L -30 Diffusion Effects in catalyst:

effectiveness factor
Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
2
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



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 are too different.

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

With the same rate of production, reaction order
and activation energy to be measured
5
Determination of apparent order of reaction



For large value of Thiele modulus
6
7
Apparent order of reaction n = (n
true
+1 )/2
8
Non isothermal pellet Energy balance
9
Non isothermal pellet effectiveness factor
10
Overall effectiveness factor (Both internal and external
diffusion are important
11
12
Slove for Cas, Conc at pellet
Surface
13
Overall rate in terms of
bulk concentration
14
Overall effectiveness factor and rate of reaction for a first order reaction
Rate of reaction, -r
A

O= (Actual overall rate of reaction) divided by
(rate that would result if the entire surface
were exposed to the bulk conditions, C
Ab
, T
s
)
"
1 a b c c
" " "
A Ab 1 Ab
' " "
A A b A a b 1 Ab a b

=
1+k S /k a
-r =(-r ) =k C
-r =-r =-r S =k C S
Mass transfer and reaction in a
packed bed
'
Az
A b
Ab
Az AB Ab
2
'
Ab Ab
AB A b
2
dW
- +r =0
dz
where
dC
W = -D +C U and
dz
U= superficial velocity
hence
d C dC
D - U +r =0
dz dz
Mole balance in flux form, where A
c
is
constant and F
A
= A
c
W
Az
=A
C
U C
A

18
Mass Balance in a Packed bed (Mass Transfer
control)

F
Az
F
AZ+Z
- (-r
A
) a Ac z = 0

A= surface area per unit volume, U superfecial
velocity.



U dC
A
/ dz = - k
c
C
A
a
c


. C
A
= C
A0
exp (- k
c
a
c
z/U)
Or ln (1-X) = ( -kc az/U)

0 . 0 ) ( ) ( = i S G i c c
Gi
G C C a k
dz
dC
U
Catalytic Fixed-Bed Reactor - Design Model
Mass Balance around the catalyst


Gas-Phase component mass balance (Plug Flow model)


Gas-Phase component mass balance (Dispersion model)


Energy Model

i net S G i c c R i C C a k ) ( ) ( ) ( = q
0 . 0 ) ( ) ( = i S G i c c
Gi
G C C a k
dz
dC
U
0 . 0 ) ( ) (
2
2
= i S G i c c
Gi
G
Gi
G C C a k
dz
dC
U
z d
C d
i D
) ( ) ( Ta T UA j H Rj
dz
dT
Cp U R G G G + A =

20
Overall Rate with in the pellet (-r
A
= (r
Ab
)

For first order reaction

: (-r
Ab;
= (r
Ab
)Sa= k
s
S
a
C
Ab

=>
(-r
A
)= (r
Ab
)

= S
a

b
k C
Ab

2
2
0 s b b
Ab Ab
A
d C dC
Da U k SaC
dz dz

| |
O =
|
\ .
Neglecting Axial Dispersion




( )
s a
Ab
Ab
dC k S
C
dz U
O
| |
=
|
\ .
=> C
Ab
= C
Ab0
exp(- Sa
b
ks Z/U)


Axial diffusion, can be neglected when

F
A
is very large

so

Finally, the conversion for
1
st
order reaction in PBR is
'
0 p A b p
a 0 Ab
U d -r d
>>
D U C
2
Ab
a
2
d C
D
dz
| |
|
\ .
"
Ab b a
Ab
dC k S
=- C
dz U
Remember the
forced
convection in
binary external
diffusion, J
A
is
also neglected
b a
-( k"S L)/U
Ab
Ab0
C
X=1- =1- e
C
Mass transfer and reaction in a packed bed
cont.
Determination of limiting situation from
reaction data
Type of
Limitatio
n
Variation of Reaction Rate with:
Velocity
Particle
Size
Temperature
External
diffusion
U


(d
p
)-
3/2
Rate= k
c
ac CA

~ Linear
Internal
Diffusion
Independen
t
(d
p
)
-1

Exponential
Surface
Diffusion
Independen
t
Independen
t
Exponential