SCH1208- Chemical Reaction Engineering -1 Unit-4

PREPARED BY:M.ARUL JAYAN

UNIT-4

DESIGN OF SINGLE AND MULTIPLE REACTORS FOR MULTIPLE REACTIONS

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. The distinction between a single reaction and multiple reactions is that the single reaction
requires only one rate expression to describe its kinetic behavior whereas multiple reactions
require more than one rate expression. Multiple reactions are of two primary types: parallel
reactions and series reactions.

Multiple Reactions
1) Parallel or competing reactions
When a reactant gives two product (desired, and undesired) simultaneously with different
rate constant then this is called a parallel reaction.

With an example

2) Series reactions
When a reactant gives an intermediate (desired product) which decomposes to product

With an example

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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3) Series-Parallel reactions
Multiple reaction that consist of steps in series and steps in parallel reaction. In these reaction
proper contacting pattern is very important.
The general representation of these reaction are

Here the reaction is parallel with respect to reactant B and in series with A.

With an example

Halogenations of alkane is a example of this kind of reaction where reaction is parallel with
respect to halogen

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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PARALLEL REACTIONS
Qualitative Discussion About Product Distribution

Consider the decomposition of A by either one of two paths

The net rate of disappearance of A

gives a measure of the relative rates of formation of D and U. This ratio is adjusted to be as large
as possible
If α > β use high concentration of A. Use PFR.
If α < β use low concentration of A. Use CSTR
Now concentration is the only factor in this equation which we can adjust and control (k1, k2,
a1(α) and a2(β) are all constant for a specific system at a given temperature) and we can keep
concentration, low throughout the reactor by any of the following means: by using a mixed flow
reactor, maintaining high conversions, increasing inerts in the feed, or decreasing the pressure in
gas-phase systems. On the other hand, we can keep CA high by using a batch or plug flow
reactor, maintaining low conversions, removing inerts from the feed, or increasing the pressure
in gas phase systems. For the reactions of whether the concentration of A should be kept high or
low.

If a1 > a2 or the desired reaction is of higher order than the unwanted reaction, Equation shows
that a high reactant concentration is desirable since it increases the R/S ratio. As a result, a batch
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 SCH1208- Chemical Reaction Engineering -1 Unit-4

PREPARED BY:M.ARUL JAYAN

or plug flow reactor would favor formation of product R and would require a minimum reactor
size.
If a1 < a2 or the desired reaction is of lower order than the unwanted reaction, we need a low
reactant concentration to favor formation of R. But this would also require large mixed flow
reactor.
If a1 = a2 or the two reactions are of the same order, then only rate constant is the deciding
authority

Hence, product distribution is fixed by k2/k1 alone and is unaffected by type of reactor used. We
also may control product distribution by varying k2/k1. This can be done in two ways:

1. By changing the temperature level of operation. If the activation energies of the two
reactions are different, k2/k1can be made to vary.

2. By using a catalyst. One of the most important features of a catalyst is its selectivity in
depressing or accelerating specific reactions. This may be a much more effective way of
controlling product distribution than any of the methods .

For reactions in parallel, the concentration level of reactants is the key to proper control of
product distribution. A high reactant concentration favors the reaction of higher order, a
low concentration favors the reaction of lower order, while the concentration level has no effect
on the product distribution for reactions of the same order.

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

PREPARED BY:M.ARUL JAYAN

For example,another case in maximizing the desired product in parallel reactions

rD kDCAa1CBb1
-ED
Æ rD = ADe RT CAa1CBb1

rU kUCAa2 CB b2
-EU
Æ rU = AUe RT CAa2 CB b2

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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Rate of disappearance of A: -rA = rD + rU

-ED -EU
-rA = ADe RT C Aa1CB b1 + AUe RT C Aa2 CB b2

Let α1 be the order of the desired reaction A + B → D and α2 be the order of the undesired
reaction A + B → U. Let ED be the activation energy of the desired reaction and EU be the
activation of the undesired reaction. We want to maximize selectivity. If α1 > α2: We want the
concentration of the reactant to be as high as possible since C α1−α2 A has a positive exponent .
If in the gas phase, the reaction should be run without inerts and at high pressure . If in the liquid
phase, the reaction should be run without dilutents . A batch or PFR should be used since CA
starts at a high value and drops over the course of the reaction whereas it is always at the lowest
concentration in a CSTR (i.e. the outlet concentration) . If α2 > α1: We want the concentration
of the reactant to be as low as possible since C α1−α2 .A has a negative exponent . If in the gas
phase, the reaction should be run with inerts and at low pressure .If in the liquid phase, the
reaction should be run without dilutents . A CSTR or recycle reactor should be used . If ED > EU
: High temperature should .If EU > ED Low temperature should be used (but not so low that the
desired reaction never proceeds) .For analyzing the effect of activatoin energies on selectivity,
one can state the following if the reaction is A → D and A → U SD/U ∼ kD kU = AD AU e
−[(ED−EU )/(RT)] . Let α1 and β1 be the order of the desired reaction A + B → D and α2 and β2
be the order of the desired reaction A + B → D if the reaction rates can be described by r = kCα
AC β B. We want to maximize the selectivity of the desired product: If α1 > α2 and β1 > β2:
Since C α1−α2 A and C β1−β2 B. Both have positive exponents, the concentration of both A and
B should be maximized. Therefore, a tubular reactor or batch reactor should be used .High

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

PREPARED BY:M.ARUL JAYAN

pressure for a gas phase reaction and a minimization of inerts should be considered .If α1 > α2
but β2 > β1: Since C α1−α2 .A has a positive exponent but C β1−β2 B has a negative exponent,
the concentration of A should be maximized, but the concentration of B should be minimized.

There are two types of selectivity and yield: Instantaneous and Overall.

Instantaneous Overall

Selectivity

Yield

desired product , rD=k1CA2CB

undesired product , rU=k2CACB

Example:

To maximize the selectivity of D with respect to U run at high concentration of A

and use PFR

Quantitative Treatment of Product Distribution and of Reactor Size.

If rate equations are known for the individual reactions, we can quantitatively determine product
distribution and reactor-size requirements. For convenience in evaluating product distribution we
introduce two terms, φ and Φ. First, consider the decomposition of reactant A, and let φ be the

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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fraction of A disappearing at any instant which is transformed into desired product R. This is
called as instantaneous fractional yield of R.

Thus at any CA .

φ = moles R formed/ moles A reacted

For any particular set of reactions and rate equations φ is a function of CA, and since CA in
general varies through the reactor, φ will also change with position in the reactor. So let us define
Φ as the fraction of all the reacted A that has been converted into R, and let us call this the
overall fractional yield of R. The overall fractional yield is then the mean of the instantaneous
fractional yields at all points within the reactor; thus we may write

φ = all R formed / all A reacted

It is the overall fractional yield that really concerns us for it represents the product distribution at
the reactor outlet. Now the proper averaging for φ p depends on the type of flow within the
reactor.

The Selectivity

The selectivity, is often used in place of fractional yield. It is usually defined as follows:

Selectivity = moles of desired product formed/moles of undesired material formed

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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SERIES REACTIONS
Qualitative Discussion About Product Distribution.

Consider the following two ways of treating a beaker containing A: First, the contents are
uniformly irradiated; second, a small stream is continuously withdrawn from the beaker,
irradiated, and returned to the beaker; the rate of absorption of radiant energy is the same in the
two cases. During this process A disappears and products are formed. In the first beaker, when
the contents are being irradiated all at the same time, the first bit of light will attack A alone
because only A is present at the start. The result is that R is formed. With the next bit of light
both A and R will compete; however, A is in very large excess so it will preferentially absorb the
radiant energy to decompose and form more R. Thus, the concentration of R will rise while the
concentration of A will fall. This process will continue until R is present in high enough
concentration so that it can compete favorably with A for the radiant energy. When this happens,
a maximum R concentration is reached. After this the decomposition of R becomes more rapid
than its rate of formation and its concentration drops. In the alternative way of treating A, a
small fraction of the beaker's contents is continuously removed, irradiated, and returned to the
beaker. Although the total absorption rate is the same in the two cases, the intensity of radiation
received by the removed fluid is greater, and it could well be, if the flow rate is not too high, that
the fluid being irradiated reacts essentially to completion. In this case, then, A is removed and S
is returned to the beaker. So, as time passes the concentration of A slowly decreases in the
beaker, S rises, while R is absent. These two methods of reacting the contents of the beaker yield
different product distributions and represent the two extremes in possible operations, one with a
maximum possible formation of R and the other with a minimum, or no formation, of R. We note
in the first method that the contents of the beaker remain homogeneous throughout, all changing
slowly with time, whereas in the second a stream of highly reacted fluid is continually being
mixed with fresh fluid. In other words, we are mixing two streams of different compositions.
This discussion suggests the following rule governing product distribution for reactions in series.

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

PREPARED BY:M.ARUL JAYAN

For irreversible reactions in series the mixing of fluid of different composition is the key to the
formation of intermediate. The maximum possible amount of any and all intermediates is
obtained if fluids of different compositions and at different stages of conversion are not allowed
to mix. As the intermediate is frequently the desired reaction product, this rule allows us to
evaluate the effectiveness of various reactor systems. For example, plug flow and batch
operations should both give a maximum R yield because here there is no mixing of fluid streams
of different compositions. On the other hand, the mixed reactor should not give as high a yield of
R as possible because a fresh stream of pure A is being mixed continually with an already
reacted fluid in the reactor.

Quantitative Treatment of Product Distribution and of Reactor Size.

A→ R→ S
The concentration- time curves for this reaction when it takes place in a mixed flow reactor.
Again, the derivation will be limited to a feed which contains no reaction product R or S. By the
steady-state material balance we obtain for any component
input = output + disappearance by reaction
which for reactant A becomes
Noting that we obtain for A, on rearranging,

dFA dC
= -k1CA Æ u0 A = -k1CA Æ CA = CA0e-k1t
dV
dF
dV
B = k1C A - k 2CB
dV

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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Æ u0
dCB
dV
(
= k1 C A0e -k1t - k 2CB )
V
t
u0

For component R the material balance, becomes and we obtain, on rearranging,

Æ
dCB
dt
(
= k1 CA0 e-k1t - k 2CB )

Æ
dCB
dt
(
+ k 2CB = k1 CA0 e-k1t )

Æ
(
d CBek 2t ) =k C (k 2 -k1)t
1 A0 e
dt

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

PREPARED BY:M.ARUL JAYAN

Example: Series Reaction in a batch reactor

This series reaction could also be written as

Reaction (1) : -r1A=k1CA

Reaction (2) : -r2B=k2CB

Mole Balance on every species

Species A:
Combined mole
balance and rate
law for a control
volume batch
reactor.

Net Rate of Reaction of A

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

PREPARED BY:M.ARUL JAYAN

rA=r1A+0

Rate Law

r1A=-k1ACA

Relative Rates

r1B=-r1A

Integrating with
CA=CA0 at t=0 and
then rearranging

Mole Balance

Species B:

Net Rate of Reaction of B

Rate Law

r2B=-k2CB

Relative Rates

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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Combine

Using
the integrating
factor, i.f.:

Evaluate

at t = 0, CB = 0

Optimization of the Desired Product B

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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Then

Species C CC = CA0 - CB - CA

And

The series reaction is when the reactant forms an intermediate product, which reacts further to
form another product (e.g.. A → B → C) . The parallel reaction occurs when the reactant is
consumed by two different reaction pathways to form different products (e.g. A breaks down to
both B and C) .Complex reactions are multiple reactions that involve a combination of both
series and parallel reactions . Independent reactions occur are reactions that occur at the same
time but neither the products nor reactants react with themselves or one another (e.g. A → B + C
and D → E + F) The selectivity is defined as S = rate of formation of desired product rate of
formation of undesired product. The overall selectivity is defined as S˜ = exit molar flow rate of
desired product exit molar flow rate of undesired product. For a CSTR, the overall selectivity
and selectivity are identical . For a CSTR, the highest overall yield (i.e. most product
formed)occurs when the rectangle under the rate vs. CA curve has the largest area .For a PFR,
the highest overall yield (i.e. most product formed) occurs when the area under the (rate) vs, CA
curve is maximized . If unreacted reagent can be separated from the exit stream and recycled, the
highest overall yield (i.e. most product formed) is at the maximum of the (rate) vs. CA curve.

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

PREPARED BY:M.ARUL JAYAN

SERIES-PARALLEL REACTIONS

Multiple reactions that consist of steps in series and steps in parallel are called series-parallel
reactions.
k1
A+B→ R

k2
R+B→S

d[A]/dt = -k1[A][B]
d[B]/dt = -k1[A][B]-k2[R][B]
d[R]/dt = k1[A][B]-k2[R][B]
d[S]/dt = k2[R][B]

Qualitative Discussion About Product Distribution.

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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There are two beakers, one containing A and the other containing B. Consider the following
ways of mixing the reactants: (a) add A slowly to B, (b) add B slowly to A, and finally (c) mix A
and B together rapidly.

(a) Add A Slowly to B. For the first alternative pour A a little at a time into the beaker
containing B, stirring thoroughly and making sure that all the A is used up and that the
reaction stops before the next bit is added. With each addition a bit of R is produced in the
beaker. But this R finds itself in an excess of B so it will react further to form S. The result is
that at no time during the slow addition will A and R be present in any appreciable amount.
The mixture becomes progressively richer in S and poorer in B. This continues until the
beaker contains only S.

(b) Add B Slowly to A. Now pour B a little at a time into the beaker containing A, again stirring
thoroughly. The first bit of B will be used up, reacting with A to form R. This R cannot react
further for there is now no B present in the mixture. With the next addition of B, both A and R
will compete with each other for the B added, and since A is in very large excess it will react
with most of the B, producing even more R. This process will be repeated with progressive
build up of R and depletion of A until the concentration of R is high enough so that it can
compete favorably with A for the B added. When this happens, the concentration of R reaches a
maximum, then decreases. Finally, after addition of 2 moles of B for each mole of A, we end up
with a solution containing only S.

(c) Mix A and B Rapidly. Now consider the third alternative where the contents of the two
beakers are rapidly mixed together, the reaction being slow enough so that it does not proceed to
any appreciable extent before the mixture becomes uniform. During the first few reaction

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increments R finds itself competing with a large excess of A for B and hence it is at a
disadvantage. Thus, when A is kept uniform in composition as it reacts, then R is formed.
However, when fresh A is mixed with partly reacted mixture, then no intermediate R forms. But
this is precisely the behavior of reactions in series. Thus, as far as A, R, and S are concerned, the
concentration level of B, whether high or low, has no effect on the path of the reaction and on the
distribution of products. But this is precisely the behavior of parallel reactions of the same order.
So it can be looked at as Irreversible series-parallel reactions can be analyzed in terms of their
constituent series reactions and parallel reactions in that optimum contacting for favorable
product distribution is the same as for the constituent reactions.

Quantitative Treatment, Plug Flow or Batch Reactor.

Quantitatively treat the reactions with the understanding that R, the intermediate, is the desired
product, and that the reaction is slow enough so that we may ignore the problems of partial
reaction during the mixing of reactants. In general, taking the ratio of two rate equations
eliminates the time variable and gives information on the product distribution. We obtain the
first-order linear differential equations . With no R present in the feed the limits of integration
are CAO to CA for A and CRO = 0 for R, and the solution of this differential equation is given
by mathematical calculation. This gives the relationship between CR and CA in a batch or in a
plug flow reactor. To find the concentrations of the other components, simply make a material
balance. An A balance gives

CAO+CRO+CSO =CA+CR+CS

from which CS can be found as a function of CA and CR. Finally, a balance about B gives CB.

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 SCH1208- Chemical Reaction Engineering -1 Unit-4

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Quantitative Treatment, Mixed Flow.

Writing the design equation for mixed flow in terms of A and R gives rate equations.
Rearranging, we obtain which the difference equation is corresponding to the differential
equation. Writing CR in terms of CA then gives equations which can be solved mathematically.
Material balances about A and B in plug flow, hold equally well for mixed flow and serve to
complete the set of equations giving complete product distribution in this reactor.

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