Distillation Tutorial II: McCabe-Thiele Method of Distillation Design

The McCabe-Thiele method of distillation design is a graphical method of design that dates back
to the early 20th century. It is used as an introductory method to teach the design of distillation
and is still in use today by engineers who design distillation columns. The McCabe-Thiele
method considers binary distillations but can also be used for what are called pseudo-binary
mixtures (i.e. mixtures that are treated as binary by identifying light and heavy key
components).

1. Introductory Concepts. The main features of the McCabe-Thiele method are that it:

Combines equilibrium with mass balance concepts.

Is a graphical approach.

Applies to (pseudo-) binary mixtures.

Uses constant molar overflow (CMO) assumptions.

Approximates energy balance effects and energy demands.

Binary Distillation. The easiest way to understand the McCabe-Thiele method is graphically.
To do this, we begin with a slightly more detailed schematic of a distillation column than shown
i
2. The McCabe-Thiele Method. One of the key features of the McCabe-Thiele method (as well
as other distillation design methods) is that it is assumed that vapor entering from the stage
below and liquid entering from the tray above come in contact with each other and leave any
given stage in equilibrium. Before presenting the equations of the McCabe-Thiele method we
illustrate it graphically for a 50-50 % mixture of saturated liquid ethylene and ethane at 100
psia. We will call this column a C2 splitter. Finally, we specify the reflux ratio to be r = 3.9. We
suggest that you follow each step by referring to Fig. 2 below.

The Graphical Steps of the McCabe-Thiele Method

Draw the yx diagram for the binary mixture of interest at the operating pressure of the
distillation column. Typically y and x refer to the mole fraction of the light component.

Draw the 45-degree line.

Draw the feed line based on the quality (or energy content of the feed). For saturated liquid, this
is a vertical line running from the feed composition through the equilibrium curve. For
saturated vapor, this line is a vertical line from the feed composition to the 45-degree line, then
a horizontal line from the 45-degree line through the equilibrium curve. Other feed conditions
can also be drawn with the aid of a simple equation and will be discussed later in this tutorial in
the section on feed quality.

Place the desired bottoms composition, xB, and the desired distillate composition, xD, on the x-
axis.

For a specified reflux ratio, r, draw the 'rectifying' line. This rectifying line begins at the point
xD on the 45-degree line and has a slope of

r / (r+1).

Draw the 'stripping' line by connecting the intersection of the feed line and the rectifying line
and the point xB on the 45-degree line. The slope of the stripping line is related to r because r
fixes the point of intersection of the rectifying line and the feed line. This intersection and
xB uniquely fix the stripping line and thus its slope. We usually denote the slope of this line by
(s+1) / s where s is the vapor boil-up ratio. In this example, s works out to be 4.5.

Beginning at the point xD on the rectifying line, draw a horizontal line to the equilibrium curve
and then a vertical line to the operating (rectifying or stripping) line.

Repeat step 7 forming a staircase until you reach or pass the point xB on the 45-degree line.

Each point where the staircase intersects the equilibrium curve denotes one stage in the
column.

We can also begin stepping off stages in any distillation column by starting at the point xB on the
45-degree line and moving upward. It is also possible to specify a desired boil-up ratio, s,
instead of a desired reflux ratio, r.

Practice Exercises. Understanding the graphical nature of the McCabe-Thiele method is an

important first step in understanding distillation design. Consider a 30-70 % mixture of ethane
and propane at 150 psia where the feed is saturated liquid at its bubble point. Suppose the
desired bottoms composition is xB = 0.05 and the desired distillate composition is xD = 0.99. Let
the boil-up ratio be specified at s = 2.

3. Equations of the McCabe-Thiele Method. There are a number of important equations that
come from the McCabe-Thiele method that are related to mass and energy balancing. These
equations include the operating lines (i.e. rectifying and stripping lines), the feed line, the
relationship between reflux ratio and boil-up ratio, and the determination of heating and
cooling requirements.

Mass Balance Considerations. Mass balancing is an important part of distillation column

design, analysis, and simulation. Suppose we return to our C2 splitter illustration, which is fed
with 100 lbmol/h of a 50-50 % mixture of ethane and ethylene, has a feed that is saturated
liquid at its bubble point, and operates at 100 psia. The desired composition of the bottoms
product is xB = 0.05 and the composition of the distillate is xD = 0.98. We now illustrate how
mass balancing determines the rectifying and stripping lines in the McCabe-Thiele method.

Operating Lines. Go back to Fig. 1 and draw an imaginary (mass balance) box that encloses the
reboiler and all stages up to and including stage j in the bottom section of the column so that
only the bottoms product and the streams entering or leaving stage j cross this imaginary box.
This imaginary box is often called a mass balance envelope. If we now write a total mass balance
for this imaginary box we get

Lj+1 = Vj + B(2.1)If we also write a component mass balance for ethylene, which we will call
component 1, we get

Lj+1xj+1 = Vjyj + BxB(2.2)Let's solve Eq. 2.2 for yj. This gives

yj = [Lj+1 / Vj] xj+1 – [B / Vj] xB(2.3)Now let's use Eq. 2.1 to eliminate Lj+1 from Eq. 2.3. To do this
simply substitute Vj + B for Lj+1 in Eq. 2.3. This gives

yj = [(Vj + B) / Vj] xj+1 – [B / Vj] xB(2.4)If we define s, the stripping or boil-up ratio, to be s = V/B,
then Eq. 2.4 can be re-written as

yj = [1 + B / Vj] xj+1 – [B / Vj] xB = [1 + 1 / s] xj+1 – [1 / s] xB(2.5)Finally, we can substitute s/s for 1

in the first term on the far right of Eq. 2.5 and get

yj = [(s + 1) / s] xj+1 – [1 / s] xB(2.6)which is called the stripping line. Now it is important for you
to see that the slope of this line is (s+1)/s and that it intersects the 45-degree line at the point xB.
First, we consider Eq. 2.6 to define yjas a function of xj+1. Thus Eq. 2.6 can be written in the
familiar form y = mx + b. If you then compare Eq. 2.6 to y = mx + b, the slope is (s+1)/s.
Understanding why Eq. 2.6 intersects the 45-degree line at xB is a little harder. Here you must
realize that intersecting the 45-degree line at xB means yj = xj+1 = xB. So if we set yj = xB in Eq. 2.6
and do some simple algebra we should get that xj+1 = xB.

Let's do that.

xB = [(s + 1) / s] xj+1 – [1 / s] xB(2.7)Adding [1 / s]xB to each side of Eq. 2.7 gives us[1 + 1/s] xB =
[(s + 1) / s] xj+1(2.8)

However, from Eq. 2.5 we know that the last term in Eq. 2.8 can also be written as [1 + 1/s]xj+1.
Therefore, Eq. 2.8 can be written as

[1 + 1/s] xB = [1 + 1/s] xj+1(2.9)By dividing both sides of Eq. 2.9 by [1 + 1/s], we see that xj+1 = xB.

Practice Exercises. To strengthen your mass balancing skills, answer the following.

Mimic the analysis we have just done to show that the equation for the rectifying line in the top
section of the distillation column is
yj = [r / (r+1)] xj+1 + [1 / (r+1)] xD, where r = L/D.

Show that this rectifying line intersects the 45-degree line at xD.
Energy Considerations in the McCabe-Thiele Method. Remember we said that distillation
can use large amounts of energy. This energy is supplied in the form of heat to the reboiler and
cooling to the condenser. Although it's not obvious, the McCabe-Thiele method does take into
account energy considerations in an approximate way through the boil-up and reflux ratios s
and r respectively. The definition of s is s = V/B where B is the bottoms product flow rate and V
is the flow of vapor from the reboiler. Using a total mass balance around the reboiler (see Fig. 1)
we see that the total amount of liquid material entering the reboiler is

L = V + B(2.10)Since liquid bottoms B and vapor V both leave the reboiler, V represents the
amount of entering liquid L that is vaporized by adding heat. We can express this portion in
terms of the boil-up ratio s as follows. Dividing both sides of Eq. 2.10 by V we get

L/V = 1 + 1/s = (s + 1) / s(2.11)Rearranging Eq. 2.11 we get

V = L[s / (s+1)](2.12)which shows that V is just L multiplied by the fraction s/(s+1). Note that
s/(s+1) must lie between 0 and 1. For s = 0, there is not vapor flow since Ls = 0 and this is
consistent with the fact that s = V/B = 0 means V = 0. For s = 0.5, the amount of vapor is V =
[0.5/1.5]L = L/3 . This says the vapor flow is one third that of the liquid flow to the reboiler
when s = V/B = 0.5. Note that it also says (by mass balance) that B = 2V. Double checking these
results with the overall mass balance for the reboiler shows that

L = V + B = L/3 + 2V = L/3 + 2L/3 = Lso everything is fine.

As s increases, the amount of vapor increases from a minimum of 0 when s = 0 to a maximum of

L when s = infinity, s/(s+1) = 1, and B = 0.
Now that we have a way to calculate the vapor rate V, we can also compute the heat energy
needed to generate that vapor. To calculate the heat required, we need to first determine the
heat of vaporization of the bottoms product. To do this, we need the heats of vaporization of
both components in our mixture and we must also use a very common engineering
approximation of weight averaging. Suppose we denote the heat of vaporization of ethylene in
our example by l1 and the heat of vaporization of ethane by l2. The bottoms product has a
composition xB, where xB is the mole fraction of ethylene since it is the light component. Thus
the mole fraction of ethane in the bottom product is (1 – xB). Calculating the heat of vaporization
of the bottoms product by weight averaging means that we use the following simple formula:

λB = xB λ1 + (1 – xB) λ2(2.13)where λB is used to denote the heat of vaporization of the bottoms

product. The amount of heat required in the reboiler, which we denote by QR, can now be
calculated using the equation

QR = VλB(2.14)We can also determine the amount of cooling required in the condenser in much
the same way that we just determined the heating requirements for the reboiler. To do this we
can simply use the weight averaging formula

λD = xD λ1 + (1 – xD) λ2(2.15)where here λD is the heat of vaporization of the distillate product,

xD is the composition of ethylene in the distillate product, and (1 – xD) is the composition of
ethane in the distillate. The amount of cooling can be calculated using the formula

QC = VλD(2.16)where V is the amount of vapor entering the condenser or the vapor from stage
N-1. Note that this assumes that all of the vapor stream entering the condenser is condensed
and then split into liquid reflux and liquid distillate.

Practice Exercises.

Calculate the heat of vaporization of the bottoms and distillate products for the C2 splitter
example using Eqs. 2.13 and 2.15.

Determine the amount of heat required in the reboiler for a specified stripping ratio of s = 4.5.

How much cooling is required in the condenser if r = 3.9?

Energy Balances and CMO Behavior. There is a subtle but important energy consideration
that is associated with constant molar overflow.

Stages Other Than Feed Stages. For any distillation stage, say stage j, without an external feed
stream, CMO implies that

Lj+1 = Lj(2.17)Vj-1 = Vj(2.18)These equations result by drawing an imaginary energy balance

envelope around any single stage in the rectifying or stripping sections of the distillation
column – other than a feed stage – as shown in Fig. 3 in combination with some physical
approximation.

Equations 2.17 and 2.18 can be interpreted physically by saying that CMO means that the heats
of vaporization of both components are equal. What this also means is that the amount of vapor
condensed at stage j is exactly balanced by the amount of liquid boiled at stage j resulting in no
net change in liquid or vapor entering and leaving stage j. Now this is not necessarily a good
assumption and can cause students to question the reliability of the McCabe-Thiele method.
However, in many cases the CMO assumption provides a reasonable approximation.

Quick Exercises. Determine how reasonable the CMO assumption is by answering the
following:

Calculate λB and λD for the C2 splitter illustration.

What is the percentage difference in these values?

Repeat questions 1 and 2 for acetone and water assuming the same product compositions as
were used in the C2 splitter.

Feed Stages. The energy balance considerations around any stage that has an external feed
must take into account the thermal quality (or energy content) of the feed stream. By this we
mean that the energy content of the feed could be any of the following:

Saturated liquid at its bubble point.

Saturated vapor at its dew point.

A mixture of vapor and liquid (see the Txy diagrams from Tutorial I).

Sub-cooled liquid at a temperature below its bubble point temperature.

Super-heated vapor at a temperature above its dew point temperature.

We use the symbol q to denote the feed quality, where q = LF/F and is the fraction of feed that is
liquid. Thus immediately we see that for saturated liquid, q = 1. For saturated vapor, q = 0. For a
mixture of liquid and vapor feed, 0 < q < 1. For sub-cooled liquid feed, q > 1 and for super-
heated vapor feed, q < 0.

Saturated Liquid Feed. For saturated liquid feed at its bubble point temperature, approximate
energy balance considerations with the CMO assumption given the following equations.

Lj+1 + F = Lj …… (2.19)
Vj-1 = Vj ……. (2.20)

Saturated Vapor Feed. For vapor feed at its dew point we get a different set of equations
resulting from energy balance approximation. Here the equations are

Lj+1 = Lj ……. (2.21)

Vj-1 = Vj + F ….. (2.22)

A Mixture of Vapor and Liquid Feed. In this case, we must either know the feed quality or
determine it. Nonetheless, since 0 < q < 1, we get the following approximate energy balance
results for a feed that is a mixture of liquid and vapor.
Lj+1 = Lj + qF …. (2.23)
Vj-1 = Vj + (1 - q)F………(2.24)

Sub-Cooled Liquid Feed. To determine the heat effects of sub-cooled liquid, we must know
how sub-cooled the liquid is; therefore, we must know its temperature. Once we know the feed
temperature, we can then compare it to the bubble and dew point temperatures of the feed to
calculate a value of q using the formula

q = 1 – [TF – Tbp] / [Tdp – Tbp]

here TF is the temperature of the sub-cooled liquid feed. This equation is correct since for any
sub-cooled liquid feed, TF < Tbp and therefore the second term in Eq. 2.25 is actually positive
making q > 1.

Super-Heated Vapor Feed. Equation 2.15 can also be used for determining q for any super-
heated vapor. Note in this case, TF > Tdp and therefore the second term in Eq. 2.25 is actually
negative and less than -1 making q < 0.

Now it is important to understand that Eqs. 2.23, 2.24, and 2.25 actually apply to all five cases of
feed quality. This is nice because then only one set of equations can be used to perform
approximated energy balance calculations and their impact on the changes in liquid and vapor
flow at any stage with an external feed.

Practice Exercises. In order to better understand Eqs. 2.23, 2.24, and 2.25, answer the
following:

For the C2 splitter example, determine the temperature of the saturated liquid feed. What do
you get for a value of q using Eq. 2.25?

Suppose this feed was sub-cooled by 1.5 K. What would be the value of q?

Suppose the feed was saturated vapor. What would be the value of q?

What is the thermal quality of a feed that is at a temperature halfway between its bubble point
and dew point temperatures?

For a vapor feed that is 20 K super-heated, what is the value of q?

q or the Slope of the Feed Line. To connect the previous discussions of approximate energy
balance, thermal quality of the feed and the McCabe-Thiele Method, we need to show that Eq.
2.25 together with the definition of q = LF/F can be placed on a McCabe-Thiele plot and make
sense. For this we need to understand that q is related to the slope of the feed line. This
calculation of q is very convenient and allows us to draw the feed line properly from the
intersection of a vertical line drawn from the feed composition and the 45-degree line.

Mathematically, the slope of the feed line is given by the simple equation
q / [q – 1](2.26)If you think about this for a minute and go back to your calculations for q, you
will see that

For a saturated liquid feed, q = 1 and the slope of the feed line is infinity. The feed line is a
vertical line.

For saturated vapor feed, q = 0 and the slope of the feed line is also zero. The feed line is
horizontal and goes toward the equilibrium line in this case.

For a mixture of liquid and vapor, 0 < q < 1 and the slope of the feed line is negative. The feed
line is a line between vertical and horizontal with a negative slope that goes toward the
equilibrium line.

For sub-cooled liquid, q > 1 and the slope of the feed line is positive but less than infinity.

For super-heated vapor, q < 0 and the slope of the feed line is also positive.

Quick Exercise. For the results from the last set of practice exercises, draw the feed line for
saturated liquid, saturated vapor, a mixture of liquid and vapor, sub-cooled liquid, and super-
heated vapor feed.

Energy Balance Relationship Between Reflux Ratio and Boil-up Ratio. Using an energy
balance around the entire distillation column, sometimes called an overall energy balance, it is
possible to show that the reflux ratio r and the boil-up ratio s are related by the following
equation

s = (r + q)[xF – xD] / [xB – xF] + q – 1 ……..(2.27)

Thus the amount of vapor generated in the reboiler is tied to the amount of vapor condensed in
the condenser, which makes sense.