CRE-Chapter 8

ENCH3115Chemica
l Reaction
Engineering
Chapter 8-
Multiple Reactions
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.
One of key factors in economic success of a chemical plant is
minimization of undesired side reactions that occur along with
desired reaction.
In this chapter, we discuss reactor selection & general
mole
balances for multiple reactions.
First, describe four basic types of multiple reactions:
-series,
-parallel,
-independent, &
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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.
Then develop algorithm that can be used to solve reaction engineering
problems
when multiple
Finally, reactions
a number are involved.
of examples are given that show how algorithm is applied to a
number of real reactions.
8.1.1 Types of Reactions
There are four basic types of multiple reactions:
series,
parallel,
complex, &
independent.
These types of multiple reactions can occur by themselves, in pairs,
or all together. When there is a combination of parallel &
reactions, they are often referred to as complex reactions.
series 3
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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:
An example of an industrially significant parallel reaction is oxidation of ethylene

to ethylene oxide while avoiding complete combustion to carbon dioxide & water.
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:
Complex reactions are multiple reactions that involve a combination of both

series & parallel reactions, such as
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.
An example is cracking of crude oil to form gasoline where two of the

many reactions occurring are
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. 6
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In parallel reaction sequence
or in series sequence
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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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).
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.
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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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
Another definition of selectivity used in the current literature,

given in terms of flow rates leaving reactor, is
overall selectivity:
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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:
It is easily shown that for a CSTR, the instantaneous and overall selectivity are
identical
8.1.3 Yield
Reaction yield, like selectivity, has two definitions: one based
ratio of reaction rates & one based on ratio of molar flow rates.
on
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.
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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.
As with selectivity, instantaneous yield & overall yield are identical for a CSTR
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).
However, in many instances, the greater conversion you achieve, not only do
you make more D, but you also form more U.
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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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3. Parallel Reactions
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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8.3.2 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,
Case 1: α1> α2 , 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): α1-α2= a
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upon substitution into Equation (8-10)
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.
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.
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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.
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.
Case 2: α2> α1, 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.
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.
The sensitivity of rate selectivity parameter to temperature can be determined from
ratio of specific reaction rates.
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.
Consequently, reaction system should be operated at
possible temperature to maximize SD/U.
highest
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
react i on U ni ver sity o f Technology and Applied Sciences - ‫ةيقيبطتلا مولعلاو ةينقتلا ةع ماج‬
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.
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 . .
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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.
rate laws for the reactions
instantaneous selectivity
to be maximized. Shown in Figure 8-2 are various reactor schemes

& conditions that might be used to maximize SD/U. 26
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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
The PFR with recycle is used for gas-phase reactions, & CSTR is used
for liquid-phase reactions.
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
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. 29
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8-2
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8-2
8-2
8-2
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8 8-2-4
In Section 8.1, we saw that undesired product could be mini8m-

by
2ized adjusting reaction conditions (e.g., concentration) & by
8-2(g
choosing proper reactor.
For series of consecutive reactions, most important variable is time:
space-time: for a flow reactor &
real-time for a batch reactor.
To illustrate importance of time factor, consider sequence species
iBs desired product. 32
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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.
If first reaction (formation of B) is fast & reaction to form C is slow, a large yield
of B can be achieved.
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.
If first reaction is slow & second reaction is fast, it will be extremely difficult to
produce species B.
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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).
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.
As an example we shall study the following complex reactions
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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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ENCH3115Chemica

An example of an industrially significant parallel reaction is oxidation of ethylene

Complex reactions are multiple reactions that involve a combination of both

An example of a combination of parallel & series reactions is formation

An example is cracking of crude oil to form gasoline where two of the

Of particular interest are reactants that are consumed in formation of

Minimize formation of U & maximize formation of D because greater

Another definition of selectivity used in the current literature,

Case 1: α1> α2 , For case where reaction order of desired

To make this ratio as large as possible. we want to carry out reaction

If reaction is in liquid phase, use of diluents should be kept to a

A CSTR should be used because concentrations of reactants are maintained at

Case 3: ED>EU , In this case, specific reaction rate of desired

Consequently. we will use a CSTR & design it to operate at

to be maximized. Shown in Figure 8-2 are various reactor schemes

The membrane reactor (k) is used for thermodynamically limited gas-phase

In making our selection of a reactor, the criteria are safety, selectivity,

In Section 8.1, we saw that undesired product could be mini8m-

A complex reaction system consists of a combination of interacting series &

As an example we shall study the following complex reactions

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