L -18 :Diffusion and Reaction in a Porous

Catalyst
Chapter 12 Fogler
Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in

Gas-Solid Contact in TWO-Phase Reactors

External
Diffusion

Internal
Diffusion

Catalytic Surface

Bulk Diffusion (External mass

transfer):
Diffusion controlled reactions are usually
fast. (High temperatures)
Design of reactors design of mass transfer
equipment.
Increase in mass velocity increases the rate.

High L/D ratio reactors (narrow tubes) are

favored.
3

Pore Diffusion:
Pore diffusion controlled reactions are few.

Design of reactors most complicated.

Approaches bulk diffusion if the pore size is
large.
Approaches Knudsen diffusion if the pore
size is small.
No effect of temperature or mass velocity.

Low L/D ratio reactors (wide) may be used

with consequent reduction in pressure drop.
4

Pore Diffusion Resistance combined with Surface Kinetics

Ist order reactions in a straight cylindrical pore

Linear Differential equation

General solution

Where,
B.C, At pore mouth x = 0, CA= CAs,
No flux or movement of mass at the end of pore (closed end),

Solving

The concentration profile in a pore

How much reaction rate is lowered because of resistance to pore diffusion

Distribution and average value of reactant concentration within a catalyst

pore as a function of the parameter Thiele modulus
m L= =

Diffusion and Reaction in a Spherical Pellet

Rate

10

Derivation of the Differential Equation

~ Diffusion and Reaction in a spherical pellet
Moles = WAr (4 r2)r

d (WAr r )
rA c r 2 0
dr
dy A
dC A
WAr cDe
De
dr
dr

Molar flux

In out disappearance =0
WAr (4 r2)r - WAr (4 r2)r+ r - rA (4 r2 c r) =0
Dividing by -4 r

d [ De (dC A / dr )r 2 ]
rA c r 2 0
dr
Order of
reaction?

-rA=c(-rA)

Boundary
conditions
=r+r

r=0, CA finite, r=R, CA=CAS

Lets simply consider 1st order

d [ De (dC A / dr )r ]
2

rA c r 0
dr
2

d [ De (dC A / dr )r 2 ] 2
r k1C A 0
dr

c(-rA) =-rA

volumetric

-rA=kCA

Differentiation &
Divide by r2De

What about n-th order ?

d [ De (dC A / dr )r 2 ] 2
r k nC An 0
dr

Differentiation &
Divide by r2De

Lets simply consider 1st order

d C A 2 dCA k1

CA 0
2
dr
r dr De
2

What about n-th order ?

d 2C A 2 dCA kn n

CA 0
2
dr
r dr De

Dimensionless Form of the Equation

Dimensionless symbol was normally introduced to
Reduce complexity in equation
Simplify operation of calculation
Scale-up the reactor

Let = CA/CAs and =r/R

dCA/dr= (dCA/d)(d/dr)= (d/d )(dCA/d) x
(d/dr)
=> dCA/dr = (d/d )(CAS /R)
d2CA/dr2= d/dr(dCA/dr)= (d2/d 2)(CAS /R2)

When
CA=CAs at r=R, =1 and =1
CA=finite at r=0, =finite and =0

Dimensionless eq. 1st order

d 2C A 2 dCA k1

CA 0
2
dr
r dr De

d 2 2 d 2
1 0
2
d r dr
Thiele
Module

k1 R 2
De

About for n-th order ?

2
2
d
2 d 2 n
d C A 2 dCA kn n
n 0

CA 0
2
2
d r dr
dr
r dr De
Thiele
Module

n 1
k n R 2C As
De

Thiele Modulus, n
2 n-1
n
k
R
C
k
RC
"a" surface reaction rate
2
n
As
n
As
n =
=
=
De
De [(CAs - 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
C
1 sinh

y=
d2y/d 2 - 2y=0
y= A Cosh + B Sinh
A=0 as must be finite
at the centre
(B. C =0, cos h 1;
1/ , and Sinh 0.

CAs

sinh1

Calculation of Catalytic Effectiveness Factor

Catalytic Effectiveness Factor:

where

1 (Coth3 1 )

3
- Thiele Modulus
1st order reaction rate:
Spherical Pellet
Cylindrical Pellet
Slab Pellet

R kSap / De
3

kSap / De
2

L kSap / De

Internal Effectiveness Factor

Actual overall rate of reaction
=
Rate of reaction that would result if entire
interior surface were exposed to the external
pellet surface conditions CAs ,Ts

Internal
effectiveness
Factor, is:
ranged 0 1
for a first-order
reaction in a
spherical catalyst
pellet

-rA
-rA'
-rA"
=
= ' = "
-rAs -rAs -rAs

3
= 2 1coth1 -1
1

Internal Effectiveness Factor