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Chapter 7
Design for Parallel Reactions
Dr. Enshirah Da'na 1
Product Distribution:
• The decomposition of A by either of the two paths:
• with corresponding rate equations Consider the decomposition:
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• Dividing rR by rS gives a measure of the relative rates of formation
of R and S:
• we wish this ratio to be as large as possible.
• CA is the only factor to adjust and control.
• k1, k2, a1, and a2 are all constant for a specific system at a given
temperature.
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• We can keep CA low by:
v Using a mixed flow reactor.
v Maintaining high conversions.
v Increasing inert in the feed.
v Decreasing the pressure in gas-phase systems.
• we can keep CA high by:
v Using a batch or plug flow reactor.
v Maintaining low conversions.
v Removing inert from the feed,
v Increasing the pressure in [Link]-
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• If a1 > a2, the desired reaction is of higher order than the unwanted
reaction, high reactant concentration increase the RIS ratio.
• Batch or plug flow reactor would favor formation of product R and
would require a minimum reactor size.
• If a1 < a2, the desired reaction is of lower order than the unwanted
reaction, low reactant concentration favor formation of R.
• This require large mixed flow reactor.
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• If a1 = a2, the two reactions are of same order,
• The product distribution is fixed by k1/k2 alone and is unaffected
by type of reactor used.
• We may control product distribution by varying k1/k2 by:
v Changing the temperature of operation. If the activation
energies of the two reactions are different, k1/k2 can vary.
v Using a catalyst with selectivity in depressing or accelerating
specific reactions.
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• For two or more reactants, combinations of high and low reactant
concentrations can be obtained by controlling the concentration of
feed materials, by having certain components in excess, and by using
the correct contacting pattern of reacting fluids.
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Example 7.1:
The desired liquid-phase reaction:
is accompanied by the unwanted side reaction:
From the standpoint of favorable product distribution, order the
contacting schemes of Fig. 7.2, from the most desirable to the least
desirable.
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Solution:
Dividing the two rate equations gives the ratio:
to be kept as large as possible.
we want to keep CA high, CB low.
Since the concentration dependency of B is more pronounced than of
A, it is more important to have low CB than high CA.
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Also, if we can use an excess of a reactant, or if it is practical to
separate and recycle unconverted reactant, then improved product
distribution is possible.
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Quantitative Treatment of Product Distribution and of Reactor Size.
Consider the decomposition of A, and let 𝝋 be the fraction of A
disappearing at any instant which is transformed into desired product
R.
𝝋 is the instantaneous fractional yield of R.
For any set of reactions and rate equations 𝝋 is a function of CA, and
since CA varies through the reactor, 𝝋 will also change with position in
the reactor.
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let us define 𝚽 as the fraction of reacted A converted into R.
𝚽 is the overall fractional yield of R.
The 𝚽 is then the mean of 𝝋 at all points within the reactor; thus :
It is 𝚽 that really concerns us and represents the product distribution
at the reactor outlet.
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The overall fractional yields from mixed and plug flow reactors
processing A from CA0 to CAF are related by:
These expressions allow us to predict the yields from one type of reactor
given the yields from the other.
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For a series of 1,2, ... ,N mixed flow reactors in which the concentration
of A is CA1, CA2, ..., CAN, the overall fractional yield is obtained by
summing the fractional yields in each of the N vessels and weighting
these values by the amount of reaction occurring in each vessel. Thus
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For mixed flow reactors, or mixed flow reactors in series, the best
outlet concentration to use, that which maximizes CR may have to be
found by maximization of rectangles.
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Before we can safely use these relationships, we must truly have parallel
reactions in which no product influences the rate to change the product
distribution.
The easiest way to test this is to add products to the feed and verify that
the product distribution is in no way altered.
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So far, the fractional yield of R has been taken as a function of CA alone
and has been defined on the basis of the amount of this component
consumed.
More generally, when there are two or more reactants involved, the
fractional yield can be based on one of the reactants consumed, on all
reactants consumed, or on products formed.
Thus, in general, we define 𝝋(M/N) as the instantaneous fractional yield
of M, based on the disappearance or formation of N.
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The Selectivity.
This definition may lead to difficulties. For example, if the reaction is
the partial oxidation of a hydrocarbon, as follows:
The selectivity is hard to evaluate, and not very useful. Thus, we stay
away from selectivity and use the clearly defined and useful fractional
yield, 𝝋(R/A) .
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Example 7.2:
Consider the aqueous reactions:
For 90% conversion of A find the concentration of R in the product stream.
Equal volumetric flow rates of the A and of B streams are fed to the reactor,
and each stream has a concentration of 20 mol/L of reactant.
The flow in the reactor follows.
(a) Plug flow
(b) Mixed flow
(c) The best of the four plug-mixed contacting schemes of Example 7.1.
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Solution:
(a) Plug Flow
The starting concentration of each reactant in the combined feed is
CA0 = CB0 = 10 mmol/L and that CA = CB everywhere,
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(b) Mixed Flow
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(c) Plug Flow A-Mixed Flow B
Assuming B is introduced into the reactor in such a way that CB = 1
mol/L throughout, Then accounting for the changing CA in the reactor:
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To summarize:
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The Side Entry Reactor
Reactant A flowed through the tubes which contained baffles to
encourage lateral mixing of fluid and approach to plug flow.
Reactant B, to be kept at a close-to-constant low concentration in the
tubes, enters the exchanger through the shell side at a somewhat
higher pressure than that in the tubes.
Thus, B diffused into the tubes along the whole length of the tubes.
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Example 7.3:
Often a desired reaction is accompanied by a variety of undesired side
reactions, some of higher order, some of lower order. To see which type of
single reactor gives the best product distribution, consider the simplest
typical case, the parallel decompositions of A, CA0 = 2,
Find the maximum expected C, for isothermal operations
(a) in a mixed flow reactor
(b) in a plug flow reactor
(c) in a reactor of your choice if unreacted A can be separated from the
product stream and returned [Link] feed at CA0 = 2.
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Solution:
Since S is the desired product, let us write fractional yields in terms
of S. Thus:
Plotting this function we find the curve whose maximum occurs where :
Solving we find:
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(a) Mixed Flow
Most S is formed when the rectangle under the cp versus CA curve has
the largest area.
The required conditions can be found either by graphical
maximization of rectangles or analytically.
Since simple explicit expressions are
available, let us use the analytical
approach. Then :
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Differentiating and setting to zero to find the conditions at which
most S is formed:
Evaluating this quantity gives the optimum operating conditions of a
mixed reactor as:
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(b)Plug Flow Reactor
The production of S is maximum when the area under the 𝝋 versus CA
curve is maximum.
This occurs at 100% conversion of A. Thus,
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(c) Any Reactor with Separation and Recycle of Unused Reactant.
Since no reactant leaves the system unconverted, what is important
is to operate at conditions of highest fractional yield.
This is at CA = 1,where 𝝋(S/A)=0.5, Thus, we should use a mixed flow
reactor operating at CA= 1. We would then have 50% of reactant A
forming product S.
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MFR operating at conditions of highest cp with separation and recycle
of unused reactant gives the best product distribution.
This result is quite general for a set of parallel reactions of different
order.
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Example 7.4:
For the reaction of Example 7.3 determine the arrangement of reactors
which would produce most S in a flow system where recycle and
reconcentration of unreacted feed is not possible. Find CStotal for this
arrangement of reactors.
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Thus, for mixed flow, from Example 7.3
For plug flow, from Example 7.3
Therefore, the total amount of C, formed is
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