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
diffusion
Internal
diffusion
Adsorption
Surface
reaction

External
diffusion

Internal
diffusion
Desorption

Pore Diffusion
r" k"C As

FACULTY OF CHEMICAL ENGINEERING

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:

CPE624

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Diffusion in Single Pore (cont.)

Average rate within the pore:
l

actual rate d p

k"C

A( x ) dx

x 0

Rate in the pore if the concentration remained at CAs:

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

actual rate

ideal rate

Thiele modulus

Effectiveness factor () fraction which the rate is reduced by

pore diffusion limitations

1 e e

e e

tanh

4k " 2
l
l
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
1

=1
= 0.762
= 1/

no pore diffusion limitation

some limitation
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

???

2
S

k
"
g c
l

DA

CPE624

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Diffusion in Porous Spheres

Shell balance:

1 d
dC A
R 2D A
dR
R 2 dR

where,

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= k" C A

3 coth 1

S g ck "
DA

Total radius of
catalyst pellet

R0

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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
r (area/volume) kmACAb
r (area/volume) kCab

Rate limiting step

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reaction limited
external mass transfer limited
pore diffusion limited

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