L -29 Diffusion Effects in catalyst:

effectiveness factor
Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
2
The total rate of consumption Of A inside a pellet
Evaluated at the surface conditions
Internal Effectiveness Factor
As s
Actual overall rate of reaction
=
Rate of reaction that would result if entire
interior surface were exposed to the external
pellet surface conditions C ,T
' "
A A A
' "
As As As
-r -r -r
= = =
-r -r -r


4
For STRONG PORE DIFFUSION
Internal Effectiveness Factor
( )
1 1
2
1
3
= coth -1

Internal effectiveness
Factor, q is: ranged 0
1
q for a first-order
reaction in a spherical
catalyst pellet
6
7
Calculation of Catalytic Effectiveness Factor
Catalytic Effectiveness Factor:


where
|- Thiele Modulus
1
st
order reaction rate:

Spherical Pellet

Cylindrical Pellet

Slab Pellet



)
3
1
3 (
1
|
|
|
q = Coth
De kSa
R
p /
3
| =
De kSa
R
p /
2
| =
De kSa L p / | =
9
How can the rate of reaction be increased?

Decrease the radius of the pellet.
increase the temperature.
Increase the concentration
Increase the internal surface area

For large value of Thiele modulus, the effectiveness factor (for n>1
efffectiveness factor decrease with increase concentration at the
external surface of the pellet
10
For n
th
order reaction
= ( 2/n+1 )
1/2
3/

= R( k C
AS
n-1
/ D
e
)
1/2

OR

2
= R
2
kS
a

p
C
AS
n-1
/De



11
Uses the measured values of the rate of reaction to
determine if Internal diffusion controls the rate.

Weisz-Prater Parameter C
WP

2
= 3( Coth -1)

2
= (observed rate/rate cal. at C
AS
) x (rate
calculated at C
AS
) / diffusion Rate)

= (-r
A(obs
)/ -r
As


2
= -r
AS
S
a

p
R
2
/De C
As
= -r
AS

p
R
2
/De C
As

Weisz Prater Criterion for internal diffusion
12
C
WP
= (-r
A(obs
)/ -r
As
)(-r
AS

p
R
2
/De C
AS
)

C
WP =
(-r
A(obs
) (
p
R
2
/De C
AS
)

These are measured or known terms.

if C
WP
<< 1, No diffusion limitations and
no concentration gradient exists in the pellet.

C
WP
>> 1, Internal diffusion limits the rate.



Falsified Kinetics
Measurement of the apparent reaction order
and activation energy results primarily when
internal diffusion limitations are present.

This becomes serious if the catalyst pellet
shape and size between lab (apparent) and
real reactor (true) regime were Too different.

Smaller catalyst pellet reduces the diffusion
limitation higher activation energy more
temperature sensitive
RUNAWAY REACTION CONDITIONS!!!!
Falsified Kinetics

With the same rate of production, reaction order
and activation energy to be measured