Dipl.-Ing.

Andreas Jrke1

Tutorial Chemical Reaction Engineering:

7. Mass Transfer in Heterogeneous Catalysis

1Institute

of Process Engineering, G25-217, andreas.joerke@ovgu.de

28-Jun-16

Tutorial CRE: Mass Transfer in Het. Catalysis

About 80% of all chemical production worldwide is catalyzed
(heterogeneous and homogeneous systems)
Haber-Bosch-process:
Contact process:
Ethylene oxide process:

-Fe/Al2O3
V2O5
Ag + Promoters

NH3
H2SO4
EO

Often use of porous structures Mass transfer phenomena

Influence of mass transfer on conversion, selectivity and yield
Mathematical description and modelling necessary!

CRE: Mass Transfer

28-Jun-16

Tutorial CRE: Mass Transfer in Het. Catalysis

7 steps of heterogeneous catalysis:

1.
2.
3.
4.
5.
6.

Diffusion to boundary layer

Film diffusion to pore
Pore diffusion to active center
Surface reaction
Pore diffusion of products
Film diffusion of products to
boundary layer
7. Diffusion of products through
boundary layer

CRE: Mass Transfer

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Tutorial CRE: Mass Transfer in Het. Catalysis

7.1 Pore Diffusion, Thiele Modulus, Pore Effectivity
Describe diffusion with 1. Ficks Law and particles are as a
homogeneous phase (constant diffusion coefficient)

c
J Deff
x

n x dx

Balancing the volume element dVx

x dx

nx
rP

n
nx nx dx k c n dVx
t
Reaction

1.8 % Co

Diffusion

Adding 1. Ficks Law yields

nx Ax J Ax Deff

n
c
Ax dx Deff
t
x

Ax Deff
x dx

c
k c n dVx
x x

n
c

n
Ax Deff

k
c
dVx

t
x

CRE: Mass Transfer

28-Jun-16

Tutorial CRE: Mass Transfer in Het. Catalysis

7.1 Pore Diffusion, Thiele Modulus, Pore Effectivity
With n c dVx c Ax dx

n 1
c
n

A
D

k
c
x eff

t Ax x
x

n x dx
x

x dx

nx

With Ax 4 x 2 (spherical particle)

rP

n 1 2
c
n
2
x
D

k
c
eff

t x x
x

1.8 % Co

2 c 2 c
n
Deff 2
kc 0
x x
x

CRE: Mass Transfer

28-Jun-16

Tutorial CRE: Mass Transfer in Het. Catalysis

7.1 Pore Diffusion, Thiele Modulus, Pore Effectivity
Solving ODE @ steady state for first order reaction n 1
requires introduction of the Thiele Modulus 0

kc0n 1
rate of reaction
0
rP
rate of diffusion
Deff

c
c0

Solution:

n x dx

rP sinh x0 rP
c x c0
x sinh 0

rP

nx

x dx
rP

1.8 % Co

CRE: Mass Transfer

28-Jun-16

Tutorial CRE: Mass Transfer in Het. Catalysis

7.1 Pore Diffusion, Thiele Modulus, Pore Effectivity
Effective rate of reaction rhet ? Integrate reaction rate law over
particle volume!

1
rhet
VP

rP

1
2
r
(
c
)
4

x
d
x

x0
VP
dV

rP

k c x 4 x 2 dx

x 0

c0 0
3
Deff
1
rP
rP tanh 0
Pore effectiveness ?

rhet

rhom

c0 0
3
Deff
1
rP
rP tanh 0

k c0

3
1
1


0 tanh 0 0

Effective rate constant keff k

CRE: Mass Transfer

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Tutorial CRE: Mass Transfer in Het. Catalysis

7.1 Pore Diffusion, Thiele Modulus, Pore Effectivity
Two limiting cases

a. Kinetic control

0 1 1 keff k and Ea,eff Ea

b. Pore diffusion control

0 5

ln keff

keff

k Deff k and Ea,eff 1 2 Ea Ed 1 2 Ea

b.
a.

T 1

Arrhenius plot gives

information about
diffusion limitations!

CRE: Mass Transfer

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Tutorial CRE: Mass Transfer in Het. Catalysis

7.2 Internal and External Diffusion Limitation
Characteristic numbers for description
of the flow regime

c0

Sh
Re
Sc

cs

dP

n x dx

vd P

f
f

nx
rP

x dx
rP

1.8 % Co

Deff

Connection via correlations

Sh k Re n Sc m k , n, m f geometry, conditions
Sh 1.6 Re0.54 Sc 0.33 for fixed bed reactors
Calculation of film thickness possible!
CRE: Mass Transfer

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Tutorial CRE: Mass Transfer in Het. Catalysis

7.2 Internal and External Diffusion Limitation
Assume 1. Ficks law as linear driving force approach! small

ndiff AP Deff

c0 cs

AP c0 cs

Deff

mass transfer coefficient

ndiff V rhet V rhom V kcs AP c0 cs / : V

kcs aV cs aV c0
cs

aV
c0
aV k

rhet kcs k

aV
c0
aV k
keff

keff

1
1
1

k aV

1
1
1

keff k aV
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Tutorial CRE: Mass Transfer in Het. Catalysis

7.2 Internal and External Diffusion Limitation
Analogous to parallel connection of resistances!

1
1
1

keff k aV
internal

external

If k high T

keff aV f T
Ea 0

ln keff

Ext. diffusion
control
Pore diffusion
control
c.
b.
a.

Kinetic
control

T 1
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Tutorial CRE: Mass Transfer in Het. Catalysis

7.2 Internal and External Diffusion Limitation
c

c0

c0

c0
cs

n x dx

n x dx
x

nx

x dx

x dx

nx

rP

rP

rP

rP

x dx

nx

a.

n x dx

rP

rP

c.

b.
Ext. diffusion
control
Pore diffusion
control
c.

ln keff

b.

a.

T 1

Kinetic
control

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Tutorial CRE: Mass Transfer in Het. Catalysis

7.2 Internal and External Diffusion Limitation
Estimation criteria from literature

External mass
transfer

Pore diffusion
limitation

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Tutorial CRE: Mass Transfer in Het. Catalysis

7.2 Internal and External Diffusion Limitation
Example: d P 4mm

k 0.25s

Deff

m2
3 10
s
7

aV 1500m 1

103

m
s

a. Effective volume based rate constant?

1
1
1

keff k aV

0 rP

kc0n 1
k
rP
1.83
Deff
Deff

3
1
1

0.83
0 tanh 0 0
keff 0.182s 1

73% of k

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Tutorial CRE: Mass Transfer in Het. Catalysis

7.2 Internal and External Diffusion Limitation
Example:

d P 2mm

k 0.25s

Deff

m2
3 10
s
7

aV ? 10 3

m
s

a. Effective volume based rate constant (half diameter particles)?

1
1
1

keff k aV

0 rP

kc0n 1
k
rP
0.91
Deff
Deff

3
1
1

0.95
0 tanh 0 0
dP2
A
6
aV f f

f
V
1 6 dP3
dP

aV,small
aV

keff,small 0.22s 1

dP
d P,small

Decreasing the particle

diameter increases the
effective rate constant!

aV,small 3000m 1

88% of k

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