CHAPTER 1

(Lecture Note Part 2)

CATALYTIC REACTION
AND
MASS TRANSFER
 Subtopic covered in Chapter 1
Catalytic Reactions and Reactors
Surface and Enzyme Reaction Rates
Introduction of Porous Catalyst
Transport and Reaction
External Mass Transfer
Pore Diffusion
Temperature Dependence of Catalytic Reaction Rates
Langmuir-Hinshelwood Kinetic Mechanism
Catalytic Wall Reaction
Application of Reaction Engineering in Microelectronic
Fabrication
Catalyst Deactivation
Steps in Catalytic Reaction

External External
diffusion diffusion

Internal
diffusion Internal
diffusion
Adsorption

Surface Desorption
reaction
Pore Diffusion
r" k"C As

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Pores in Pellet

Or
 Diffusion in Single Pore
A shell balance:
[Net flux in at x] [net flux out at x+dx]= [rate of reaction on wall between x and x+dx]

Assuming the single pore is cylinder, the shell balance for a first-order
reaction is:
 Diffusion in Single Pore (cont.)

Letting dx 0 and then dividing the equation by dx

yields:

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 Diffusion in Single Pore (cont.)
Average rate within the pore:

l
actual rate d p k"C
x 0
A( x ) dx

Rate in the pore if the concentration remained at CAs:

ideal rate [area] r" d p lk"C As

actual rate
Thiele modulus
ideal rate
Effectiveness factor () fraction which the rate is reduced by
pore diffusion limitations
1
4k " 2
1 e e tanh
l l

e e
d pDA

 Diffusion in Single Pore (cont.)
Thus,
r" k"C As
Relation between and can be seen by the following log-log
plot:

The limits of :
1, =1 no pore diffusion limitation
=1 = 0.762 some limitation
1 = 1/ strong pore diffusion limitation
 Diffusion in Honeycomb Catalyst

The honeycomb porous slab is just a collection of

many cylindrical pores so the solution is exactly the
same as we have just worked out for a single pore.
 Diffusion in Porous Catalyst Slab

Consider slab with average diameter dp

and length, l with irregular pores:

tanh
???

1

g c
S k " 2

l

DA

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 Diffusion in Porous Spheres
Shell balance:
1 d dC A
R 2D A = k" C A
R 2 dR dR

3 coth 1


Total radius of
1 catalyst pellet
where, S g ck " 2

= R0
DA

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 While the expressions for () appear quite differently
for different catalyst geometry, they are in fact very
similar when scaled appropriately, and they have the
same asymptotic behavior:

In consideration of the internal diffusion effect, the

pseudo homogeneous rate of a catalytic reaction in a
reactor with porous catalyst pellets can be written as:
r rideal
 Temperature Dependence of Catalytic Reaction
Rates
Limiting rate expression for catalytic reaction rates:
r (area/volume) kCab reaction limited
r (area/volume) kmACAb external mass transfer limited
r (area/volume) kCab pore diffusion limited

Rate limiting step Temperature dependence

Reaction Activation energy E
Mass transfer Nearly constant
Pore diffusion Activation energy E/2

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CPE624 FACULTY OF CHEMICAL ENGINEERING
 Answer: 14.7 cm

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press
 Answer: 190 cm
Answer: 548 cm

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press