Unit Operations Lab

Distillation

Theory
There are two different distillation experiments in the Unit Operations lab,
namely continuous and batch distillation. The first step in analysis of both the
continuous and batch distillation processes is to obtain the equilibrium curve,
= ()

(1)

Here, x and y denote molar fractions of the more volatile component (in our case,
ethanol) in the liquid and vapor phases, respectively. The equilibrium relationship (1)
can be obtained, e.g. by using the relative volatility of components of the mixture,
=

/
(1 )/(1 )

(2)

The next step is to account for the column efficiency and obtain the
quasi-equilibrium curve. The column efficiency can be obtained by operating the
system at total reflux. Once the quasi-equilibrium line is obtained you should choose
operating conditions for the column operation at a finite reflux ratio. This can be
accomplished using the McCabe-Thiele analysis. Since construction of
McCabe-Thiele diagrams for the continuous and batch distillation is very similar, it is
reviewed in the section of the continuous distillation only. Make sure to review this
section even if you are working on the batch distillation experiment.
The review of theory presented below is based on Ref. [1].

Column at Total Reflux

The first experiment with both the batch and continuous distillation systems
should be performed at total reflux in order to obtain the column efficiency. The
overall column efficiency is defined as

=
(3)

where Nactual is the actual number of trays in the column and Ntheoretical is the number
of theoretical stages, i.e. the number of trays that would be required to achieve the
experimentally observed separation.

Figure 1. Column at total reflux.

Unit Operations Lab

Distillation

A distillation column operating at total reflux is shown in Figure 1. Let us number

the stages in the ascending order from top to bottom. Assume that the constant molar
overflow condition is satisfied, i.e. that the molar flow rates of both the liquid and
vapor phases are the same at all stages. Let us denote these flow rates as V and L,
respectively.
Consider material balance between the n-th stage and the top of the column (area
enclosed by the dashed rectangle in Figure 1). The material balances for the entire
mixture and the volatile component are
=

and

+1 = ,

(4)

respectively. Here, xn and yn are the molar fractions at the n-th stage. The material
balances (4) yield the following operating line equation:
=

(5)

The McCabe-Thiele analysis of an ideal column at total reflux is shown in Figure 2a.
Starting from the distillate composition xD, draw the step diagram until you reach the
bottoms composition, xB (the values of xD and xB should be measured in your
experiment at total reflux). The number of steps in the diagram corresponds to the
number of equilibrium stages, which in turn equals to the number of trays in the
column plus one (since the bottom equilibrium stage is the reboiler).

Figure 2. McCabe-Thiele analysis of a distillation column operated at total reflux: (a)

determining the number of equilibrium stages; (b) validation of the quasi-equilibrium line by
calculating the total number of stages in the real column.

The real column should be analyzed using the quasi-equilibrium line,

= + ( () )

(6)

Note that at 100% efficiency the quasi-equilibrium line coincides with the equilibrium
line (1), as one would expect. The quasi-equilibrium line should be validated by
performing the McCabe-Thiele analysis for the actual column, as illustrated in Figure
2b. The number of trays obtained with this analysis should coincide with the number
of trays in the real column.

Unit Operations Lab

Distillation

Local Tray Efficiency

Local efficiency of the n-th tray is defined as follows:
local =

+1
1
=
( ) +1 ( )

(7)

The system will have 100% local efficiency if = ( ), i.e. if the n-th stage is at
equilibrium. The second equality in Eq. (7) follows from the material balance (4). It is
more practical to use the latter formula since it is much easier to take samples of the
liquid phase.

Unit Operations Lab

Distillation

Continuous Distillation (Finite Reflux Ratio)

Schematics of the column operating at a finite reflux ratio R is shown in Figure 3.
This figure also contains summary of notation for flow rates and compositions of
various streams in the system.
Molar Flow Rates
L = liquid in the rectifying section
V = vapor in the rectifying section
= liquid in the stripping section
= vapor in the stripping section
F = feed
D = distillate
B = bottoms product
Molar Fractions of Volatile Component
zF = feed
xD = distillate
xB = bottoms product
Reflux ratio: R = L/D
Figure 3. Continuous distillation at finite reflux

Similarly to the previous section, assume the constant molar overflow, i.e. that the
molar flow rates of both the liquid and vapor phases are the same at all stages above
the feed line (rectifying section) and below the feed line (stripping section). Note that
while L, V, and are constant in their respective sections, in general and
.
Operating Lines
Material balance between the n-th stage in the rectifying section and the top of
the column (area enclosed by the blue rectangle in Figure 3) is
+1 = +

(8)

Substituting D = V L, we obtain the operating line for the rectifying section,

=

+ (1 )

(9)

The slope of this operating line is

=

=
=
+ +1

(10)

Material balance between the m-th stage in the stripping section and the bottom of
the column (area enclosed by the red rectangle in Figure 3) is:

Unit Operations Lab

Distillation
1 = +

(11)

Substituting = , we obtain the operating line for the stripping section,

=

+ (1 )

(12)

Feed Line
The equations (9) and (12) are not very practical because they contain flow rates

V, and that are not directly controlled during the experiment. Let us obtain these
flow rates in terms of the control parameters, namely the quality q, flow rate F, and
composition zF of the feed stream1. For this, we will need to take into account material
and energy balances involving the feed stream.
The material balance for the volatile component over the entire column is
= +
(13)
The material and energy balances for the feed plate are
= ( ) + ( )

(14)

= ( ) + ( ),

(15)

and
where H and h are the enthalpies of vapor and liquid at the feed plate and hF is the
feed enthalpy. Combining equations (14) and (15), we obtain
= and = (1 )

(16)

where
=

(17)

is the quality of feed.

Let us now obtain the point of intersection of the operating lines. The coordinates
(x, y) of this point should satisfy both operating line equations (9) and (12).
Combining these equations, we obtain:
( ) = ( ) + ( + )
(18)
Substituting (13) and (16) into Eq. (18), we obtain the feed line equation:
=

+
1
1

(19)

McCabe-Thiele Diagram
A typical McCabe-Thiele diagram for continuous distillation is shown in Figure 4.
A practical approach to plotting the diagram for a given reflux ratio R, quality of the
feed q, and compositions of the distillate (xD), the bottoms product (xB), and the feed
(zF) is the following:
1. Plot the operating line for the rectifying section. This line passes through the point
1

We use letter z instead of x or y to denote the molar fraction of the volatile component in the feed

stream because the feed stream may contain both the liquid and vapor phases

Unit Operations Lab

Distillation

x = y = xD and has a slope R/(R+1).

2. Plot the feed line. This line passes through the point x = y = zF and has a slope
q/(q-1).
3. Plot the operating line for the stripping section. This line passes through the point
x = y = xB and the point of intersection of the feed and rectifying lines.

Figure 4. McCabe-Thiele diagram for continuous distillation at a finite reflux ratio.

Minimum Reflux Ratio and Optimal Feed Stage

Prior to starting distillation at a finite reflux ratio, it is necessary to choose the
reflux ratio that would produce a meaningful result. For example, if the reflux ratio is
chosen so that the rectifying and feed lines intersect on the quasi-equilibrium curve,
you will need an infinite number of stages to reach the specified distillate composition,
as illustrated in Figure 5. If the rectifying and feed lines intersect above the
quasi-equilibrium curve, the specified distillate composition will never be reached.
Therefore, the minimum reflux ratio Rmin at which the desired separation is possible
corresponds to the rectifying line intersecting the feed line on the quasi-equilibrium
curve (see Figure 5). In practice, the reflux ratio chosen for the column operation
exceeds Rmin to ensure that the desired separation can be achieved within a finite
number of stages. A typical reflux ratio for column operation is in the range of 1.2~1.5
Rmin.
Practical approach to determining Rmin:
1. Plot the feed line corresponding to the given composition zF and quality q of the
feed.
2. Plot a straight line connecting the point of intersection of the feed and
quasi-equilibrium lines with the point x = y = xD. This new line is the rectifying
line corresponding to the minimum reflux ratio. Obtain the minimum reflux ratio
from the slope of this line, see Eq. (10).
Once the reflux ratio is chosen, it is easy to choose the optimum feed plate: the
step in the staircase of the McCabe-Thiele diagram corresponding to the optimum
feed plate should contain intersection of the operating lines (make sure you
understand why!).

Unit Operations Lab

Distillation

Figure 5. Determining the minimum reflux ratio.

Unit Operations Lab

Distillation

Batch Distillation
In batch distillation the feed is loaded into the reboiler and the product is
withdrawn from the top of the column as illustrated in Figure 6. Let B and D be the
amount (in moles) of liquid in the reboiler and the molar flow rate of the distillate,
respectively. The overall differential mass balance is

(20)

Figure 6. Schematic of a distillation column operated in the batch regime.

Let xB and xD denote the molar fractions of the volatile component in the liquid
contained in the reboiler and the distillate, respectively. Then the differential mass
balance for the volatile component is
( )

= =

(21)

Multiplying Eq. (21) by dt and collecting terms with dB and dxB, we obtain

(22)

Integrating the last equation, we obtain the Rayleigh equation for batch distillation:
()

()

ln
=
(0)
( )

(23)

(0)

The initial time, t = 0, in Eq. (23) is the time at which the batch distillation
process is started. In our experiments, we will first bring the system to a steady-state
under the total reflux conditions and then switch it to the batch distillation. Therefore,

Unit Operations Lab

Distillation

you will have to measure the amount and composition of liquid in the reboiler at total
reflux and use results of your measurements as initial conditions in Eq. (23).
In order to solve Eq. (23), we need to know dependence between the bottoms
composition xB and the distillate composition xD. In the case of a single-stage
distillation, xD is simply the equilibrium vapor composition corresponding to the
liquid composition xB. However, the situation is more complex for a multi-stage
distillation: in this case we need to perform a McCabe-Thiele analysis in order to find
a relationship between xD and xB.
A distillation column operated in the batch mode contains only the rectifying
section. The equation for the operating line in this section is the same as for the
continuous distillation, see Eqs. (9), (10). An important difference between the
operating lines of the batch and continuous distillation processes is that the operating
line of the batch process is time-dependent.
Let us consider batch distillation at a constant reflux ratio R. Then the slope of the
operating line will remain constant but its intercept will change with time (since xD
will be changing). Let us consider an operating line at a particular value of xD and
perform the McCabe-Thiele analysis starting with this xD. After performing (N+1)
steps (where N is the number of stages in the column), we will obtain xB
corresponding to this xD. Repeating this procedure for several xD, we will obtain a
relationship between xD and xB, which is precisely what we need to solve the Rayleigh
equation (23).
Solving the Rayleigh equation will yield dependence of xB on B. To obtain
dependence of these quantities on time, we can integrate Eq. (20). For this, it is
necessary to obtain the distillate flow rate. This can be accomplished by considering
the energy balance for the entire column.
Reference
1. P. C. Wankat, Equilibrium Staged Separations (Prentice-Hall, 1988).