Heterogeneous Reactions (p719, Scott Fogler)

Shrinking Core Model

Pharmcokinetics (eg dissolution of pills in water or stomach juice)

Burning of coal particle

Catalyst regeneration ( zeolite catalyst coated with a layer of
carbon)


Catalyst Regeneration

Removal of carbon from the catalysts
Carbon penetrated to the core of catalysts





Carbon is first removed from the outer edge of the pellet






In the final stages of regeneration from the centre core of the
pellet.








Derivation of Shrinking Core Model

Core of unreacted carbon contained between and 0 = r R r =
Carbon has been removed from the porous matrix between
and
R r =
o
R r =


Oxygen diffuses from outter radius to
o
R R
at oxygen reacts with carbon, represented by eqn below:
R

2 2
CO O C +


Reaction at the surface is very rapid oxygen diffusion to the
surface control the rate of carbon removal from the core

Core of carbon shrinking with time (an steady state process) we
assume the concentration profiles at any instant in time to be the
steady-state profiles over the distance quasi-
steady state assumption (QSSA).
) ( R R
o

Step 1: The mole balance on O
2
(i.e. A) between and is: r r r +


| | | | | | | on accumulati of rate generation of rate out rate in rate . . . . . . = + |



0 0 4 4
2 2
= +
+ r r
Ar
r
Ar
r W r W


Dividing by and taking the limit gives:
r 4


0
) (
2
2 2
0
lim
= =

+

dr
r W d
r
r W r W
Ar r
Ar
r r
Ar
r





Step 2: For every mole of O
2
that diffuses into the spherical pellet, 1
mol of CO
2
diffuses out (W ), that is, EquiMolecular Counter
Diffusion (EMCD). The constitutive equation for constant total
concentration becomes:
2 2
O CO
W =


dr
dC
D W
A
e Ar
=


where is an effective diffusivity in the porous catalyst.
e
D




Step 3: Combining the previous 2 equations

0
2
=
|
.
|

\
|
r
dr
dC
D
dr
d
A
e

dividing by gives
e
D

0
2
=
|
.
|

\
|
dr
dC
r
dr
d
A





Step 4: The boundary conditions are:

At the outer surface of the particle, C
:
o
R r =
Ao A
C =

At the fresh carbon/gas interface,
: ) (t R r = 0 =
A
C
(rapid reaction)



Step 5: Integrating twice yields

1
2
K
dr
dC
r
A
=



2
1
K
r
K
C
A
+ =


Using the boundary conditions to eliminate and , the
concentration profile is given by:
1
K
2
K


o Ao
A
R R
r R
C
C
/ 1 / 1
/ 1 / 1

=



Figure 11-16 Oxygen concentration profile shown from the external
radius of the pellet ( ) to the pellet center. The gas-carbon interface
is located at .
o
R
R





Step 6: The molar flux of to the gas-carbon interface is
2
O

( )
2
/ 1 / 1 r R R
C D
dr
dC
D W
o
Ao e A
e Ar

= =



Step 7: An overall balance on elemental carbon elemental carbon
does not enter or leave the particle.


(

=
(

+
(

on accumulati
of rate
generation
of rate
out
rate
in
rate . .



dt
R d
R r
C C
c
|
.
|

\
|
= +

3
2 "
3
4
4 0 0


where is the molar density of the carbon and

is the volume
fraction of carbon in the porous catalyst. Simplifying gives
C

c


C C
c
r
dt
dR

"
=



Step 8: The rate of disappearance of carbon is equal to the flux of
to the gas-carbon interface:
2
O


o
Ao e
R r
Ar C
R R R
C D
W r
/
2
"

= =
=

Hence

|
|
.
|

\
|

=
o c c
Ao e
R R R
C D
dt
dR
/
1
2




Step 9: Integrating with limits at , the time necessary for
the solid carbon interface to recede inward to a radius is
o
R R =
0 = t
R


(
(

+
(

=
3 2
2
2 3 1
6
o o Ao e
c o c
R
R
R
R
C D
R
t




As the reaction proceeds, the reacting gas-solid moves closer to the
center of the core. The corresponding oxygen concentration profiles
at three different times ae shown in Figure 11-17


The time necessary to consume all the carbon in the catalyst pellet is

Ao e
c o c
C D
R
t
6
2

=

For a 1-cm diameter pellet with a carbon volume fraction of 0.04. Show that
the regeneration time is the order of 10s.