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IV Year B. Tech.

Petrochemical Engineering
II Sem.
Multicomponent Distillation

Azeotropes
Azeotropes

The term azeotrope means nonboiling by any means (Greek: a -non, zeo -
boil, tropos -way/mean), and denotes a mixture of two or more components
where the equilibrium vapor and liquid compositions are equal at a given
pressure and temperature .

It was Wade and Merriman who had first introduce the term azeotrope in
1911 to designate mixtures that have a minimum or maximum boiling point
at constant pressure or, equivalently, in the vapour pressure under isothermal
conditions. They define the azeotropy state as a stationary point in the
equilibrium T-x,y or P-x,y. The mixture whose composition corresponds to an
extremal point is called an azeotrope.

If at the equilibrium temperature the liquid mixture is homogeneous, the
azeotrope is a homoazeotrope.

If the vapor phase coexists with two liquid phases, it is a heteroazeotrope.
Systems which do not form azeotropes are called zeotropic (Swietoslawski,
1963).
Figure 1: Graphical representations of
the VLE for the most common types of
binary mixtures at constant pressure:
a) Non-azeotropic;
b) Minimum-boiling homoazeotrope;
c) Minimum-boiling
heteroazeotrope;
d) Maximum-boiling azeotrope. Left:
boiling temperature Tbp and
condensation temperature Tdp and
the equilibrium mapping vectors in
T - x; y space. Right: x -y
relationship (equilibrium line)
The formation of azeotrope is due to the differences in the
intermolecular forces of attraction among the mixture components.
There are 3 groups that particularly deviate from the ideality that
simply explains the binary mixtures. They are :

1. Positive deviation from Raoults law: The components
dislike each other. The attraction between identical
molecules (A-Aand B-B) is stronger than between different
molecules (A-B). This may cause the formation of a minimum-
boiling azeotrope and heterogeneity.

2. Negative deviation from Raoults law: The components like
each other. The attraction between different molecules(A-B)
is the strongest. This may cause the formation of a maximum-
boiling azeotrope.

3. Ideal mixture obeys Raoults law: The components have
similar physiochemical properties. The intermolecular forces
between identical and different molecules (A-A, B-B and A-B)
are equal.
The tendency a mixture to form an azeotrope depends on 2 factors
(Horsely, 1973; King, 1980):

1. The differences in the pure component boiling point
2. The degree of nonideality.

Due to azeotrope and resulting phase behaviour, there are
profound effects on the feasibility and technology for distillation-
based operation.
6
Azeotropic Mixtures

Large deviations from ideal liquid
solution behaviour relative to the
difference between the pure
component vapour pressures result
in azeotrope formation.
we are interested in:
1. Describing azeotropic
mixtures both physically and
in thermodynamic terms.

2. Detecting azeotropic
conditions and calculating
their composition.

7
Azeotropic Mixtures
Water / Hydrazine, P=1atm Water / Pyridine, P=1atm
Lecture 24 8
Azeotropes - Impact on Separation Processes
Separation processes that
exploit VLE behaviour (flash
operations, distillation) are
influenced greatly by
azeotropic behavior.


An azeotropic mixture boils
to evolve a vapour of the
same composition and,
conversely, condenses to
generate a liquid of the same
composition.


Ethanol(1)/Toluene(2) at P=1
atm
9
Predicting Whether an Azeotrope Exists
To determine whether an azeotrope will be encountered at
a given pressure and temperature, we define the relative
volatility. For a binary system, a
12
is


where x
i
and y
i
are the mole fractions of component i in the
liquid and vapour fractions, respectively.


At an azeotrope, the composition of the vapour and liquid
are identical. Since, y
1
=x
1
and y
2
=x
2
at this condition,
To determine whether an azeotropic mixture exists, we
need to determine whether at some composition, a
12
can
equal 1.
2 2
1 1
12
x y
x y

1
12

10
Predicting Whether an Azeotrope Exists
We can derive an expression for
12
using modified Raoults Law
as our phase equilibrium relationship,


which when substituted into the relative volatility, yields

12
is therefore a function of T (P
i
sat
, g
i
) and the composition of
the liquid phase. Calculation of
12
therefore requires:
Antoines equation
an activity coefficient model (Margules, Wilsons, )
a liquid composition
Our goal is to determine whether an azeotrope exists.
At some composition, can a
12
=1?
sat
i i i i
P x P y
sat
2 2
sat
1 1
12
P
P


11
Predicting Whether an Azeotrope Exists
One means of determining
whether
12
=1 is possible is to
evaluate the function) over
the entire composition range.

This is plotted for the
ethanol(1)/toluene(2) system
using Wilsons equation to
describe liquid phase non-
ideality.

According to this plot, a
12
=1 at
x
1
= 0.82, meaning that an
azeotrope exists at this
composition.
12
Predicting Whether an Azeotrope Exists
Because equation is continuous and monotonic, we do not need
to evaluate a
12
over the whole range of x
1
.
It is sufficient to calculate a
12
at the endpoints, x
1
=0 and
x
1
=1

At x
1
= 0, we have


and at x
1
= 1, we have

If one of these limits has a value greater than one, and the other
less than one, at some intermediate composition we know a
12
=1.
This is a simple means of determining whether an
azeotrope exists.
sat
2
sat
1 1
0 x
12
P
P
1



sat
2 2
sat
1
1 x
12
P
P
1


13
Determining the Composition of an Azeotrope
For an azeotropic mixture, the relative volatility equals one:



at an azeotrope.
To find the azeotropic composition, two methods are available:
trial and error (spreadsheet)
analytical solution
Rearranging as above yields:


The azeotropic composition is that which satisfies this equation.
Substitute an activity coefficient model for g
1
, and g
2
.
Solve for x
1
.
1
P
P
sat
2 2
sat
1 1
12


sat
1
sat
2
2
1
P
P

14
Example
While azeotropes are undesirable from a processing point of
view, we can still benefit from this phenomenon in obtaining
parameters for GE models.

For example, the binary mixture of 1,4-dioxane (1)/water (2)
exhibits an azeotrope at x1=0.554 at T= 50
o
C and P=0.223
bar. How can we use this information in the estimation of the
Margules parameters A
12
and A
21
for the mixture?

Given: P
1
sat
(50
o
C)=0.156 bar; P
2
sat
(50
o
C)=0.124 bar.
Set all fugacity coefficients equal to 1.00.
Azeotropic Distillation & Extractive Distillation

Azeotropic distillation usually refers to the specific technique of
adding another component to generate a new, lower-boiling
azeotrope that is heterogeneous (e.g. producing two immiscible liquid
phases) to facilitate the separation of components in the original
mixture into pure components or the desired compositions beyond
the azeotropic compositions.

A common historical example of azeotropic distillation is its use in
dehydrating ethanol and water mixtures. For this, a near azeotropic
mixture is sent to the final column where azeotropic distillation takes
place.

Several entrainers can be used for this specific process: benzene,
pentane, cyclohexane, hexane, heptane, isooctane, acetone,
trichloroethylene and diethyl ether are all options as the mixture.

Of
these benzene and cyclohexane have been used the most extensively.
Mixture % Composition of
azeotrope
Boiling point
(pressure = 1 atm)
1.
2.
3.
4.
Water-Ethanol
Pyridine-Water
Ethanol-Benzene
Acetic acid-Toluene
95.97 Ethanol
57.00 Pyridine
32.40 Ethanol
28.00 Acetic-acid
78.13
o
C
92.6
o
C
67.8
o
C
105.4
o
C
Table: Some azeotropic mixtures
There are several liquid pairs which form maximum boiling point
azeotrope. Some examples are tabulated below:
Mixture % composition
of azeotrope
Boiling point (pressure
= 1 atm)
1. Nitric acid-Water 68% Nitric acid 125.5C
2. Acetic acid-Pyridine 65% Pyridine 139.0 C
3. Chloroform-Acetone 80% Chloroform 65.0 C
4. Hydrogen chloride-Water 79.8% Water 108.6 C
Separation of Azeotropic Mixtures

Recall from previous lecture that an zoetrope is a special class of
liquid mixture that boils at a constant temperature at a certain
composition. It behaves as if it were one component with one
constant boiling point. Such mixture cannot be separated using
conventional distillation methods.

Distillation of a mixture that exhibits azeotropic behaviour begins
similarly to conventional distillation. The difference is that, as the
process continues, a temperature is reached at which the
compositions of the vapour phase and liquid phase become the
same.

Once this happens an azeotrope has been formed, and the
individual components can no longer be separated by conventional
distillation. The compositions of the liquid and vapour remain the
same until all of the liquid is eventually vapourised.
Separation of Azeotropic Mixtures can be broadly classified into
the following methods:

by changing system pressure
by addition of an entrainer (azeotropic distillation)
by combination with other processes (hybrid systems)

Azeotropic Distillation - Separation of Binary Azeotropes by
Addition of Entrainer
Basic Concepts

Azeotropic distillation refers to processes whereby a new component (called
the entrainer) is added to the original feed mixture to form (or nearly form)
an azeotrope with one (or more) of the feed components. The azeotrope is
then removed as either the distillate or the bottoms.

Azeotropic distillation also refers to those processes in which a new
component is added to an original feed mixture to break an azeotrope that
otherwise would be formed by the feed components.

Thus, the purpose of deliberately adding the entrainer is either to separate
one component of a closely boiling pair or to separate one component of an
azeotrope.

To illustrate the basic concepts consider the set-up in the Figure below for
the separation of a mixture A-B that forms a minimum-boiling azeotrope.
The entrainer E is a medium boiler (i.e. its boiling point in intermediate
between components A and B), or is a low boiler that can form an
intermediate boiling maximum azeotrope with A.
he feed (A and B) is mixed with the entrainer E before entering column C1.
Component B (which is essentially free of the azeotrope A-E) is removed from
the bottom of column C1, while the overhead vapour from C1 is fed to column
C2. Component A is removed as overhead product and entrainer E as the
bottoms product. The entrainer is recycled back to column C1.

One example of such a separation is for the mixture acetone-heptane with
benzene as the entrainer. The respective boiling points are: A - acetone (56.2
o
C), B - heptane (98.4
o
C), E - benzene (80.1
o
C) and A-B Minimum-boiling
azeotrope (55.6
o
C).

Alternatively, component A can be separated first as overhead from column C1.
In such a process, the column C2 then splits the bottoms from C1 into the
entrainer E (as overhead product) and component B (as bottoms product).

For a maximum-boiling azeotrope, the entrainer should either be a medium
boiler or a high boiler that forms an intermediate-boiling azeotrope with
component B.
Separation by Changing System Pressure (Pressure-Swing
Distillation)

Sometimes azeotropic distillation can be carried out without the use
of entrainer. Instead the distillation columns are operated at different
pressures, as it has been known that the azeotropic concentration can
be shifted substantially by changing system pressure. This method of
separation is especially feasible for systems with low-boiling
azeotropes, as the azeotropic concentration depends significantly on
temperature, which can be changed by changing the operating
pressure.

For example, as shown in the Figure, the system tetrahydrofuran (THF)
and water forms a minimum-boiling azeotrope. In the first column,
which operates at lower pressure (1 bar), the high boiling component
(water) is removed as bottoms. The composition of the overhead
product is as close as possible to that of the azeotrope at this
pressure.
The pressure is increased to 8 bar in the second column. At this higher
pressure, the azeotrope forms at a lower concentration of the low boiling
component (THF), which can then be removed as bottoms. The overhead
product of the second column is returned to the first column (in vapour
state) after pressure reduction.

In some systems, reducing the operation pressure can eliminate azeotropic
behaviour. For example, in the ethanol-water system, azeotropism
disappears at a pressure below 70mm Hg.
Some other examples include:
PRESSURE SWING METHOD
USES PRESSURE TO SHIFT AZEOTROPE CONCENTRATIONS
Extractive distillation is defined as distillation in the presence of a miscible,
high boiling, relatively non-volatile component, the solvent, that forms no
azeotrope with the other components in the mixture. The method is used for
mixtures having a low value of relative volatility, nearing unity.

Close boiling mixtures cannot be separated by simple distillation, because the
volatility of the two components in the mixture is nearly the same, causing
them to vaporize at nearly the same temperature at a similar rate, making
normal distillation impractical.

This process is very similar to azeotropic distillation. Extractive distillation
refers to those processes in which a high-boiling solvent is added alter the
relative volatilities of components in the feed.

The boiling point of the solvent is generally much higher than the boiling
points of the feed mixture that formation of new azeotropes is impossible.
The high boiling point will also ensure that the solvent is will not appreciably
vapourise in the distillation process.

As an illustration, consider the simplified system shown in the Figure below
for separation of toluene and iso-octane using phenol as the solvent.
The separation of toluene (boiling point 110.8
o
C) from iso-octane (boiling
point 99.3
o
C) is difficult using conventional distillation. Addition of phenol
(boiling point 181.4
o
C) results in the formation of phenol-toluene mixture
that leaves the extractive distillation column as bottoms, while relatively
iso-octane is recovered as overhead product. The phenol-toluene mixture
is further separated in a second column (solvent recovery column)
whereby toluene appears as distillate and the bottoms product, phenol, is
recycled back to the first column.

In the above example, when the solvent is added to the original feed
mixture it forms a new mixture with one of the feed components by
"absorbing" that component. This new mixture has a much higher boiling
point than the other feed component that is not absorbed so that it leaves
as bottoms product from the extractive distillation column. The
unabsorbed feed component then leaves as the overhead product.

The absence of azeotropes plus the fact that the solvent can be recovered
by simple distillation makes extractive distillation a less complex and more
widely useful process than azeotropic distillation.
Selection of A Solvent

The choice of solvent determines which of the two components in the original
feed is removed predominantly in the distillation.

For example, if the fresh feed to the distillation is a mixture of 83 mole% ethanol
and 17 mole% water, and ethylene glycol (boiling point 197.35
o
C) is the solvent;
the volatility of ethanol is increased more than that of water. Therefore, ethanol
is removed as the distillate from the extractive distillation column, and water is
separated in the solvent recovery column.

On the other hand, if a high-boiling hydrocarbon such as iso-octane (boiling
point 99.3
o
C, vs. n-octane with boiling point 125.6
o
C) is used as solvent, the
volatility of water is enhanced relative to that of ethanol, and water now
becomes the distillate in the extractive distillation column.

The number of possible solvents available for separation by extractive distillation
is usually much larger than for an azeotropic distillation because of less severe
volatility restrictions. A general approach is to chose a compound that is more
similar to the higher-boiling component in the original feed, and then go up the
homologous series for that compound until a homolog is found that boils high
enough to make the formation of azeotrope impossible
Comparison between Azeotropic and Extractive Distillation

Many of the entrainers used in azeotropic distillation are either
proven or suspected carcinogens or otherwise classified as hazardous
pollutants. Using the example of ethanol-water from previous section,
noted that benzene is the entrainer. Ethanol is removed as the
bottoms product from the column. Benzene is too hazardous for
various reasons ranging from workplace to product to environmental
safety.

An alternative to recover ethanol is to use extractive distillation. The
solvent used is Propylene Glycol. Recall also that ethanol forms a
minimum-boiling azeotrope with water at approximately 89.4 mole%
(96 wt%) ethanol.


A process schematic for the process is shown in the Figure below:
For this separation, propylene glycol meets all the requirements of
an ideal extractive solvent:

It is miscible with water at all concentrations
It has a higher boiling point than water (187
0
C at 1 atm)
It does not form an azeotrope with water
It has a molecular affinity for water (the hydroxyl -OH
group forms a weak bond with water molecule)
It is a relatively safe workplace material

.
In the above system, the first column is the ordinary
azeotropic distillation that produces an ethanol-water
azeotrope as the distillate and nearly pure water as the
bottoms. The distillate is fed to the second column for
extractive distillation, where propylene glycol is added.
Ethanol is produced as the distillate, leaving the top of the
column.

This column can be conceptually divided into 3 sections.
The middle section is the rectifying section where ethanol is
purified by the removal of water. Bonding of the water
molecules with glycol raises ethanol's relative volatility with
respect to water, thus facilitating separation. The following
table shows the change in relative volatility in the columns
The top section reduces the concentration of propylene glycol in
the ethanol distillate to negligible level. The bottom section
strips ethanol from water. The bottoms from the second column
is sent to the third column, a glycol stripper, where the glycol is
recovered. The propylene glycol leaves the stripper as a bottoms
product and is recycled back to the extraction column as the
source of solvent. The overhead from the glycol stripper
(containing mainly water and some ethanol) is sent back to the
first column where it combined with fresh feed.
We distinguish between three different conventional entrainer-addition
based distillation methods depending on the properties and role of the
entrainer and the organization (scheme) of the process:

1. Homogeneous azeotropic distillation (ordinary distillation of
homoazeotropic mixtures): The entrainer is completely miscible with
the components of the original mixture. It may form homoazeotropes
with the original mixture components. The distillation is carried out
in a conventional single-feed column.

2. Heteroazeotropic distillation (decanter-distillation hybrids that
involve heteroazeotropes): The entrainer forms a heteroazeotrope
with at least one of the original mixture components. The distillation
is carried out in a combined column and decanter system.

3. Extractive distillation: The entrainer has a boiling-point that is
substantially higher than the original mixture components and is
selective to one of the components. The distillation is carried out in a
two-feed column where the entrainer is introduced above the original
mixture feed point. The main part of the entrainer is removed as
bottom product.
4. Reactive distillation: The entrainer reacts preferentially and
reversibly with one of the original mixture components. The reaction
product is distilled out from the non-reacting component and the
reaction is reversed to recover the initial component. The distillation
and reaction is usually carried out in one column (catalytic
distillation).

5. Chemical drying (chemical action and distillation): The volatility of
one of the original mixture components is reduced by chemical
means. An example is dehydration by hydrate formation. Solid
sodium hydroxide may be used as an entrainer to remove water from
tetra hydro furan (THF). The entrainer and water forms a 35-50 %
sodium hydroxide solution containing very little THF.

6. Distillation in the presence of salts: The entrainer (salt) dissociates in
the mixture and alters the relative volatilities sufficiently so that
theseparation becomes possible. A salt added to an azeotropic liquid
mixture will reduce the vapor pressure of the component in which it
is more soluble. Thus extractive distillation can be applied using a
salt solution as the entrainer. An example is the dehydration of
ethanol using potassium acetate solution (Furter, 1968)