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Reaction Engineering Chapter 6 Class Notes
Reaction Engineering Chapter 6 Class Notes
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6.2.1 Single reactions
The main characteristic of a single reaction is that it requires only one rate
expression to describe its kinetic behavior.
A Product
The product distribution of such reaction is fixed and to compare the reactor
type only depends on the size of a reactor or a unit output of a reactor which
is a function of conversion.
6.2.1.1 Comparison of batch, plug-flow and tank reactor
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Again recalling modified material balance equation gives us,
This is because of the nature of CSTR that the low reactant concentration is
taking place in the reactor
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From the Figure 6.1 one can see easily that for a small conversion there occurs
no significant change when we use CSTR or PFR. It implies that a volume
difference significantly occurs for higher conversions. As an example for
conversion say 80% or above, more than five as much volume is required for CSTR.
This is demonstrated in the Figure 6.1 depicting the ratio of volume of CSTR & PFR
versus conversion. By using the ratio of equation (6.2.1) and (6.2.2) we obtain
XA
F kC n -1A,0
1 X A n
m
XA
kC n -1A,0 dX A
F P
0 1 X A n
For
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Figure 6.1 Comparison of performance of single mixed flow and plug
flow reactors for the nth-order reactions
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Figure 6.2. Comparison of performance of mixed flow and plug flow reactors for
any reaction kinetics.
For reactions with arbitrary but known rate the performance capabilities of
mixed and plug flow reactors are best illustrated in Fig. 6.2.
The ratio of shaded and of hatched areas gives the ratio of space-times needed in
these two reactors.
The rate curve drawn in Fig. 6.2 is typical of the large class of reactions whose rate
decreases continually on approach to equilibrium (this includes all nth-order
reactions, n > 0). For such reactions it can be seen that mixed flow always needs
a larger volume than does plug flow for any given duty.
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One can investigate the role of the order of reaction in reactor volume.
For zero order reaction the reactor size is independent of the type
of reactor.
However, the ratio of the volume increases with the order i.e.
higher volume of CSTR is required compared to that of PFR for
higher orders of reaction.
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There are two basic types of multiple reactions, namely series and parallel.
Series Rxns k1 k2
A B
C
k1
A B C
k2
B C
D
Multiple reactions are described more than one rate expression to
demonstrate its kinetic behavior. Due to the nature of the reaction, in
addition to the size of the reactor, the product distribution or yield
or selectivity of the product, are the important parameters which
describes the product to the maximum
While designing for multiple reactions, our target is to maximize the wanted
product and minimize the unwanted product. To achieve such condition, the
most important factor to be considered, is the analysis of the product
distribution in terms of the yield and the selectivity of the wanted
product. 12
Here we define the same by studying the so called selectively and yield
ratio. The instantaneous selectivity or differential selectivity ratio,
can be defined as the ratio of the rate formation of the desired
product to the formation of undesired product.
k1
Consider the reactions A B desired product (r )
D
k2
A
C unwanted product (r )
U
The differential selectivity ratio for the reaction becomes
r
SC U
r
D
Recalling the differential equation
k1C A1
dC B
dt
k 2C A 2
dC C
dt
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Then the selectivity ratio becomes
r
CA 2 - 1
U dCC k2 (6.4.2)
SC
r dCB k1
D
Our target therefore, would be to keep the selectivity ratio in equation
(6.4.2) as small as possible.
The ratio depends on the kinetic behavior of the reaction i.e.
by describing the condition of the reaction
the concentration of the reactant
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The different rate equation is given accordingly as
k1C A1
dC P
r
P dt
r C k 2C A1
dC
C dt
The differential selectivity ratio then becomes
U
r dCC k2 - (6.7)
SC CA 2 1
r dCP k1
D
As we said our target is to keep the ratio, as small as possible so
that we can maximize the desired product.
This can be regulated by using concentration of reactant A high or
low.
This depends
on the type of reactor used
the kinetic behavior of the reaction
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Generally based on the characteristics of the reactor
for low concentration, we use CSTR
for higher concentration we use PFR and BR.
To keep concentration of the reactant as low as possible through out
the reaction,
we have to maintain the conversion as high as possible
or we have to increase the inert in the feed
or decrease the pressure when we are working in the gas phase
system.
If we want to keep the reactant concentration high through out the
reaction, we have to use adverse effect to the above,
namely maintain low conversion,
remove inert from the feed
or increase the pressure in gas system.
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kinetic behavior of the reaction to maximize the desired product using
equation (6.7) becomes .
1. 1 2
i.e. the desired reaction is of higher order than the unwanted reaction
2 CA 2 - 1 2
dCC k k 1
SC
dCP k1 k1 C 2 1
A
2. 1 2
i.e. the desired reaction is of lower order than the unwanted reaction
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CA 2 - 1
dCC k2
SC
dCP k1
A lower reactant concentration favors to form minimum selectivity
ratio. This is achieved in a CSTR which gives an effect of a large
reactor size. There is a conflicting demand of, in one side to keep that
ratio small and on the other a big size of reactor
In such case, analysis of economic justification is essential.
3. 1 2 i.e. the two reactions are of the same order
dCC k
SC 2
dCP k1
The product distribution here is fixed and unaffected by the type of
reactor used. This equation can vary only by changing the
temperature of the reaction and or by using a catalyst.
The relation of equation (6.11) and (6.12) is often not a simple one and
depends among others such as the reactor type.
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Let us consider the reactor type.
rP dCP
Taking equation (6.11) YP
- rA dC A
or dCP - Y dCA
C A, f
Both sides integration gives (6.13)
C P,f - YdC A
C A,0
On the other side equation (6.12) can be rearranged into
CP,f S P ( - CA ) S P C A,0 - CA,f (6.12.1)
The overall yield from mixed and plug flow reactor converting A from CA,0
to CA,f are related by
dSP
SP m at CA, F (6.17)
A
dC
C A, f
1
S P P SP m dCA (6.18)
CA C 22
A,0
Equation (6.17) and (6.18) allows us to predict the overall yield from one type
of reactor given by the overall yield from the other
6.2.2.2.3 Mixed flow reactor in series
One of the characteristics of mixed reactor in series is the reactant
concentration drops immediately to a low level at the entrance of each reactor
The overall yield is obtained for N series reactors by summing the equation
(6.12), which gives
Y1C A,0 - CA,1 Y2 C A,1 - CA,2 - - - - YN C A, N 1 - CA, N S P,mixed C A,0 - CA,1
from which (6.19)
Y1C A,0 - CA,1 Y2 C A,1 - CA,2 - - - - YN C A, N 1 - CA, N
S P,mixed
C A,0 - CA,1
For any reactor type the exit concentration of the desired product is obtained
by using directly equation (6.12), thus
CP,f S P (C A,0 - CA,f ) (6.12.1)
Since an integral and a summation are not equal in general, the instantaneous
yields obtained by batch or plug flow reactor are not the same to those obtained
from mixed and cascade reactors 23
6.3 Operating temperature
In multiple reactions both the size of a reactor and product distribution might
be affected by operating temperature. Next we can observe the influence of
temperature for both the size of a reactor as well as the product distribution
for two competing multiple reactions of having the rate constants k1 and k2 , the
relative rate of such reaction is given
-E1 / RT
k 1 A1 e A1 (E 2 - E1 ) / RT
- E 2 / RT
e
k2 A2 e A2
One can easily see that the ratio changes with temperature depending on whether
E1 is greater or smaller than E2 , that is
k1
increases if E1 E 2
k2
when T rises
k1
decreases if E1 E 2
k2
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This can be concluded that a general statement of a high temperature favors
the reaction of higher activation energies; a low temperature favors the
reaction of lower activation energies.
Having this in mind one can find the operating temperature for various types of
multiple reactions in favor of product distribution and reactor size
•Parallel reactions k1
A P desired product
k2
A
C undesired product
For the same order of reaction, we have
dCP A1 (E 2 - E1) / RT
e
dCC A2
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Applying the above statement, the desired product becomes
if E1 > E2 using high T
if E1 < E2 using low T
Consecutive reactions 1 2
A P C
where P is desired and C is unwanted product having the same order
of reaction. The production of P can be written
k2
CP k1 k2 - k1
C A,0 k2
The production of P is increased if k1 / k2 is increased,
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6.3.2 Reactor size and temperature
Our target in multiple reactions is to have higher selectivity to the
desired product with a minimum size of a reactor.
The minimum size (volume) will be achieved if the reaction rate is
maximum at all position in the reactor.
The optimum temperature will be chosen to establish a maximum
rate at any conversion level.
It is, therefore, essential to investigate the relation of
kinetics (reaction order),
activation energy,
reactor size and
temperature.
For the flow process the reactor size will be represented by space time
V
F
FV,0
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The influence of the value of activation energy can be easily seen by
analyzing its value of desired and unwanted reaction as we did
previously. Again to summarize this;
In case if the activation energy is such that a desired product is
obtained at a higher temperature (E1 > E2) then we should use the
highest allowable temperature.
The reason is that at higher temperature we obtain high rate of
reaction and consequently smaller size of a reactor
When E1< E2, on the other hand, the desired product is obtained by
lowering the temperature.
This causes the rate of reaction to be low and the size of the
reactor large.
These are a conflicting factor.
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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
A C undesired product
where (E1< E2), P desired product and C unwanted product
a) If F is of no concern, use the lowest allowable temperature and
with larger space time to favor the production P. This is best carried
out in mixed reactor, CSTR. The optimum temperature for the
maximum desirable product is obtained when
E2
T R
ln A2 F 2 - 1
E
E1 29
b) when a temperature progression is permitted to carry out in PFR,
for a given, F still it is better to use a rising temperature progression
than the best isothermal optimum. these conflicting factors can be
reduced by using an economic balance to use the appropriate
temperature and size of a reactor
Generally, for the series reaction, high intermediate product is obtained by using
PFR, and the end product is obtained by increasing temperature, which leads to
increase both k1 and k2. 30
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