Design for

Multiple Reactions
A. SARATH BABU
1
Scope:
Limited to Qualitative treatment
Design aspects not included
2
What is a multiple reaction ?

Require rate w.r.t. more than one species

Require more than one stoichiometric
equation and equilibrium expression

Classification:
Series (consecutive) reactions
A R S
Parallel (competing) reactions
A R
A S
Series Parallel reactions
3
Criteria for selecting the reactor:
Good product distribution
Size of the reactor

Good product distribution could be the dominant
criteria in many cases.

The above two criteria are contradictory to each
other. Good design w.r.t one requirement may be
poor w.r.t. the other.

An economic analysis will give the best
compromise.
4
Selectivity:
A R (desired reaction)
A S (undesired reaction)

Selectivity = r
desired
/r
undesired

The selectivity should be maximum for the
chosen reactor.

Yield = r
desired
/-r
A
5
Parallel reactions
Series reactions
6
Series-Parallel reactions
7
Parallel reactions
A R (desired reaction)
A S (undesired reaction)

o
A
R
R
C k
dt
dC
r
1
= =
|
A
S
S
C k
dt
dC
r
2
= =
k
1
, k
2
, o, | are all constant for a specific system
at a given temperature.

How to maximize S ??
| o
= =
A
S
R
C
k
k
dC
dC
S
2
1
8
| o
= =
A
S
R
C
k
k
dC
dC
S
2
1
How to decide the concentration level??
Case 1: o > |, n
desired
> n
undesired

High concentration is desirable as it
maximizes the selectivity.
Case 2: o < |, n
desired
< n
undesired

Low concentration is desirable as it
maximizes the selectivity.
Case 3: o = |, n
desired
= n
undesired

Concentration level does not affect
the selectivity.
9
Concentration can be maintained low:
Using a CSTR
Designing for high conversions
Increasing inerts in the feed
Decreasing pressure in gas phase reactions
Concentration can be maintained high:
Using a PFR
Designing for low conversions
Decreasing inerts in the feed
Increasing pressure in gas phase reactions
10
How to decide the temperature level??
Case 1: E
D
> E
U

High temperature is desirable as it
maximizes the selectivity.
Case 2: E
D
< E
U

Low temperature is desirable as it
maximizes the selectivity.
Case 3: E
D
= E
U
Temperature level does not affect
the selectivity.
S is maximized at higher k
1
/k
2

| o
= =
A
S
R
C
k
k
dC
dC
S
2
1
11
Example: A + B R (desired reaction)
A + B S (undesired reaction)
2 2 1 1
2
1
| o | o
= =
B A
S
R
C C
k
k
dC
dC
S
Case 1: o
1
> |
1
and o
2
> |
2

Maintain both C
A
and C
B
high.
Case 2: o
1
< |
1
and o
2
< |
2

Maintain both C
A
and C
B
low.
Case 3: o
1
= |
1
and o
2
= |
2

C
A
and C
B
levels will not affect S.
Temperature levels can be decided based on the
activation energies
12
Contacting patterns for batch operation:
13
Contacting patterns for continuous operation:
14
For parallel reactions, the concentration level of
the reactants is the key to control product
distribution.
High reactant concentration favors the higher
order reaction
Low reactant concentration favors the lower
order reaction
Similarly high temperature favors the reaction
with high activation energy
Low temperature favors the reaction with low
activation energy
Conclusions:
15
Series reactions:
A R S (I order at constant density)
mean opt
k
k k
k k
t

=

=
log
1 2
1 2
/ 1
) / ln(
) (
2
1
0
max ,
1 2
2
k k
k
A
R
k
k
C
C

|
|
.
|

\
|
=
Batch Reactor:
mean opt
k
k k
k k

=
log
1 2
1 2
/ 1
) / ln(
t
) (
2
1
0
max ,
1 2
2
k k
k
A
R
k
k
C
C

|
|
.
|

\
|
=
Plug Flow Reactor:
16
CSTR:
A
A A
A
A A
C k
C C
r
C C
1
0 0

=

= t
t
1
0
1 k
C
C
A
A
+ =
Material balance for species R:
vC
R0
= vC
R
+ (-r
R
)V
0 = vC
R
+ (-k
1
C
A
+ k
2
C
R
)V
0 = C
R
+ (-k
1
C
A
+ k
2
C
R
)t
C
R
(1 + k
2
t) = k
1
C
A
t
17
) 1 )( 1 ( 1
2 1
0 1
2
1
t t
t
t
t
k k
C k
k
C k
C
A A
R
+ +
=
+
=
For maximum concentration of R: dC
R
/dt = 0
| |
2
1 2
0
max ,
1 /
1
+
=
k k
C
C
A
R
2 1
1
k k
opt
= t
18
Consecutive I-order reactions
C
B
exhibits a maximum at t
opt
PFR
CSTR
C
B,max
(PFR) > C
B,max
(CSTR)
19
For series reactions, the time of reaction /
space time is the key for obtaining the maximum
concentration of the desired product.
For higher order reactions and series-parallel
reactions, such analytical derivations for
optimum space time would be tedious.
In such cases, optimization methods can be used
to find the optimum space time and the
corresponding maximum concentration of the
desired product.
Conclusions:
20
Assignment:
1. Find expressions for optimum space time and
maximum concentration of R for the following
series reaction, if k
1
= k
2
in both CSTR and PFR
A R S (I order at constant density)
2. Find expressions for optimum space time and
maximum concentration of R for the following
series reaction, if k
1
= 2k
2
in both CSTR and
PFR
A R S (I order at constant density)
21
ANY CLARIFICATIONS ?
Berrill, N.J .
A great teacher is not simply one who imparts knowledge to his
students but is one who awakens their interest in the subject and
makes them eager to pursue it for themselves. An outstanding teacher
is a spark plug, not a fuel line.
22