catalytic solid-
promoter reactions,
e.g., reaction of Ru metal and Al
2
O
3
to form
inactive surface and bulk Ru aluminates in auto
emissions control.
Solid-state transformation of catalytic phases
during reaction
H
2
O-induced Al migration from the zeolite frame-
work during regeneration of zeolites.
Inactive phase
2. Mechanisms
Mechanical failure may be due to:
Fracture or crushing of granular, pellet or
monolithic catalyst forms due to a stress
attrition, the size reduction and/or breakup of
catalyst granules or pellets to produce fines,
especially in fluid or slurry beds, and
erosion (due to collision) of catalyst particles or
monolith coatings at high fluid velocities.
Mechanical
2. Mechanisms
Six types:
Mechanism Mitigation
Poisoning
Dedicated reactor to regenerate
Purification of feed
Fouling / coking
Dedicated reactor to regenerate
Purification of feed
Sintering / Aging Little we can do, replacement
Vapourized Purification of feed, replacement
Form inactive phase
Regenerate, purification of feed,
replacement
Crush / grind / erode Little we can do, replacement
Mitigations
2. Mechanisms
Six types:
Mechanism With concentration term
Poisoning Yes
Fouling / coking Yes
Sintering / Aging No
Vapourized No
Form inactive phase Yes
Crush / grind / erode No
Decay law
3. Determine order of decay
We use try and error to find the order of reaction
that fits the data
Consider at steady-state in CSTR
(we need to make it steady state to find out the order of decay)
Mole balance
Solving for activity
B A
( )W t a r F F
A A A
'
0
=
(No accumulation)
( )
( )
|
|
.
|

\
|

=

=
n
A
A A
A
A A
kC
C C
W
v
r W
C v C v
t a
0 0 0 0 0
'
3. Determine order of decay
A A
n
A
R d
C C
C
k t k

+ =
0
ln ln
First order
Log both side
First-order decay in a CSTR
Wk
v
k
R
0
=
a k
dt
da
d
=
( )
t k
d
e t a

=
3. Determine order of decay
If first order does not fit, we try second order decay
Mole balance
Solving for activity for second order
( )W t a r F F
A A A
'
0
=
( )
n
A R
A A
d
C k
C C
t k
t a

=
+
=
0
1
1
2
a k
dt
da
d
=
( )
t k
t a
d
+
=
1
1
3. Determine order of decay
t
k
k
k C C
C
R
d
R A A
n
A
+ =

1
0
Rearrange
Second-order decay in a CSTR
3. Determine order of decay
For packed bed:
For first order reaction, mole balance
Solving for activity
( )
A
A
C t ka
dW
dC
v =
0
a k
dt
da
d
=
( )
t k
d
e t a

=
( )
|
|
.
|

\
|
=
n
A
A
C
C
Wk
v
t a
0 0
3. Determine order of decay
A
A
d
C
C
Wk
v
t k
0 0
ln ln ln + =
Log both side
First-order decay in a packed bed reactor
3. Determine order of decay
There are basically two types of questions
The one shown in lecture note (as just shown)
Given the plant data, see how activity changes
with time
Or like in Tutorial 5 question 6
However for most of the problems we deal with,
order of decay will be provided
4. Catalyst decay in CSTR
A simple example showing :
Catalyst decay in fluidized bed modeled as CSTR
Order of decay is given
Fluidized catalytic
cracking unit
We are not using Kunii-
Levenspiel bubbling
model
Instead we assume
well-mixed reactor and
model the bed as a
CSTR
Fluidized catalytic cracking 4. Catalyst decay in CSTR
3. Work examples Fluidized catalytic cracking Fluidized catalytic cracking 4. Catalyst decay in CSTR
Determine concentration, activity and conversion:
Mole balance
Rate law
Decay law (first order)
V r vC C v
dt
dC
V
A A A
A
+ =
0 0
A A
kaC r =
A d
aC k
dt
da
=
Fluidized catalytic cracking 4. Catalyst decay in CSTR
Remember for poisoning, there is
an extra concentration term
(m
3
/s)(mol/m
3
) (mol/m
3
s)(m
3
)
Determine concentration, activity and conversion:
Stoichiometry
1 mol of A reacted 1 mol of B + 1 mol of C
( )
0 0
0 0
0
0
I A
I C B A
T
T
F F
F F F F v
F
F
v v
+
+ + +
= =
A A C B
F F F F = =
0
0
0 0
0
2
T
A A I
F
F F F
v
v +
=
0
0 0 0
T
A A A I
F
F F F F + +
=
Fluidized catalytic cracking 4. Catalyst decay in CSTR
mol/s
Determine concentration, activity and conversion:
Stoichiometry
0 0
0
0
0 0 0
1
T
A
T
A
T
A A A I
F
F
F
F
F
F F F F
+ =
+ +
=
0 0
0
0
1
v C
v C
y
v
v
T
A
A
+ =
0
0
0
/ 1
1
T A
A
C C
y
v v
+
+
=
where
0
0
0
T
A
A
C
C
y =
Fluidized catalytic cracking 4. Catalyst decay in CSTR
Determine concentration, activity and conversion:
From mole balance
Substitute
We get
V r vC C v
dt
dC
V
A A A
A
+ =
0 0
0
0
0
/ 1
1
T A
A
C C
y
v v
+
+
=
( )
V kaC C
C C
y v
C v
dt
dC
V
A A
T A
A
A
A
+
+
+
=
0
0 0
0 0
/ 1
1
Fluidized catalytic cracking 4. Catalyst decay in CSTR
Determine concentration, activity and conversion:
Dividing both sides by volume
Therefore, change of concentration with time is:
( )
( )
A A
T A
A A A
kaC C
C C
y C
dt
dC
+
+
+
=
0
0 0
/ 1
1
t t
( ) ( )
A
T A A A A
C
ka C C y C
dt
dC
t
t
t
+ + +
=
0 0 0
/ 1 / 1
Fluidized catalytic cracking 4. Catalyst decay in CSTR
1
Determine concentration, activity and conversion:
Conversion
Space time
Previously
|
|
.
|

\
|
|
|
.
|

\
|
+
+
= =

=
0 0
0
0 0 0
0
/ 1
1
1 1
A
A
T A
A
A
A
A
A A
C
C
C C
y
C v
vC
F
F F
X
( )( )
h 02 . 0
/h m 5000 kg/m 500
kg 000 , 50
3 3
0 0
= = = =
v
W
v
V
b

t
Fluidized catalytic cracking 4. Catalyst decay in CSTR
2
A d
aC k
dt
da
=
3
Determine concentration, activity and conversion:
Solve equations 1, 2, 3 simultaneously with ODE
integrator such as POLYMATH or MATLAB ode
solver (e.g. Runge-Kutta)
We will then get a plot with:
Concentration
Activity
Conversion
Changing with time
Fluidized catalytic cracking 4. Catalyst decay in CSTR
Fluidized catalytic cracking 4. Catalyst decay in CSTR
What do you see?
Space time:
Decay time:
The assumption of quasi-steady state is valid
But catalyst decay in less than an hour
Fluidized bed would not be a good choice to carry
out this reaction
We will see what other strategies can be used to
mitigate the decay
Fluidized catalytic cracking 4. Catalyst decay in CSTR
0.02h
0. 5h
The steps will be the same for other type of reactors,
but we might need to change the following:
mole balance equation
Order of reaction (rate law)
Order of decay
Stoichiometry
to get differential equations of:
Concentration
Activity
conversion
Fluidized catalytic cracking 4. Catalyst decay in CSTR
dt
dC
A
dt
da
X
5. Reactor Design for Catalyst Decay
How reactors are designed to counteract the effect
of catalyst decay:
Slow decay
Temperature-Time Trajectory
Moderate decay
Moving bed reactor
Rapid decay
Straight-Through Transport Reactor
In many large-scale reactors, catalyst decay is slow
But constant conversion is necessary
So that downstream processes are not upset
How to maintain constant conversion?
We can replace the catalysts
But if turnaround is not due or cost ineffective
Increase the feed temperature slowly
Therefore keeping the reaction rate constant
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
How do we know what temperature to operate at
particular time?
For first order reaction (not first order decay)
We neglect any change in concentrations,
We want to see how temperature is increased
with time
( ) ( ) ( )
A A
C T k T t a C T k r ,
0 0
= =
( ) ( )
0
, k T t a T k =
( )( )
0
/ 1 / 1 /
0
0
k a e k
T T R E
A
=

Temperature-time trajectory 5. Reactor Design for Catalyst Decay


Initial temperature Higher temperature to counter decay
At t = 0, T
0
How do we know what temperature to operate at
particular time?
Solve
( )( )
| | 1 ln ln
/ 1 / 1 /
0
=

a e
T T R E
A
0 ln
1 1
0
= +
|
|
.
|

\
|

|
.
|

\
|
a
T T R
E
A
0
1
ln
1
T
a
R
E
T
A
+ =
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
How do we know what temperature to operate at
particular time?
Decay law
from
( )( ) n T T R E
d
a e k
dt
da
d
/ 1 / 1 /
0
0

=
( )
A d
E E n
d
n
A
d
d
a k a a
E
E
k
dt
da
/
0 0
ln exp

=
|
|
.
|

\
|
=
a
T T R
E
A
ln
1 1
0
=
|
|
.
|

\
|

|
.
|

\
|
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
How do we know what temperature to operate at
particular time?
Integrating with a = 1, t = 0:
We get time dependence on temperature
( )
A d
E E n
d
n
A
d
d
a k a a
E
E
k
dt
da
/
0 0
ln exp

=
|
|
.
|

\
|
=
( )
A d d
d A A
E E n k
T T R
E nE E
t
/ 1
1 1
exp 1
0
0
+
(

|
|
.
|

\
|

=
Decay constant at temperature T
0
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
How do we know what temperature to operate at
particular time?
For first order decay:
However, in many industrial reactions, decay rate
law changes as temperature increases
Initial stage: fouling of acidic sites
Slow coking linear regime
Accelerated coking exponential increase in T
( )
A d d
d
E E k
T T R
E
t
/
1 1
exp 1
0
0
(

|
|
.
|

\
|

=
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
Temperature-
time trajectory
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
Work examples (from Tutorial 5 Q5)
The decomposition of spartanol to wulfrene and CO
2
is often
carried out at high temperatures. Consequently, the
denominator of the catalytic rate law is easily approximated as
unity, and the reaction is first order with an activation energy of
150 kJ/mol. Fortunately, the reaction is irreversible.
Unfortunately, the catalyst over which the reaction occurs
decays with time on stream. The following conversion-time
data were obtained in a differential reactor.
Assume the order of decay is 2.
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
Work examples
a) If the initial temperature of the catalyst is 480 K, determine
the temperature-time trajectory to maintain constant
conversion
b) What is the catalyst lifetime?
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
Work examples
Decay law
Refer to our note:
2
a k
dt
da
d
=
( )
t k
t a
d
+
=
1
1
( ) ( )
0
, k T t a T k =
0
1
1
k
t k
k
d
=
+
( ) t k k
T T R
E
k
d
+ =
|
|
.
|

\
|
|
|
.
|

\
|
1
1 1
exp
0
0
0
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
Work examples
From the data given:
t k
T T R
E
d
=
|
|
.
|

\
|
|
|
.
|

\
|
1
1 1
exp
0
d
k
T T R
E
t
1
1 1
exp
0

|
|
.
|

\
|
|
|
.
|

\
|

=
|
.
|

\
|
=

T
k
d
314 . 8
84344
exp 10 296 . 1
3
Temperature-time trajectory 5. Reactor Design for Catalyst Decay
Work examples
|
.
|

\
|

|
.
|

\
|
|
.
|

\
|

=

T
T K mol J
mol kJ
t
314 . 8
344 , 84
exp 10 296 . 1
1
1
480
1
. / 314 . 8
/ 150
exp
3
T (K) t (min)
480 0
485 44.3
490 87.3
495 130.4
500 174.9
Plot a graph
For significant decay, we can use moving bed reactor
Example: Fluidized catalytic cracking
Moving bed reactor 5. Reactor Design for Catalyst Decay
Fresh catalysts enter from
top
Moves through the bed as
compact packed bed
Catalysts are coked
continually as it moves
Catalysts exit from the
reactor into kiln
Air is used to burn off the
carbon
Moving bed reactor 5. Reactor Design for Catalyst Decay
Moving bed reactor:
Regenerated catalysts are
lifted from the kiln by an
airstream and then fed into
a separator
Catalysts return back into
the reactor
The reactant flows rapidly
through the reactor relative
to the flow of the catalyst
If feed rate of catalyst and reactants do
not vary with time, the reactor is
operating at steady state
Modelling moving bed reactor at steady state
Mole balance of A
Differential form
Reaction rate
0 '
, ,
= A + +
A +
W r F F
A W W A W A
A A
r
dW
dX
F '
0
=
( ) ( ) | |
P B A A
C C C k t a r ,..., , fn ' =
Moving bed reactor 5. Reactor Design for Catalyst Decay
1
(mol/s) (g) (mol/s)
(mol/s)
Modelling moving bed reactor at steady state
Decay law
Contact time
Differential form
n
d
a k
dt
da
=
Moving bed reactor 5. Reactor Design for Catalyst Decay
s
U
W
t =
g/s
s
U
dW
dt =
2
3
g
Modelling moving bed reactor at steady state
Combine and
Combine into
Moving bed reactor 5. Reactor Design for Catalyst Decay
n
s
d
a
U
k
dW
da
=
2 3
4
4 1
( ) ( ) | |
0
0 '
A
A
F
t r W a
dW
dX =
=
Activity based on W
from da/dW
Example of moving bed reactor
Moving bed reactor 5. Reactor Design for Catalyst Decay
Example of moving bed reactor
Moving bed reactor 5. Reactor Design for Catalyst Decay
Mole balance of
) ' )( (
0 A A
r W a
dW
dX
F =
1
Activity based on W
from da/dW, only for
moving bed
Example of moving bed reactor
Rate law
Decay law
Combining equations
Moving bed reactor 5. Reactor Design for Catalyst Decay
2
'
A A
kC r =
a k
dt
da
d
=
a
U
k
dW
da
s
d
=
( )W U k
s d
e a
/
=
2
3
s
U
dW
dt =
Example of moving bed reactor
Combining
Separating and integrating
Moving bed reactor 5. Reactor Design for Catalyst Decay
( )
( )
2
2
0
/
0
1 X kC e
dW
dX
F
A
W U k
A
s d
=

( )
( )
} }

=

X W
W U k
A
A
dW e
X
dX
kC
F
s d
0 0
/
2 2
0
0
1
( )
s d
U W k
d A
s A
e
k F
U kC
X
X
/
0
2
0
1
1

=

Example of moving bed reactor


Numerical evaluation
Moving bed reactor 5. Reactor Design for Catalyst Decay
( )
s d
U W k
d A
s A
e
k F
U kC
X
X
/
0
2
0
1
1

=

( )
1 -
cat
2
3
cat
6
min 72 . 0
. g 000 , 10
mol/min 30
mol/dm 075 . 0
.min mol.g
dm 6 . 0
1
s
X
X
=

( )( )
24 . 1
kg/min 10
kg 22 min 72 . 0
exp 1
1 -
=
|
|
.
|

\
|
(



Example of moving bed reactor
Numerical evaluation
Moving bed reactor 5. Reactor Design for Catalyst Decay
% 55 = X
Straight-Through Transport Reactor
Used for reaction systems in which catalyst
deactivates very rapidly
Commercially is used in the production of
gasoline from cracking of heavier petroleum
fractions where coking occurs very rapidly
Straight-Through Transport Reactor 5. Reactor Design for Catalyst Decay
Straight-Through Transport Reactor
Straight-Through Transport Reactor 5. Reactor Design for Catalyst Decay
Catalyst pellets and reactant
enter together and are
transported very rapidly through
the reactor (usually travel at
same velocity)
Bulk density of catalyst pellets
are significantly smaller than in
moving-bed reactors
Modelling STTR at steady state
Mole balance of A over reactor volume
Differential form
In terms of conversion and catalyst activity
z A V
c
A = A
0 = A +
A +
z A r F F
c A z z A z A
( ) | | ( ) t a t r
F
A
dz
dX
A
A
c B
0 '
0
=
|
|
.
|

\
|
=

Moving bed reactor 5. Reactor Design for Catalyst Decay
1
c B A c A
A
A r A r
dz
dF
' = =
Modelling STTR
Residence time
Substituting in terms of z (i.e. a(t) = a(z/U
p
))
p
U
z
t =
Moving bed reactor 5. Reactor Design for Catalyst Decay
( ) | |
|
|
.
|

\
|
=
|
|
.
|

\
|
=
p
A
A
c B
U
z
a t r
F
A
dz
dX
0 '
0

( ) | |
|
|
.
|

\
|
=
|
|
.
|

\
|
=
p
A
A g
B
U
z
a t r
C U dz
dX
0 '
0

0 0 A c g A
C A U F =
2
Mechanisms of catalyst deactivation
How to model decay
Summary
Catalyst
Deactivation
Determine the order of decay
Catalyst decay in CSTR
Sintering
Mitigation
Poisoning
Fouling/coking
Vapourization
Inactive phase
Temperature-Time
trajectory
Reactor Design for catalyst decay Moving Bed Reactor
Straight-Through
Transport Reactor
Mechanical
Try and error
Separable
kinetic
0,1,2
Summary
Look at batch reactor example in sintering section
See the steps for how to work out the change
of conversion with time
Do it for other systems
Steps:
Design equation mole balance
Rate law
Decay law
Stoichiometry
Combine and derive
Look at how the order of decay is determined

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