1

CHE 611
Advanced Chemical Reaction
Engineering








Dr. Muhammad Rashid Usman
Institute of Chemical Engineering and Technology
University of the Punjab, Lahore 54590
mrusman.icet@pu.edu.pk
Fixed bed reactor models
[10]
2
Fixed bed reactor models
[10]
3
4
Steady-state two-dimensional pseudo-
homogeneous model






5
Steady-state two-dimensional pseudo-
homogeneous model

( ) ( ) ( )
( ) ( ) mass of on accumulati of Rate n consumptio mass of Rate
generation mass of Rate out mass of Rate in mass of Rate
balance Mass
=
+
:
( ) ( ) ( )
( ) ( ) energy of on accumulati of Rate n consumptio energy of Rate
generation energy of Rate out energy of Rate in energy of Rate
balance Energy
=
+
:
6
Steady-state two-dimensional pseudo-
homogeneous model
Continuity equation (Constant D
ea
and D
er
):



Energy equation (Constant c
p,
h
rxn
and k
er
):





For the derivations, see class notes and book by Missen, Ref. 10.
7
Steady-state two-dimensional pseudo-
homogeneous model with negligible axial
diffusion
Peclet number for mass transfer:




Peclet number for heat transfer:





r
p
r
p
m r
D
d G
D
d u
Pe

,
r
p p
r
p
h r
k
d c G
k
d u
Pe

=

=
,
conduction by rate transfer ass M
convection by rate trasnfer Mass
number Peclet =
conduction by rate transfer Heat
convection by rate trasnfer Heat
number Peclet =
8
Boundary conditions
0
0 T T and X = =
0 = z
0 =
c
c
=
c
c
r
T
r
X
0 = r
0 =
c
c
r
X
) ( T T U
r
T
k
f i r
=
c
c

i
R r =
i
R r =
9
Overall heat transfer coefficient, U



How can one find the overall heat transfer
coefficient?
10
Overall heat transfer coefficients:
hollow cylinder






r
2
r
1
Outside fluid
film resistance
Inside fluid
film resistance
Pipe wall
resistance
11
Individual and overall heat transfer
coefficients: hollow cylinder






o o
i i
i i
A h
A
L k
r r A
h U
+

+ =
t 2
) / ln( 1 1
1 2
o
o
i i
o
o
h L k
r r A
A h
A
U
1
2
) / ln( 1
1 2
+

=
t
12
Bed properties





1 ) ( +
= =
P
v
density Particle
s
s
p

p
B
B
oidage v Bulk

c = = 1
) 1 ( ) 1 (
B p p B
density Bulk c c = =

G d
Re number Reynolds Particle
p
p

= =
13
Effective radial mass diffusivity [7]





14
Wall heat transfer coefficient [7]
15
Effective radial thermal
conductivity [7]





16
Ergun equation for pressure drop





3
2
3
2
2 2
1 75 . 1 ) 1 ( 150
B
B
v s B
B
v s
d
G
d
G
dz
dp
c
c
| c
c
|

=
17
Thermodynamic properties of
a mixture
Heat capacity:









) ( ) ( ) ( ) (
, , , ,
T c y T c y T c y T c y c
I p I C p C B p B A p A p
+ + + =
4
, 4
3
, 3
2
, 2 , 1 , 0
,
T a T a T a T a a
M R
c
i i i i i
i
i p
+ + + + =

Average molecular weight:

I I C C B B A A ave
M y M y M y M y M + + + =
T R
M p
ave

=
Density: (applicable at low pressure)
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Thermodynamic properties of
a mixture
Transport properties such as mass diffusivity, thermal
conductivity, viscosity should not be taken as additive.
Recommended mixing rules should be applied for such
calculations. See Bird et al. Ref. 8. Chapters 1, 9, and
17.









19
Steady-state one-dimensional pseudo-
homogeneous model with negligible axial
diffusion for adiabatic operation
Continuity equation:


or

Energy equation (Constant c
p
and

h
rxn
):
0
2
4
) (
A
A B i A
F
r D
dz
dX

=
t
p
rxn A B
c G
h r
dz
dT

A
=
) ( ) (
0
0
) (
A
A B A
y G
M r
dz
dX

=

20
Steady-state one-dimensional pseudo-
homogeneous model with negligible axial
diffusion for non-adiabatic operation
Energy equation (Constant c
p
and

h
rxn
):



i p
f i
p
rxn A B
D c G
T T U
c G
h r
dz
dT

A
=
) ( 4
) ( ) (
21
Steady-state one-dimensional pseudo-
homogeneous model with negligible axial
diffusion





What would be the boundary
conditions for each case?





22
Packed column: A few rules of
thumb
1. Usually d
p
is chosen so that the ratio D
i
/d
p
> 10.
2. In one of the criteria, the effect of axial dispersion depends
on the ratio of the length of the reactor to the particle size.
If the ratio is 100 or more, the effect is usually negligible
compared to convective mass transfer.
3. Carman-Kozeny equation is suitable for fine particles.
Ergun equation works well for both laminar and turbulent
regions.
23
Solution of partial differential
equations
Finite difference approach
Finite element approach

Finite difference:
Explicit methods
(Easy to put but beware of convergence and stability)
Implicit methods
The Crank-Nicolson method

Finite element:
Comsol Multiphysics (old name Femlab), Fluent etc.
24
Eulers method
Eulers method is employed for approximate solution of ordinary
differential equations with initial value problems.







Take interval h as low as possible. Take at least 100 steps for the
Eulers method for a better accuracy.
Runge-Kutta 4
th
order method has better efficiency than Eulers
method.
Euler 1707-1783
) , (
1 n n n n
y x f h y y + =
+
n n
x x h =
+1
25
Polymath software
Polymath software is an excellent source for solving single and
simultaneous ordinary differential equations.









26
Problem



27
Problem



28

References
[1] Froment, G.F., Bischoff, K.B., and De Wilde, J. 2011. Chemical reactor analysis and
design. 3
rd
ed. John Wiley & Sons, Inc.
[2] Fogler, H.S. 1999. Elements of chemical reaction engineering. 3
rd
ed. Prentice-Hall.
[3] Levenspiel, O. 1999. Chemical reaction engineering. 3
rd
ed. Wiley & Sons, Inc.,
Singapore.
[4] Catalysis looks to the future. 1992. Panel on New Directions in Catalytic Science
and Technology, National Research Council, National Academy Press, Washington, D.C.
[5] Usman, M.R. 2011. Catalytic Dehydrogenation of Methylcyclohexane over
Monometallic Catalysts for On-board Hydrogen Storage, Production, and Utilization.
Energy Sources A 33, 22312238.
[6] Usman, M.R.; Aslam, R.; Alotaibi, F. 2011. Hydrogen storage in a recyclable organic
hydride: Kinetic modeling of methylcyclohexane dehyrogenation over 1.0 wt% Pt/-
alumina. Energy Sources, Part A 33, 22642271.
[7] Yaws, C.L. 1999. Chemical properties handbook. McGraw-Hill.
[8] Bird, R.B. Stewart, W.E. Lightfoot, E.N. (2002). Transport phenomena. 2
nd
ed. John
Wiley & Sons, Inc. Singapore.
[9] Poling, B.E.; Prausnitz, J.H.; OConnell, J.P. 2000. The properties of gases and
liquids. 5
th
ed. McGraw-Hill.
[10] Missen, R.W., Mims, C.A., and Saville, B.A. 1999. Introduction to chemical
reaction engineering and kinetics. John Wiley & Sons, Inc., New York.
[11] Satterfield, C.N.1970. Mass transfer in heterogeneous catalysis. MIT Press.

29

References
[12] Welty, J.R.; Wicks, C.E.; Wilson, R.E.; Rohrer, G.L. 2007. Fundamentals of
momentum, heat, and mass transfer, 5
th
ed., John Wiley & Sons, Inc.
[13] Smith, J.M. 1981. Chemical engineering kinetics. 3
rd
ed. McGraw-Hill Int. Book
Co., Singapore.
[14] Walas, S.M. 1990. Chemical process equipment: Selection and design.
Butterworth-Heinemann, London.
[15] Brtz, W. 1965. Fundamentals of chemical reaction engineering. Addison-Wesley
Publishing Company, Inc., Reading.
[16] Rase, H.F. 1990. Fixed bed reactor design and diagnostics: Gas-phase reactions,
Butterworths, Boston.
[17] Richardson, J.T. Principles of catalyst development,