ASSUMPTION AND CONSIDERATION.

The reaction occurs only on the external surface of a pellet only the external surface is reactive (e.g: non porous pellets)
Steady state assumption: there is no accumulation on the
surface:
[rate of transport to surface] = [rate of reaction at surface]

For a first-order irreversible reaction on a single spherical pellet

of radius R, the total rate of reaction on the external surface of
the pellet is:

4R 2 k mA (C Ab C As ) 4R 2 r" 4R 2 k"C As
CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

4R 2 kmA (C Ab C As ) 4R 2 r" 4R 2 k"C As

Transport

The rate of reaction on the pellet with surface area 4R is equal

to the rate of mass transfer from the bulk fluid to the surface
2

4R 2 k mA (C Ab C As ) 4R 2 k " C As

C As k " k mA k mAC Ab

k mA (C Ab C As ) k " C As

C As

k mAC Ab
k" kmA

C As

C Ab

k"
1

k mA

k mAC Ab k mAC As k " C As

k " C As k mAC As k mAC Ab

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Eliminate C As from the rate expression and solve for the rate to
yield

r" k " C As
r"

k " C Ab

k"
1

k mA

keff'' C Ab

The reaction rate has an effective rate constant:

''
eff

k"

k"
1

k mA

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

LIMITING CASES:

''
eff

If k << kmA, then.....

k" C Ab
r"
k" C Ab
1 0
If kmA << k

k"

k"
1

k mA

Reaction limited

then.....

r" kmAC Ab
Mass transfer limited

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Consider the effect of pore diffusion on the overall rate

r" k"C As
Diffusion effects are handled
through an effectiveness factor
of , which is a function of rate
coefficients and geometry of the
catalyst

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

HONEYCOMB
CATALYST

SINGLE PORE

PORE DIFFUSION

POROUS
CATALYST
SLAB

POROUS
SPHERES AND
CYLINDERS

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

 Consider a single pore of length l and diameter dP.

The walls are uniformly reactive with r=kCA(x).
The concentration at the pore mouth (x = l) is CAS
and the end of the pore is assumed to be unreactive
so that dCA/dx = 0 at x = 0.
A shell balance between x and x+dx:
[Net flux in at x] [net flux out at x+dx]
= [rate of reaction on wall between x and x+dx]

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Average rate within the pore:

Rate in the pore if the concentration remained at CAs:

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Effectiveness factor fraction which the rate is reduced by

pore diffusion limitations

actual rate

ideal rate
Thus:

r" k"C As

1 e e

e e

tanh

4k " 2
l
l
d pDA

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

The limits of :

1,
=1
1

=1
= 0.762
= 1/

no pore diffusion limitation

some limitation
strong pore diffusion limitation

Where is Thiele Modulus

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Consider slab with average diameter dp and length, l

with irregular pores

tanh

S g c k" 2
l

D
A

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Shell balance:

dC A
1 d 2
R DA
S g b k"C A
2
dR
R dR

3 coth 1

= 1,
= 0.8,
= 1/

S g c k" 2
R0 R0

DA

1
= 1
1

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

CHE594: CHEMICAL REACTION ENGINEERING