BY :

SHELMA HAJAR A.P. (2314100010) 12.4-12.6

AINURAZIS RAMADHANA P. (2314100107)
12.4 DISTILLATION AT TOTAL REFLUX
CONDITIONS
Assume : The liquid entering and vapor leaving the reboiler are the same at total
reflux conditions. This is the same as the vapor entering and liquid leaving the bottom
stage.
yi,n = xi,n−1
Knowing the composition of the liquid leaving the second from bottom stage, the
composition of the vapor leaving the second from bottom stage can be calculated
from vapor–liquid equilibrium. The pressure is usually assumed to be constant.
If the liquid composition at each stage is plotted on a triangular diagram, a distillation
line is obtained.
Figure 12.7a involves a simple system with no azeotropes. Distillation lines in a distillation line map
can never cross each other, otherwise vapor–liquid equilibrium would not be unique for the system.
A more complex distillation line map is shown in Figure 12.7b. This involves two binary azeotropes.
The closeness of the dots on a distillation line is indicative of the difficulty of separation. As an
azeotrope is approached, the points become closer together, indicating a smaller change in
composition from stage to stage.
To begin, consider the mass balance around the rectifying section of a staged column, this
time not at total reflux, as illustrated in Figure 12.8a.
A mass balance around the top of the column for Component i gives:
Vyi,n+1 = Lxi,n + Dxi,D (12.9)
 Equation 12.18 allows us to predict the
concentration profile through a packed
column operating at total reflux conditions.
The resulting profile is known as a residue
curve, since they were first developed by
considering the batch vaporization of a
mixture through time.
Figure 12.9a shows a residue curve map that does not exhibit any azeotropes. Residue
curves in a residue curve map can never cross each other, otherwise vapor–liquid equilibrium
would not be unique for the system.
A slightly more complex residue curve map is shown in Figure 12.9b. This residue curve
shows a binary minimum-boiling azeotrope between the light and intermediate-boiling
components.
An even more complex residue curve map
is shown in Figure 12.10. This has binary
azeotropes between each of the three
components. It also has a ternary
minimum-boiling azeotrope involving all
three components.
Figure 12.11 superimposes distillation lines and residue curves for the same ternary
systems. Figure 12.11a shows the system n-pentane, n-hexane and n-heptane, which is a
relatively wide boiling mixture. It can be observed in Figure 12.11a that there are
significant differences between the paths of the distillation lines and the residue curves.
By contrast, the ternary system ethanol, isopropanol and water shown in Figure 12.11b is a
more close-boiling mixture.
At total reflux, for a packed column to be feasible, both the distillate and bottoms product
should be located on the same residue curve, as well as the feed and products being
located on the same straight line.
All that can be determined from the two separations shown in Figure 12.12a is that they
are likely to be feasible.
By contrast, two different separations are shown for the same residue curve map in Figure
12.12b. This time, the suggested separations run across the residue curves. In this case, the
separations will not be feasible.
The residue curve map in Figure 12.13a shows two binary azeotropes. Starting anywhere
in the residue curve map will always terminate at the same point, in this case at the binary
azeotrope between the intermediate-boiling and heavy components in Figure 12.13a.
Starting at any point to the left of the distillation boundary in Figure 12.13b will always
terminate at the intermediate-boiling component. Starting anywhere to the right of the
distillation boundary will always terminate at the heavy boiling component.
12.5 DISTILLATION AT MINIMUM
REFLUX CONDITIONS
 This is operating at minimum reflux, as there is a pinch in the column in which the changes in composition are incrementally
small.
 A mass balance around the top of the column indicates that the liquid composition leaving the top section of the column, the
liquid composition of the distillate and the vapor composition of the vapor entering the top section must all be on a straight
line on a triangular diagram, as illustrated in Figure 12.14b.
 at a pinch condition the change in composition is incremental.
 For an incremental change in composition with height in the residue curve, as illustrated in Figure 12.14b, both incremental
points of the pinch must be on the residue curve, and an incremental change defines the line to be a tangent to the residue
curve.
 Thus, it follows that the tangent to the residue curve at a pinch point xi must pass through the distillate composition xi,D. This
principle gives a very simple way to follow the path of pinch conditions for any given distillate composition.
Figure 12.15 shows a distillate composition D and a series of tangents drawn to the residue
curves.
The locus of points joining the tangents to the residue curves defines the pinch point curve12.
12.6 DISTILLATION AT FINITE REFLUX
CONDITIONS
Equation 12.12 relates the composition of passing vapor and liquid streams at any
stage, given the reflux ratio and distillate composition.
Specifying the distillate composition from the rectifying section in Figure 12.8a allows
the vapor composition leaving the top stage of the distillation column to be calculated
from vapor–liquid equilibrium.
This would allow the composition of the vapor leaving the first stage and the liquid
composition entering the first stage (being the same as the distillate composition) to be
determined.
The liquid composition leaving the first stage will be at equilibrium with the vapor
composition leaving the first stage. Thus, from a vapor–liquid equilibrium calculation, the
liquid leaving the first stage can be calculated from the composition of the vapor
leaving the first stage. The composition of the vapor entering the first stage can then be
calculated from Equation 12.12. This is the vapor leaving the second stage. Thus, the
composition of the liquid leaving the second stage can be calculated from vapor–liquid
equilibrium. The vapor entering the second stage can then be calculated from Equation
12.12, and so on down the column.
In this way, the composition through the rectifying section can be calculated by
specifying the reflux ratio and distillate composition, based on the assumption of
constant molar overflow.
 A mass balance around the bottom of the
column for Component i gives:

An overall balance around the bottom of the

column gives:

Equation 12.22 relates the compositions of vapor and

Figure 12.16. Mass balance for the liquid streams passing each other in the stripping
stripping section at finite reflux section of a column.
conditions.

The section profiles starting from D and B
intersect each other before reaching a
pinch conditions.
Rectifying section
 Starting from an assumed distillate composition D,
the calculation works down the column with a given
reflux ratio.
 Working down the column, the changes from stage
to stage gradually decrease as the lighter
components become depleted.
 The distillate section profile approaches
a pinch condition towards its termination.
Stripping section
 Starting at bottoms composition B with a given
reboil ratio, the section profile works up the
column.
 Towards the end of the section profile for the
stripping section, again the changes from stage to
stage become smaller as the section becomes
depleted in the heavier components and again
approaches a pinch condition.
 The intersection would correspond with the feed condition.

 Because the section profiles for the rectifying and stripping

sections intersect, these settings would, in principle, lead to a
feasible column.

 If the discrete points do not intersect, then usually some

small adjustments to the product compositions, reflux ratio
or reboil ratio can be used to fine-tune for feasibility.

 The stripping section profile starting at B follows a path different from the profile starting at B
and does not intersect the rectifying section profile. This means that the combination of distillate
compositions D and B could not lead to a feasible column design.
 The intersection of section profiles as illustrated in Figure 12.17 can be used to test the
feasibility of given product compositions and settings for the reflux ratio and reboil ratio.
 Figure 12.18 shows a product composition for the system chloroform, benzene
and acetone with a series of section profiles for the stripping section of a column
starting from bottoms composition B.

 For a defined product composition, the section profiles can be projected for
different settings of the reboil ratio (or the reflux ratio for a rectifying section).
 The rectifying or stripping section of a column must operate somewhere between total reflux and
minimum reflux conditions.
 The range of feasible operation of a column section can thus be defined for a given product
composition.
 Figure 12.19 that these section profiles are bounded for a stage column by the distillation line
and the pinch point curve.
 The area enclosed within the residue curve and the pinch point curve thus provides the feasible
compositions that can be obtained by a packed column section from a given product composition.
 For any given product composition, the operation leaf of feasible operation for a column section
can be defined by plotting the distillation line (or residue curve) and the pinch point curve
 For the stripping and rectifying sections to become a feasible column, the two operation leaves
must overlap.
 The operation leaf for a distillate composition D intersects with the operation leaf for a bottoms
composition B1 in Figure 12.20. This means that there is some combination of settings for the
reflux ratio and reboil ratio that will allow the section profiles to intersect and become a feasible
column design.
 Bottoms composition B2 shows an operation leaf that does not intersect with
the operation leaf of distillate D. This means that the two products D and B2 cannot be produced
in the same column, and the design is infeasible. No settings of reboil ratio or reflux ratio can
make the combination of B2 and D a feasible design.