CN2116 Homework Set #11 (no need to submit)

CN2116-XJP-2012-HW11

1. The reaction A B is carried out in a differential packed-bed reactor at different

temperatures, flow rates, and particle sizes. The results are shown in the following Figure.

(a)
(b)
(c)
(d)

What regions (i.e., conditions dp, T, FT0) are reaction-rate-limited?

What regions are external mass transfer-limited?
What regions are internal-diffusion-controlled?
What is the internal effectiveness factor at T = 400 K and dp=0.8 cm?

Solution
(a) 300 K, any dp smaller than 0.8 cm, any flow rate
400 K, 0.03 d p 0.1cm
(the rate of reaction is independent of particle sizes.)
(b) 400 K, dp = 0.8 cm and FT0 < 2500 mol/s (the rate of reaction increases with the flow rate.)
(c) 400 K, 0.1 d p 0.8cm and FT0 > 2500 mol/s (the rate of reaction increases with the
decreasing of particle sizes)
rate with d p 0.8 10
(d)

0.625
rate with d p 0.03 16
2. A first-order, heterogeneous, irreversible reaction is taking place within a catalyst pore which
is plated with platinum entirely along the length of the pore (as shown in the following figure).
The reaction concentration at the plane of symmetry (i.e., equal distance from the pore mouths)
of the pore is equal to one-tenth the concentration of the pore mouth. The concentration at the
pore mouth is 0.001 mol/dm3, the pore length (2L) is 210-3 cm, and the diffusion coefficient
is 0.1 cm2/s.

(a) Derive an equation for the effectiveness factor.

1

CN2116 Homework Set #11 (no need to submit)

CN2116-XJP-2012-HW11

(b) What is the concentration of reactant at L/2?

(c) To what length should the pore length be reduced if the effectiveness factor is to be 0.8?
Solution
(a) 1st order irreversible reaction: A B
rA ' ' k ' ' C A
Mole balance:
(In at z) - (Out at z z) (Generation within z) 0
D 2
D 2

WAz z -
WAz z z Dz rA'' 0
4
4

D dWAz

rA'' 0
4 dz
EMCD:
dC A
WAz De
dz
Therefore:
DDe d 2C A
D dWAz

rA'' 0
k ' ' CA 0
4 dz
4 dz 2
C
Lz
Set dimensionless variables A ,
C As
L
dC A dC A d d d
1 C As d

(C As )
dz
d d dz d
L d
L

d 2C A d dC A d C As d

dz 2
dz dz dz L d
Therefore:
d 2
C As d 2 4k ' ' C As

L2 d2 DDe
d

d C As d d C As d 2
2

d L d dz
L d2
4k ' ' L2
0

DDe

4k ' ' L2

DDe
2
1

d 2
12 0
2
d

Solution to the linear differential equation

A1e B1e
1

d 2
12 0 is:
d2

The boundary conditions are

B.C.1 : 1@ 1( the pore entrance)
d
0 @ 0(no flux or movement of material through the plane of symmetry)
d
The dimensionless concentration profile is:
B.C.2 :

CN2116 Homework Set #11 (no need to submit)

CN2116-XJP-2012-HW11

C A cosh 1

C As
cosh 1

Lz
L
4k ' ' L2
12
DDe
Definition of the effectiveness factor:

rA ,with diffusion
actual mean reaction rate within pore

rate if not slowed by pore diffusion

rA,withoutdiffusionresistance

For 1st order reactions

CA
, because the rate is proportional to the concentration.
C As

From

cosh 1
cosh 1
1
C As 1
C As 1
cosh(1 )
tanh 1
C A C As
d
cosh(1 )d
sinh(1 ) 10 C As

0
cosh 1
cosh 1 0
cosh 1 1
1
Therefore
C
tanh 1
A
C As
1
C A C As

L 0.5L
0.5 C A, 0.5 ?
L
We need to first calculate the Thiele modulus, 1 .
1
at z L, C A C As
10
1 cosh 1
0 and

10 cosh 1

(b)

1 2.9932
Therefore
at 0.5

cosh 1 cosh(0.5)(2.9932)

0.235
cosh 1
cosh(2.9932)

C A 0.2345C As (0.2345)(110 3 ) 2.345 10 4 mol / dm3

(c) 0.8 L ?
From part (a), we know the Thiele modulus: 1 2 L

k''
L , which is proportional
DDe

to the pore length L.

3

CN2116 Homework Set #11 (no need to submit)

CN2116-XJP-2012-HW11

For the old catalyst particle, 1,old 2.9932 .

Next we need to calculate the Thiele modulus, 1,new for the new catalyst particle.
From part (b)
tanh 1

new

tanh 1,new

1,new

0.8

1,new 0.888

Therefore:

1,old Lold

1,new Lnew

Lnew Lold

1,new
0.888
(110 3 )
2.97 10 4 cm
1,old
2.9932

CN2116 Homework Set #11 (no need to submit)

CN2116-XJP-2012-HW11

[Discussion Topics]
1. The catalytic reaction A B takes place within a fixed bed containing spherical porous
catalyst. The following figure shows the overall rates of reaction at a point in the reactor as a
function of temperature for various entering total molar flow rates, FT0.

(a) Is the reaction limited by external diffusion?

(b) If your answer to part (a) was yes, under what conditions [of those shown (i.e., T, FT0)]
is the reaction limited by external diffusion?
(c) Is the reaction reaction-rate-limited?
(d) If your answer to part (c) was yes, under what conditions is the reaction limited by the
rate of the surface reactions?
(e) Is the reaction limited by internal diffusion?
(f) If your answer to part (e) was yes, under what conditions is the reaction limited by the
rate of internal diffusion?
(g) For a flow rate of 10 g mol/h, determine (if possible) the overall effectiveness factor, ,
at 360 K.
(h) Estimate (if possible) the internal effectiveness factor, at 367 K.
(i) If the concentration at the external catalyst surface is 0.01 mol/dm3, calculate (if possible)
the concentration at r = R/2 inside the porous catalyst at 367 K. (Assume a first-order
reaction)
Additional information:
Gas properties:
Diffusivity: 0.1 cm2/s
Density: 0.001 g/cm3
Viscosity: 0.0001 g/cms

Bed properties:
Tortuosity of pellet: 1.414
Bed permeability: 1 milidarcy
Porosity: 0.3

Solution
(a) Yes
(b) All temperatures, FT0 = 10 g mol/h.
T > 362 K, FT0 = 100 g mol/h
The rate of reaction changes with the flow rate and increases linearly with temperature.
(c) Yes
(d) T < 362 K, FT0 = 1000 g mol/h, 5000 g mol/h.
5

CN2116 Homework Set #11 (no need to submit)

CN2116-XJP-2012-HW11

T < 362 K, FT0 = 100 g mol/h

The rate of reaction does not change with the flow rate and increases exponentially with
temperature (typically for low temperature).
(e) Yes
(f) T > 367 K, FT0 = 1000 g mol/h, 5000 g mol/h.
The rate of reaction does not change with the flow rate (no external resistance), and
increases exponentially with temperature (not as strong as the reaction-rate-limited).
(g)
rA ' (at 360 K, FT0 10 g mol/h )
actual rate of reaction

ideal rate of reaction rA ' (at 360 K, FT0 5000 g mol/h )

0.26
0.37
0.70
(h) At FT0 = 5000 g mol/h, there is no external diffusion limitation, so the external
effectiveness factor is 1.
actual rate of reaction rA ' (at 367 K, FT0 5000 g mol/h )

extrapolated rate of reaction rA ' (at 367 K, FT0 5000 g mol/h )

1.2
0.86
1.4
(i) For 1st order reaction
The dimensionless concentration profile is:
C
1 sinh 1
, 1/2
A
C As sinh 1

sinh 0.51

1/2 2
sinh 1
We can calculate the Thiele modulus, 1 , from the internal effectiveness .
3
For first order reaction : 2 (1 coth 1 1) 0.86 1 1.6 .

Therefore:

sinh 0.51 sinh 0.5(1.6)

2
0.75
sinh

sinh(1.6)
1

1/2 2

C Ar R / 2 0.75C As 0.75(0.01) 0.0075mol / dm3

CN2116 Homework Set #11 (no need to submit)

CN2116-XJP-2012-HW11

2. A second order catalytic reaction A B is carried out in an isothermal packed-bed reactor

containing porous spherical catalyst pellets. The exit conversion is 80%. The reactant and
product are gases. Only pure A is fed to the reactor at temperature of 250 oC. What happens
to the required bed length to achieve 80% conversion if the feed pressure is doubled and the
feed volumetric flowrate is held constant? Consider the following two cases (you may
neglect the pressure drop and the axial diffusion across the bed).
(a) What is the new required bed length if the overall pellet reaction rate is controlled by the
intrinsic reaction rate?
(b) What is the new required bed length if the overall pellet reaction rate is controlled by the
pellet diffusion rate?
You may assume the entire bed length is either in the intrinsic reaction rate or pellet diffusion
rate limited regimes and that the external mass transfer resistance between the fluid and the solid
catalyst is negligible.
Solution:
Mole balance in a packed-bed (ideal plug-flow):
(In at z) - (Out at z z) (Generatio n within z) 0

A W - A W
c

Az z

Az z z

Ac z 0

dWAz
rA 0
dz
dC Ab
U
rA 0
dz

(a) If the overall pellet reaction rate is controlled by the intrinsic reaction rate:
2
rA rAb k2C Ab
Substituting this equation for rA , we form the differential equation describing a 2nd order
reaction in a catalyst bed:
dC Ab
2
U
k2C Ab
0
dz
Therefore
dC Ab
dC Ab
k 2
2
U
k2C Ab

2 C Ab
dz
dz
U
Separate and integrate the design equation:
dC Ab
1
1
k
k
2 dz

2 z
2
C Ab
C Ab C Ab 0 U
U
The conversion at the reactors exit, z = L, is:
1
1
k

2 L
C Ab 0 (1 X ) C Ab 0 U
Therefore, the length of the packed-bed reactor can be estimated by:
7

CN2116 Homework Set #11 (no need to submit)

CN2116-XJP-2012-HW11

U 1

L
1

k2C Ab 0 1 X

P
, and doubling P will double the initial concentration of A (CAb0). If we
RT
keep the volumetric flowrate of the feed as a constant, U will be a constant. Therefore, to achieve
the same conversion (X = 80%), we need to cut the reactor length in half.
For ideal gas, C Ab 0

2
(b) For the internal diffusion limited: rA rAs rAb k2C Ab
, therefore

dC Ab
k 2
2 C Ab
dz
U
Next we need to estimate the internal effectiveness factor, .
First estimate the Thiele modulus, 2 .

k 2 R 2C As
.
De
For large value of the Thiele modulus (internal diffusion controlled), the effectiveness factor is:
1/ 2
De
2 3 2.4

R k2C As
n 1 2
Internal diffusion limited CAs = CAb . Therefore
De
De
2.4
2.4

R k2C As
R k2C Ab
Substitute in the design equation:
2.4

De

k2
dC Ab
2.4
R k 2C Ab 2
k 2
2 C Ab

C Ab
k 2 De C 1Ab.5

dz
U
UR
U

For 2nd order reaction, and spherical catalyst pellets, we have 22

Separate and integrate the design equation:

dC Ab
1
1
1.2 z
2.4

k2 De dz

k2 De
1.5
C Ab
UR
C Ab
C Ab 0
UR

The conversion at the reactors exit, z = L, is:

1
1
1.2 L

k 2 De
UR
C Ab 0 (1 X )
C Ab 0
Therefore, the length of the packed-bed reactor can be estimated by:

1
UR

L
1
1.2 k D C 1 X

2 e
Ab 0

CN2116 Homework Set #11 (no need to submit)

CN2116-XJP-2012-HW11

Doubling the feed pressure P will double the initial concentration of A (CAb0). If we keep the
volumetric flowrate of the feed as a constant, U will be a constant. Therefore, to achieve the
same conversion (X = 80%), we need to decrease the reactor length by a factor of 1/ 2 0.707 .