Chemical Reaction Engineering

Lecture 6: Complex Reactions

Jayant M. Modak
Department of Chemical Engineering
Indian Institute of Science, Bangalore
Topic 3: Complex systems
! Analysis of Simple complex systems
! Kinetics of complex systems
" Chain reaction
" Catalysis
" Polyermization
! Lumping analysis
Complex systems - Examples
! Large number of reactions and reactants
3 8 3 6 2
3 8 2 4 4
3 8 2 4 2 6 3 6
Thermal cracking of alkanes
C H C H H
C H C H CH
C H C H C H C H
Cracking of crude to petrol
Metabolic network insidecell
! +
! +
+ ! +
Complex systems - Examples
! Chain reactions
3 4
2
( )
Thermal decomposition
CH CHO CH CO
Auto oxidation
R H O ROOH
Polymerization
styrene poly styrene
! +
"
" + !
!
Complex systems - Examples
! Catalytic reactions

Thermal decomposition
C
12
H
22
O
11
+ H
2
O
acid
! " !!C
6
H
12
O
6
+ C
6
H
12
O
6
Ammonia synthesis
1
2
N
2
+
3
2
H
2
Fe
! " ! NH
3
Yield conversion diagram
Polymer weight distribution
Catalytic reaction kinetics
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0.061
0.132
0.263
0.526
0.789


r
a
t
e
p
Ethylene
p
O2
Complex reactor behavior
Cracking of ethane to ethylene
! New questions
" Are all products useful?
" How to monitor the reaction?
" Is conversion of ethane the only criteria for design?
26 24 2
CHCHH !+
26 38 4
2CHCHCH !+
24 2
22 CHCH !+
Parallel reactions
2 6 2 4 2
2 6 38 4
2
CHCHH
CHCHCH
!+
!+

A
1
!
A
3
"
A
2
Series reactions
2 6 2 4 2
2 4 2
2 2
CH CHH
CH CH
! +
!+

A
1
! A
2
! A
3
Complex (Series-parallel) reactions
2 6 2 4 2
2 6 3 8 4
3 8 2 4 4 8 4
2
CH CHH
CH CHCH
CHCH CHCH
! +
! +
+ ! +

A
1
!
A
3
"
A
2
A
2
+ A
3
! A
4
Independent Reactions
2 6 2 4 2
3 8 3 6 2
CH CHH
CHCHH
! +
! +

A
1
! A
2
A
3
! A
4
Desired and Undesired Reactions

A
1
! A
2
A
1
! A
3
A
1
! A
2
! A
3
26 24 2
CHCHH !+
26 38 4
2CHCHCH !+
Yield

Desired reaction A
1
! A
2
r
1
Undesired reaction A
1
! A
3
r
2

Overall
Yield
Y
2
=
Exit molar flowrateof desired product
Inlet molar flowrateof reactant
Selectivity

Desired reaction A
1
! A
2
r
1
Undesired reaction A
1
! A
3
r
2

Instantenous
Selectivity
s
2
=
r
1
r
1
+ r
2

Overall
Selectivity
!
S
2
=
Exit molar flowrateof desired product
Exit molar flowrateof all products
Selection of reactor type and conditions

CSTR
C
2
C
10
! C
1
=
r
1
r
1
+ r
2
PFR
C
2
C
10
! C
1
=
1
C
10
! C
1
r
1
r
1
+ r
2 C
1
C
10
"
dC
1

Desired reaction A
1
! A
2
r
1
Undesired reaction A
1
! A
3
r
2
Complex systems - selectivity

1
0
-1

s
e
l
e
c
t
i
v
i
t
y

(
C
1
)
C
10
-C
1
q
2
-q
1
Complex systems series reactions
0 10
0.0
0.2
0.4
0.6
0.8
1.0

!=0.1
A
1
A
2
A
3

C
o
n
c
e
n
t
r
a
t
i
o
n
Time

A
1
! A
2
r
1
= k
1
C
1
A
2
! A
3
r
1
= k
2
C
2
" = k
2
/ k
1
Concept of yield-conversion diagram

A
1
! A
2
r
1
= k
1
C
1
A
2
! A
3
r
1
= k
2
C
2
" = k
2
/ k
1
Concept of rate determining step
0 10
0.0
0.2
0.4
0.6
0.8
1.0

!=0.1
A
1
A
2
A
3

C
o
n
c
e
n
t
r
a
t
i
o
n
Time

A
1
! A
2
r
1
= k
1
C
1
A
2
! A
3
r
1
= k
2
C
2
" = k
2
/ k
1
Concept of rate determining step
0 10
0.0
0.2
0.4
0.6
0.8
1.0

!=5
A
1
A
2
A
3

C
o
n
c
e
n
t
r
a
t
i
o
n
Time

A
1
! A
2
r
1
= k
1
C
1
A
2
! A
3
r
1
= k
2
C
2
" = k
2
/ k
1
Concept of quasi-equilibrium approximation
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
1.0
k
1
=1, k
-1
=0.5, k
2
=k
-2
=1
C
1
C
2
C
3
c
o
n
c
e
n
t
r
a
t
i
o
n
time

A
1
! A
2
r
1
= k
1
C
1
! k
!1
C
2
A
2
! A
3
r
1
= k
2
C
2
! k
!2
C
3
Concept of quasi-equilibrium approximation
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
1.0
C
1
C
2
C
3
c
o
n
n
t
r
a
t
i
o
n
time
k
1
=1, k
-1
=0.5, k
2
=k
-2
=10
A
1
! A
2
r
1
= k
1
C
1
! k
!1
C
2
A
2
! A
3
r
1
= k
2
C
2
! k
!2
C
3
Concept of quasi-equilibrium approximation
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
1.0
C
1
C
2
C
3
C
1
(e)
C
2
(e)
c
o
n
n
t
r
a
t
i
o
n
time
k
1
=1, k
-1
=0.5, k
2
=k
-2
=10
A
1
! A
2
r
1
= k
1
C
1
! k
!1
C
2
A
2
! A
3
r
1
= k
2
C
2
! k
!2
C
3
Concept of quasi-steady state approximation
0 10
0.0
0.2
0.4
0.6
0.8
1.0

!=5
A
1
A
2
A
3

C
o
n
c
e
n
t
r
a
t
i
o
n
Time

A
1
! A
2
r
1
= k
1
C
1
A
2
! A
3
r
1
= k
2
C
2
" = k
2
/ k
1
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
1.0
1
10
50
!
C
3
/
C
1
0
k
1
t
k
2
Concept of quasi-steady state approximation


A
1
! A
2
r
1
= k
1
C
1
A
2
! A
3
r
1
= k
2
C
2
" = k
2
/ k
1
Chemical Reaction Engineering
Lecture 6: Complex Reactions
Jayant M. Modak
Department of Chemical Engineering
Indian Institute of Science, Bangalore
Chain reactions
! Combustion reactions
! Decomposition reactions
! Autooxidation
! Polymerization

Chain reactions decomposition of acetaldehyde
CH
3
CHO!CH
4
+ CO
CH
3
CHO!CH
3

+ CHO

CH
3

+ CH
3
CHO!CH
3
CO

+ CH
4
CH
3
CO

!CH
3

+ CO
2CH
3

!C
2
H
6
r = kC
CH
3
CHO
3/ 2
Polymerization
! Chain polymerization of
" Ethylene (X=H), vinyl chloride (X=Cl)
" Styrene (X=C
6
H
5
) etc
! Initiator I (!-!)


CH
2
= CHX (RX)

Initiation C
6
H
5
COO! OOCC
6
H
5
"2C
6
H
5
COO
# +RX "#! RX
Propogation #! RX +RX "#! (R) ! RX
#! (R)
j !1
! RX +RX "
#! (R)
j
! RX
Termination
#! (R)
j !1
! RX + XR ! (R)
i !1
! #"
#! (R)
j !1
! RX ! XR ! (R)
i !1
! #
Polymerization

Initiation I
k
0
! " ! 2# k
0
= 10
$4
$10
$6
#+ M
k
i
! " ! R
1
Propogation R
1
+ M
k
p
! " ! R
2
k
p
= 10
2
$10
4
R
j $1
+ M
k
p
! " ! R
j
Termination R
j
+ R
i
k
a
! " ! P
i + j
k
a
= 10
6
$10
8
Polymerization

Species Appearance disappearance
I k
0
I
! r
0
= 2 fk
0
I r
i
= k
i
!M
R
1
r
i
k
p
MR
1
+ k
a
R
1
R
j
"
R
j
k
P
MR
j
k
p
MR
j
+ k
a
R
j
R
i
"
P
j
k
a
2
R
j #i
R
i
"
Polymerization

Initiation rate r
i
= 2 fk
0
I
Total radicals !R
j
= "
0
=
r
i
k
a
#
$
%
&
'
(
1/ 2
Monomer consumption r
M
= k
p
M"
0
Radical concn R
j
=
r
i
k
P
M
#
$
%
&
'
(
1
1+ r
i
/ r
M
#
$
%
&
'
(
j
polymer generation r
P
j
= R
j
j )1
( )
k
a
2
r
i
k
P
M
#
$
%
&
'
(
Polymerization
0 500 1000 1500 2000 2500 3000
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
w
e
i
g
h
t

f
r
a
c
t
i
o
n
number of monomers
0.04
0.02
0.08
Initiator
0 500 1000 1500 2000 2500 3000
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
w
e
i
g
h
t

f
r
a
c
t
i
o
n
number of monomers
360
180
60
time (min)
Polymer weight distribution
Chemical Reaction Engineering
Catalytic reactions
Jayant M. Modak
Department of Chemical Engineering
Indian Institute of Science, Bangalore
Catalytic reactions
Solid
Gas
(2
nd
Liquid)
Liquid
Catalyst
Heterogeneous catalysis
Catalytic reactions
H
2
O
2

soluti
on
25C
stable over
months
>320C
uncontrolled,
thermal
decomposition in
seconds
25C
controlled, catalytic
or
enzymatic
decomposition
in seconds
Example: Hydrogen peroxide
decomposition
2H
2
O
2
2H
2
O + O
2
Catalytic reactions
Efficiency of Phthalic Acid Anhydride Production
Non-catalytic Oxidation of
naphthalene in fluid phase
with MnO
2
+HCl (1872),
Chromic acid (1881),
Oleum (1891)
Catalytic Oxidation of
o-Xylene in the gas phase
on V
2
O
5
-catalyst
Yield: 5-15%
Yield: 75-87%
Catalytic reactions
Efficiency of nitrogen fixation
catalytic
processes
Catalytic reactions
Product spectrum from partial oxidation of propene
substrates
catalysts
products
propene +
oxygen
acrolein
acrylic
acid
acetone
propylene
oxide
acetic acid
1,5-hexa-
diene
benzene
Catalytic reactions
Steps during the course
of the reaction
External diffusion
Internal diffusion
Adsorption on the active
sites
Surface reaction
forming the products
Desorption of the
products
Internal diffusion
External diffusion
!
"
#
$
%
&
'
reaction:
substrate A product P
fixed bed
reactor
Boundary
layer
Lumping analysis
0.0 0.1 0.2 0.3 0.4 0.5
0.0
0.2
0.4
0.6
0.8
1.0
A
1
A
2
A
3
C
o
n
c
e
n
t
r
a
t
i
o
n
s
Time
A
10
=1, A
20
=0, A
30
=0
0.0 0.1 0.2 0.3 0.4 0.5
0.0
0.2
0.4
0.6
0.8
1.0
A
10
=1, A
20
=0, A
30
=0
A
1
+A
2
A
3

1

2
C
o
n
c
e
n
t
r
a
t
i
o
n
s
Time
0.0 0.1 0.2 0.3 0.4 0.5
0.0
0.2
0.4
0.6
0.8
1.0
A
10
=0.5, A
20
=0.5, A
30
=0
C
o
n
c
e
n
t
r
a
t
i
o
n
s
Time
B
0.0 0.1 0.2 0.3 0.4 0.5
0.0
0.2
0.4
0.6
0.8
1.0
A
10
=0.5, A
20
=0.5, A
30
=0
A
1
+A
2
A
3

1

2
C
o
n
c
e
n
t
r
a
t
i
o
n
Time
Lumping analysis
0.0 0.1 0.2 0.3 0.4 0.5
0.6
0.8
1.0

1
=A
1
+A
3
,
2
=A
2
1,0,0
0,0,1
C
o
n
c
e
n
t
r
a
t
i
o
n
Time
Initial A
1
,A
2
,A
3