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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.
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
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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.
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.
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
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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.
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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
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rate laws for the reactions
instantaneous selectivity 8
68
The two reactors with recycle
shown in (i) & (j) can be used for
highly exothermic reactions.
69
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
71
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
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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.
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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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