Chemical Reaction Engineering

(S1.2012)
Fogler Chapter 11
External Diffusion Effects on Heterogeneous
Reactions
Gia Hung Pham
Catalysis reactor types
1. Two phase reactor
- Fixed bed reactor
- Fluidized bed reactor
2. Three phase reactor
- Slurry reactor
Fixed bed reactor
Lit.: Jens Hagen; Industrial Catalysis A Practical Approach; Wiley-VCH; 1999
Fluidised bed reactor
Gas
Gas
Solid catalyst
Reactor
Cyclone
Compare: Fixed bed and Fluidised bed reactor
1. Catalyst pellet size
Fixed bed reactor : large (Heat and mass transfer will influence the rate and product selectivity)
Fluidised bed reactor: small
2. Catalyst weight
Fixed bed reactor requires much more catalyst than fluidised bed reactor.
3. Temperature control
Fixed bed reactor: bad, non-isothermal operation and hot spots ruin the catalyst.
Fluidised bed reactor: very good (rapid mixing of solid)
4. Pressure drop
Fixed bed reactor: high
Fluidised bed reactor: low
5. Catalyst deactivation - regeneration
Fixed bed reactor: less advantages (not suitable)
Fluidised bed reactor: more advantages
6. Scale-up
Fixed bed reactor: easy
Fluidised bed reactor: difficult
Three phase reactor
Lit.: Jens Hagen; Industrial Catalysis A Practical Approach; Wiley-VCH; 1999
Notes: reaction rate units
( ) s m mol C k
dt
dN
V
r
A
A
A
3
/
1
= =
( ) s g mol C k
dt
dN
w
r
cat A
A
A
/
1
' '
= =
( ) s m mol C k
dt
dN
S
r
A
A
A
2 ' ' ' '
/
1
= =
Chapter 11: External diffusion effects on heterogeneous reaction
Effective reaction rate constant
Two steps involve in the reaction (External mass transfer and surface
reaction )
Catalyst pellet
1
4
Gas
Boundary layer

C
Ab
C
As
A
P
4
1
P
Reaction first-order
A P
External mass transfer
Ficks law
with
- k
c
: Mass transfer coefficient (m/s)
- D
AB
: Diffusion coefficient (m
2
/s) (is a function of T and P)
- : Boundary layer thickness (m) (is unknown, depends on fluid velocity,
particle diameter, viscosity, density, temperature.)
- J
AZ
: average molar flux from the bulk fluid to the surface (mol/m
2
.s)
( )
As Ab c
A
AB Az
C C k
dz
dC
D J = =
o
AB
c
D
k =
Concentration
Positional coordinate
Gas

Cat
C
Ab
C
As
Mass transfer rate
Surface reaction rate (first order reaction)
Determination of C
As
At steady state r
MT
= r
s
) (
As Ab c MT AZ
C C k r J = =
As r S
C k r =
As r As Ab c
C k C C k = ) (
r c
Ab c
As
k k
C k
C
+
=
Derive the effective reaction rate
k
eff
Rate limiting
1. Mass transfer is faster than surface reaction rate
k
c
k
r
we have k
c
+ k
r
k
c
k
eff
= k
r
2. Surface reaction is faster than mass transfer
k
r
k
c
we have k
c
+ k
r
k
r
k
eff
= k
c
Ab
r c
r c
eff A
C
k k
k k
r
+
=
,
,
Determination of k
c
by using correlation equation
Sherwood number
Flow over a sphere
Reynolds and Schmidt number
u : fluid flow velocity (m/s)
l : characteristic length (particle diameter) (m)
: kinematic viscosity (m
2
/s)
k
c
increases with increasing fluid velocity. (Why ?)
AB
c
D
l k
Sh =
3 / 1 2 / 1
Re 6 . 0 2 Sc Sh + =
AB
D
Sc
v
=
v
l u
= Re
Frossling correlation
From Sherwood number and Frossling correlation equation
3 / 1 2 / 1
Re 6 . 0 2 Sc
D
l k
AB
c
+ =
l
D
D
l u
k
AB
AB
c
|
|
.
|

\
|
|
|
.
|

\
|
|
.
|

\
|
+ =
3 / 1
2 / 1
6 . 0 2
v
v
Fluid velocity affects k
c
Effect of fluid velocity on the effective reaction rate
r
eff
u
With mass transfer effect
Without mass transfer effect
Example: Rapid reaction on a catalyst surface
Determine the effective rate of reaction per unit surface area of catalyst.
l = d
p
= 1 cm
C
As
= 0 mol/L
C
Ab
= 1 mol/L
u = 0.1 m/s
= 0.5x10
-6
m
2
/s
Catalyst pellet
1
4
Fluid
Boundary layer

C
Ab
C
As
A
P
P
Reaction first-order
A P
D
AB
= 10
-10
m
2
/s
Solution
( )
As Ab c MT
C C k r =
7 . 460 Re 6 . 0 2
3 / 1 2 / 1
= + = = Sc
D
d k
Sh
AB
p c
2000
10 5 . 0
1 . 0 ( ) 01 . 0 (
Re
1 2 6
1
=
|
|
.
|

\
|

= =

s m
ms m
u d
p
v
5000
10
10 5
1 2 10
1 2 7
=

= =


s m
s m
D
Sc
AB
v
1 6
1 2 10
10 61 . 4
01 . 0
7 . 460 10


=

= = ms
m
s m
d
Sh D
k
p
AB
c
C
Ab
= 10
3
mol/m
3
r
MT
= 4.61x10
-6
m/s x (10
3
0) mol/m
3
= 4.61x10
-3
mol/m
2
s
This is the effective reaction rate.
s m mol r
eff A
2 3 ' '
,
/ 10 6 . 4

=
Mass transfer-limited reaction in packed bed
Reaction A + B P
At steady state
z z+z
Mass balance for this slice
of the catalyst bed
( ) 0
' '
\ \
= A +
A +
z A a r F F
c c A z z Az z Az
Molar rate in
Molar rate out
Molar rate of accumulation
( ) 0
' '
\ \
= A +
A +
z A a r F F
c c A z z Az z Az
Rate of generation of A per unit
Catalytic surface area (mol/s.m
2
)
External surface area of catalyst per volume of
catalyst bed (m
2
/m
3
)
( )
P
d
u
=
1 6
Particle diameter (m)
Porosity of the bed (-)
Cross-sectional area of tube (m
2
)
Dividing the above equation by A
c
z and z 0

flow in tube: J
Az
<<B
Az
0
1
' '
= +
|
.
|

\
|

c A
Az
c
a r
dz
dF
A
( )
c Az Az Az c Az
A B J W A F + = =
Molar flux of A (mol/m
2
s)
Molecular diffusive flux (mol/m
2
s)
Flux of A resulting from
Bulk flow (mol/m
2
s)
c A Az c Az c Az
A UC B A W A F = = =
superficial velocity (m/s) = constant
Cat
Surface
C
A
C
As
) (
' '
As A c Ar A
C C k W r = =
= 0
A c c
A
C a k
dz
dC
U =
|
.
|

\
|

= z
U
a k
C
C
c c
A
A
exp
0
Axial concentration profile in the reactor
C
A
/C
A0
1
z
Integrating with the limit, at z =0, C
A
= C
A0
0
Determine the reactor length L necessary to achieve a conversion X
At z = L
|
.
|

\
|
= z
U
a k
C k r
c c
A c A
exp
0
' '
Reaction rate along the length of the reactor
0
0
A
AL A
C
C C
X

=
L
U
a k
X
c c
=
1
1
ln
In class exercise
Tubular fixed bed reactor with spherical catalyst
External mass transfer control
Calculate final conversion X of the reaction A P
Additional information:
- Catalyst bed length L = 2 m
- Catalyst bed diameter d
R
= 6 cm
- Bed porosity = 0.5
- Catalyst sphere diameter d
p
= 3 mm
- Superficial gas velocity U = 3 m/s
- Sherwood number Sh = 60
- Diffusion coefficient D
AB
= 10
-7
m
2
/s
Solution
- Reorganise the equation
- Calculate k
c
- Calculate a
c
(specific surface area)
- Calculate k
c
a
c
L / U
- Calculate X