1
/
j j o j
X a X a a Y
2 2 1 1
+ + =
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 16
Parameter Estimation
Parameters for analysis
Y
j
=P
H
*P
T
/(-r
T
)
X
1j
=P
B
X
2j
=P
T
Parameters to be estimated
a
o
=1/k
a
1
=K
B
/k
a
2
=K
T
/k
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 17
Data for Regression Analysis
Run # Rate P
T
X
1
P
H
X
2
P
T
P
H
/Rate
Y
7 71.8 1 1 0.0129
8 142 1 2 0.0141
9 284 1 4 0.0141
10 47 0.5 1 0.0110
12 117 5 1 0.0427
13 127 10 1 0.0787
14 131 15 1 0.1150
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 18
Least-Squares Analysis
Multiple Linear Regression
Analysis
N= number of runs
Three equations are formed for
obtaining the values of a
o
, a
1
and
a
2
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 19
Equation 1
= = =
+ + =
N
j
j
N
j
N
j
j o j
X a X a Na Y
1
2 2
1 1
1 1
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 20
Equation2
= = = =
+ + =
N
j
j j
N
j
N
j
j
N
j
j o j j
X X a X a X a Y X
1
2 1 2
1 1
2
1 1
1
1 1
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 21
Equation3
= = = =
+ + =
N
j
j
N
j
j j
N
j
N
j
j o j j
X a X X a X a Y X
1
2
2 2
1
2 1 1
1 1
2 2
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 22
Input Data for the Regression
Y
j
X
1
X
2
X
2
1
X
2
2
X
1
Y
j
X
2
Y
j
X
1
X
2
0.0129 1 1 1 1 0.0129 0.0129 1
0.0141 1 2 1 4 0.0141
0.0282
2
0.0141 1 4 1 16 0.0141
0.0516
4
0.0110 0.5 1 0.25 1 0.005
0.0110
0.5
0.0427 5 1 25 1 0.214
0.0427
5
0.0787 10 1 100 1 0.787
0.0787
10
0.1150
15
1 225 1 1.725
0.1150
15
0.289 33.5 11 353.25 25 2.758 0.3401 37.5
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 23
Equations Formed
0.289=7a
o
+33.5a
1
+11a
2
2.758=33.5a
o
+353.25a
1
+37.5a
2
0.3401=11a
o
+37.5a
1
+25a
2
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 24
Solution of the equations
Using Gauss Elimination Method
Program MATLAB can be used for this
solution
The set of equations is a 3X3 Matrix
Solution will be:
Axa=c
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 25
Values of Estimated Parameters
k= 154.46 (mol/kgCat.s.atm)
K
B
=1.39 (1/atm)
K
T
=1.038 (1/atm)
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 26
Design of Packed Bed Catalytic Reactor
Design Equation:
Rate Law:
Stoichiometry:
To
T
F
r
dW
dX
/
=
B T
H T
T
P P
P P
r
39 . 1 038 . 1 1
46 . 154
/
+ +
=
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 27
|
.
|
\
|
+
=
X
X
P P
To T
c 1
1
|
.
|
\
|
+
=
X
X
P P
To B
c 1
|
.
|
\
|
+
+ O
=
X
X
P P
H
To H
c 1
2
2
Solution of Design Equations
Combining the Design Equation,
Rate Law and Stoichiometry and
solve the equation using any
Numerical Techniques
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 28
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 29
On of the big problem facing catalytic
reactor designers is the decay of catalyst
with time.
Types of Catalyst Deactivation
There are three types of catalyst
Deactivation
Deactivation by Sintering or
Aging
Deactivation by Coking or
Fouling
Deactivation by Poisoning
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 30
Deactivation by Sintering or Aging
Commonly aging is considered as 2
nd
order
r
d
=k
d
a
2
=-da/dt
Integrating with a=1 at t=0
a(t)=1/(1+k
d
t)
Amount of sintering is given by measure of
active surface area
S
a
=S
ao
/(1+k
d
t)
The decay constant can be given by the
Arrhenius equation
( )
(
|
|
.
|
\
|
=
T T
T k k
o
R
E
o do d
d
1 1
exp
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 31
Deactivation by Coking or Fouling
o The decay is caused by coke materials
deposited on the catalyst surface
o The amount of coke on the surface is given
by
o C
C
=At
n
where A and n are fouling
coefficients
o % coke =0.47t
0.5
o There are some commonly used relation for
the decay by fouling
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 32
Common forms
or
Light oil cracking
C
C
e a
2
o
=
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 33
1
1
+
=
np p
t n
a
1
1
+
=
P
C
C
a
2 / 1
6 . 7 1
1
t
a
+
=
C
C
a
2
1
1
o +
=
Deactivation by Poisoning
Poisoning molecules are
irreversibly chemisorbed on an
active site
The number of active site is then
reduces
Poisoning molecules can become a
Reactant or a Product
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 34
Poisoning in the feed stream
A + S A.S
A.S B.S +C(g)
B.S B + S
P + S P.S
The rate of reaction:
B B A A
A
A
C K C K
kC
t a r
+ +
=
1
) (
\
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 35
Poisoning in the feed stream
Rate of decay:
The rate of poisoning is proportional to the
no. of unpoisoned sites
q m
P d D
a C k
dt
da
r
\
= =
P S P to S P
C C C k r ) (
. .
=
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 36
P S P to d S P
S P
C C C k r
dt
dC
) (
. .
.
= =
Poisoning by Reactants or Products
Main
A + S B + S -r
A
=k
A
C
n
A
Poison
A + S A.S r
d
=k
\
d
C
m
A
a
q
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 37
Modified Algorithm of reactor design
Mole Balance
Rate law
Decay Law
Stoichiometry
Combining and Solve
Numerical Technique
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 38