CRE

• The Shrinking Core Model

• Diffusion and Reaction in
Porous Catalysts
Lars J. Pettersson

2008
 The shrinking core model

• Regeneration of catalysts
deactivated by coking
• Poisoning of catalysts by
diffusion-limited reaction
• Fluid-solid reactions
e g coal combustion, dissolution of
medicines, oxidation of pyrite, corrosion
The unreacted core model
 Shell progressive regeneration of fouled pellet

Shrinking core model

 Partially regenerated catalyst pellet

Shrinking core model

 Sphere with unreacted carbon core of radius R

Shrinking core model

 Oxygen concentration profile

Shrinking core model

 Oxygen concentration profile at various times

Shrinking core model

 The shrinking core model
Application:
Poisoning of a catalyst layer (washcoat)
[pore-mouth poisoning]

Derive: The extent of deactivation as a a function of time

Other models

Progressive conversion model

 Limitations of the shrinking
core model
• Reactions occurring along a diffuse front
• Reactions giving rise to large temperature
gradients within the particle
• Slow reaction of a gas with a very porous
solid
• Solid converted by the action of heat, and
without needing contact with gas
Factors controlling the design of
a fluid-solid reactor
• Reaction kinetics for single particles
• Size distribution of solids
• Flow patterns of solids and fluid in the
reactor
 Web problem 3131
The shrinking core model
Calculate, for a particle which reacts under ash diffusion
control, the ratio between the time that is needed to
reduce the radius of the unreacted core to half and the time
for complete reaction.

Solution published on ”Bilda” November 14

 Web problem 3132
The shrinking core model
Zinc spheres with 5 mm diameter are dissolved in acid. The
reaction at the zinc surface is the rate-determining step and
experiments show that, at current acid concentration, Zn is
consumed at a rate of 3 · 10-4 kmol/(m3 · s).
(a) How much time is needed to dissolve half of the zinc?
(b) How much time is needed for complete reaction?

Solution published on ”Bilda” November 14

 Diffusion and reaction in porous
catalysts (HSF Chap. 12)
• The Thiele modulus
• The internal effectiveness factor
• Falsified kinetics
• The overall effectiveness factor
• The Weisz-Prater criterion
• Web problem 3120
Steps in a heterogeneous catalytic reaction

External mass transfer

Pore diffusion

Adsorption Desorption

Surface reaction
Diffusion and reaction in porous catalysts

Chap. 12 HSF
Concentration profile in a spherical catalyst pellet
Internal effectiveness
factor, η

Actual rate of reaction

__________________________
Reaction rate if entire interior
surface is exposed to
concentration at pellet surface
Internal effectiveness factor
 Reaction and diffusion in
porous catalysts
Hyperbolic functions
exp ( x ) − exp (− x )
sinh ( x ) =
2
exp ( x ) + exp (− x )
cosh ( x ) =
2
sinh ( x )
tanh ( x ) =
cosh ( x )
cosh ( x )
coth ( x ) =
sinh ( x )
 Internal-diffusion-limited reactions
How to increase the reaction
rate

• Decrease the particle size

• Increase the temperature
• Increase the concentration
• Increase the internal
surface area
The Weisz-Prater criterion

Uses measured values of the

reaction rate to determine
internal diffusion-limitations
Temperature dependence of a
catalytic reaction

Falsified kinetics
 External (film) resistances

• Calculations (e g Problem 3110)

• Experiments with varying flow rate
• From temperature-rate diagram
 Internal resistances
(pore diffusion)

• Calculations
(e g Weisz-Prater criterion)
• Experiments with varying particle size
• From temperature-rate diagram
(effect on apparent activation energy)
Overall effectiveness factor, Ω
Overall effectiveness
factor, Ω

Actual rate of reaction

__________________________
Reaction rate if entire surface
area is exposed to bulk
concentration
 Overall effectiveness factor
can be used to analyze
• Diffusion
• Flow and
• Reaction in packed beds
 Determination of limiting
situations from reaction data
Variation of reaction rate with:

Type of Velocity Particle Temperature

limitation size
External U1/2 (dp)-3/2 ≈ Linear
diffusion
Internal Independent (dp)-1 Exponential
diffusion
Surface Independent Independent Exponential
reaction