Multiple Reactors

Chemical Reaction Engineering
Vinod Kallur, R V College of Engineering, Bangalore, vinod_kallur@rediffmail.com

It is desired to carry out a reaction on an industrial
scale. Which reactor to design?
It is possible to design batch, mixed and plug flow
reactor. Which is to be preferred and why?
Let us look at Batch Reactor first and explore when it
is preferable.
The choice of the reactor is ultimately dictated by the
economics. Deciding which reactor is economical is
not easy and straight forward.
Choice of reactor
Batch Reactor revisited
Small instrumentation cost
flexibility of operation (can be used to produce
different products using the same equipment with
very little or no modification)
High labor and handling cost
Considerable shut down time in between batches
High labor and handling cost
Poorer quality of product
Batch Reactor revisited
Suitable for small production rate or to produce
variety of products based on requirement
Widely used in pharmaceutical industry
For large production rates, only flow reactors are
more suitable and economical.
The choice of type of reactor that is optimum should
be based upon several factors. We consider here the
size of the reactor as the criterion.
Let us compare the sizes of MFR and PFR
For given duty and for all positive
reaction orders, MFR is always
greater than PFR. The ratio of
sizes (Vm / Vp) increases with
order.
For small conversions, volume is
same for both. Volume ratio
approaches unity as conversion
approaches zero. Type of reactor
plays important role for high
conversions.
Density changes contribute to the
type to a lesser degree. However
it has some effect and must also
be looked into.
0 A
C
1 A
C
1 A
C
2 A
C
1 AN
C
AN
C
1 A
1 A
0 A
) r (
X
C
=
t
t t t = = =
2 1
1 A 0 A
1 A 0 A
0 A
kC C
C C
C
=
t
1 A
1 A 0 A
kC
C C
= t
1 A 0 A 1 A
C C kC = t
Reactors in series
0 A
C
1 A
C
1 A
C
2 A
C
1 AN
C
AN
C
t t t = = =
2 1
0 A 1 A
C ) k 1 ( C = + t
t k 1
C
C
0 A
1 A
+
=
=
2 A
C
t k 1
C
1 A
+
t k 1
C
C
1 AN
AN
+
=

Reactors in series
t k 1
1
C
C
1 AN
AN
+
=
Consider,
N
1 AN
AN
1 A
2 A
0 A
1 A
) k 1 (
1
k 1
1
....
k 1
1
k 1
1
C
C
....
C
C
C
C
t t t t +
=
+ +
+
=
N
0 A
AN
) k 1 (
1
C
C
t +
=
Space-time for the system is given by t t N
system
=
AN
0 A
N
C
C
) k 1 ( = + t
N / 1
AN
0 A
C
C
k 1
'
+
'
= + t
N / 1
AN
0 A
C
C
k 1
'
+
'
= + t
'
+
'
= 1
C
C
k
1
N / 1
AN
0 A
t
'
+
'
= 1
C
C
k
N
N / 1
AN
0 A
system
t
If the number of tanks are increased, or
, N g p
'
+
'
=
g p g p
1
C
C
k
N
lim lim
N / 1
AN
0 A
N
system
N
t
'
+
'
=
g p
1
C
C
k
N
lim
N / 1
AN
0 A
N
N
k
1
C
C
lim
N / 1
AN
0 A
N
'
+
'
=
g p
a ln
x
a
) a (
dx
d
x
1
) a (ln
dx
dy
y
a ln
x
1
y ln
a y
2
x / 1
x / 1
2
x / 1
=
'
+
'
=
=
=
2
2
N / 1
AN
0 A
N
system
N
k
N
C
C
lim
'
+
'
=
g p
t
'
+
'
=
AN
0 A
C
C
ln
k
1
flow _ plug
t =
As N tends to infinity, system tends to behave as if it
is a plug flow reactor.
'
+
'
=
g p g p
1
C
C
k
N
lim lim
N / 1
AN
0 A
N
system
N
t
'
+
'
=
AN
0 A
C
C
ln
k
1
flow _ plug
t =
Unequal sized MFRs in series
0 A
C
1 A
C
2 A
C
1
t
2
t
A
r
A
C
0 A
1 A 0 A
1 A 1 A
1 A
0 A
1
C
C C
r
1
r
X
C
=
t
2 A
2 A
1 A
2
) r (
X
C
=
t
0 A 1 A
1 A
1
C C
) r ( 1
=
t
1 A
C
0 A
C
1 A 2 A
2 A
2
C C
) r ( 1
=
t
2 A
C
Unequal sized MFRs in series
0 A
C
1 A
C
2 A
C
1
t
2
t
A
r
1
A
X
1 A
1 A
0 A
1
r
X
C
=
t
2 A
2 A
1 A
2
) r (
X
C
'
=
t
1 A
X
2 A 1 A
2 A 1 A
) r ( C
C C
=
2 A 1 A
2 A 1 A
1 A
2
) r ( C
C C
C
=
t
2 A 0 A
2 A 1 A
0 A
2
) r ( C
C C
C
=
t
2 A 0 A
1 A 0 A 2 A 0 A
) r ( C
) C C ( ) C C (
=
0 A
1 A 0 A
0 A
2 A 0 A
2 A
C
) C C (
C
) C C (
) r (
1
) X X (
) r (
1
1 A 2 A
2 A
=
A
r
1
A
X
1 A
X
2 A
X
=
0 A
2
C
t
Area of white rectangle
Area of white rectangle
Area of light blue rectangle
For some given conversion,
A
r
1
A
X
1 A
X
2 A
X
=
0 A
2
C
t
=
0 A
1
C
t
How many values are there
for individual space-times?
0 A
C
1 A
C
2 A
C
1
t
2
t
For some fixed conversion, C
A2
is fixed.
What is the effect of changing one space time on
the other?
What should be the criterion to fix C
A1
?
For minimum total volume,
area of the blue rectangle must be maximum.
A
r
1
A
X
1 A
X
2 A
X
f i f i i
y ) x x ( y x A + =
0
dx
dA
i
=
0 ) 1 0 ( y y
dx
dy
x
f i
i
i
i
= + +
i
i f
i
i
x
y y
dx
dy

=
Choose x
i
such that the diagonal of dark blue
rectangle is parallel to the tangent to the curve.
y
x
f
x
i
x
i
y
f
y
Arrangement of reactors
For first order equal sized mixed flow reactors are best.
For n > 1, smaller reactor should come first. Keep
concentration of the reactant as high as possible.
For n < 1, larger reactor should come first. Keep
concentration of the reactant as low as possible.
The best way to decide is to look into 1/-r
A
vs. C
A
.
The aqueous reaction A + B pProducts with
B A A
C C min) . mol / liter 500 ( r =
is to take place in an experimental tubular reactor (assume
PFR) under the following conditions:
Reactor volume = 0.1 liter
Volumetric feed rate = 0.05 liter/min
liter / mol 01 . 0 C C
0 B 0 A
= =
a) What conversion is expected?
b) For the same conversion, what size MFR is required?
c) What conversion is expected in MFR of the same size as
PFR?
2
A A
kC r =

=
A
X
0 A
A
0 A
r
dX
C
t
After integration in terms of conversion,
A
A
0 A
X 1
X
k C
= t
A
A
X 1
X
05 . 0
1 . 0
) 500 ( 01 . 0
'
+
'
909 . 0 X
A
=
A
A
0 A
M
r
X
C
=
t
For mixed flow reactor with the same conversion,
2
A
2
0 A
A
0 A
M
) X 1 ( kC
X
C
=
t
2
A
A
M 0 A
) X 1 (
X
k C
= t
2
A
A
M 0 A
) X 1 (
X
k C
= t
77 . 109 k C
M 0 A
= t
min 9 . 21
) 500 ( 01 . 0
77 . 109
M
= = t
a)
b)
liter 1 . 1 0975 . 1 ) 05 . 0 ( 95 . 21 V
v
V
M
} = =
= t
c) Same sized MFR
For the given PFR, min 2
05 . 0
1 . 0
= = t
2
A
A
M 0 A
) X 1 (
X
k C
= t
2
A
A
) X 1 (
X
2 ) 500 ( 01 . 0
=
0 10 X 19 X 10
A
2
A
= +
73 . 0 7298 . 0 X
20
41 21
) 10 ( 2
) 10 )( 10 ( 4 ) 21 ( 21
X
A
2
A
} =
=

=
The kinetics of the aqueous phase decomposition of
A is investigated in two mixed flow reactors, the
second having twice the volume of the first reactor. At
steady state with a feed concentration of 1 mol A / lt
and mean residence time of 96 sec in the first
reactor, the concentration in the first reactor is 0.5
mol / lt and in the second reactor is 0.25 mol / lt. Find
the kinetic equation for the decomposition.
t
1
= 96 sec t
2
= 2(96) = 192 sec
C
A0
=1
C
A1
= 0.5
C
A2
= 0.5
(-r
A
)
1
= 0.005208 mol / lt.sec
Performance equation for MFR,
1 A
1 A
0 A
1
) r (
X
C
=
t
1 A
) r (
5 . 0
1
96
=
C
A0
= 1
C
A1
= 0.5
C
A2
= 0.25
(-r
A
)
2
= 0.0013 mol / lt. sec
2 A
2 A
1 A
2
) r (
X
C
=
t
2 A
) r (
5 . 0
5 . 0
196
=
5 . 0
5 . 0
25 . 0 5 . 0
X
2 A
=
=
Assuming first order
It is not first order
A A
kC r =
1 1
) (
A A
kC r =
01041 . 0
5 . 0
005208 . 0
= = k
2 2
) (
A A
kC r =
0052 . 0
25 . 0
0013 . 0
= = k
Assuming second
order
2
A A
kC r =
)
2
1 A 1 A
C k ) r ( =
02083 . 0
5 . 0
005208 . 0
k
2
= =
)
2
2 A 2 A
C k ) r ( =
0208 . 0
25 . 0
0013 . 0
k
2
= =
s . lt / mol , C 0208 . 0 r
2
A A
=
The elementary irreversible aqueous phase reaction
A + B pR + S
is carried out isothermally as follows. Equal volumetric
flow rates of two liquid streams are introduced into a 4
liter mixing tank. One stream contains 0.02 mol A / lt,
the other 1.4 mol B / lt. The mixed stream is then
passed through a 10 liter PFR. We find that some R is
formed in the mixing tank, its concentration being
0.002 mol / lt. Assuming that the mixing tank acts as a
mixed reactor, find the concentration of R at the exit of
PFR and conversion of A in the system.
C
i A0
C
iB0
C
A1
C
A
v
v
2v
t
1
t
2
MFR can give us information on k.
2v
=
1
t
v 2
4
=
2
t
=
v 2
16
1
4t
C
i A0
C
iB0
C
A1
C
A
v
v
2v
2v
t
1
t
2
1 ) r (
X
C
A
1 A
0 A
1
=
t
=
0 A
C
lt / mol 01 . 0
v 2
C
0 iA
=
lt / mol 002 . 0 C
1 R
=
=
1 A
C lt / mol 008 . 0 002 . 0 01 . 0 =
lt mol C
S
/ 002 . 0
1
=
=
1 A
X 02 . 0
01 . 0
008 . 0 01 . 0
=
A
r
2 . 0
) 01 . 0 ( v 2
4
=
1 B 1 A A
C kC v 001 . 0 r = =
1 B 0 B 1 A 0 A
C C C C =
lt / mol 698 . 0 008 . 0 01 . 0 7 . 0 C
1 A
= + =
) 698 . 0 )( 008 . 0 ( 001 . 0 k v =
v k 179 . 0 =
Performance equation of PFR is
For II order bimolecular reactions,

=
2 A
X
0
A
A
1 A
2
) r (
dX
C
t
2 1 A
2 A
2 A
k ) 1 M ( C
) X 1 ( M
X M
ln t =
25 . 87
C
C
M
1 A
1 B
= =
v 2
16
) v 179 . 0 )( 1 25 . 87 ( 008 . 0 ln =
686 . 2
98808 . 0 ln
=
=

Since M = 87.25,
Over-all conversion,
A reacted in PFR
686 . 2
) X 1 ( M
X M
2 A
2 A
=
63 . 0 X
2 A
=
1 A
A 1 A
C
C C
63 . 0

=
704 . 0
C
C C
X
0 A
A 0 A
A
=
=
lt / mol 00504 . 0
00296 . 0 008 . 0
=
=
lt mol C
A
/ 00296 . 0 ) 63 . 0 1 ( 008 . 0 = =
R formed in PFR = 0.00504 mol / lt
R at the exit of PFR = 0.002 + 0.00504
= 0.00704 mol / lt
A first order reaction is to be treated in a series of
two mixed reactors. Show that the total volume is
minimumwhen the reactors are equal in size.
Given: k,
t
1
, t
2
C
A0
v
C
A1
C
A2
t
1
t
2
C
A0
v
C
A1
C
A2
t
1
t
2
What are variables and what are constants?
For a given operation, v and C
A0
are constants
What about C
A1
and C
A2
?
Let us say we want to get some duty done.
Which means that X
A
is also a constant
VINOD KALLUR
C
A0
v
C
A1
C
A2
t
1
t
2
Constants:
v
C
A0
X
A
What about C
A1
and C
A2
? What about t
1
and t
2
?
If we fix some t
1
,
since X
A
is fixed,
there is only one fixed t
2
.
How about the other way ?
VINOD KALLUR
C
A0
v
C
A1
C
A2
t
1
t
2
Constants:
v
C
A0
X
A
How many values are there for t
1
and t
2
?
Then there are infinite pairs of V
1
and V
2
.
Question is:
for what values total volume is
least ?
Problem is to minimize V = V
1
+ V
2
Or minimize t = t
1
+ t
2
VINOD KALLUR
C
A0
v
C
A1
C
A2
t
1
t
2
Constants:
v
C
A0
X
A
For every pair of t
1
and t
2
values, there is one C
A1
Variables are: t
1
and t
2
, C
A1
1 A 0 A
1 A 0 A
0 A
1
kC C
C C
C
=
t
Similarly,
t = t
1
+t
2
VINOD KALLUR
1 A 0 A
1 A 0 A
0 A
1
kC C
C C
C
=
t
1 A
1 A 0 A
1
kC
C C
= t
=
2
t
1 A
1 A 0 A
kC
C C
C
A1
is variable and t should be minimum.
2 A
2 A 1 A
1 A
1 A 0 A
kC
C C
kC
C C
+
= t
'
+
'
'
+
'
= 1
C
C
k
1
1
C
C
k
1
2 A
1 A
1 A
0 A
t
0
dC
d
1 A
=
t
'
+
'
'
+
'
= 0
C
1
k
1
C
C
k
1
dC
d
2 A
1 A
0 A
1 A
2
t
0 0
C
1
k
1
C
C
k
1
2 A
1 A
0 A
2
=
'
+
'
'
+
'
'
+
'
'
+
'
2 A
2
1 A
0 A
C
1
k
1
C
C
k
1
2 A
1 A
1 A
0 A
C
C
C
C
=
2 A 0 A 1 A
C C C =
t
2
For volume to be minimum, reactors must
be of the same size.
2 A
1 A
1 A
0 A
C
C
C
C
=
=
2
t
2
2 1
A
A A
kC
C C
1 A
1 A 0 A
1
kC
C C
= t
'
+
'
= 1
C
C
k
1
1 A
0 A
'
+
'
= 1
C
C
k
1
2 A
1 A
=
'
+
'

=
2 A
2 A 1 A
C
C C
k
1
At present 90 % A is converted into product by a second
order reaction in a single mixed flow reactor. We plan to
place a second reactor similar to the one being used in
series with it.
a) For the same treatment rate as used at present, how will
this affect the conversion?
b) For the same 90 % conversion, by how much can the
treatment rate be increased?
2
1 A
1 A
1 0 A
) X 1 (
X
k C
= t
90
) 9 . 0 1 (
9 . 0
2
=
=
2
2 A
2 A
2 1 A
) X 1 (
X
k C
= t
1 A
2 A 1 A
2 A
C
C C
X

=
0 1 0 1
1 . 0 ) 1 (
A A A A
C X C C = =
2
2
2
2 1
) 1 (
A
A
A
X
X
k C
= t
2
2 A
2 A
1 0 A
) X 1 (
X
k C 1 . 0
= t
9 ) 90 ( 1 . 0
) X 1 (
X
2
2 A
2 A
= =
) X X 2 1 ( 9 X
2
2 A 2 A 2 A
+ =
0 9 X 20 X 9
2 A
2
2 A
= +
18
76 20
) 9 ( 2
) 9 )( 9 ( 4 ) 20 ( ) 20 (
X
2
2 A
=

=
6267 . 0 X
2 A
=
) 6267 . 0 1 ( 1 . 0 ) 1 (
0 2 1 2
= =
A A A A
C X C C
) 6267 . 0 1 ( 1 . 0
0 2
=
A A
C C
03733 . 0
0
2
=
A
A
C
C
9626 . 0 03733 . 0 1 1
0
2
= = =
A
A
A
C
C
X
Conversion increases marginally by 6.26 %.
(b)
For the single reactor,
90
0
= t
A
kC
The performance equation is rewritten as
A A A
C C kC =
0
2
t
1
t Let be the space-time for the second reactor.
(1)
1
0
,
v
C
A 1 A
C
Let C
A1
be the intermediate concentration.
A A A
C C kC =
0
2
t
Applying to the first reactor,
0
1 . 0
A Af
C C =
1 0 1
2
1 A A A
C C kC = t
(2)
Applied to the second reactor,
Af A Af
C C kC =
1 1
2
t
0 1 1
2
0
1 . 0 ) 1 . 0 (
A A A
C C C k = t
0 1 1 0 0
1 . 0 ) 01 . 0 (
A A A A
C C C kC = t
From (1),
0 1 1 0
1 . 0 ) 01 . 0 (
90
A A A
C C C = t
t
0 1
1 0
1 . 0
9 . 0
A A
A
C C
C
=
t
t
'
+
'
+ = 1 . 0
9 . 0
1
0 1
t
t
A A
C C
Substituting this in (2),
1 0 1
2
1 A A A
C C kC = t
'
+
'
+ =
'
+
'
+ 1 . 0
9 . 0
1 . 0
9 . 0
1
0 0 1
2
1
0
t
t
t
t
t
A A A
C C C k
'
+
'
'
+
'
+ 1 . 0
9 . 0
1 1 . 0
9 . 0
1
0 1
2
1
2
0
t
t
t
t
t
A A
C kC
t
t
t
t
t
1
2
1
1 0
9 . 0
9 . 0 1 . 0
9 . 0
=
'
+
'
+
A
kC
'
+
'
'
+
'
+ 1 . 0
9 . 0
1 1 . 0
9 . 0
1
0
2
1
1
2
0
t
t
t
t
t
A A
C kC
From (1),
t
t
t
t
t
t
1
2
1 1
9 . 0
9 . 0 1 . 0
9 . 0 90
=
'
+
'
+
Let
x =
t
t
1
) x x x 9 . 0 9 . 0 1 . 0 9 . 0 90
2
= +
0 9 . 0 8 . 1 2 . 16 9 . 72
2 3
= + + x x x
Solving this we get 1515 . 0 = x
1515 . 0
1
=
t
t
1515 . 0
/
/
1
=
v V
v V
1515 . 0
1
=
v
v
6 . 6
1
=
v
v
Production rate can be
increased 6.6 times

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Chemical Reaction Engineering

Vinod Kallur, R V College of Engineering, Bangalore, vinod_kallur@rediffmail.com

Chemical Reaction Engineering

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