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Kin 6
Kin 6
FA,0 ; FV,0
(-rA) =(-rA)exit
(-XA) =(XA)exit
(-rA); XA; CA
(CA) =(CA)exit
Q
and or in parallel.
Let
X A,1, X A,2 ,.... X A, N 1, X A, N
VT N V V V2 Vn VN
∑ n 1 (5.20)
FA,0 FA,0 FA,0
n 1
Product
To design a cascade reactors,
Normally required size of reactors for specified conversion
Additionally we have to get answers to the
following questions
series?
De ac
gn
Re
•
si ss
C - C (-r )
A,0 A,1 A,1 F,1
C - C (-r )
A,1 A,2 A,2 F,2
(5.21.1)
C - C (-r )
A,n-1 A,n A,n F, n
Assuming the first - order reaction for the condition that
T, m = constant equation (5.21.1) becomes
C - C k C
A,0 A,1 1 A,1 F,1
C - C k C
A,1 A,2 2 A,2 F,2 (5.21.2)
C - C knC
A,n-1 A,n A,n F, n
C A,0
C A,n (5.22.4)
(1 k1 F,1 )(1 k 2 F,2 ) (1 k n F, n )
C A,0
C A,n
(1 k F ) n (5.22.5)
n
1
C
1 A,0
-1
F, n k C
A
CA,2
CA CA,3
V1 V2 V3 VR
XA XA,3
XA,2
XA,1
V1 V2 V3 VR
Substituting equation (5.22.5) to equation (5.23.1) gives
CA,n
1
X A,n 1 -
X A,n 1- CA,0
(5.23.2)
(1 k F ) n C A,0
C A,n
(1 k F ) n
Recalling the space time
VR C A,0 X A
F
FV ,0 (-rA )
And we can use this equation for n, number of reactors, we have
VR,n X A,n - X A,n 1
F ,n C A,0
FV ,0 (-rA )
X A,1
V1 V2 V3 V
As always,
the reactor design is to find the size of
the reactor for the specified conversion
Hence,
Main parameters required in Designing
CSTRs in series
Obtaining concentration/conversion
FA,0
CA,3
V1 CA, 1
V2 CA V3
,2
or
1
(-rA ) ( C A,n -1 - C A,n )
F
1
(-rA ) ( C A,n -1 - C A,n ) (5.25)
F
1 FA,0
Slope tan - -
F VC A,0
1 FV,0 FA,0
Slope tan - - -
F V VC A,0
-rA
C A,0
(-rA ) A n -1 X A,n (5.27)
F
FA,0
Slope tan
V
XA,1 XA,2 XA,3 XA
Figure : Graphical method to find the required conversion for each reactor
using (-rA ) f(X A )
B. Obtaining volume of the reactor knowing
In such operation, CA,0; CA,f
initial CA,0 and
final concentration CA,f should be known.
For identical series of reactors to ascertain the
volume,
one must attempt on a trial and error basis.
Consider the two identical volumes of reactors in series as
shown in the following Figure
V1 V2
Here C A,0 and C A,2 are known, and C A,1 is unknown
As starting, we write operating line equation,
1
(-rA ) ( C A,n -1 - C A,n )
F
1
(-rA ) A n -1 - C A,n
F
and
1 FV,0
Slope tan - -
F V
R1
CA, 2 C A, 1 C A, 0 C A
1 FV,0
Slope tan - -
F V
Figure : Graphical method to find the volume of equal
sized two mixed reactors
6.3.2.2 Design of different size CSTR in series
V1 V2
V3
Due to the nature of the reactants, which involves the
mixing behavior, heat effect, conversion ability etc, there
is a need to set up a reactor of different size. In designing
of a different size CSTR, there is also a need to evaluate
the following considerations
• To find the outlet concentration/conversion from a
given reactor system
V1 C A,0 - C A -1
t F,1
FV,0 (-rA,1)
Rearranging gives
1 FV,0 (-rA,1)
-
F,1 V1 C A,1 - C A,0
Similarly for the nth-reactor we may derive
1 FV,0 (-rA,n )
-
F, n Vn C A,n - C A,n -1
or
1
(C A,n - C A,n -1) (-rA,n )
F, n
or 1 1
(-rA,n ) C A,n -1 - C A,n
F, n F, n
(-rA,n ) An 1 - 1 C A,n
F, n
by plotting rA
versus C
A we can find for each reactor,
1
different slope of -
F,n
( rA ) ( rA )1
Slope
C A,1 C A,0
( rA ) 2
Slope
C A,2 C A,1
V XA
FA ,0 (- rA )
Arrangement # 1
Intermediate
XA,1 and XA,2 conversion
XA,3 > XA,1
Arrangement # 2 Final conversion
XA,3 and XA,4 XA,2 = XA,4
V V
Area F ,2 2 Area F ,2 2
C F C F
A,0 A,0 A,0 A,0
P Q
1 P Q
(r ) 1
A (r )
A S R
S R
V
F,1 V Area F,1 1
Area 1 C F
C F A,0 A,0
A,0 A,0
Figure 5.30 Different set up with intermediate conversion
One can see from the above Figure that the intermediate
conversion changes (which depends on the size of the
reactor) so does
(A) the size ratio of the units (represented by the
two shaded areas)
increasing yield,
XA,0 X A, f XA
Figure: smaller size in Plug flow over CSTR
General consideration #2
The rate – conversion curve
s
t i (Kinetics) is a useful method to
c
ne
Ki determine which reactor comes
first to give a total smaller volume
for specified conversion
Mainly focus on
Order of reaction and
Type of reaction
6.2.3.1 Kinetics method to determine which
reactor comes first using the rate
conversion curve
Let us see reactors of different sizes arranged in
series. Figure shows reactors arranged mixed
followed by a plug flow and then again in turn
with the mixed one.
V2 XA,2
V1 XA,1 XA,3
V3
V3
1 Area
FA,0
( rA ) V1
Area
FA,0
V2
Area
FA,0
XA,0 X A, 1 X A, 2 X A, 3
Figure 5.32 Graphical representations for reactors in series.
The design equations for the three reactors are
V X A,1 - X A,0
First - Reactor, CSTR, 1
FA,0 (-rA,1)
V2
Area
FA,0
Large CSTR
CSTR
PFR
1
( rA ) 1
( rA )
XA XA
Figure 5.34 Typical rate concentration curve for
an autocatalytic reaction
In Autocatalytic reaction the rate - conversion
curve is a useful method to determine which
reactor is superior (i.e., which reactor requires a
smaller volume for specified conversion)
1
( rA )
CSTR
Plug flow
PFR
1
( rA )
CSTR
XA
XA,0 X A,1 X A,2
Exercise 6.1 The demirazation reaction,
2A R
•Operating temperature
•Planned scaled of production
Batch process
n
mol
Pr C
(C)
t
h
C
Flow process
Pr FC
mol
(C)
h
For a BR, the rate of production of C, may be
rewritten as, with XA,2 = XA and XA,l = 0,
n n X C X V
Pr C C A,0 A C A,0 A BR
(C) t tr t (1 a)t r
C d
Where : a = td / tr , down time
XA
dX A
t r C A,0 0 ( - rA )
For a CSTR, in steady-state operation at a
flow rate FV,0 , the rate of production of C is
the molar rate of flow of C, that is
Pr F C F F C X (r )V
(C) C C V ,0 V ,0 C A,0 A C A CS
The ratio of the vessel sizes for the same P(C) (and
XA,) may be determined by equaling
Pr(C),BR = Pr(C),CS
and substituting for tr we get:
X
A
(1 a) dX (r )
V A A
BR 0
V X (r )
CS A A
PF R V F X A dX
A - 1 C A dC
A
F A,0 C A,0 0 ( - rA ) C A,0 C ( - rA )
A,0
V X A dX C A dC
F C A,0 A - A
FV,0 0 ( - rA ) C A,0 ( - rA )
shows that an element of fluid
reacts for the same length of time in
the batch and in the plug flow
Recalling equation for constant density
F
VR
and
V F
Fv,0 R v,0 F
dV F d
R v,0 F
For plug flow reactor
X
A, f dX
C A
0 (rA)
F A,0
X
A
C dX (r )
t A,0 A A
r, BR 0 1
X
F , PFR C A
dX (r )
A,0 A A
0
The above equation shows us,
for an isothermal first-order reaction
taking place in a constant-volume BR but
at varying density in a PFR,
t
r,BR F ,PFR
V
PFR
For a big production we must correct
the size requirement estimate to
account for the down-time between
batches.
For a small production the same
volume of these reactors is needed to
do a given job.
6.3.1.3 Comparison of CSTR and
PFR
For a given duty the ratio of sizes of mixed
and plug flow reactors will depend on
the stoichiometry,
A) The form of the rate equation.
THE l / rA PLOT
General
From the curve of plots of r versus (CA,0 - CA) for r
= kCn for several values of the order n
It is obvious that r is a monotonically
decreasing function of CA,0 – CA if n > 0,
a horizontal line if n = 0, and
increases with CA,0 – CA if n < 0.
The l/r plots obviously have reversed slopes.
Note that 1 /r goes to infinity as CA 0
for any kinetics because reaction rates
must go to zero when reactants have been
consumed.
This is equivalent to saying that the
kinetics of all reactions must become
positive order in the limit of any reactant
disappearing
THE l / rA PLOT
C A,0 - CA 1
F ,CS (C A,0 - CA )
(-rA) (-rA)
and
CA 1
F , PF - dC A
C A,0 ( - rA )
The size in a CSTR is the area under the
rectangle of width (CA,0 - CA) and height
l/r(CA),
while the size in a PFR is the area
under the curve l/r(CA) from CA,0 to CA.
Sizes Comparison looking to the above
Fig.
This construction also shows why the CSTR
becomes much less efficient (requires much
larger volume) at high conversions.
The l/r curve increases rapidly as CA 0,
and therefore the size in a CSTR becomes
very large compared to the size of PFR.
Large CSTR rectangle if 1 /r is a
monotonically increasing function of
CA,0 - CA (r monotonically decreasing),
n>0
Areas are equal for
n = 0, and
Smaller area for
n < 0.
Thus it is evident that a PFR is
always the reactor of choice
(smaller V) for greater than zero-
order kinetics in an isothermal
reactor.
The CSTR may still be favored for
n > 0 for cost reasons as long as
the conversion is not too high, but
the isothermal PFR is much
superior at high conversions
whenever n > 0.
Analogy we compare for “normal” kinetics
the sizes of a CSTR and a PFR required to
achieve the same conversion.
Considering the design equation for both reactors
we have F X
V A,0 A
CS (r )
A
X
and A
V F dX (r )
PFR A,0 A A
0
V X (r )
Thus CS A A
V X (a)
PFR A
dX A (rA)
0
Let us make the comparison for the large class of
reactions approximated by the simple nth-order
rate law
(a)
(b)
or
Equations (a) and (b) are displayed in the
following graph to provide a quick comparison of
the performance of plug flow with mixed flow
reactors
Cn
V F
A,0 A,0 CS
n n=2
C V F
A,0 A,0 PF
n=1
n=0.5
0 1 - XA 1.0
The above Figure shows the following:
1. For any particular duty and for all positive
reaction orders the mixed reactor is
always larger than the plug flow reactor.
The ratio of volumes increases with
reaction order.
2. When conversion is small, the reactor
performance is only slightly affected by
flow type. The performance ratio
increases very rapidly at high conversion;
V X kC (1 X )
CS A A,0 A
V X
PFR A
A kC A,0(1 X A)
dX
0
X
A
(1 X ) ln1 (1 X )
A A
Second – order reaction V X (r )
CS A A
V X
PFR A
dX A (rA)
0
V X kC 2 (1 X )2
CS A A,0 A
V X
PFR A
2 2
dX
A
kC (1 X )
A,0 A
0
1
1 X
A
Table : VCS / VPFR for different n
XA
VCS / VPFR
(a)first-order,
(b)second-order with respect to A. and
(c)What conclusions can be drawn?
t
r,BR F ,PFR
For batch reactor, dC A (r ) k C n
A A
rA
After integration,
dt
n 1 n 1
1 C
- C
- kt
n 1 A
A,0
or,
C 1- n - C 1 n (n 1) kt
A A,0 n # 1
C (t) 1 ( n - 1 )kC
C t
A A,0
A,0
C 11 - n
A
n - 1
(a)
1 ( n - 1 )kC
t
C A,0
A,0
C 1
A 1 (n 1)M
1n
(a)
C
A,n
A,0
C
A 1 - X
C A
or conversion A,0
1
1n
X 1 - 1 (n 1)M
(b)
A
A,n
C 1
A 1 (n 1)M 1n
C
A
C
A,0 A 1 - X
C A
A,0
Fig. CA /CA,0 for various orders of reaction in a BR
or PPR as a function of M
Design equation for CSTR
F X (r )V
V A,0 A X A
A F
(r ) A,0
A
n kC n (1 - X ) n
kC V A,0 A V
X A A
F C F
A,0 A,0 V ,0
X kC n1 (1 - X )n
A A,0 A F
X M (1 - X )n
A A,n A
Concentration ratio for CSTR C
A 1 - X
C A
A,0
C
A 1 - M (1 - X )n
C A,n A
A,0
n
C C
A 1 - M A
(b)
C A,n C
A,0
A,0
n
C
C
M A
A 1 0
A,n C
C
A,0
A,0
C
A 1 - M (1 - X )n
C A,n A
A,0
C
A 1 - M (1 - X )n
C A,n A
A,0
CS C
A,n A
/B
C
A
A,0
R
A,0
PF
1 C
C A 1 - M (1 - X )n
A 1 (n 1)M 1n
A
C
A
C A,n
A,0 A,0
CSTR
PFR or BR
performance is always
obtained in a PFR,
6.3.2 Reactor comparisons for Multiple
Reaction’s
Optimum temperature
for minimum size of
6.3.2.1 Boosting selectivity of the desired product
for Multiple Reaction’s
Consider the parallel reactions,
k
A 1 B
desired product (r )
B
k
A 2 C
unwanted product (r )
C
The selectivity ratio for the reaction becomes
r
S rC
C
B
Recalling the differential equation for BR
n
dC
B kC 1
dC n dt 1 A
C k C 2
dt 2 A
Then the selectivity ratio becomes
r dC k
S rC C 2 C n -n (a)
C dC k A 2 1
B B 1
activation energy,
temperature.
Considering Reactor size and temperature
For the flow process the reactor size will be
V
represented by space time F
FV,0
Optimum temperature
In such a case an alternative solution
such as an intermediate temperature
should be found by using analytical
method or by search procedures.
Alternative solution
i) parallel reactions
E1
A P desired product
E2
AC undesired product