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L -27 Diffusion Effects in Spherical Pellet

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
2
Pore Diffusion Resistance combined with Surface Kinetics
I
st
order reactions in a straight cylindrical pore
3
Solving
The concentration profile in a pore
How much reaction rate is lowered because of resistance to pore diffusion
4
Distribution and average value of reactant concentration within a catalyst
pore as a function of the parameter Thiele modulus
m L= =
5
Diffusion and Reaction in a Spherical Pellet
Rate
6
Derivation of the Differential Equation
~ Diffusion and Reaction in a spherical pellet
dr
dC
D
dr
dy
cD W
A
e
A
e Ar
= =
0
) (
2
2
=
'
r r
dr
r W d
c A
Ar

0
] ) / ( [
2
2
=
'

r r
dr
r dr dC D d
c A
A e

=r+r
Moles = W
Ar
(4 r
2
)
r

Boundary
conditions
Order of
reaction?
-r
A
=
c
(-r
A
)

r=0, C
A
finite, r=R, C
A
=C
AS
Molar flux
In out disappearance =0
W
Ar
(4 r
2
)
r
- W
Ar
(4 r
2
)
r+ r
r
A
(4 r
2

c

r) =0
Dividing by -4 r
Lets simply consider 1
st
order
0
] ) / ( [
2
2
=
'

r r
dr
r dr dC D d
c A
A e

0
] ) / ( [
1
2
2
=

A
A e
C k r
dr
r dr dC D d

c
(-r
A
)

=-r
A volumetric

-r
A
=kC
A

What about n-th order ?
0
] ) / ( [
2
2
=

n
A n
A e
C k r
dr
r dr dC D d
Differentiation &
Divide by r
2
D
e

1
st
order
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



13
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
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The total rate of consumption Of A inside a pellet
Evaluated at the surface conditions
Internal Effectiveness Factor
Internal
effectiveness
Factor, q is:
ranged 0 1
q for a first-order
reaction in a
spherical catalyst
pellet
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

( )
1 1
2
1
3
= coth -1

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For STRONG PORE DIFFUSION
Internal Effectiveness Factor