1

Chapter 10
Introduction to Complex
Distillation Methods

In the preceding chapters concerning distilla-
tion (chapters 2-7), we have learned how to sepa-
rate binary and multi-component mixtures by the
rather simple distillation systems (either continu-
ous or batch)

Unfortunately, however, the knowledge of such
simple distillation systems only is normally not
enough for the industrial-scale distillation, as
the simple distillation systems are not capable of,
e.g.,
2
completely separating azeotropic mixtures
separating the mixtures when the relative
volatility is close to unity (1) [in other
words, when the boiling temperatures of
the components in the mixtures are
relatively close to each other/one another];
note that if we try to do so, the distillation
cost could be very expensive

To overcome such problems/complications,
the complex distillation systems/techniques must
be employed


3
Such complex distillation methods include
azeotropic distillation
pressure-swing or two-pressure distillation
extractive distillation
reactive distillation

The details of these complex distillation tech-
niques are as follows

10.1 Breaking Azeotropes with Other Separators

When the mixture becomes azeotropic (i.e.
the mixture behaves as it is the pure substance),
it limits the separation by distillation (i.e. it
cannot be separated from each other/one
another by distillation)
4
For example, when the mixture of ethanol
(EtOH) and water reaches the concentration of
0.8943 mole fraction of EtOH, it can no longer
be separated by the simple/ordinary distillation

To break the azeotrope, or to get the mixture
with the mole fraction of EtOH higher than
0.8943, how would we do?

Lets consider the simplest, but less likely to
be used, technique, illustrated in Figure 10.1

5
By employing this technique, the distillate (or
the mixture of A and B) whose concentration is
close/near to the azeotropic point from the first
distillation column is sent to another separation
device, which is able to yield pure A


Figure 10.1: The distillation column coupled
with another separating device for braking the
azeotrope
(from Separation Process Engineering by Wankat, 2007)
6
Note that the waste stream in Figure 10.1 is
the stream that contains the mixture of the sepa-
rating components (e.g., the mixture of A + B)

However, some questions arise:
If the other technique or the other separa-
tion device is more effective than the dis-
tillation in separating the mixture, why do
we use the distillation in the first place?
or why dont we use the other technique
in the first place?
What/how would we do with the waste
stream (i.e. the mixture of separating
components)?
7
Lets consider another technique, which is
more likely to be employed, shown in Figure 10.2


Figure 10.2: The distillation column coupled
with another separating device in which the
bottom product of the other separating device
is recycled back to the distillation column
(from Separation Process Engineering by Wankat, 2007)

8
In this separating scheme, the distillate at or
near the azeotropic concentration is sent to the
other separation device(s), in which the waste
stream from the other separation device(s) is sent
back to the distillation column

By employing this technique, the first distilla-
tion column operates as a two-feed column (i.e.
the feed and the recycle stream)

This arrangement is commonly used in indus-
try

A more complex system used to break an
azeotrope or azeotropes is as illustrated in Figure
10.3
9

Figure 10.3: The complex separation system, com-
prising the distillation column and another sepa-
rating device, used for breaking azeotrope(s)
(from Separation Process Engineering by Wankat, 2007)

The product from the additional separating
device(s) is returned to the distillation column as
a reflux, in which
1 o
x y >

10
When the reflux has higher concentration
( )
o
x
than the azeotropic distillate
( )
1
y , as depicted in
the McCabe-Thiele diagram in Figure 10.3, the
distillation can continue until the desired concen-
tration of A (or even pure A) is obtained

10.2 Binary Heterogeneous Azeotropic
Distillation Processes

Surprisingly, the presence of another azeotro-
pic mixture can be used to separate the existing
azeotropic system, especially when the two azeo-
tropic systems are heterogeneous to each other

Such technique is called the azeotropic dis-
tillation
11
Azeotropic distillation is performed by adding
a solvent or an entrainer to the system; this
entrainer forms an azeotropic mixture with one
or both of the components

An example of the rather simple (although
not common) azeotropic distillation is the distil-
lation of n-butanol and water

When the vapour that comes out of the top
of the distillation column with the concentration
of
az
y (this is an azeotropic concentration) is con-
densed by a condenser, it is separated into two
separate liquid phases:

12
one is the water-rich phase (the a phase)
another one is the organic (i.e. n-butanol)
phase (the b phase)
as shown in Figure 10.4; note that each phase has
the same vapour phase concentration of n-buta-
nol,
B
y , but different liquid phase concentrations
( )
0.01 0.02 and 0.41 0.42
B B
x x
a b
- -

The distillation system used for this binary
heterogeneous azeotropic system is as depicted in
Figure 10.5

In this distillation system, the column 1 is
the stripping column receiving the a (water-rich)
phase with the concentration of
B
x
a
from the
separator
13

Figure 10.4: The heterogeneous azeotropic system
of n-butanol and water
(from Separation Process Engineering by Wankat, 2007)

The McCabe-Thiele diagram for the 1
st
column
is on the left hand side (LHS) of Figure 10.6; note
that, for the 1
st
column, n-butanol is the more
volatile than water; thus, the bottom product can
be pure water (i.e.
, bot
0
B
x )
14

Figure 10.5: The distillation system for the
heterogeneous binary azeotrope
(from Separation Process Engineering by Wankat, 2007)

Another liquid phase, or the b (organic) phase
is sent to the column 2 (the 2
nd
column), which is
also a stripping column

15

Figure 10.6: The McCabe-Thile diagram for the
two-column distillation system for the heteroge-
neous binary azeotrope
(from Separation Process Engineering by Wankat, 2007)

On the contrary to the 1
st
column, in the 2
nd

column, n-butanol is the less volatile component,
as it is evident that the equilibrium line is under
the operating line
16
This phenomenon can occur since a solvent
or an entrainer with a high boiling temperature
that can dissolve only n-butanol is added to the
distillation system

As a result, the bottom stream of the 2
nd
co-
lumn can have a very high concentration (or even
pure) of n-butanol

Another commercial example of breaking aze-
otrope using the entrainer is the addition of
benzene (i.e. the entrainer) into the mixture of
ethanol (EtOH) and water

17
10.3 Pressure-swing or Two-pressure Distillation

As we have learned previously, the changes in
both temperature and pressure affect the vapour-
liquid equilibrium (VLE)

The changes in temperature and pressure can
also alter () the composition of the azeo-
trope

For example, at 1 atm (760 mm Hg), the aze-
otropic concentration of the ethanol-water mix-
ture is at 0.8943 mole fraction of ethanol, as
mentioned previously

18
However, at the pressure below 70 mm Hg,
the azeotrope disappears completely

Note that, since, the distillation is commonly
operated at a constant pressure, it is more con-
venient to alter the systems pressure than the
temperature

To appreciate () how the pressure-swing
or the two-pressure distillation works, lets con-
sider the pressure-swing distillation system, which
is used to separate the mixture of methyl ethyl
ketone (MEK) and water, shown in Figure 10.7

19

Figure 10.7: The pressure-swing distillation
system for breaking the azeotrope
(from Separation Process Engineering by Wankat, 2007)

The column 1 (or the 1
st
column) operates at
1 atm, and the azeotropic concentration of the
mixture is 35 wt% water and 65% MEK; note
that, at 1 atm, MEK is more volatile than water
20
If the feed to the 1
st
column has a concentra-
tion of MEK lower than 65%, which is lower than
the azeotropic concentration,
the distillate can have as high concentra-
tion of MEK as 65% (i.e. at the azeotropic
concentration)
the bottom can be the mixture with a very
high concentration of water (or even pure
water)

The relative volatility of MEK and water
changes after the pressure reaches ~6.8 atm (or
~100 psia)

21
At the pressure higher than ~6.8 atm, water
becomes more volatile than MEK

Additionally, the azeotropic concentration at
the pressure of ~6.8 atm changes from 35% water
(at 1 atm) to 50% water

To obtain pure MEK, the distillate from the
1
st
column, which contains the mixture of 35%
water and 65% MEK, is sent to the column 2 (or
the 2
nd
column) operating at ~6.8 atm

Since, at this pressure (~6.8 atm), water is
more volatile than MEK, and the azeotropic con-
centration is at 50% water and 50% MEK,
22
the distillate of the 2
nd
column can be the
mixture with the concentration of water of
as high as 50%
the bottom of the 2
nd
column can be the
mixture with a very high concentration of
MEK (or even pure MEK)

10.4 Extractive Distillation

Extractive distillation is another complex dis-
tillation system used for separating the azeotropic
mixture(s)

23
In the extractive distillation, a solvent is added
to the distillation column such that only one com-
ponent (e.g., B from the mixture of A + B) is
attracted to it

If the solvent has a high boiling point, the
volatility of the mixture of the solvent and species
B is reduced, until it is lower than that of species
A

Accordingly, species A becomes the more vo-
latile component (than the mixture of species B
+ solvent); thus, it can easily be removed from
the distillation system as the distillate
24
An example of extractive distillation is as illu-
strated in Figure 10.8


Figure 10.8: An extractive distillation system
(from Separation Process Engineering by Wankat, 2007)

In this system, the solvent with a high boiling
point is added to the 1
st
column several stages
above the feed stage and a few stages below the
top of the column
25
In the top section (i.e. the section above the
solvent feeding point), species A is removed from
the column as the distillate; this is because the
solvent, which is a high boiling temperature sub-
stance, is mixed with species B, and the resulting
mixture has a very high boiling temperature rela-
tive to that of species A

In the middle section (i.e. the section from
the feeding point of the solvent to the feed stage),
the solvent separates species B from the mixture
of A + B

26
It is important to note that the amount of
the solvent must be large enough to completely
separate species B from species A, otherwise, the
distillate will not be pure A, as species B can
form an azeotropic mixture with species A

In the bottom section (i.e. the section below
the feed stage), since the mixture of the solvent
and species B is less volatile than species A, the
mixture of species B and the solvent is removed
from the 1
st
column as the bottom

The solvent can then be separated from spe-
cies B in the 2
nd
distillation column
27
If the solvent is chosen properly, it should
easily be removed from species B by the simple
distillation column with only a few equilibrium
stages

The solvent obtained from the 2
nd
column can
be recycled to the 1
st
column to be used as the
solvent again

Note that, generally, the extractive distillation
is not applicable for separating the mixture of
isomers

28
10.5 Azeotropic Distillation with Added Solvent

When a homogeneous azeotrope is formed,
the procedures used for heterogeneous azeotropic
distillation cannot be employed

In order to solve this problem, the solvent (or
an entrainer) that forms a binary or ternary
azeotrope is added to the system to enable the
separation of the mixture

An example of the azeotropic distillation with
added solvent is as illustrated in Figure 10.9

29

Figure 10.9: The separation of butadiene from
butylenes using ammonia as an entrainer
(from Separation Process Engineering by Wankat, 2007)

At the temperature of 40
o
C, the azeotrope of
the mixture of butadiene and butylene exiting the
1
st
column as the top product is homogeneous,
and, as a result, very difficult to be separated
from each other; note that, as butadiene is the
less volatile component, it leaves the 1
st
column
purely (or nearly purely) as the bottom
30
Ammonia is added to the distillation column
either as a reflux or as a feed

The mixture of butadiene + butylenes + am-
monia is condensed at the condenser

At a temperature below 20
o
C (note that, the
colder the temperature of the settler, the purer
the two liquid phases), two liquid phases are
formed at the liquid-liquid settler:
the upper phase: contains mainly butylene
and ammonia (with a small amount of
butadiene)
the lower phase: contains mainly ammonia,
with small amounts of butadiene and buty-
lene
31
The lower phase is returned to the distillation
column (to be used as the recycle entrainer),
while the upper phase is sent to the subsequent
stripping column

In the stripping column, the mixture of buty-
lene and ammonia can be distilled and thus sepa-
rated into
the top product (the distillate), which is
the azeotropic mixture of butylene and
ammonia
the bottom product (the bottom), which
can be pure butylene

The distillate of the stripping column is recy-
cled to the liquid-liquid settler
32
Another example of the azeotropic distillation
with the added solvent is as shown in Figure 10.10

In Figure 10.10, species A and the solvent (or
the entrainer) form the azeotrope with a low
boiling point; thus leaving the distillation column
as the distillate

Species B, whose boiling temperature is higher
than the mixture of species A and the solvent (in
other words, species B is a less volatile compo-
nent) can be removed from the column as pure B
as the bottom

33

Figure 10.10: An azeotropic distillation with a
low boiling temperature azeotrope
(from Separation Process Engineering by Wankat, 2007)

Species A can be removed from the solvent
by a water-wash extraction

34
The additional distillation column (on the
RHS of Figure 10.10) is used to separate the sol-
vent from water

The third example is commonly used for sepa-
rating ethanol (EtOH) from water, using a hydro-
carbon as an entrainer, as depicted in Figure
10.11

Previously, benzene is used as the solvent
(entrainer); however, because of its toxicity (as
it is a carcinogenic agent), it has been replaced
by some other hydrocarbons, e.g., diethyl ether,
n-pentane, or n-hexane
35

Figure 10.11: A ternary azeotropic distillation
for separating ethanol from water
(from Separation Process Engineering by Wankat, 2007)

The mixture of EtOH and water at nearly
azeotropic concentration (~70-90% EtOH) is fed
into the azeotropic distillation column, in which
the hydrocarbon solvent/entrainer is added to
the column as a reflux

36
The vapour distillate is condensed and then
separated into two liquid phases:
the upper layer or the solvent layer
the water layer

The composition of each layer depends on the
solvent used

For example, if n-hexane is used,
the upper layer contains 96.9 wt% hexane,
2.9% EtOH, and 0.5% water
the lower or water layer contains 6.2%
hexane, 73.7% EtOH, and 20.1% water

The upper layer is returned to the azeotropic
column as a reflux to be used as the recycle en-
trainer
37
The lower layer (with a small amount of
n-hexane, which is used to break the azeotrope)
is sent to the stripping column, to obtain pure
water as the bottom

The addition of solvent (e.g., n-hexane) into
the azeotropic column (the LHS column) makes
the azeotropic mix-ture of EtOH + water and
the solvent become more volatile than EtOH

Thus, EtOH (which is now less volatile) can
be removed purely as the bottom

10.6 Reactive Distillation

The advantage of having the reactive distilla-
tion system or the distillation with a chemical
38
reaction is that the product(s) of the reaction can
be removed continuously by the distillation, which
drives the reversible reaction to completion

The arrangement of the distillation system for
the reversible reactions:
A C
or A C + D
is as depicted in Figure 10.12

If the reactant is less volatile than the pro-
duct(s), the arrangement on the LHS (A) is ap-
propriate; note that the bottom bleed is required
to prevent the build-up of non-volatile impurities
39

Figure 10.12: The reactive distillation system for
a single-reactant reaction
(from Separation Process Engineering by Wankat, 2007)

If the reactant is more volatile than the pro-
duct(s), the arrangement on the RHS (B) is ap-
propriate; note that the top bleed is required to
re-move volatile or gaseous components

The arrangement for the reaction:
A + B C + D
40
in which the reactants are of intermediate volati-
lity between the two products (i.e. C and D), is
as shown in Figure 10.13


Figure 10.13: The reactive distillation system
with two reactants
(from Separation Process Engineering by Wankat, 2007)

Note also that the arrangements C and D are
widely used for the esterification reaction:
Fatty acid + Alcohol Ester + Water
used for producing bio-diesel