CRE

External Diffusion Effects on

Heterogeneous Reactions

Lars Pettersson

2008
 Contents
• Catalyst deactivation

• External diffusion effects

 Catalyst deactivation
• Aging (thermal
deactivation, sintering)
Pore closure

• Coking (fouling)
Agglomeration

• Poisoning
Catalyst deactivation by coking
Catalyst deactivation by poisoning

Movement of activity in a packed bed

Exit conversion as a function of time

Conversion conservation
Temperature changing strategy

Example: A catalytic reaction

with a first order decay rate law
(e. g. poisoning by an impurity)
Reactor with preheater to increase feed temperature
Temperature-time trajectories
 Diffusion effects on
heterogeneous reactions
• External resistance

• Internal resistance
 External resistance to mass transfer
Surface concentration
Bulk conc. Boundary
layer
Catalyst Boundary layer
particle
 External resistance to
mass transfer
• Mass transfer correlations for packed
beds
• Mass transfer-limited reactions on
metallic surfaces
• Class Problem No 9: Waste gas treatment
Steps in a heterogeneous catalytic reaction

External mass transfer

Pore diffusion

Adsorption Desorption

Surface reaction
 Diffusion

Conc.
Driving force
for diffusion

Boundary Driving force

layer for the reaction
 Diffusion
• Bulk diffusion large pores and high P

• Knudsen diffusion small pores and/or low P

• Surface diffusion transport by movement of

molecules over a surface
(often neglected)
HSF, p. 770
HSF, p. 771
Mass transfer to a single particle
 Influence of diffusion on reaction rate

- rA′′
Reaction rate

Kinetically controlled

Diffusion U - superficial fluid velocity

controlled dp – Catalyst particle diameter
 Mass transfer correlations
• Colburn J factor

• Chilton-Colburn analogy JD = JH
 Mass transfer-limited
reactions in packed beds
• Rapid surface reaction

• They respond quite differently to changes

in temperature and flow conditions
Mass transfer correlation for packed beds
Packed-bed reactor
How to use mass transfer
correlations in practice
Problem 3110

Bilda
Old exams and more/Chapter 5,
Heterogeneous Catalysis
 Next lecture
• The shrinking core model

• Diffusion and reaction in porous catalysts