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L12 CRE II Heterogeneous

Catalysis
Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
2
Exercise: Al
2
O
3

n-pentane i-Pentane
Suggested Mechanism:
N + o No
No + o Io + o
Io I + o
Rate laws for each of the steps:
N A V N A
k p k Adsorption of rate Net u u

=
v I S v N S
k k reaction Surface of rate Net u u u u

=
V I D I D
p k k Desorption of rate Net u u

=
3
Case-1
Case-2
N S A N A
eq
I
N S A D
N
p K K p K
K
p
p K K k
r
+ +

=
1
) (
2
) / 1 (
) (
D I N A
eq
I
N A S
N
K p p K
K
p
p K k
r
+ +

=
D
I
D S
I
eq
I
N A
N
K
p
K K
p
K
p
p k
r
+ +

=
1
) (
N A
p k r =
0
2
0
) 1 (
N A
N A S
p K
p K k
r
+
=
Case-3
N S A N A
N S A D
p K K p K
p K K k
r
+ +
=
1
0
n-pentane (N) i-Pentane (I)
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EXERCISE
5
How to verify whether the rate law confirms
to experimental data or not ??
D
B
C A
eq
B P
C A S
C
K
p
p K
K
p p
p K k
r
+ +

=
1
) (
A S
D
B
C A
C
eq
B P
C
K k
K
p
p K
r
K
p p
p
+ +
=

1
B C
C
eq
B P
C
cp bp a
r
K
p p
p
+ + =

Use regression
How to decide whether the fit is reasonable
??
If the fit is reasonable, evaluate the
constants
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Design of Fixed Bed Reactor:
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Design Equation (Reading Assignment Ch.10 (10.4 -10.6 ) Fogler IV
General Mass Balance Equation:
Rate of input = rate of output + accumulation
+ rate of disappearance
F
A
= F
A
+ dF
A
+ 0 + (-r
A
) dW
- dF
A
= (-r
A
) dW

F
A0
dx
A
= (-r
A
) dW
dW
A A
r dW dF = /
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}
=
A
x
A A A
r dx F W
0
0
/ /
General design equation for a FBR:
dt
dN
W Weight unit time unit
d disappeare A of Moles
r
A
A
1
) )( (

= =
Definition of rate of reaction:
When the rate is expressed in terms of catalyst weight,
mass transfer effects between the catalyst and the bulk
fluid & also within the catalyst are ignored. Such mass
transfer aspects could be important in some cases.

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Fixed Bed Reactor Integral form
}
=
A
x
A A A
r dx F W
0
0
/ /
1 /-r
A
x
A

W / F
A0
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Fixed Bed Reactor differential form
A A
r dW dF = /
F
A
W
-r
A x
A
W/F
A0

-r
A
A A A
r dW dx F = /
0
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How to find the rate data ??
How can we calculate the weight of
the catalyst needed for obtaining the
given conversion ??
D
B
A A
eq
B C
A A S
A
K
p
p K
K
p p
p K k
r
+ +

=
1
) (
}
=
A
x
A A A
r dx F W
0
0
/ /
Express the partial pressures in terms of x
A

A A
A
A
A
x
x
p
p
c +

=
1
1
0 A A
A R
A
R
x
x a r M
p
p
c +
+
=
1
) / (
0
) (
A A
x f r =
Use numerical / graphical integration
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Finding a Mechanism consistent with the experimental data
Deducing Rate law from experimental data (Example 10.2 , 10.3:
Example : Hydrodemethylation of Toluene
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Use of Multiple regression technique (Rate or CONVERSION Data from
Differential reactor identical to CSTR)

Y = a
0
+ a
1
X
1J
+ a
2
X
2J



A
0
, a
1
are the parameters of the model.

Use regression methods / Polymath, MATLAB,
etc.

k, K
B
, K
T
are the parameters of the equation
Evaluation of Rate law Parameters