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6 The Choice of a reactor for a particular reaction Looking to the above factors, we can always choose the
reactors based on two criteria namely the character of the
ε =0

The question is always asked about:
‰ how we choose the right type of reactor for the desired
production / reaction / ?.
¾ To answer the question we have to look into different
factors affecting the choice of reactor such as:
• The reaction type
• Operating temperature
• Planned scaled of production
• Cost of equipment and operation
• Working safety, stability and flexibility
• Equipment life expectancy
• Easiness of convertibility of the equipment
No net formula is available to select the reactor,
we can only use our technical judgment and the
affordability of the process including the economic factor.
reactor and the general knowledge about the kinetics of
the type of reaction
6.1 Characteristics of individual reactor
9This is based on their process of operation namely
batch or continuous operation.
6.1.1 Batch operation
p
¾ often used for small scale production
¾ having long reaction times.
The advantage of such type of reactor
9is the cost of the equipment and
9flexibility of operation
The disadvantage
‰ the relatively extensive manual operation of
emptying, cleaning and refilling required
‰ this process is difficult to use for automation

‰restricted only to produce small amount of material 6.2.1 Single reactions

6.1.2 Continuous operation The main characteristic of a single reaction is that it requires
only one rate expression to describe its kinetic behavior.
Advantage A → Product
ƒ can make products 24 hours a day,
ƒ parameters such as temperature and product quality The product distribution of such reaction is fixed and to
controlling are easier. compare the reactor type only depends on the size of a reactor
ƒ little supervision, suited for the application of or a unit output of a reactor which is a function of
automatic control conversion.
6 2 Kinetics behavior
6.2 6.2.1.1 Comparison of batch, plug
plug-flow
flow and tank reactor
A) Batch and plug-flow reactor
The main criteria which can be used to choose the type of an
appropriate reactor is the kinetic behavior which is governed Reactor size for specified conversion is obtained by using the
by the reaction type. Reaction type is categorized in two material balance. For constant density system, we have
equations C A dC
distinct classifications namely single and multiple reactions. batch reactor : t = - ∫ A
C A,0 ( - rA )
C A dC
plug flow reactor : θ F = - ∫ A
C A,0 ( - rA )

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¾Both the equations show an element of fluid which reacts for Again recalling modified material balance equation gives us,
the same length of time in the batch and as well as in the ⎛ V ⎞ ⎛C V⎞ C X
plug flow reactor. Tank : θ F,T = ⎜ ⎟ = ⎜ A,0 ⎟ = A,0 A (6.1)
⎜F ⎟ ⎜ F ⎟
¾ This demonstrates that the same size of these reactors is ⎝ V,0 ⎠T ⎝ A,0 ⎠T ( - rA)
needed to do a given job and it is possible to relate the
performance capabilities of these reactors ⎛ V ⎞ ⎛C V⎞ XA
Plug flow : θ F,P = ⎜ ⎟ = ⎜ A,0 ⎟ = CA,0 ∫ dX A (6.2)
B) Plug flow reactor and tank reactor ⎜F ⎟ ⎜ F ⎟
⎝ V,0 ⎠ P ⎝ A,0 ⎠ P 0 ( - rA )
Generally spealing, For a first order reaction
p
ƒ the capacityy of the tank of a CSTR is alwaysy smaller than (− rA ) = kCA = kC A,0
A 0 (1 - X A )
that of a plug flow reactor, if the reaction volume and the The above equation (6.1) becomes
condition are identical in both the cases.
ƒ for a given duty the ratio of the size of tank and plug flow ⎛ CA,0V ⎞ C A,0 X A XA
reactors will depend on the form of a rate equation (i.e. Tank : θ F,T = ⎜ ⎟ = =
⎜ F ⎟ kC A,0 (1 − X A ) k (1 − X A )
order of reaction). ⎝ A,0 ⎠T
For the nth – order reaction
(− rA ) = kC n A = kC n A,0 (1 - X A ) n
Substituting these equations we can derives,

This is because of the nature of CSTR that the low reactant

⎛C V⎞
A,0 ⎟ C A,0 X A XA (6.2.1) concentration is taking place in the reactor
θ F,T = ⎜⎜ ⎟
= =
kC n A,0 (1 − X A ) n n −1 n
⎝ FA,0 ⎠ T kC A,0 (1 − X A ) From the Figure 6.1 one can see easily that for a small
conversion there occurs no significant change when we use
In the same manner it can also be formulated for the nth order
CSTR or PFR. It implies that a volume difference significantly
reaction in the plug-flow reactor
occurs for higher conversions. As an example for conversion
⎛ CA,0V ⎞ XA dX A say 80% or above, more than five as much volume is required for
θ F,P = ⎜⎜ ⎟ = ∫
⎟
(6.2.2)
F n −1 (1 − X ) n CSTR. This is demonstrated in the Figure 6.2 depicting the ratio of
⎝ A,0 ⎠ P 0 kC A,0 A volume of CSTR & PFR versus conversion
To compare both the reactors, the equation (6.2.1.) and (6.2.2) By using the ratio of equation (6.2.1) and (6.2.2) we obtain
are simplified for n = 1 to give
θ F,T + k
Tank , X A = (6.3) ⎛⎜θ kCn -1A,0 ⎞⎟
XA
1 + θ F,T k
(6.4) ⎝ F ⎠T
=
(1 − X A )n
- kθ F,P
PFR, X A = 1 - e ⎛⎜θ kC A,0 ⎞⎟
n -1 X A dX A
The effect of the equations (6.3) and (6.4) are showen in the Figure ⎝ F ⎠P ∫
0 (1 − X A )
n
6.1. It is clear from the figure that for any conversion the
volume required is larger for the CSTR.

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One can investigate the role of the order of reaction in reactor There are two basic types of multiple reactions, namely series
volume. and parallel.
¾ For zero order reaction the reactor size is Series Rxns k1 k2
A ⎯⎯→ B ⎯⎯→
⎯ C
independent of the type of reactor. k1
¾However, the ratio of the volume increases with the A + B ⎯⎯→ C
order i.e. higher volume of CSTR is required k2
B + C ⎯⎯→
⎯ D
compared to that of PFR for higher orders of reaction. Multiple reactions are described more than one rate
6.2.2 Multiple reactions expression to demonstrate its kinetic behavior. Due to the nature
of the reaction, in addition to the size of the reactor, the
Mostt reactions
M ti especially
i ll for
f organici industrial
i d t i l products,
d t
product distribution or yield or selectivity of the product,
involve more than one reaction. As for example, let us consider
are the important parameters which describes the product to
the following ethanol manufacturing from ethylene reaction
the maximum
While designing for multiple reactions, our target is to
k1
H 2C = CH 2 + H 2SO 4 ⎯⎯→ C2 H 5 0 − S03 H maximize the wanted product and minimize the unwanted
k2 product. To achieve such condition, the most important
H 2C = CH 2 + C2 H 5 0 − S03 H ⎯⎯→
⎯ (C2 H 5O) 2 SO4 factor to be considered, is the analysis of the product
distribution in terms of the yield and the selectivity of the
wanted product.

Here we define the same by studying the so called selectively Then the selectivity ratio becomes
and yield ratio. The instantaneous selectivity or r
= 2 C Aα 2 - α1
dCC k
SC = U = (6.4.2)
differential selectivity ratio, can be defined as the ratio of r dC B k1
D
the rate formation of the desired product to the formation
of undesired product. Our target therefore, would be to keep the selectivity
k1 ratio in equation (6.4.2) as small as possible.
Consider the reactions A ⎯⎯→ B desired − product ( rD ) The ratio depends on the kinetic behavior of the reaction
k2 i.e.
A ⎯⎯→⎯ C unwanted − product (r ) ‰ by describing the condition of the reaction
U
The differential selectivity ratio for the reaction becomes
‰ the concentration of the reactant
r
SC = U 6.2.2.1 Product distribution for parallel reaction
r
D Consider the decomposition of a single reactant
Recalling the differential equation
k1
= k1C Aα1
dC B A ⎯⎯→ P − − − − − desired − product
dt
k2
= k 2C Aα 2 A ⎯⎯→
⎯ C − − − − − unwanted − product
dC C
dt

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The different rate equation is given accordingly as Generally based on the characteristics of the reactor
r = P = k1C Aα1 9 for low concentration, we use CSTR
dC
P dt 9 for higher concentration we use PFR and BR.
r = C = k 2C Aα1
dC To keep concentration of the reactant as low as
C dt possible through out the reaction,
The differential selectivity ratio then becomes ¾we have to maintain the conversion as high as possible
r ¾ or we have to increase the inert in the feed
= 2 C Aα 2 - α1 (6.7)
dCC k
SC = U = ¾or to decrease the pressure when we are working in the gas
r dC P k1
D phase system.
A we said
As id our target
t t is
i to
t keep
k th ratio,
the ti as smallll as
possible so that we can maximize the desired product. If we want to keep the reactant concentration high
This can be regulated by using concentration of through out the reaction,
reactant A high or low.
‰ we have to use adverse effect to the above,
This depends
‰namely maintain low conversion,
ƒ on the type of reactor used ‰remove inert from the feed
ƒ the kinetic behavior of the reaction ‰or increase the pressure in gas system.

kinetic behavior of the reaction to maximize the

If

= 2 C Aα 2 - α1
dCC k
desired product using equation (6.7) becomes . SC =
dC P k1
1. α1 > α 2 A lower reactant concentration favors to form minimum
i.e. the desired reaction is of higher order than the selectivity ratio. This is achieved in a CSTR which gives an
unwanted reaction 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
= 2 CAα 2 - α1 = 2
dCC k k 1
SC = size of reactor
dCP k1 k1 C α 2 −α1
A ¾In such case,, analysis
y of economic jjustification is essential.
T k
To keep the
th selectivity
l ti it ratio
ti , SC low 3. α1 = α 2 i.e. the two reactions are of the same order
we need higher reactant concentration and this is done in SC =
dC C k
= 2
plug flow or batch reactor which means a smaller size of a dC P k1
reactor The product distribution here is fixed and unaffected by the
2. α1 < α 2 type of reactor used. This equation can vary only by
changing the temperature of the reaction and or by using a
i.e. the desired reaction is of lower order than the
catalyst.
unwanted reaction
All parallel reactions follow the same reasoning

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6.2.2.2 Product distribution and reactor size for

and this leads us to that instantaneous yield will also change
parallel reaction with position in the reactor.
Depending on the kinetics product distribution may be ¾In another word, it demonstrates also the size of a reactor
different on the type of reactor. The product distribution is
expressed in terms of yield and conversion. For the reaction Overall yield ratio, which is the fraction of all the reacted A,
k1
A ⎯⎯→ P − − − − − desired − product is converted into P. This terminology also known as local
selectivity
k2 (6.12)
A ⎯⎯→
⎯ C − − − − − unwanted − product
S P = ⎛⎜
All P formed ⎞ C P,f C P,f
⎟ = = = Yin, reactor
The Instantaneous Yield ⎝ All A reacted ⎠ C A,0 - C A,f ( - ΔC A )
r
YP = P = dC P (6.11) Equation (6.12) represents the actual product distribution at
- rA − dC A
the reactor outlet and this one much concerns us and the
Here YP = 1 when all A is converted into P. proper averaging of Y
This demonstrates that instantaneous yield is specific function 9depends on the type of flow within the reactor.
of CA and the reactant concentration The relation of equation (6.11) and (6.12) is often not a
concentration A varies throughout the reactor simple one and depends among others such as the reactor
type.

Let us consider the reactor type. which gives, the overall yield in plug flow reactor
6.2.2.2.1 Plug flow and batch reactor 1
C A, f
1
C A, f
the characteristics of these types of reactor
[ S P ]P = - ∫ Y dCA = ∫ Y dCA (6.15)
C A,0 - CA,f C ΔCA C
9 the reactant concentration changes progressively A,0 A,0
through the reactor 6.2.2.2.2 Mixed flow reactor, CSTR
Taking equation (6.11) r
YP = P =
dC P
Here the composition CA,f is every where and is constant
or - r − dC A
A throughout the reactor, and then equation (6.14) for the
dC P = - Y dC A
overall y
yield in mixed flow reactor becomes
B th sides
Both id integration
i t ti gives
i C A, f
= - (6.13) [SP ]m = Y evaluated at C A,f (6.16)
C P,f YdC ∫ A
CA,0 The overall yield from mixed and plug flow reactor converting
On the other side equation (6.12) can be rearranged into A from CA,0 to CA,f are related by
[dS]P ⎤
C P,f = S P ( - ΔC A ) = S P (C A,0 - C A,f ) (6.12.1) [SP ]m = ⎡⎢ ⎥ at CA,F (6.17)
C A, f ⎣ dC A ⎦
Equation (6.13) and (6.12.1) combines to obtain C A, f 1
S P (C A,0 - CA,f ) = -
[S P ]P = ∫ [SP ]m dCA
∫ YdC A (6.14) ΔCA C (6.18)
CA,0 A,0

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Equation (6.17) and (6.18) allows us to predict the overall C P,f = S P (C A,0 - C A,f ) (6.12.1)
yield from one type of reactor given by the overall yield
from the other Since an integral and a summation are not equal in general, the
instantaneous yields obtained by batch or plug flow reactor are not the
6.2.2.2.3 Mixed flow reactor in series
same to those obtained from mixed and cascade reactors
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
Y1(CA,0 - CA,1) + Y2(CA,1 - CA,2) + - - - - + YN (CA,N−1 - CA,N) = SP,mixed(CA,0 - CA,1)
from which (6.19)
( ) ( ) (
Y1 CA,0 - CA,1 + Y2 CA,1 - CA,2 + - - - - + YN CA,N−1 - CA,N )
SP,mixed =
(
CA,0 - CA,1 )
For any reactor type the exit concentration of the desired
product is obtained by using directly equation (6.12), thus

6.3 Operating temperature This can be concluded that a general statement of a high
temperature favors the reaction of higher activation
In multiple reactions both the size of a reactor and product
energies; a low temperature favors the reaction of lower
distribution might be affected by operating temperature.
activation energies.
Next we can observe the influence of temperature for both the
Having this in mind one can find the operating temperature for
size of a reactor as well as the product distribution
various types of multiple reactions in favor of product
for two competing multiple reactions of having the rate distribution and reactor size
constants k1 and k2 , the relative rate of such reaction is given
6.3.1 Product distribution and Temperature
E / RT
k1 A e 1 A (E - E ) / RT Consider two kinds of multiple reactions
= 1 = 1e 2 1
k2 E / RT A2 •Parallel reactions k1
A2e 2 A ⎯⎯→ P desired product
One can easily see that the ratio changes with temperature k2
A ⎯⎯→⎯ C undesired product
depending on whether E1 is greater or smaller than E2 , that is
For the same order of reaction, we have
k1 increases if E1 > E 2
k2 dC P A (E - E ) / RT
when T rises
k1 = 1 e 2 1
decreases if E1 < E 2 dCC A2
k2

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Applying the above statement, the desired product becomes 6.3.2 Reactor size and temperature
if E1 > E2 using high T ¾Our target in multiple reactions is to have higher selectivity
if E1 < E2 using low T to the desired product with a minimum size of a reactor.
ƒ Consecutive reactions 1 2 9The minimum size (volume) will be achieved if the
A → P → C
reaction rate is maximum at all position in the reactor.
where P is desired and C is unwanted product having the
same order of reaction. The production of P can be written 9The optimum temperature will be chosen to establish a
k2 maximum rate at any conversion level.
CP ⎛ k1 ⎞ k2 - k1 It is, therefore, essential to investigate the relation of
= ⎜ ⎟
C A,0 ⎝ k2 ⎠
the production of P is increased if k1 / k2 is increased, ¾kinetics (reaction order),
¾activation energy,
¾reactor size and
if E1 > E2 we use high T ¾ temperature.
if E1 < E2 we use low T For the flow process the reactor size will be represented by
space time V
θF =
FV,0

In such a case an alternative solution such as an

The influence of the value of activation energy can be easily intermediate temperature should be found by using
seen by analyzing its value of desired and unwanted reaction analytical method or by search procedures.
as we did previously. Again to summarize this; Alternative solution
9 In case if the activation energy is such that a desired product i) parallel reactions E1
is obtained at a higher temperature (E1 > E2) then we A ⎯⎯→
⎯ P desired product
should use the highest allowable temperature. E2
A ⎯⎯⎯→ C undesired product
¾The reason is that at higher
g temperature
p we where (E1< E2), P desired product and C unwanted product
obtain high rate of reaction and
consequently smaller size of a reactor a) If θ F is of no concern, use the lowest allowable
9When E1< E2, on the other hand, the desired product is temperature and with larger space time to favor the
obtained by lowering the temperature. production P. This is best carried out in mixed reactor,
CSTR. The optimum temperature for the maximum
‰This causes the rate of reaction to be low desirable product is obtained when E2
and the size of the reactor large. T = R
These are a conflicting factor. ln ⎡ A2θ F ⎛⎜ E2 - 1⎞⎟⎤
⎢⎣ ⎝ E1 ⎠⎥⎦

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θF
b) when a temperature progression is permitted to carry out
in PFR, for a given, θ 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
ii) For the consecutive reaction E1 E2
A → P → C
where (E1< E2), P is desired product and C is unwanted product
a) when θF is no concern use the lowest allowable
ttemperature
t with
ith the
th proper reactor
t size,
i θ F to
t maximize
i i
the desired product P
b) If a temperature progression is permitted to use PFR,
then a falling temperature progression is better than to
use isothermal operation
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.