Plant Design and Economics

Prof. Debasis Sarkar

Lecture No -32
Reactor Synthesis for Complex Reactions by Attainable Region: Fundamentals

Welcome to module 7 of plant design and economics. In this module we are talking about reactor
network synthesis. Now reactor network synthesis is essentially establishing the configuration of
chemical reactors and establishing interconnections, among them. Reactor network synthesis for
complex reactions is much more complex problem compared to synthesis for single reactions. In
this module we will learn about a method known as attainable region.

Attainable region has a geometric flavor in it and will start with the fundamentals of attainable
region today. In the next two lectures will learn more about attainable region method through
examples.
(Refer Slide Time: 01:31)

So today we will start with fundamentals of attainable region. So the kind of problem that you
are talking about is as follows. Given the complex reaction mechanism and kinetics, what is the
optimum type and arrangement of the reactors that would maximize product yield? So consider
the given chemical reaction. A reversibly undergoes to B, which irreversibly undergoes to C and
2A goes to D, the rate expressions are given.
Now we can carry out this reaction in various configurations of chemical reactors. So what is the
optimum type and arrangement of the reactors that would maximize the productivity, for
example let us say I want to maximize the product of B. What should be my optimum reactor
configurations.
(Refer Slide Time: 03:06)

The traditional way for reactor synthesis is to consider a large number of combinations of units.
Let us say we will make use of CSTR and PFR for simplicity. So the traditional method will be
to use a large number of combinations of CSTRs and PFR and compute their performance for
various designs. Obviously this method is TDS. It takes lot of time and does not ensure that the
best reactor network has been found.

So there are two approaches one is attainable region, which is a geometric method, another is
optimization method where you formulate the reactor network synthesis problem as an
optimization problem and solve the optimization problem to obtain the optimal reactant network.
In this module, we will learn about attainable region.
(Refer Slide Time: 04:24)
So let us refine the reactor network synthesis problem. Suppose we are given systems of
reactions with known reaction kinetics, we are given the feed state and we are given a number of
fundamental processes such as chemical reactions, mixing, heating or cooling. So we have been
given units to perform these fundamental processes. For example CSTR PFR mixing, heating,
cooling etcetera.

Now once these are given would like to know what is the best combination of these fundamental
processes that will give us the optimal chemical reactor network, as well as the optimal operating
conditions to achieve my target? So every optimization problem will have an objective functions.
The target is your objective function which is frequently considered as process economics. But
also safety concern, environmental concern can also be considered process objectives.

When you talk about attainable region will consider only system of steady flow chemical
reactors. So process of mixing and reaction only. So we will talk about CSTR, PFR and mixing
of streams. So, these are the three fundamental process we will consider to derive at an optimal
reactor network through method of attainable region. And we are considering isothermal system
with no volume change or reaction or mixing will be considered.

So, only isothermal systems with no volume change on reaction or mixing will be considered.
Note that although we are considering here only continuous operations, we are making use of
only CSTR and PFRs but in the literature at enabled region has also been used to obtain batch
chemical reactor networks. But for the purpose of this course will restrict ourselves to continuous
processes, again we will also restrict ourselves to isothermal systems with no volume change on
reaction or mixing.
(Refer Slide Time: 07:47)

Attainable region is a graphical method that is used to determine the entire space of achievable
concentrations using fundamental operations such as reaction and mixing. So when a heat stream
enters a reactor or a reactant network and from the other effluent from the reactor come up. So
we are interested in the concentrations of the desired products in the effluent stream. The product
distributions in the fluid stream the concentrations of the desired product in the effluent stream.

Attainable region is a graphical method that can be used to determine all the achievable
concentrations. In the reactor effluent stream that can be obtained through chemical reactor
networks and using fundamental operations such as CSTR, PFR and mixing. Attainable region
can be used to determine the highest selectivity. It can be used to identify reactor configurations
for optimal products.

The attainable region was first introduced by Horn in 1964 and later it was extended by Glasser
Hilderbrandt and co-workers during 1987 to 90s. Even now also the research on attainable region
is very active in literature.
(Refer Slide Time: 09:43)

So what is attainable region? As we just discussed, it gives you the all achievable concentrations
by fundamental operations using reactant networks. Now what you see in figure are examples of
attainable region. So consider these entire region, entire color region either in this figure or this
figure. Any point within this region represents a concentration. Note that these figures are plot of
concentration of A versus concentration of B.

So we are considering a reaction let us say a complex reactions and we are interested in only
concentration of A and concentration of B. So A and B are my important species for the
chemical reactions. Let us say A is the feed and B is the desired product. Let us say there are
other species such as C, D, E etcetera in the complex network, in the reaction network. But let us
say the reaction mechanism is such that it is possible to express the concentration of B by
looking at concentration of A alone.

So it is possible to make a plot of CA versus CB and obtain all the possible concentrations that
are achievable through a reactor network see that can be achieved. Then we can find out my
desired concentrations in the reactor effluent from such a figure using an objective function now.
For example the point G corresponds to the maximum concentration of CB, maximum
concentration of B.
And here their concentration is this. So this point corresponds to the concentration of A and B in
the effluent of some reactor network. Note that we start with say 1 mole per liter of A and during
reaction it has decrease to this value whereas B has increased to this value. Similarly each and
every point on this region is achievable by some reactor network. So, attainable region method
will allow us to find out those reactor networks.
(Refer Slide Time: 14:14)

So, attainable region is a systematic geometric method for the synthesis of a complex chemical
reactor network. Will illustrate this method by considering only isothermal steady state
continuous operation, so make use of CSTR, PFR and also as fundamental process will be using
mixing, mixing of streams. The Attainable region defines all the achievable compositions that
may be obtained from a network of chemical reactors as we discussed in the previous slides.

We will consider attainable region that represents the set of all possible steps that can be
achieved by combination of two fundamental processes reaction and mixing. Mixing is
performed by a continuous start time reactor CSTR, while reaction is performed by the plug flow
reactor. Note that CSTR and PFR stay at completely two ends when it talks about the mixing
within the reactor.
CSTR represents a reactor, which is completely mixed whereas the PFR there is no axial mixing.
So the operation in this CSTR and PFR respectively mimics the two fundamental processes, such
as mixing and reaction.
(Refer Slide Time: 15:48)

So now we will look into some introductory elements that are necessary to understand and
construct attainable region for chemical reactant networks.
(Refer Slide Time: 16:06)

First the phase plane and phase portrait consider a system described by these two differential
equations. dx1d2, dx1 dt = f1 dx2 dt = f2, f1 and f2 are both functions of x1 and x2. Now with
various initial conditions I can solve these two differential equations and then can mark a plot of
x1 versus x2. So the trajectories of x1 and x2 can be plotted and what I will get is a phase portrait
on the phase plane of x1, x2.

So a phase-portrait is a geometric representation of the trajectories of a dynamic system in the

Now, let us consider a batch chemical reactor and let us consider that we are interested in two
components concentration of A and concentration of B in the reactor. So I measure the
concentration of A and concentration of B in the batch reactor at various time intervals. So this
table gives you the data for concentration of A and concentration of B starting from minute 1 to
5. Now, I can make a plot of concentration of A and concentration of B on CA, CB diagram.

Note that these 5 points CA, CB are plotted using CA CB axis. So you say the concentration data
has been plotted on the phase plane. Note that we have done away with the time by making a plot
of CA versus CB. So each point on the CA, CB plane represents a concentration in the reactor.
(Refer Slide Time: 19:32)
This is another example consider the benzene toluene system. This figure shows you how the
concentration of benzene changes with time and how the concentration of toluene changes with
time. So as the reactant the concentration of benzene decreases with time and as the product
concentration of toluene increases with time goes through maxima and again comes down. Now
these time data concentration of benzene versus time and concentration of toluene versus time
this can be plotted on concentration of benzene versus concentration of toluene.

So, this is the phase plane plot that I obtained from benzene toluene system from this
concentration plot. For example, let us consider time 0.5 hour. So read the concentration of
benzene and the concentration of toluene. So concentration of toluene is around 0.06, whereas
concentration of benzene is quite small. This value may be even 0.05 around 0.05, so 0.05, 0.06,
0.05 around 0.05 or close to 0.01, 0.05, 0.06 something like that and 0.06 so obtain this point.

Similarly you obtain all other points and get this phase plane on concentration of benzene and
concentration of toluene. So we will make use of such phase plane for construction of attainable
region.
(Refer Slide Time: 22:35)
Now there is an interesting property of attainable region, attainable region has to be convex. So,
attainable region has the property of convexity. Take any two points A and B in a region. The
region will be convex if the line segment A B lies completely within the region. So a convex
region is defined as follows. You take any two points within the region join these two points by
line segment it if every point on this line segment lies completely within the region this is convex
region.

Otherwise it is non convex region, concave region. Note that this is convex region, whereas this
is not convex because when I join A and B by the line segment there are several points on the
line, which lies outside the region. In a converse region all the vectors point out into the region or
there tangent at most to its boundary or 0. So when you have a convex region all the vectors
point out into the region or they tangent at most to its boundary or 0.

This will make use later when you discuss more about the attainable region. Let us now define
convex hull. The convex hull of a set of points is defined as the smallest convex polygon that
encloses all of the points in the set. So the convex hull of a set of points is defined as the smallest
convex polygon that encloses all of the points in the set. The polygon has no corner that is bent
inwards.
A concave region can be transformed into a convex 1 by adding a convex hull. So it is possible
to convert a concave region into a convex region by adding a convex hull.
(Refer Slide Time: 25:16)

So, let us see how we do that. What do you see is example of convex polygon and non convex
polygon. Now you consider these sets and here look at the polygon constructed by the green line.
So these polygon represents the smallest polygon and the smallest convex polygon that encloses
all the points. So, this is the convex hull. Another example of convex hull so; this polygon
represented by this blue line is the convex hull.

Whereas the polygon represented by this green line is not a convex hull, it represents a concave
hull. But note that the convex hull the concave polygon has been converted to a convex polygon
by putting a convex hull around it.
(Refer Slide Time: 27:06)
Next will define a term concentration vector, consider that you have a set containing N species
with moral concentration c1, c2 up to cn. These concentrations can be represented by vector
containing n component concentrations. So we can represent the concentration vector as the
column vector which contains concentrations of all the species in your reactor. These
concentrations may be a result of mixing pure components or reactions between them.

So in two dimensions I can make a plot C represents a unique coordinate in concentration space
that may indicate the instantaneous concentrations within a reactor or the resulting composition
form from a combination of mixing many effluent streams. So in two dimensions, you can make
a plot of C1 versus C2 and any point within this C1, C2 plot will represent a concentration
vector.
(Refer Slide Time: 28:25)
A mixture can be represented by a vector where the elements of the vector correspond to the
species concentrations of the mixture. So look at this CA, CB plot we have represented C1, C2,
C3 etcetera as different vectors and each vectors represents a mixture. For example, C1 is this
vector and what are the components of the vector? CA and CB. So, this is CA and this is CB,
similarly C2, similarly C3.

Multiple mixtures can be represented as vectors from the origin in concentration space that is
what we have done in the figure. Since each mixer is represented as a vector each is associated
with a unique magnitude and direction. You can find out the direction, you can find out the
magnitude of the vector as shown for vector C1.
(Refer Slide Time: 30:12)
Now let us see how we represent mixing geometrically when density is assumed constant mixing
as a special geometric property. Mixtures lie on a straight line joining the two concentrations
being mixed in concentration space. Mixing is therefore a linear process. If you look at the figure
the concentration plots C1 and C2 represent 2 mixtures. So C1, C2 are 2 vectors representing
concentrations.

Now if I mix them I may get siesta and siesta will be obtained as a linear combinations of C1 and
C2. So siesta is obtained as a linear combination of C1 and C2. So siesta equal to lambda C2 + 1
– lambda C1, where lambda is values between 0 and 1.This we can extend for any number of
compositions on necessary 2.Graphically, it is easier to represent 2 compositions. But for any
number of k compositions this relation will hold.

That the mixtures when you add say C1, C2, C3 upto Ck the resulting mixtures will be linear
combinations of this C1, C2, C3 up to Ck as shown in this figure equation. Here again lambda 1,
lambda 2 up to lambda k must be equal to 1.
(Refer Slide Time: 32:19)
This figure again shows geometrically the concentrations and mixing. So you have two vector
C1 and C2 representing concentrations. So mixtures now when you add them you get siesta.
Although we have assumed constant density, the mixing may be viewed as a linear process even
when this assumption does not hold. For example gaseous mixture, or highly non-ideal mixtures,
however in such cases we can replace the concentration by mass fraction.
(Refer Slide Time: 33:13)

Now consider this figures this is a concave set. This region represents let us say achievable
points by an arbitrary set of reactors or feed points. So these concave set let us say it is represents
achievable points by an arbitrary set of reactors or feed points. So, apparently it does not seem to
be possible that will be able to obtain the concentrations lying within the concave region.
So the region of concavity does not appear to be part of the achievable set. But when you add C1
and C2 that means when you mix this two points C1 and C2, the straight line connecting point
C1 and C2 is now attainable and points on the line C1 C2 can be used to achieve other attainable
region in the concavity. So when you add C1 and C2, it will fill in the concave region. So from
the concave set here, I obtain the convex set through mixing.

So mixing is able to fill in concave regions and what initially appeared to be not achievable now
becomes achievable. So mixing expands the region the concave region can be converted to a
convex region.
(Refer Slide Time: 35:05)

This leads to an important result given a convex set of points there are infinitely many ways in
which to achieve points within the region. Interior points can be obtained as intersection of many
states that all cross at the same point. There is generally no unique combination of boundary
points that can be used to achieve points located within the region. So, what do you mean is let
us consider point x1, x2 and x3.

Now point x3 can be obtained by linear combinations of point x1 and x2, x3 can also be obtained
by let us say point x4 and point x5 by linear combinations of point x4 and x5. So we can
consider several such mixing where the line passes through x3, x3 is a point within the region.
So there may be various combinations of points on the boundary of the region which when added
will get a point within the region.

So this leads to an important conclusion that one is only concerned with the boundary points of
the attainable region. As all other points within the region may be attained by mixing attainable
region must therefore also be convex formed from the convex hull of its boundary points.
(Refer Slide Time: 36:48)

Next we will define one more term known as reaction rate vector. We have defined a mixture
concentration compactly as a vector of species concentrations. Similarly it is also possible to
form a vector associated with the rate of reaction. Let us consider this reaction A to B to D and A
to E. If A and B are the components of interest to the problem then the concentration vector is of
course is a vector with two components CA and CB.

It is natural to express the corresponding rates of reactions for A and B as the two component
column vector, will call that vector as rate vector. So rate of reaction for A and for B so the rate
vector in C.A, CB space will be a 2 dimensional vector with components rate of reaction rA and
rB. For example for this reaction if these are the rate constants given, rate expressions given we
can find rA and rB and can put it here and we get the reaction vector, reaction rate vector.
(Refer Slide Time: 38:30)
So this figure shows the reaction rate vectors. So, several rate vectors have been shown on the
concentration space. So, all can be obtained from such expression for the rate vector. So, you
must know the reaction rate expressions for the chemical reaction at hand.
(Refer Slide Time: 39:06)

Now, let us assume that we are now given a system of reactions with a known set of kinetic
expressions for each component. Similar to concentration vector the rate of formation for each
species is also expressible by rate vector and that is what we are seen in the previous slides. For
each point in the concentration space the rate vector can be computed and thus a vector field is
formed we call these the rate field.
Note in the figure in the concentration space, we have shown all the rate vectors and these
constitute a vector field and we call this a rate field.
(Refer Slide Time: 40:03)

This figure shows you a PFR trajectory interest, several PFR trajectories are shown. Starting
from different initial concentration of the feed and the rate vectors are also shown. If we focus
your attention on only one particular trajectory, the rate vectors are seen to be tangent to the PFR
trajectory. This is another important interesting property the rate vectors are tangent to the PFR
trajectory.

With this we will discuss our discussions on attainable region here and we will continue with this
discussion in the next class.