L -17 : External Mass Transfer

Effects
Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in

Mass transfer and reaction in a

packed bed

Steady state mole balance on reactian A

 Mole balance in flux form, where Ac is

constant and FA = AcWAz
dWAz
+ rA' b = 0
dz
where
dC Ab
WAz = -D AB
+ C AbU and
dz
U = superficial velocity
hence
D AB

d2C Ab
dC Ab
'
U
+
r
A b = 0
2
dz
dz

For mass transfer controlled reaction CA>>CAS

=>

Therefore variation of reaction rate along the length

To investigate the effect of flow rate and T on conversion correlation for mass
transfer coefficient.
For flow through packed bed: Thoenes and Kramers relation ( modified
numbers)

Monolith Reactors/ Wire Gauge

EX.: A mass transfer limited reaction is being carried out in two reactors of equal
volume and packing, connected in series. The conversion is 86.5 at this condition. If
the reactors are placed in parallel and flow rate is divided equally in to two to
decrease the pressure drop. What will be conversion in this case?

For a mass transfer controlled reaction

Z=0, CA= CA0

Solve for X2
10

Diffusion and Reaction in a Porous Catalyst

Effective Diffusivity: Bulk diffusion ( Large pore)and

Knudsen diffusion(small pore) Dk(cm2/s)=9.7 *103 r (cm) (TK/M)1/2

De =

D c p c

where
= tortousity =

Actual distance a molecule travels btw 2 points

p = pellet porosity =

Shortest distance btw 2 points

Volume of void space
Total volume(voids and solids)

c = Constriction factor, f( )

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

tortuosity,

= 10. Typical value=0.8.

t = 3.0
12

Derivation of the Differential Equation

~ Diffusion and Reaction in a spherical pellet
Moles = WAr (4 r2)r

d (WAr r )
rA c r 2 0
dr
dy A
dC A
WAr cDe
De
dr
dr

Molar flux

In out disappearance =0
WAr (4 r2)r - WAr (4 r2)r+ r - rA (4 r2 c r) =0
Dividing by -4 r

d [ De (dC A / dr )r 2 ]
rA c r 2 0
dr
Order of
reaction?

-rA=c(-rA)

Boundary
conditions
=r+r

r=0, CA finite, r=R, CA=CAS

Lets simply consider 1st order

d [ De (dC A / dr )r ]
2

rA c r 0
dr
2

d [ De (dC A / dr )r 2 ] 2
r k1C A 0
dr

c(-rA) =-rA

volumetric

-rA=kCA

Differentiation &
Divide by r2De

What about n-th order ?

d [ De (dC A / dr )r 2 ] 2
r k nC An 0
dr

Differentiation &
Divide by r2De

Lets simply consider 1st order

d C A 2 dCA k1

CA 0
2
dr
r dr De
2

What about n-th order ?

d 2C A 2 dCA kn n

CA 0
2
dr
r dr De

Dimensionless Form of the Equation

Dimensionless symbol was normally introduced to
Reduce complexity in equation
Simplify operation of calculation
Scale-up the reactor

Let = CA/CAs and =r/R

dCA/dr= (dCA/d)(d/dr)= (d/d )(dCA/d) x
(d/dr)
=> dCA/dr = (d/d )(CAS /R)
d2CA/dr2= d/dr(dCA/dr)= (d2/d 2)(CAS /R2)

When
CA=CAs at r=R, =1 and =1
CA=finite at r=0, =finite and =0

Dimensionless eq. 1st order

d 2C A 2 dCA k1

CA 0
2
dr
r dr De

d 2 2 d 2
1 0
2
d r dr
Thiele
Module

k1 R 2
De

About for n-th order ?

2
2
d
2 d 2 n
d C A 2 dCA kn n
n 0

CA 0
2
2
d r dr
dr
r dr De
Thiele
Module

n 1
k n R 2C As
De

Thiele Modulus, n
2 n-1
n
k
R
C
k
RC
"a" surface reaction rate
2
n
As
n
As
n =
=
=
De
De [(CAs - 0)/R]
"a" diffusion rate
If n is large internal diffusion limits the
overall rate
If n is small the surface reaction limits the
overall rate
C
1 sinh

y=
d2y/d 2 - 2y=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.

CAs

sinh1

Calculation of Catalytic Effectiveness Factor

Catalytic Effectiveness Factor:

where

1 (Coth3 1 )

3
- Thiele Modulus
1st order reaction rate:
Spherical Pellet
Cylindrical Pellet
Slab Pellet

R kSap / De
3

kSap / De
2

L kSap / De

Internal Effectiveness Factor

Actual overall rate of reaction
=
Rate of reaction that would result if entire
interior surface were exposed to the external
pellet surface conditions CAs ,Ts

Internal
effectiveness
Factor, is:
ranged 0 1
for a first-order
reaction in a
spherical catalyst
pellet

-rA
-rA'
-rA"
=
= ' = "
-rAs -rAs -rAs

3
= 2 1coth1 -1
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, -rA

= (Actual overall rate of reaction) divided by
(rate that would result if the entire surface
were exposed to the bulk conditions, CAb, Ts)

=
"
1+k1Sab /k c ac
-r = (-r ) = k CAb
"
A

"
Ab

"
1

-rA = -r = -r Sab = k CAbSab

'
A b

"
A

"
1

Mass transfer and reaction in a packed bed

cont.
Axial

d2CAb
diffusion,Da
dz 2

U0 dp
Da

so

>>

-rA' b dp
U0 C Ab

can be neglected when

FA is very large

bk "Sa
dCAb
= -
CAb
dz
U

Finally, the conversion for

1st order reaction in PBR is

CAb
X =1=1- e-(bk"SaL)/U
CAb0

Remember the
forced
convection in
binary external
diffusion, JA is
also neglected

Determination of limiting situation from

reaction data
Type of
Limitatio
n

Variation of Reaction Rate with:

Velocity

Particle
Size

Temperature

External
Linear
U
(dp)-1/2
diffusion
Internal
Independent
Exponential
(dp)-1
Diffusion
Surface
Independe
Independent
Exponential
nt
Diffusion