L -21 External Mass Transfer

Effects
Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
Thermofer Catalytic cracking unit (MBR ,Used for reactions with moderate
decay)
Fresh/regenerated catalyst enters from top
of reactor=> gets coked as moves down
and exits in a furnace where air is uded to
burn off carbon (C+ O2- CO2 )
Catalyst pellet size ~ 1/8 in inch in dia)
CATALYST DEACTIVATION
L -21 External Mass Transfer
Effects
Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
Thermofer Catalytic cracking unit (MBR ,Used for reactions with moderate
decay)
Fresh/regenerated catalyst enters from top
of reactor=> gets coked as moves down
and exits in a furnace where air is uded to
burn off carbon (C+ O2- CO2 )
Catalyst pellet size ~ 1/8 in inch in dia)
CATALYST DEACTIVATION
Ist Order deactivation
II
nd
order Rate
Straight through Transport Reactor
(Circulating Fluidized bed reactor)
Used when deactivation is rapid.
Used for production of gasoline
Catalyst pellet and feed enter
together and transported rapidly.
Bulk density of the catalyst is low
compared to Moving bed.
STTR : Used when coking is rapid.
Bulk density of catalyst is smaller than
MBR. Particle velocity = gas velocity.
Mole balance
r
A
=
b
r
A


Or
Z= Height (m),and Up is velocity of catalyst
(m/s)
( )
a
| |
|
|
\ .
1 R 1
= ln +
T E T
a o
Temperature/Time Trajectories
A control strategy involves maintaining a constant
conversion with catalyst decay by increasing
operating temperature.
develop a temperature/time trajectory to find T -t
relationship: How T should increase with time.
-r
A
(t=0,T
0
) = -r
A
(t= t,T) = a(t ,T)[-r
A
(t=0,T) ]


( ) ( )
k T a T,t =k
o
| || |
| |
| |
| |
| |
\ .\ .
E
1 1
a
-
R T T
o
k e a =k
o o
Arrhenius type T dependence
Temperature/Time Trajectories
a
| |
| |
|
|
|
|
|
|
|
|
|
\ .
\ .
0
E
1 1
d
-
R T T
da o
n
r = - =k e
d d
dt
decay law is:
a
| |
|
|
|
|
|
\ .
E
d
- lna
E
da a
n
- =k e
d
dt
o
a
| |
|
|
|
|
|
\ .
E
d
n-
E
a
=k
d
o
( )
a
| |
|
|
\ .
1 R 1
= ln +
T E T
a o
Substitute T value
Integrate with a=1 at t=0
Temperature/Time Trajectories
( )
| |
|
|
\ .
1- n+ E E
a
d
1- a
t =
k 1- n+ E E
a
d d
o
( )
a
| |
|
|
\ .
1 R 1
= ln +
T E T
a o
| || |
| |
| |
| |
| |
\ .\ .
E
1 1
a
-
R T T
o
a = e
| |
| |
|
|
|
|
|
|
|
|
|
\ .
\ .
| |
|
|
\ .
E -n E +E
a a
1 1
d
-
R T T
o
1- e
=
E
d
k 1- n+
d
E
o
a
a
a
| |
|
|
|
|
|
\ .
} }
E
d
-n+
E
a
t
da = -k dt
1
0
d
o
| |
|
|
\ .
E
d
- n 1
E
a
For
13
External Diffusion effects in Heterogeneous Reactions
TWO TYPES of Diffusion Resistance
1. External diffusion
2. Internal Diffusion
14
Mass Transfer Fundamentals
Diffusion : Spontaneous intermingling or mixing of Atoms or molecules
by random thermal motion.
Gives rise to motion of the species relative to motion of mixtures.

W
A
or N
A
= Molar flux of A relative to a fixed coordinates (Vector)

Molar flux of A = Diffusive flux (J
A
)

+ Convective flux (B
A
)

(in direction of concn. Gradient)

B
A
= C
A
V due to bulk fluid motin, V = Molar average velocity , V= y
i
v
i

For Binary system
15
Or
For Equi molar Counter Diffusion (EMCD): W
A
= -W
B
EMCD
Ficks Law of diffusion
16
Boundary Conditions
17
For Equi molar counter diffusion
Ist Order deactivation
II
nd
order Rate
Straight through Transport Reactor
(Circulating Fluidized bed reactor)
Used when deactivation is rapid.
Used for production of gasoline
Catalyst pellet and feed enter
together and transported rapidly.
Bulk density of the catalyst is low
compared to Moving bed.
STTR : Used when coking is rapid.
Bulk density of catalyst is smaller than
MBR. Particle velocity = gas velocity.
Mole balance
r
A
=
b
r
A


Or
Z= Height (m),and Up is velocity of catalyst
(m/s)
( )
a
| |
|
|
\ .
1 R 1
= ln +
T E T
a o
Temperature/Time Trajectories
A control strategy involves maintaining a constant
conversion with catalyst decay by increasing
operating temperature.
develop a temperature/time trajectory to find T -t
relationship: How T should increase with time.
-r
A
(t=0,T
0
) = -r
A
(t= t,T) = a(t ,T)[-r
A
(t=0,T) ]


( ) ( )
k T a T,t =k
o
| || |
| |
| |
| |
| |
\ .\ .
E
1 1
a
-
R T T
o
k e a =k
o o
Arrhenius type T dependence
Temperature/Time Trajectories
a
| |
| |
|
|
|
|
|
|
|
|
|
\ .
\ .
0
E
1 1
d
-
R T T
da o
n
r = - =k e
d d
dt
decay law is:
a
| |
|
|
|
|
|
\ .
E
d
- lna
E
da a
n
- =k e
d
dt
o
a
| |
|
|
|
|
|
\ .
E
d
n-
E
a
=k
d
o
( )
a
| |
|
|
\ .
1 R 1
= ln +
T E T
a o
Substitute T value
Integrate with a=1 at t=0
Temperature/Time Trajectories
( )
| |
|
|
\ .
1- n+ E E
a
d
1- a
t =
k 1- n+ E E
a
d d
o
( )
a
| |
|
|
\ .
1 R 1
= ln +
T E T
a o
| || |
| |
| |
| |
| |
\ .\ .
E
1 1
a
-
R T T
o
a = e
| |
| |
|
|
|
|
|
|
|
|
|
\ .
\ .
| |
|
|
\ .
E -n E +E
a a
1 1
d
-
R T T
o
1- e
=
E
d
k 1- n+
d
E
o
a
a
a
| |
|
|
|
|
|
\ .
} }
E
d
-n+
E
a
t
da = -k dt
1
0
d
o
| |
|
|
\ .
E
d
- n 1
E
a
For
26
External Diffusion effects in Heterogeneous Reactions
TWO TYPES of Diffusion Resistance
1. External diffusion
2. Internal Diffusion
27
Mass Transfer Fundamentals
Diffusion : Spontaneous intermingling or mixing of Atoms or molecules
by random thermal motion.
Gives rise to motion of the species relative to motion of mixtures.

W
A
or N
A
= Molar flux of A relative to a fixed coordinates (Vector)

Molar flux of A = Diffusive flux (J
A
)

+ Convective flux (B
A
)

(in direction of concn. Gradient)

B
A
= C
A
V due to bulk fluid motin, V = Molar average velocity , V= y
i
v
i

For Binary system
28
Or
For Equi molar Counter Diffusion (EMCD): W
A
= -W
B
EMCD
Ficks Law of diffusion
29
30
Boundary Conditions
31
For Equi molar counter diffusion
32
Solve for concentration profile C
A
vs z
=>
33
Diffusion through Stagnant Gas (Evaporation or
gas absorption)
Gas B is stagnant then there is no net flux of B
with respect to a fixed coordinate.
34
35
External mass transfer / boundary layer
Diffusion through a film to a catalyst particle
C
Ab
= concn of gas A at the ext. boundary of gas film B (dilute gas)
Cas = at the external cat surface
Correlation for mass transfer for flow around a
spherical pellet
Frossling correlation
36
Boundary layer around a catalyst pellet
External Resistance to Mass Transfer
Diffusion and Reaction
37
Isomerisation Reaction
Diffusion and reaction
LHHW surface
reaction
For weak adsorption or at high T,
=>
38
For rapid reaction : sp. reaction rate constant is much greater than mass
transfer coefficient
For slow reaction
39
Mass transfer and reaction in a
packed bed
'
Az
A b
Ab
Az AB Ab
2
'
Ab Ab
AB A b
2
dW
- +r =0
dz
where
dC
W = -D +C U and
dz
U= superficial velocity
hence
d C dC
D - U +r =0
dz dz
Mole balance in flux form, where A
c
is
constant and F
A
= A
c
W
Az

Diffusion and Reaction in a Porous Catalyst
c
t
D
p c
D =
e
where
Actual distance a molecule travels btw 2 points
= tortousity =
Shortest distance btw 2 points
Volume of void space
= pellet porosity =
p
Total volume(voids and solids)
= Constriction factor,
c
| f( )
Effective Diffusivity: Bulk diffusion ( Large pore)and
Knudsen diffusion(small pore) D
k
(cm
2
/s)=9.7 *10
3
r (cm) (T
K
/M)
1/2

43
Effective Diffusivity: Pores are not straight cylindrical.
These are a series of Tortuous, interconnecting paths of
varying cross sectional area.

Pellet porosity = volume of void space/ total volume
(voids and solids)

Constriction factor , ( )accounts for the variation in the
cross sectional area that is normal to the diffusion. It is a
function of the ratio of maximum to minimum pore areas
().

= f(), =1 if =1. =0.5 if = 10. Typical value=0.8.
tortuosity, t = 3.0
Derivation of the Differential Equation
~ Diffusion and Reaction in a spherical pellet
dr
dC
D
dr
dy
cD W
A
e
A
e Ar
= =
0
) (
2
2
=
'
r r
dr
r W d
c A
Ar

0
] ) / ( [
2
2
=
'

r r
dr
r dr dC D d
c A
A e

=r+r
Moles = W
Ar
(4 r
2
)
r

Boundary
conditions
Order of
reaction?
-r
A
=
c
(-r
A
)

r=0, C
A
finite, r=R, C
A
=C
AS
Molar flux
In out disappearance =0
W
Ar
(4 r
2
)
r
- W
Ar
(4 r
2
)
r+ r
- r
A
(4 r
2

c

r) =0
Dividing by -4 r
Lets simply consider 1
st
order
0
] ) / ( [
2
2
=
'

r r
dr
r dr dC D d
c A
A e

0
] ) / ( [
1
2
2
=

A
A e
C k r
dr
r dr dC D d

c
(-r
A
)

=-r
A volumetric

-r
A
=kC
A

What about n-th order ?
0
] ) / ( [
2
2
=

n
A n
A e
C k r
dr
r dr dC D d
Differentiation &
Divide by r
2
D
e

Differentiation &
Divide by r
2
D
e

Lets simply consider 1
st
order
What about n-th order ?
0
2
2
2
=
|
.
|

\
|
+
n
A
e
n A A
C
D
k
dr
dC
r dr
C d
0
2
1
2
2
=
|
.
|

\
|
+
A
e
A A
C
D
k
dr
dC
r dr
C d
Dimensionless Form of the Equation
Dimensionless symbol was normally introduced to
Reduce complexity in equation
Simplify operation of calculation
Scale-up the reactor
Let += C
A
/C
As
and =r/R
dC
A
/dr= (dC
A
/d)(d/dr)= (d+/d )(dC
A
/d+) x
(d/dr)
=> dC
A
/dr = (d+/d )(C
AS
/R)
d
2
C
A
/dr
2
= d/dr(dC
A
/dr)= (d
2
+/d
2
)(C
AS
/R
2
)
When
C
A
=C
As
at r=R, +=1 and =1
C
A
=finite at r=0, +=finite and =0
Dimensionless eq. 1
st
order
About for n-th order ?
0
2
2
2
=
|
.
|

\
|
+
n
A
e
n A A
C
D
k
dr
dC
r dr
C d
0
2
1
2
2
=
|
.
|

\
|
+
A
e
A A
C
D
k
dr
dC
r dr
C d
0
2
2
1
2
2
=
|
.
|

\
|
+ |

dr
d
r d
d
0
2
2
2
2
=
|
.
|

\
|
+
n
n
dr
d
r d
d
|

Thiele
Module
Thiele
Module
e
D
R k
2
1
e
n
As n
D
C R k
1 2
Thiele Modulus, |
n

2 n-1 n
2
n As n As
n
e e As
k R C k RC "a" surface reaction rate
= = =
D D [(C - 0)/R] "a" diffusion rate
| |
|
\ .
A 1
As 1
C sinh 1
= =
C sinh
If |
n
is large internal diffusion limits the
overall rate
If |
n
is small the surface reaction limits the
overall rate

y= +
d
2
y/d
2
-
2
y=0
y= A Cosh + B Sinh
A=0 as must be finite
at the centre
(B. C =0, cos h 1;
1/ , and Sinh 0.

Calculation of Catalytic Effectiveness Factor
Catalytic Effectiveness Factor:


where
|- Thiele Modulus
1
st
order reaction rate:

Spherical Pellet

Cylindrical Pellet

Slab Pellet



)
3
1
3 (
1
|
|
|
q = Coth
De kSa
R
p /
3
| =
De kSa
R
p /
2
| =
De kSa L p / | =
Internal Effectiveness Factor
Internal
effectiveness
Factor, q is:
ranged 0 1
q for a first-order
reaction in a
spherical catalyst
pellet
As s
Actual overall rate of reaction
=
Rate of reaction that would result if entire
interior surface were exposed to the external
pellet surface conditions C ,T
' "
A A A
' "
As As As
-r -r -r
= = =
-r -r -r

( )
1 1
2
1
3
= coth -1

Internal Effectiveness Factor

Falsified Kinetics
Measurement of the apparent reaction order
and activation energy results primarily when
internal diffusion limitations are present.

This becomes serious if the catalyst pellet
shape and size between lab (apparent) and
real reactor (true) regime were Too different.

Smaller catalyst pellet reduces the diffusion
limitation higher activation energy more
temperature sensitive
RUNAWAY REACTION CONDITIONS!!!!
Falsified Kinetics
Apostrophe/ prime sign denotes the
apparent parameter vice versa
With the same rate of production, reaction
order and activation energy to be measured
Rate of reaction, -r
A

O= (Actual overall rate of reaction) divided by
(rate that would result if the entire surface
were exposed to the bulk conditions, C
Ab
, T
s
)
"
1 a b c c
" " "
A Ab 1 Ab
' " "
A A b A a b 1 Ab a b

=
1+k S /k a
-r =(-r ) =k C
-r =-r =-r S =k C S
Axial diffusion, can be neglected when

F
A
is very large

so

Finally, the conversion for
1
st
order reaction in PBR is
'
0 p A b p
a 0 Ab
U d -r d
>>
D U C
2
Ab
a
2
d C
D
dz
| |
|
\ .
"
Ab b a
Ab
dC k S
=- C
dz U
Remember the
forced
convection in
binary external
diffusion, J
A
is
also neglected
b a
-( k"S L)/U
Ab
Ab0
C
X=1- =1- e
C
Mass transfer and reaction in a packed bed
cont.
Determination of limiting situation from
reaction data
Type of
Limitatio
n
Variation of Reaction Rate with:
Velocity
Particle
Size
Temperature
External
diffusion
U

(d
p
)-
1/2
~ Linear
Internal
Diffusion
Independent
(d
p
)
-1

Exponential
Surface
Diffusion
Independent
Independe
nt
Exponential