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Chapter 8: Multiple Reactions

Seldom is the reaction of


interest only one that occurs
in a chemical reactor.
Typically, multiple reactions
will occur, some desired &
some undesired.
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One of key factors in
economic success of a
chemical plant is
minimization of undesired
side reactions that occur
along with desired
reaction. 2
In this chapter, we
discuss reactor
selection & general
mole balances for
multiple reactions.
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First, describe four basic
types of multiple reactions:
-series,
-parallel,
-independent, &
-complex.
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Next, define selectivity
parameter & discuss how it
can be used to minimize
unwanted side reactions by
proper choice of operating
conditions & reactor
selection.
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Then develop algorithm
that can be used to solve
reaction engineering
problems when multiple
reactions are involved.
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Finally, a number of
examples are given that
show how algorithm is
applied to a number of
real reactions.
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8.1.1 Types of Reactions
There are four basic types of
multiple reactions:
series,
parallel,
complex, &
independent.
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These types of multiple reactions
can occur by themselves, in pairs,
or all together.

When there is a combination of


parallel & series reactions, they
are often referred to as complex
reactions.
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Parallel reactions
(also called competing reactions)
reactions where the reactant is
consumed by two different
reaction pathways to form
different products:

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An example of an industrially
significant parallel reaction is
oxidation of ethylene to ethylene
oxide while avoiding complete
combustion to carbon dioxide &
water.

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Series reactions
(also called consecutive reactions)
are reactions where reactant
forms an intermediate
product, which reacts further
to form another product:

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An example of a series
reaction is reaction of ethylene
oxide (EO) with ammonia to
form mono-, di-, &
triethanolamine:

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Complex reactions are
multiple reactions that
involve a combination of both
series & parallel reactions,
such as

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An example of a combination
of parallel & series reactions
is formation of butadiene from
ethanol

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Independent reactions are
reactions that occur at same time
but neither products nor reactants
react with themselves or one
another.

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An example is cracking of
crude oil to form gasoline
where two of the many
reactions occurring are

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8.1.2 Selectivity
Desired & Undesired Reactions.

Of particular interest are reactants


that are consumed in formation of
a desired product D, & formation
of an undesired product, U, in a
competing or side reaction.
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In parallel reaction sequence

or in series sequence

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Minimize formation of U & maximize
formation of D because greater the
amount of undesired product formed,
greater the cost of separating the
undesired product U from the desired
product D (Figure 8-1).

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In a highly efficient & costly
reactor scheme in which very
little of undesired product U
is formed in reactor, the cost
of separation process could
be quite low.
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On other hand, even if a
reactor scheme is
inexpensive & inefficient
resulting in formation of
substantial amounts of U,
cost of separation system
could be quite high.
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Normally, as cost of a
reactor system increases in
an attempt to minimize U,
the cost of separating
species U from D
decreases (Figure 8-2).
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8

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Selectivity tells us how one product is
favored over another when we have
multiple reactions.
Quantify formation of D with respect
to U by defining selectivity & yield of
system.
Instantaneous selectivity of D with respect to U is
8

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Another definition of
selectivity used in the current
literature,
given in terms of flow rates
leaving reactor, is overall
selectivity:
8

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For a batch reactor, overall
selectivity is given in terms of
number of moles of D & U at
end of reaction time:

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It is easily shown that
for a CSTR, the
instantaneous and
overall selectivity are
identical
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8.1.3 Yield
Reaction yield, like
selectivity, has two
definitions: one based on
ratio of reaction rates & one
based on ratio of molar
flow rates. 29
In first case, yield at a point can
be defined as ratio of reaction
rate of a given product to
reaction rate of key reactant A.
This is sometimes referred to as
instantaneous yield.
8

30
In case of reaction yield based on molar
flow rates, overall yield, is defined as
ratio of moles of product formed at end
of reaction to number of moles of key
reactant, A, that have been consumed.
8

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As with selectivity,
instantaneous yield &
overall yield are identical
for a CSTR

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There often is a conflict
between selectivity &
conversion (yield) because
you want to make a lot of
your desired product (D) &
at same time minimize
undesired product (U). 33
However, in many
instances, the greater
conversion you achieve,
not only do you make
more D, but you also form
more U.
P 286-288, 8.2 34
8.2 Algorithm for Multiple Reactions
The availability of software packages
(ODE solvers) makes it much easier to
solve problems using moles Nj , or molar
flow rates Fj rather than conversion. For
liquid systems, concentration is usually
the preferred variable used in the mole
balance equations.
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The mole balances for the various types of
reactors we have been studying are shown
in Table 8-1. The resulting coupled
differential mole balance equations can be
easily solved using an ODE solver.

In fact, this section has been developed to


take advantage of the vast number of
computational techniques now available
on personal computers (e.g., Polymath).
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8.2.1 Modifications to the Chapter 6 CRE Algorithm for Multiple Reactions

The main change in the CRE algorithm in


Table 6-2 is that the Rate Law step in our
algorithm has now been replaced by the step
Rates, which includes three sub-steps:

Rate Laws
Net Rates
Relative Rates
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8.3 Parallel Reactions
8.3.1 Selectivity
In this section, we discuss various
means of minimizing undesired
product, U, through selection of
reactor type & conditions.
We also discuss development of
efficient reactor schemes.
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8

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8
8
8

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8.3.2 Maximizing Desired Product for One Reactant

In this section, examine ways


to maximize instantaneous
selectivity, SD/U , for different
reaction orders of desired &
undesired products,
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Case 1: 1> 2 , For case where
reaction order of desired product
is greater than reaction order of
undesired product.
Let a be a positive number that is
difference between these reaction
orders (a > 0): 1-2= a
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upon substitution into Equation (8-10)
8

To make this ratio as large as possible.


we want to carry out reaction in a
manner that will keep concentration of
reactant A as high as possible during
reaction.
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If reaction is carried out in gas
phase, should run it without inerts
& at high pressures to keep CA,
high.

If reaction is in liquid phase, use


of diluents should be kept to a
minimum.
46
A batch or plug-flow reactor
should be used in this case
because, in these two
reactors, concentration of A
starts at a high value & drops
progressively during course
of reaction.
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In a perfectly mixed CSTR,
concentration of reactant
within reactor is always at its
lowest value (i.e., that of outlet
concentration) & therefore
CSTR should not be chosen
under these circumstance.
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Case 2: 2> 1, When
reaction order of undesired
product is greater than that of
desired product,

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This low concentration
may be accomplished by
diluting feed with inerts &
running reactor at low
concentration of A.

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A CSTR should be used because
concentrations of reactants are
maintained at a low level.

A recycle reactor in which product


stream acts as a diluent could be
used to maintain entering
concentrations of A at a low value.
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Because activation energies
of two reactions in cases 1
& 2 are not given, it cannot
be determined whether
reaction should be run at
high or low temperatures.
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The sensitivity of rate
selectivity parameter to
temperature can be
determined from ratio of
specific reaction rates.
8-13

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Case 3: ED>EU , In this case,
specific reaction rate of desired
reaction kD (& therefore overall
rate rD) increases more rapidly
with increasing temperature than
does specific rate of undesired
reaction kU.
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Consequently, reaction
system should be
operated at highest
possible temperature to
maximize SD/U.
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Case 4: EU>ED In this case,
reaction should be carried out
at a low temperature to
maximize SD/U, but not so low
that desired reaction does not
proceed to any significant
extent.
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8-1

(a)

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(b) How could the conversion of B be increased and still keep selectivity relatively
high?

8-1.1

8-1

8-1
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As we can see, selectivity
reaches maximum at a
concentration .
Because concentration changes
down length of a PFR, we
cannot operate at this
maximum.
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Consequently. we will use a
CSTR & design it to operate at
this maximum.
To find maximum, , we
differentiate SB/XY wrt CA, set
derivative to zero, & solve for
. . 8-1

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8-1

8-1

8-1

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8-1

8-1

8-1

8-1

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P 293-294 Part (b)

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8.3.3 Reactor Selection & Operating Conditions

Next consider two simultaneous


reactions in which two reactants, A &
B, are being consumed to produce a
desired product, D, & an unwanted
product. U, resulting from a side
reaction.

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rate laws for the reactions

instantaneous selectivity 8

to be maximized. Shown in Figure 8-2 are


various reactor schemes & conditions that
might be used to maximize SD/U.
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8-2

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The two reactors with recycle
shown in (i) & (j) can be used for
highly exothermic reactions.

Here recycle stream is cooled &


returned to reactor to dilute & cool
inlet stream thereby avoiding hot
spots & runaway reactions

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The PFR with recycle is
used for gas-phase
reactions, & CSTR is
used for liquid-phase
reactions.
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Last two reactors, (k) & (l), are
used for thermodynamically
limited reactions where
equilibrium lies far to left
(reactant side) & one of products
must be removed (e.g., C) for
reaction to continue to completion

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The membrane reactor (k) is used
for thermodynamically limited gas-
phase reactions, while reactive
distillation (1) is used for liquid-
phase reactions when one of
products has a higher volatility (e.g..
C) than other species in reactor.
In making our selection of a reactor, the
criteria are safety, selectivity, yield,
temperature control, & cost. 72
8-2

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8
8-2

8-2 (b)

8-2

8 8-2

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8-2

8-2

8-2

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8 8-2.3

8-2
8-2

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8 8-2-4

8-2

8-2(g)
------------------

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8.4 Reactions in Series Reactions

In Section 8.1, we saw that


undesired product could be
minimized by adjusting reaction
conditions (e.g., concentration) &
by choosing proper reactor.

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For series of consecutive
reactions, most important
variable is time:
space-time: for a flow
reactor &
real-time for a batch
reactor. 79
To illustrate importance
of time factor, consider
sequence species B is
desired product.

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If first reaction is slow
& second reaction is
fast, it will be
extremely difficult to
produce species B.
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If first reaction
(formation of B) is fast
& reaction to form C is
slow, a large yield of B
can be achieved.
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However, if reaction is
allowed to proceed for a long
time in a batch reactor, or if
tubular flow reactor is too
long, desired product B will be
converted to undesired
product C.
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In no other type of reaction
is exactness in the
calculation of time needed
to carry out reaction more
important than in series
reactions.
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8.5 Complex Reactions
A complex reaction system consists of a
combination of interacting series &
parallel reactions. An overview of this
algorithm is very similar to one given in
Chapter 6 for writing mole balances in
terms of molar flow rates &
concentrations (i.e., Figure 6-1).
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After numbering each reaction, write a
mole balance on each species, similar to
those in Figure 6-1.

The major difference between two


algorithms is in rate law step. As shown
in Table 8-2, we have three steps (3, 4 &
5) to find net rate of reaction for each
species in terms of concentration of
reacting species.
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As an example we shall
study the following complex
reactions

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8.5.2 Multiple Reactions in a CSTR
For a CSTR, a coupled set of algebraic
equations analogous to PFR differential
equations must be solved. These equations
are arrived at from a mole balance on CSTR
for every species coupled with rates step &
stoichiometry.
For q liquid phase reactions occurring where
N different species are present, we have
following set of algebraic equations:
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8.6 Membrane Reactors to Improve
Selectivity in Multiple Reactions
In addition to using membrane reactors to
remove a reaction product in order to shift
equilibrium toward completion, we can use
membrane reactors to increase selectivity in
multiple reactions. This increase can be
achieved by injecting one of reactants along
length of reactor.

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