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L -28 Diffusion Effects in Spherical Pellet

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
1
st
order Reaction in Spherical Pellet
What about n-th order ?
0
2
2
2
=
|
.
|

\
|
+
n
A
e
n A A
C
D
k
dr
dC
r dr
C d
0
2
1
2
2
=
|
.
|

\
|
+
A
e
A A
C
D
k
dr
dC
r dr
C d
Dimensionless Form of the Equation
Dimensionless symbol are normally introduced to
Reduce complexity in equation
Simplify operation of calculation
Scale-up the reactor
Let += C
A
/C
As
and =r/R
dC
A
/dr= (dC
A
/d)(d/dr)= (d+/d )(dC
A
/d+) x
(d/dr)
=> dC
A
/dr = (d+/d )(C
AS
/R)
d
2
C
A
/dr
2
= d/dr(dC
A
/dr)= (d
2
+/d
2
)(C
AS
/R
2
)
When
C
A
=C
As
at r=R, => +=1 and =1
C
A
=finite at r=0, => +=finite and =0
Dimensionless eq. 1
st
order
for n-th order ?
0
2
2
2
=
|
.
|

\
|
+
n
A
e
n A A
C
D
k
dr
dC
r dr
C d
0
2
1
2
2
=
|
.
|

\
|
+
A
e
A A
C
D
k
dr
dC
r dr
C d
2
2
1
2
2
0
d d
d d



| |
+ =
|
\ .
2
2
2
2
0
n
n
d d
d d



| |
+ =
|
\ .
Thiele
Module
Thiele
Module
e
D
R k
2
1
e
n
As n
D
C R k
1 2
Thiele Modulus, |
n

2 n-1 n
2
n As n As
n
e e As
k R C k RC "a" surface reaction rate
= = =
D D [(C - 0)/R] "a" diffusion rate
If |
n
is large internal diffusion limits the
overall rate

If |
n
is small the surface reaction limits the
overall rate



6
Define y= + => + = y/
d +/d = 1/ (dy/d ) y/2

d
2
+/d
2
= 1/ d
2
y/d
2
- 2/
2
dy/d + 2y/
3
d
2
y/d
2
-
2
y=0 Solution
y= A Cosh + B Sinh

A=0 as must be finite at the centre

(B. C =0, cos h 1; 1/ , and




Sin h 0.

| |
|
\ .
A 1
As 1
C sinh 1
= =
C sinh
7
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


9
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
11
12
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 / | =
14
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
15
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



16
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
17
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
20
Determination of apparent order of reaction



For large value of Thiele modulus
21
22
Apparent order of reaction n = (n
true
+1 )/2
23
Non isothermal pellet Energy balance
24
Non isothermal pellet effectiveness factor
25
Overall effectiveness factor (Both internal and external
diffusion are important
26
27
Slove for Cas, Conc at pellet
Surface
28
Overall rate in terms of
bulk concentration
29
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

33
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 =

35
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