Maximizing Product Selectivity in Multiple Parallel Reactions

Reactor Design for
Multiple Reactions-Tutorial
L9-1
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L9b-2
Review: Multiple Rxns & Selectivity

1) Parallel / competing rxns
A
k1
k2
k1
A
Desired product
2) Series rxns
3) Complex rxns
instantaneous rate selectivity, SD/U

SD U
rate of formation of D rD
rate of formation of U rU
overall rate selectivity,S%D U

ND
Final moles of desired product
%
SD U
NU Final moles of undesired product
A+B
k1
k2
C+D A+C
k2
instantaneous yield, YD
(at any point or time in reactor)

r
rate of formation of D
YD
D
rate of consumption of A rA
F
Exit molar flow rate of desired product
S%D U D
FU Exit molar flow rate of undesired product
overall yield, Y
%
FD
%
flow YD F F
A0
A
at
exit
ND
batch Y%
D
NA0 NA
at
tfinal
Maximize selectivity / yield to maximize production of desired product

Review: Maximizing SD/U for

Parallel Rxns
SD U
ED EU
AD
e RT
AU
CA
1 2
CB
1 2
L9b-3
What reactor conditions and

configuration maximize selectivity?
Specific rate of desired reaction kD increases:

a) If ED > EU
b) If ED < EU
more rapidly with increasing T
less rapidly with increasing T
Use lower temperature(not so low
Use higher temperature
that the reaction rate is tiny)
To favor production of the desired product
Now evaluate concentration:
a) 1 2 1 2 0
b) 1 2 1 2 0
Use large CA
Use small CA
c) 1 2 1 2 0
d) 1 2 1 2 0
Use large CB
Use small CB
Concentration Requirements &

Reactor
Selection
k
D
A+B
kU
How do concentration requirements play

into reactor selection?
CA00
CB00
PFR
PFR (or PBR): concentration is
high at the inlet & progressively
drops to the outlet
concentration
CA(t)
CB(t)
L9b-4
Batch:
concentration is
high at t=0 &
progressively drops
with increasing time
CB0
CA
CA0
CB0
CSTR:
concentration is
always at its
lowest value
(that at outlet)
Semi-batch: concentration
of one reactant (A as
shown) is high at t=0 &
progressively drops with
increasing time, whereas
concentration of B can be
kept low at all times
kD
A+B
kU
High CA favors undesired

High
C
favors
desired
A
product formation
product formation
U
(keep CA low)
High CB
favors
desired
product
formation
L9b-5
Batch reactor
When CA & CB are low (end time
or position), all rxns will be slow
PFR/PBR
High P for gas-phase rxn, do not
add inert gas (dilutes reactants)
PFR/PBR
Side streams feed low CA
CA
Semi-batch
reactor slowly feed
High CB
A to large amt of B
CA
CA
CA
CSTRs in
series
CA00
CB00
CA0
CB
CSTR
PFR/PBR w/ side streams feeding

High CB
low CB
CB
favors
Semi-batch
High CA
PFR/PBR
undesired reactor, slowly
PFR/PBR
w/ high
feed B to large amount of A
product
recycle
CB
CB
CB
formation
CSTRs in
Dilute feed with inerts that are
(keep CB series
easily separated from product
low)
B consumed
before&leaving
CSTR
Low
P if gas
phaseUrbana-Champaign.
Slides courtesy of Prof
M L Kraft, Chemical
Biomolecular
Engr
University
of Illinois,
n Dept,
L9b-6
Different Types of Selectivity

rate of formation of D rD
instantaneous rate selectivity, SD/U

rate of formation of U rU
overall rate selectivity,S%
SD U
DU
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
(at any point or time in reactor)
YD
r
rate of formation of D
D
rate of consumption of A rA
%
overall yield, Y
D
% FD
Y
flow D F F
A0
A
Evaluated
at outlet
batch Y%
D
ND
NA0 NA
Evaluated
at tfinal
L9b-7
Series (Consecutive) Reactions

A
k1
k2
U
D
(desired) (undesired)
Spacetime for a flow reactor
Time is the key factor here!!!
Real time t for a batch reactor
To maximize the production of D, use:

CSTRs in series
Batch
or
PFR/PBR
or
n
and carefully select the time (batch) or spacetime (flow)

L9b-8
Concentrations in Series Reactions

k1
k2
-rA = k1CA
rB,net = k1CA k2CB
How does CA depend on ?

dFA
dC A
k1C A 0
k1C A C A C A0e k1
dV
dV
How does CB depend on ?
dFB
dCB
k1C A k 2CB 0
k1 C A0e k1 k 2CB
dV
dV
Substitute
0
dCB
dCB
k1 C A0ek1 k 2CB
k 2CB k1 CA0e k1
d
d
Use integrating
factor (reviewed
on Compass)
d CBek 2
d
k C
1
ek1 ek 2
k 2 k1 CB k1CA0
A0
k
k
2
1
CC CA0 CA CB
L9b-9
Reactions in Series: Cj & Yield

CA CA0ek1
B
C
ek1 ek 2
CB k1C A0
k
2
1
CC CA0 CA CB
opt
The reactor V (for a given 0) and that maximizes CB occurs when dCB/dt=0
dCB k1CA0
k1
k 2
k
e
k
e
0
1
2
d
k 2 k1
opt
k
1
ln 1
k1 k 2 k 2
V
so Vopt 0 opt
0
L9b-10
What reactor/reactors scheme and conditions would you use to maximize
the selectivity parameters for the following parallel reaction?
A+C
A+C
kD
kU1
D desired
U1 undesired
Need to maximize SD/U1

SD U1
rD
rU1
Plug in
800
SD U1
e
numbers:
10
E/R
300
2000
rU 10e T CA CC
rD 800e T C A 0.5 CC
1
E
k T AeRT
ED EU
1
D U
D U
AD
T
1
1
e
CA
CC
AU1
2000 300
T
CA0.51 CC11
1700
SD U1 80e T C A 0.5
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
E > EU, so use higher T
c)As low as possible (but not so low the rate = 0) D
d)Doesnt matter, T doesnt affect the selectivity
e)Not enough info to answer the question
L9b-11
A+C
A+C
kD
kU1
D desired
U1 undesired
rD

SD U1
ED EU
1
AD
T
e
rD
rU1 AU1
Plug in
800
SD U1
e
numbers:
10
2000
800e T C A 0.5 CC
2000 300
T
k T
rU
1
E
AeRT
300
10e T C
A CC
C D U1 C D U1
A
C
CA0.51 CC11
1700
SD U1 80e T C A 0.5
To maximize the production of the desired product, CA should be

a)As high as possible
D < U1, so high CA favors undesired
b)Neither very high or very low
product formation (keep CA low)
c)As low as possible
d)Doesnt matter, CA doesnt affect the selectivity
e)Not enough info to answer the question
L9b-12
A+C
A+C
kD
kU1
D desired
U1 undesired
2000
rD 800e T C A 0.5CC

SD U1
ED EU
1
AD
T
e
rD
rU1 AU1
rU
300
10e T C
A CC
C D U1 C D U1
A
C
2000 300
1700
Plug in
800
T
SD U1
e
CA 0.51 CC11 SD U 80e T C A 0.5
numbers:
1
10
Since ED>EU1, kD increases faster than kU1 as the temperature increases
Operate at a high temperature to maximize CD with respect to CU1

D<U1, 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 (thats a good thing)
What reactor should we use?
L9b-13
kD
300
2000
A+C
D desired
rU 10e T C A CC
rD 800e T C A 0.5CC
kU1
1
A+C
U1 undesired
1700
SD U1 80e T C A 0.5
ED>EU1, operate at a high temperature to maximize CD with respect to CU1

D<U1, 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 (thats a good thing)
What reactor should we use?
C
PFR
A
PFR/PBR w/ side streams feeding low CA
CA
Semi-batch reactor
slowly feed A to large
amount of C
High CC
How does the selection of reactor/reactors scheme and conditions

change if D can react with C and form another undesired product?
A+C
kD
D desired
2000
rD 800e T C A 0.5CC
A+C
rU
kU1
U1 undesired
300
10e T C
A CC
D+C
kU2
L9b-14
U2 undesired
8000
rU 106 e T CCCD
2
Need to maximize SD/U1 and SD/U2
SD U2
rD
rU2
ED>EU1, operate at a high T

1700
D<U1, keep CA low
0.5
SD U1 80e T C A
High CC increases rxn rate &
offsets slow rxn from low CA
2000
6000
800e T CA 0.5CC
4
T C 0.5C 1
10
e
D U2
A
D
8000
106 e T CCCD
Since ED<EU21, kD increases slower than kU2 as T increases operate at low

T to maximize CD Conflicts with maximizing SD/U1!
Conflicts with maximizing SD/U1!
D>U2, keep CA high to maximize CD
rD, rU1 & rU2 are all 1st order in CC, so changing CC does not influence
selectivity, but high CC will offset the rate decrease due to low CA
Low CD reduces the production of U2 Conflicts with producing the product D!!!
A+C
kD
D desired
1700
SD U1 80e T C A 0.5
A+C
kU1
U1 undesired
Maximize SD/U1 & SD/U2
ED>EU1, operate at a high T

D<U1, keep CA low
D+C
kU2
L9b-15
U2 undesired
6000
SD U2 8 104 e T C A 0.5CD1
ED<EU2, operate at low T

D>U2, keep CA high
Want to maximize CD
Low CD reduces production of U2
High CC increases rxn rate & offsets slow rate caused by low CA
Consider relative magnitude of SD/U1 and DD/U2 as a function of position in PFR

PFR w/ side streams feeding low CA
C
PFR, high T
PFR 2, low T
A
High T, CC is initially high, CA is low
high SD/U1
Initially CD=0 rU2=0. Both gradually
increase down reactor
Initially high SD/U2 (because CD is low),
but SD/U2 gradually decreases down
reactor
At some distance down the reactor,

significant amounts of D have formed
SD/U2 becomes significant with respect
to SD/U1
At this point, want low T, high CA &
low CC
L9b-16
If a CSTR were used with CA = 1 mol/L and CD= 1 mol/L, at what

temperature should the reactor be operated?
A+C
kD
D desired
A+C
2000
rD 800e T C A 0.5CC
rU
kU1
U1 undesired
300
10e T C
Need to maximize SD/(U1+U2)

rD
SD U U
1 2
rU1 rU2
D
U1U2
800
e
10
300
10 T
e
10
2000
T
10e
A CC
2000
800e T C A 0.5CC
300
8000
T C C 106 e T C C
A C
C D
S D
U2 undesired
8000
rU 106 e T CCCD
2
U1U2
CA=1
CD=1
2000
80e T
0.5
8000
106
e T
10
D+C
kU2
300
8000
105 e T
Plot SD/(U1+U2) vs temperature to find the temperature that maximizes SD/(U1+U2)

L9b-17
If a CSTR were used with CA = 1 mol/L and CD= 1 mol/L, at what
temperature should the reactor be operated?
k
k
k
A+C D D desired
A+C U1 U1 undesired
D+C U2 U2 undesired
2000
rD 800e T C A 0.5CC
rU1
300
10e T C
Need to maximize SD/(U1+U2)

4
3.5
SD/(U1+U2)
2.5
D
U1U2
8000
rU2 106 e T CCCD
A CC
600K
2000
80e T
300
8000
105 e T
2
1.5
1
0.5
0
200
400
600
Temperature (K)
800
1000
L9b-18
Calculate the yield of forming B in a CSTR and PFR when the conversion
of A is 90% and CA0 = 4 mol/L. The following reactions occur in the reactor:
mol
kB
kC
A
B rB kB 2
rC k CC A k C 1 min1
A
C
L min
What is the expression for the yield of B for a CSTR?
CB0
CB
FB
%
%
%
Y
YB
B
B
C A00 CA0
CA0 CA
FA0 FA (overall yield)
We know CA0 and CA when XA=0.9. How do we get CB?

In - Out + Gen. = Accum.
C
dNB
FB0 FB rB V
FB rB V 0 rB B 0
V
dt
0
0
mol
CB
mol
CB
2
CB
rB 2
rB
L
min
L min
Use the mole balance on A to find (at 90% conversion)
In - Out + Gen. = Accum.

dNA
C A00 CA0 rA V
FA0 FA rA V
dt 0
C A0 C A rA
C CA
V
CA0 CA rA A0
0
rA
L9b-19
mol
kB
kC
r
2
rC k CC A k C 1 min1
A
B B
A
C
B
L min
Y%
B
CB
CA0 CA
mol
2
CB
L min
rA kB k CCA
CA0 CA

rA
Y%
B
rB
CA 0 CA
What is rA?
mol
1
rA 2
CA
L min min
C A0 CA
mol
1
2
CA
L min min
mol
mol
0.4
L
L

mol
1
mol
2
0.4
L min min
L
4
CA0 CA
rA
rA rB rC
Plug -rA back into

expression for
CA0 = 4 mol/L, and at

XA=0.9, CA= 0.4 mol/L
1.5 min Residence time for XA = 0.9
mol
1.5min
L min
Y%
Y%
B
B 0.83
mol
mol
4
0.4
L
L
2
L9b-20
kC
mol
kB
1
r
k
C
A
C
r
2
k
1
min
C
C
A
A
B B
B
C
L min
mol
1
CA
rA kB k CCA rA 2
L min min
What is the expression for the yield of B for a PFR?
CB0
CB
FB
%
%
(overall
yield)
%
Y
YB
B
B
C A00 CA0
CA0 CA
FA0 FA
Use the mass balance to get CB
dCB
mol
dCB0
dFB
dCB
2
rB
rB
rB
d
L min
dV
dV
d
CB
mol
mol
mol
dCB 2
0 CB 2
d CB CB0 2
min
L min
L min
CB0
0
0
Use the mole balance on A to find (at 90% conversion)
dFA
rA
dV
dCA
mol
1
dC A
rA
A
d
d
L min min
CA
dCA
1
mol
1

d
2
CA
min 0
L
CA0 2mol L C A
min
dC A0
rA
dV
dCA
L9b-21
mol
kB
kC
A
B rB kB 2
A
C rC k CC A k C 1 min1
L min
mol
1
C
rA kB k CCA rA 2
L min min A
CB
mol
Y%
B
C
Use mole balance on A to find (at XA = 0.9)

B
CA0 CA
L min
mol
C
CA
A0
dCA
1
L
1 0

ln
mol
min 0
min
mol
CA0 2
A
L
L
mol
mol
2
1
L
L
CA0 = 4 mol/L ln
0.92 min
mo
l
mol
min
CA = 0.4 mol/L
2
0.
4
L
L
Yield was better

mol
2
0.92m in
C
r
in the CSTR, but

B
B
L
min
%
%
%
YB
YB
YB 0.51
the residence
mol
mol
CA0 CA C A0 CA
4
0.4
time was longer
L
L

Maximizing Product Selectivity in Multiple Parallel Reactions

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Reactor Design for

Usually, more than one reaction occurs within a chemical reactor

Review: Multiple Rxns & Selectivity

instantaneous rate selectivity, SD/U

overall rate selectivity,S%D U

NU Final moles of undesired product

(at any point or time in reactor)

Maximize selectivity / yield to maximize production of desired product

Review: Maximizing SD/U for

What reactor conditions and

Specific rate of desired reaction kD increases:

Concentration Requirements &

How do concentration requirements play

High CA favors undesired

PFR/PBR w/ side streams feeding

Different Types of Selectivity

instantaneous rate selectivity, SD/U

Series (Consecutive) Reactions

Spacetime for a flow reactor

Time is the key factor here!!!

Real time t for a batch reactor

To maximize the production of D, use:

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

Concentrations in Series Reactions

How does CA depend on ?

Reactions in Series: Cj & Yield

Need to maximize SD/U1

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

Need to maximize SD/U1

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

Need to maximize SD/U1

Operate at a high temperature to maximize CD with respect to CU1

Need to maximize SD/U1

ED>EU1, operate at a high temperature to maximize CD with respect to CU1

PFR/PBR w/ side streams feeding low CA

How does the selection of reactor/reactors scheme and conditions

Need to maximize SD/U1 and SD/U2

ED>EU1, operate at a high T

Since ED<EU21, kD increases slower than kU2 as T increases operate at low

Maximize SD/U1 & SD/U2

ED>EU1, operate at a high T

ED<EU2, operate at low T

Consider relative magnitude of SD/U1 and DD/U2 as a function of position in PFR

At some distance down the reactor,

If a CSTR were used with CA = 1 mol/L and CD= 1 mol/L, at what

Need to maximize SD/(U1+U2)

Plot SD/(U1+U2) vs temperature to find the temperature that maximizes SD/(U1+U2)

Need to maximize SD/(U1+U2)

We know CA0 and CA when XA=0.9. How do we get CB?

Use the mole balance on A to find (at 90% conversion)

In - Out + Gen. = Accum.

Plug -rA back into

CA0 = 4 mol/L, and at

1.5 min Residence time for XA = 0.9

Use the mole balance on A to find (at 90% conversion)

Use mole balance on A to find (at XA = 0.9)

Yield was better

in the CSTR, but

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