Topic 6

Multiple Reactions

AECH 3132 Chemical Reaction Engineering

 Introduction
• Usually, more than one reaction occurs within a chemical reactor.
• Minimization of undesired side reactions that occur with the desired reaction contributes to the
economic success of a chemical plant.
• Goal: determine the reactor conditions and configuration that maximizes product formation.
• Reactor design for multiple reactions
• Parallel reactions
• Series reactions
• Independent reactions
• More complex reactions
• Use of selectivity factor to select the proper reactor that minimizes unwanted side reactions.

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 Classification of Multiple Reactions
1) Parallel or competing reactions

k1 B
A
k2 C
Desired product

2) Series reactions k1 k2
A B C
Desired product

3) Independent reactions Crude oil cracking

k1 k2
A B C D

4) Complex reactions k
1 C+D
A + B ¾¾® 2 ®E
A + C ¾¾¾
k
3
 Parallel Reactions
Purpose: maximizing the desired product in parallel reactions
-ED
kD
D (desired) rD = kDCAa1CB b1 ® rD = AD e RT CAa1CB b1
A+B -EU
kU
U (undesired) rU = kUCAa 2 CB b2 ® rU = AUe RT CAa 2 CB b2
-E
Rate of disappearance of A: -rA = rD + rU
k (T) = AeRT
-ED -EU
-rA = ADe RT C Aa1CB b1 + AUe RT C Aa2 CB b2
Define the instantaneous rate selectivity, SD/U
- ED

rate of formation of D rD AD e RT
C A a1CBb1
SD U = = sD U = - EU
rate of formation of U rU A Ue RT
C A a2 CBb2
-(ED -EU )
SD U =
kD
kU
( )
CAa1-a 2 CB b1- b2 ® SD U =
AU
AD
e RT ( )
CAa1-a 2 CB b1- b2

Goal: Maximize SD/U to maximize production of the desired product 4

 Different Types of Selectivity
rate of formation of D rD
instantaneous rate selectivity, SD/U SD U = =
rate of formation of U rU
overall rate selectivity, S D U
F Exit molar flow rate of desired product
S D U = D =
FU Exit molar flow rate of undesired product

N Final moles of desired product

S D U = D =
NU Final moles of undesired product

instantaneous yield, YD rate of formation of D rD

YD = =
(at any point or time in reactor) rate of consumption of A -rA
overall yield, Y
D

FD Evaluated ND Evaluated
flow Y D = batch Y D =
FA0 - FA at outlet NA0 - NA at tfinal
5
 Maximizing SD/U for Parallel Reactions: Temperature Control
-(ED -EU )
SD U =
AD
AU
e RT ( )
CAa1-a2 CB b1- b2

What reactor conditions and configuration maximizes the selectivity?

Start with temperature (affects k):
a) If ED > EU b) If ED < EU

-(ED -EU ) -(ED -EU )

ED - EU ED - EU
> 0 ® e RT <1 < 0 ® e RT >1
RT RT

Specific rate of desired reaction kD Specific rate of desired reaction kD

increases more rapidly with increasing T increases less rapidly with increasing T

Use higher temperature to favor Use lower T to favor desired product formation
desired product formation (not so low that the reaction rate is tiny)
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Maximize SD/U for Parallel Reactions using Temperature
D -(ED -EU )
kD AD
A SD U = e RT CAa1-a2
AU
kU U What reactor temperature maximizes the selectivity?

ED = 20 kcal/mol, EU = 10 kcal/mol, T = 25 ◦C (298K) or 100 ◦C (373K) ED > EU

T = 25 ◦C æ cal cal ö
-ç 20,000 -10,000 ÷
(298K): è mol mol ø
æ cal ö
1.987 ÷298K
( )
AD ç AD
SD U = e è mol ×K ø CAa1-a2 ® SD U = 4.6 ´ 10-8 CAa1-a2
AU AU
T = 100 ◦C æ cal cal ö
-ç 20,000 -10,000 ÷ kD/U
(373K): è mol mol ø
æ cal ö
1.987 ÷373K
( )
AD ç AD
SD U = e è mol ×K ø CAa1-a2 ® SD U = 1.4 ´ 10-6 CAa1-a2
AU AU
SD/U is greater at 373K, higher temperature to favors desired product formation
7
Maximizing SD/U for Parallel Reactions: Concentration
kD -(ED -EU )
D
A+B
kU
SD U =
AD
AU
e RT ( )
CAa1-a2 CB b1- b2
U
What reactor conditions and configuration maximizes the selectivity?
Now evaluate concentration:
a) a1 > a 2 ® a1 - a 2 > 0 b) a1 < a 2 ® a1 - a 2 < 0

C Aa1-a 2 C Aa1-a 2
→ Use large CA → Use small CA

c) b1 > b2 ® b1 - b2 > 0 d) b1 < b2 ® b1 - b2 < 0

CB b1- b2 CB b1- b2
→ Use large CB → Use small CB
How do these concentration requirements affect reactor selection?
8
Figure 8-2. Different reactors and schemes for maximizing Selectivity.

9
Choice of Reactor and Conditions to Minimize Unwanted Products

10
Choice of Reactor and Conditions to Minimize Unwanted Products

11
Choice of Reactor and Conditions to Minimize Unwanted Products

12
Choice of Reactor and Conditions to Minimize Unwanted Products

13
 Series (Consecutive) Reactions
k1 k2
A D U Time is the key factor here!!!
(desired) (undesired)

Spacetime t for a flow reactor Real time t for a batch reactor

To maximize the production of D, use:

Batch CSTRs in series

or PFR/PBR or
n

and carefully select the time (batch) or spacetime (flow)

14
 Concentrations in Series Reactions
k1 k2 -rA = k1CA
A B C rB,net = k1CA – k2CB
How does CA depend on t?
dFA dC A
= -k1C A ® u0 = -k1C A ® C A = C A0e -k1t
dV dV
How does CB depend on t?
dFB
dV
= k1C A - k 2CB ® u0
dCB
dV
= k1 C A0e -k1t - k 2CB ( ) Substitute
V
u0
=t

®
dCB
dt
= k1 CA0e (
-k1t
- k 2CB ®
dCB
dt
)
+ k 2CB = k1 CA0e-k1t ( )
Use integrating
factor (reviewed ®
(
d CBek 2t ) æ e-k1t - e-k 2t
= k1CA0e( 2 1) ® CB = k1CA0 çç k - k
k -k t
ö
÷÷
on Compass) dt è 2 1 ø
CC = CA0 - CA - CB
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 Reactions in Series: Cj & Yield
B C A = C A0 e -k1t
A C
æ e-k1t - e-k 2t ö
CB = k1CA0 ç ÷÷
ç k 2 - k1
è ø
CC = CA0 - CA - CB
topt
The reactor V (for a given u0) and t that maximizes CB occurs when dCB/dt=0
dCB æ k1CA0 ö
=ç ÷
dt è k 2 - k1 ø
-(
k1e -k1t
+ k 2 e -k 2t
)
=0

1 k
t opt = ln 1
k1 - k 2 k 2

V
= t so Vopt = u0t opt
u0
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Exercise 1: What reactor/reactors scheme and conditions would you use to maximize the
selectivity parameters for the following parallel reaction?
kD -2000 E/R -300
A+C D desired
kU1 rD = 800e T CA 0.5 CC rU1 = 10e T CA CC
A+C U1 undesired
-E
Need to maximize SD/U1
( )
k T = AeRT
(- ED -EU
1 )
rD AD æ aD -aU ö bD - bU
SD U1 = = e T
ç CA 1
÷ CC 1
rU
1
AU
1
è ø
-( 2000 -300 ) -1700
Plug in
numbers: SD U1 =
800
10
e T
( )
CA 0.5-1 CC1-1 ® SD U = 80e T CA -0.5
1

To maximize the production of the desired product, the temperature should be

a) As high as possible (without decomposing the reactant or product)
b) Neither very high or very low
ED > EU, so use higher T
c) As low as possible (but not so low the rate = 0)
d) Doesn’t matter, T doesn’t affect the selectivity
e) Not enough info to answer the question
Exercise 1: What reactor/reactors scheme and conditions would you use to maximize the
selectivity parameters for the following parallel reaction?
kD -2000 -300
A+C D desired
kU1 rD = 800e T CA 0.5 CC rU1 = 10e T C A CC
A+C U1 undesired
-E
Need to maximize SD/U1
k (T) = AeRT
(
- ED -EU
1 )
r AD æ C aD -aU1 ö C bD - bU1
SD U1 = D = e T
ç A ÷ C
rU
1
AU
1
è ø
-( 2000 -300 ) -1700
Plug in
numbers: SD U1 =
800
10
e T
( )
CA 0.5-1 CC1-1 ® SD U = 80e T CA -0.5
1

To maximize the production of the desired product, CA should be

a) As high as possible
αD < αU1, so high CA favors undesired product
b) Neither very high or very low formation (keep CA low)
c) As low as possible
d) Doesn’t matter, CA doesn’t affect the selectivity
e) Not enough info to answer the question
Exercise 1: What reactor/reactors scheme and conditions would you use to maximize the
selectivity parameters for the following parallel reaction?
kD -2000 -300
A+C D desired
kU1 rD = 800e T C A 0.5CC rU1 = 10e T C A CC
A+C U1 undesired
Need to maximize SD/U1
(
- ED -EU
1 )
r AD æ C aD -aU1 ö C bD - bU1
SD U1 = D = e T
ç A ÷ C
rU
1
AU
1
è ø
-( 2000 -300 ) -1700
Plug in
numbers: SD U1 =
10
800
e T
( )
CA 0.5-1 CC1-1 ® SD U = 80e T CA -0.5
1
• Since ED>EU1, kD increases faster than kU1 as the temperature increases
• Operate at a high temperature to maximize CD with respect to CU1
• aD<aU1, keep CA low to maximize CD with respect to CU1
• rD and rU1 are 1st order in CC, so changing CC does not influence selectivity
• HOWEVER, high CC will increase the reaction rate and offset the slow reaction rate
that is caused by low CA (that’s a good thing)
What reactor should we use?
Exercise 1: What reactor/reactors scheme and conditions would you use to maximize the
selectivity parameters for the following parallel reaction?
kD -2000 -300
A+C D desired rD = 800e T C A 0.5CC rU1 = 10e T C
kU1 A CC
A+C U1 undesired
Need to maximize SD/U1
-1700
SD U1 = 80e T CA -0.5
• ED>EU1, operate at a high temperature to maximize CD with respect to CU1
• aD<aU1, keep CA low to maximize CD with respect to CU1
• rD and rU1 are 1st order in CC, so changing CC does not influence selectivity
• HOWEVER, high CC will increase the reaction rate and offset the slow reaction rate
that is caused by low CA (that’s a good thing)
What reactor should we use?

C PFR CA

Semi-batch reactor
A slowly feed A to large
PFR/PBR w/ side streams feeding low CA amount of C ←High CC
credit to lecture notes :
https://websites.umich.edu/~elements/6e/lectures/index.html 21