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Intra-particle (internal) diffusion in heterogenous (solid) catalysis

1. The reaction is first order. Find the role played by internal diffusion in the
following cases. The experiments are conducted in a CSTR. Classify as diffusionfree, strong diffusional resistance, and intermediate case. Units are all consistent
with each other.
(a)
dp
W
CA0
Vol flow rate
XA
3
1
100
9
0.4
12
4
300
8
0.6
(b)
dp
4
8

W
1
3

CA0
300
100

Vol flow rate


60
160

XA
0.8
0.6

W
4
6

CA0
50
100

Vol flow rate


10
5

XA
0.2
0.6

(c)
dp
2
1

2. Consider the first order decomposition of A. The following data is given:


k e 1.6kJ / m / hr / K
De 5 x10 5 m 2 / hr
L 4 x10 4 m
hT 160 kJ / hr / m 2 / K

C Ab 20 mol / m

k m 300 m / hr
5

H 160 kJ / molA
3

robs 10 mol / m / hr

Answer the following questions:


(a) Is external mass transfer important to consider?
(b) Are there significant limitations due to pore diffusion?
(c) Do we expect significant temperature gradients within the pellet & outside? (not
covered in the class. Pl refer Fogler)
3. Consider the liquid phase reaction CH 3 COOH 2O2 2CO2 2 H 2 O . The catalyst
consists of Mn, Co, La oxides on a zinc aluminate carrier. Three sizes of the
catalysts (in terms of equivalent spherical diameter) are used 0.038; 0.054; 0.18
3
3
cm. At 260 0C, the robs 2mol / m / hr (0.054 cm) & robs 1.4mol / m / hr (0.18
cm).
(a) For the 0.054 cm, it is to be assumed that the effectiveness factor is 1. Find
the effectiveness factor for the 0.18 cm pellets
(b) Based on the following data, calculate the true & apparent activation
energies
1000/T (K-1)
rco2x107 (gmol/gcat/s)
0.054 cm
0.18 cm
1.807
3.55
2.10

1.842
1.876
1.912

2.60
2.00
1.42

1.70
1.40
1.13

4. In the following cases confirm whether intra-particle diffusion is important:


i)

ii)

iii)

Cracking of gas oil at 500oC: Catalyst particle diameter 1/8th inch. Mean pore
radius 30A. Pore volume is 0.37 cc/gm. The molecular weight oil is 150. At
atmospheric pressure with 30 oA radius the diffusion is of Knudsen type.
The rate constant interpreted from the experiments is 0.25 cc/s.g catalyst.
Assume that tortuosity factor of 3.0 is applicable.
Dehydrogenation of n-butane takes place on spherical chriomia-alumna
catalyst at 530oC. The catalyst size is 0.32 cm and the experimental data in
laboratory suggest a first order rate constant of about 0.94cc/s.g catalyst. The
pore radius is given as 110 oA. Assuming Knudsen diffusivity at this low
pressure and estimating the pore volume as 0.35 cc/g, predict an effectiveness
factor of the catalyst. Tortuosity factor of 3.0 is applicable.
Pyrolysis of n-octane gives an apparent rate constant of 0.25 cc/sec. g catalyst.
The data was obtained at atmospheric pressure with a monodispersed catalyst
whose average pore size of 30 oA. Other properties are: Particle size: 1/8 inch,
porosity: 0.35 cc/gm, tortuosity factor 2.0 and surface area 230 m2/gm cat.
Given: Knudsen diffusivity is related to temperature as

1/ 2

Dk 9.7 x 10 a
MA
Where a is pore radius in cm, D in cm2/sec and T is in K
3

5. Derive the equation for the effectiveness factor for the porous slab (thickness L)
of the catalyst in which diffusion takes place only in one direction i.e
perpendicular to the face of the slab. Reaction is first order reversible and external
mass transfer is negligible. .