CRE-1

Multiple Reactions
1

Quiz 3
Find expressions for optimum space
time and maximum concentration of
R in CSTR for the following
elementary series reaction if 2k1 = k2
ARS

Outcomes
The student should be able to:1. Distinguish and utilize selectivity and yield
2. Propose the appropriate reactor system that
would maximize selectivity of the desired
product
3. Design a reactor using

What is a multiple reaction ?

Require rate with regard to (w.r.t.) more than one

species

Require more than one stoichiometric equation and

equilibrium expression

Classification:
Series (consecutive) reactions
ARS
Parallel (competing) reactions
AR
AS
Series Parallel reactions
4

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.
5

Selectivity:
A R (desired reaction)
A S (undesired reaction)
Selectivity = rdesired/rundesired
The selectivity should be maximum for the
chosen reactor.
Yield = rdesired /-rA

Parallel reactions

Series reactions

Series-Parallel reactions

Parallel reactions
A R (desired reaction)
A S (undesired reaction)
dC R
rR
k1C A
dt

dC S
rS
k 2C A
dt

dC R k1
S
CA
dCS k 2

k1, k2, , are all constant for a specific system

at a given temperature.
How to maximize S ??
9

How to decide the concentration level??

dC R k1
S
CA
dCS k 2

Case 1: > ,
High concentration is desirable as it
maximizes the selectivity.
Case 2: < ,
Low concentration is desirable as it
maximizes the selectivity.
Case 3: = ,
Concentration level does not affect
the selectivity.
10

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

11

How to decide the temperature level??

dC R k1
S
CA
dCS k 2

S is maximized at higher k1/k2

Case 1: ED > EU
High temperature is desirable as it
maximizes the selectivity.
Case 2: ED < EU
Low temperature is desirable as it
maximizes the selectivity.
Case 3: ED = EU
Temperature level does not affect
the selectivity.
12

Example: A + B R (desired reaction)

A + B S (undesired reaction)
dC R k1 1 1 2 2
S
C A CB
dCS k 2

Case 1: 1 > 1 and 2 > 2

Maintain both CA and CB high.
Case 2: 1 < 1 and 2 < 2
Maintain both CA and CB low.
Case 3: 1 = 1 and 2 = 2
CA and CB levels will not affect S.

Temperature levels can be decided based on the

activation energies 13

Contacting patterns for batch operation:

14

Contacting patterns for continuous operation:

15

Conclusions:
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
16

SELF TEST: Parallel Reaction

Determine the instantaneous selectivity, SD/U, for the liquid phase reactions:
2

A B D,rD k1C A C B
A B U1,rU 1 k 2C AC B
3

A B U 2 ,rU 2 k3C A C B
Sketch the selectivity as a function of the concentration of A. Is there an
optimum and if so what is it?

17

S D / U 1U 2

rD
k 1C A C B
k1C A

3
2
rU 1 rU 2
k 2 C A C B k 3C A C B
k 2 k 3C A

dS
2
k1C A ( k 2 k3C A ) 1
dC A
Let u k1C A , v k 2 k3C A

2 k 3C A
du
dv
k1 ;

2
dC A
dC A
( k 2 k 3C A ) 2
2

2k1k3C A
k1
udv vdu

2 2
2
( k 2 k3C A )
k 2 k3C A
2

k1 ( k 2 k3C A ) 2k1k3C A 0
CA

k2
k3
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Series reactions:
A R S (I order at constant density)
Batch Reactor:
topt

ln( k 2 / k1 )

1 / k log mean
k 2 k1

C R ,max
C A0

k1

k2

k2

( k 2 k1 )

Plug Flow Reactor:

opt

ln( k 2 / k1 )

1 / k log mean
k 2 k1

C R ,max
C A0

k1

k2
19

k2

( k 2 k1 )

CSTR:

C A0 C A C A0 C A C A 1 k
1

C A0
rA
k1C A
Material balance for species R:
vCR0 = vCR + (-rR)V
0 = vCR + (-k1CA+ k2CR)V
0 = CR + (-k1CA + k2CR)
CR(1 + k2) = k1CA

20

k1C A0
k1C A
CR

1 k 2 (1 k1 )(1 k 2 )
For maximum concentration of R: dCR/d = 0

C R ,max
C A0

opt

k 2 / k1 1

1
k1k 2
21

PFR

CSTR

Consecutive I-order reactions

CB exhibits a maximum at opt
CB,max (PFR) > CB,max (CSTR)

22

Conclusions:
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.
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Multiple Reactions

24

Multiple Reactions

25

SELF TEST: Net rates of

formation

The reactions:
1) A+2B2C
2) 2C+1/2 B3D
are elementary.
a) Write net rates of formation for A, B, C and D
b) If the entering volumetric flow rate is 100 dm3/min and the
entering concentration of A is 4M, identify the PFR volume if
the liquid phase of output consist of CB=1/2CA

dm 3 2
(
)
k1 A 0.1 mol
min
3 3
dm 2
(
)
k 2 D 2 mol
min

26

1) Net rate formation of A

r1 A k1C AC B

2
2

rA r1 A r2 A k1C ACB 0 k1C ACB

2) Net rate formation of B

r1B r1 A

2 1
2
r1B 2r1 A 2k1C AC B
r2 B
r2 D

1/ 2
3
1
r2 B r2 D
6
1/ 2
2
r2 D k 2 D C B CC
rB r1B r2 B 2k1C AC B

1
1/ 2
2
k 2 D C B CC
6

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2) Net rate formation of C

r1C r1 A

2 1
2
2
r1C 2r1 A 2(k1C AC B ) 2k1C AC B
r2C r2 D

2
3
2
r2C r2 D
3
1/ 2
2
r2 D k 2 D C B CC
rC r1C r2C 2k1C AC B

2
1/ 2
2
k 2 D C B CC
3
28

2) Net rate formation of D

1/ 2

r2 D k 2 DCB CC

2
1/ 2

1/ 2

rD r1D r2 D 0 k 2 DCB CC k 2 DCB CC

29

b) PFR
dFA
1
1
2
2
2
rA , C B ( ) 2 C A
CA
dV
2
4
dC A 0
1
2
3
k1C AC B
k1C A
dV
4
4 0

k1

4 0
k1

CA

C A0

1
dC A
3
CA

1
1

2 C A2

2 0 1
1

k1 C A
C A0

dV
0

CA

V
CA0

0.4

V
4

V 12375dm 3

30

Multiple Reactions
Mole Balances
Reactor Type

Gas Phase

Liquid Phase

Batch
Semibatch

CSTR
PFR
PBR
31

Selectivity issues in EP
Relevant to multiple reactions when reaction
yield can decrease due to the side reactions
Operational problems arise when dealing
with concentration-limiting or temperaturelimiting process due to selectivity and
reversibility of the reaction.
Costs of material transfer increased.

These issues begin in the 2nd level

32

Case Study: Benzene production Hydrodealkylation of Toluene

Toluene + H 2 Benzene + CH 4
2 Benzene

Diphenyl + H 2

H2 feedstock comes with CH4 (impurities) fed in excess. Decided to

have post-reactor incineration
Unreacted Hydrogen and Toluene are recycled in the process, X =1
But H2-CH4 stream varies with selectivity following

S 1

0.0036

1 X

1.544

From Literature

The input-output structure considers selectivity and purge (to

incineration) ratio
33

Selectivity and Reaction

Stoichiometry
5
Purge H2, CH4
3 Benzene

1 H2, CH4
2 Toluene

Process

4 Diphenyl

34

Extent of Reaction Analysis

1) Toluene + H 2 Benzene + CH 4
2) 2 Benzene

Diphenyl + H 2

Component mole balances: Net benzene produced, PB = 1 - 22

Methane produced = 1
Diphenyl produced = 2
Toluene consumed = 1
Hydrogen consumed = 1 - 2

Extent of Reaction
1 = PB/S
1 - 22 = PB
2 = (1 PB) = PB (1-S)/(2S)

Selectivity, if it is not given,

S = (1 - 22)/1
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HPD of Toluene mole balance

Component

H2

FH2

FE

CH4

FM

FM + PB/S

Benzene

PB

Toluene

PB/S

Diphenyl
Temperature

PB(1-S)/(2S)
100

100

Pressure
550
15
Where:- S 1 0.0036
1.544
1 X

FM

1 yFH

100

100

100

15
15
1 S
FH 2 FE PB

2S
1 S

FE PB

465

FG FH 2 FM

yFH
36

Assignment:
1. Find expressions for optimum space time and
maximum concentration of R for the following
series reaction, if k1 = k2 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 k1 = 2k2 in both CSTR and
PFR
A R S (I order at constant density)
37