Laboratory Instruction Manual

Theoretical Background

Distillation/63

DISTILLATION
(Batch Distillation of Water-Ethanol Mixture)
Laboratory Instruction Manual No. 51B-6

Theoretical Background
Distillation is the core operation in oil refineries and is most widely used to separate liquid
mixtures into their several constituents 3. It is based on the difference in composition
between a liquid mixture and its vapor caused by dissimilar effective vapor pressures, or
volatilities, of the components. When such dissimilarity does not exist, as at an azeotropic
point, it is not possible for separation to occur effectively by simple distillation and more
complicated methods have to be employed. 8
In its most elementary form, distillation includes boiling the liquid to produce the vapor
which is then separated and condensed to obtain a product. However, techniques of
distillation have been developed continually due to the demand for purer products in the
chemical industry combined with a relentless pursuit of greater efficiency. The objective is
not only to achieve the desired product quality at minimum cost, but also to provide constant
purity of product even though there may be some variation in feed composition. To cope
with these requirements, distillation columns with a larger range of capacity have to be
designed. Currently, single columns have diameters that range from 0.3 to 10 m and heights
from 3 to 75 m. A distillation column can be operated individually although it is usually
operated in combination with several other separate units. Moreover, it must never be
considered without its associated control unit. 3
The methods used in distillation practice (refer to Table 1) rely on the basic fact that the
vapor is always richer in the more volatile component than the liquid from which it is
formed. Among these techniques, the most important is rectification, sometimes referred to
as fractional distillation or distillation with reflux 6. It entails the returning of a portion of
the condensate to the still. Flash distillation or simple continuous distillation 8 involves
keeping all the vapor and liquid in intimate contact so that the separated vapor is in
equilibrium with the residual liquid 1. In differential distillation or simple batch distillation, a
liquid is vaporized, and the vapor is removed from contact with the liquid immediately as it
is formed 5. Succeeding discussions will be focused on batch distillation as the setup in the
experiment to be performed is based on this method.
Table 1. Three Main Methods of Distillation 3
Method
Description
Differential or Simple
The feed mixture is available as an isolated batch of material and the
Batch Distillation
compositions of the collected vapor and residual liquid are time
dependent.
Flash or Equilibrium
The process is continuous with respect to feed and product flows. It
Distillation
consists of vaporizing a definite fraction of the liquid feed in such a way
that the vapor evolved is in equilibrium with the residual liquid.
Rectification
The vapors are enriched by contact with counterflowing liquid reflux.

Batch Distillation
Batch distillation is used extensively in the laboratory and small production units where the
same unit may have to serve for many different mixtures. At the start of the distillation
process, a batch of liquid is charged to the reboiler and the system is brought to steady state
under total reflux. A portion of the overhead product is then continuously withdrawn in
accordance with the established reflux policy. The entire column operates as an enriching
section. As time proceeds, the composition of the material being distilled becomes less rich
in the more volatile component (MVC), and the distillation is terminated when the distillate
attains the desired average composition. This can be controlled by at least two ways,
namely: (1) constant reflux ratio, and (2) constant product composition.
____________________________________________________________Chemical Engineering Department
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Laboratory Instruction Manual

Theoretical Background

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Constant Reflux, Varying Overhead

Composition
In this operation, the reflux ratio R is set at a
predetermined value and maintained for the
whole run. The concentration of the more volatile
component in the top product continuously falls.
A mass balance on this component over a small
interval of time for the system shown in figure 1
gives 3:

x D dD d Lx L

Product

[1]

But dD dL therefore:

Boiler

x D dL Ldx L x L dL

Ldx L dL x D x L

[2]

Steam

Separating variables and integrating Equation

[2]:
dL

dx

L
x
L
L0f L x LLf0 x x
D
L

Figure 1. Column for Batch Distillation

L
dx L
x
ln 0 Lf
x
L0 x D x L
Lf

[3]

where xD is the mole fraction of the MVC in the distillate, xL0 the mole fraction of MVC in
the still at the start, xLf the mole fraction of the MVC in the still at end of experiment, and Lo,
Lf, D are the number of moles of liquid feed at the start, at the end, and distillate
respectively.
Equation [3] is used to determine graphically the amount of distillate at a specified average
1
composition. This is done by plotting values of
x D x L against xL ranging from xL0 to xLf.
This will enable the ratio of the initial to final quantity in the still to be found for any desired
change in xL, and hence the amount of distillate. For each value of L0 L f , the average
composition of the distillate is then calculated from the equation,
Lf

x Lf x L0

L f x Lf L0 x L0 L0

x D ave

L f - L0
Lf

Lf

L0

[4]

The heat to be supplied H R to provide the reflux is:

H R RD

[5]

where is the latent heat per mole, and R the reflux ratio.
Constant Overhead Composition, Varying Reflux
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Theoretical Background

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If it is desired to maintain a constant overhead composition, the amount of reflux returned to

the column must be constantly increased throughout the run. As time proceeds, the reboiler
is gradually depleted of the lighter component. Finally the point is reached where the reflux
ratio has attained a very high value that the still is virtually running at total reflux and the
operation becomes uneconomical to proceed further.
In this case, the amount of product obtained by material balance is 3:
x L0 x Lf
x D x Lf

D L0

[6]

The total reflux liquor Lb flowing down the column is given by:
L
R
0 b dLb R12 RdD

[7]

where R1, R2 are the respective reflux ratios at the start and the end of the distillation
process.
And finally, the heat to be supplied H R to provide the reflux is:
H R 0Lb dLb R2 RdD
R1

[8]

This equation can be integrated graphically if the relation between R and D is first
determined.
Vapor-Liquid Equilibrium 3
The composition of the vapor that is obtained from a liquid mixture at a given pressure and
temperature can be determined through several relationships. Most of these equations are
based on ideal mixtures and thus, are limited in their accuracy for predicting vapor
concentrations. The following are the more commonly used ones:
Daltons Law of Partial Pressure
This law states that the total pressure P is equal to the summation of the partial pressures,
i.e. P Pi . For an ideal gas or vapor, the partial pressure is proportional to the mole
fraction of the constituent A through the equation: P A y A P .
Raoults Law
The partial pressure is related to the concentration in the liquid phase in the following
manner: P A x A P A where P A is the vapor pressure of pure A at the same temperature as
the mixture. This is usually true only for high values of xA or correspondingly low values of
other components in the mixture. Mixtures of organic isomers and some hydrocarbons
follow the law closely. If a binary mixture follows this law, then the vapor pressure of a
mixture can be obtained graphically from a knowledge of the vapor pressure of the two
components.
Henrys Law
This gives a linear relationship between the concentration of a constituent in the liquid phase
and its partial pressure, that is P A Hx A where H is Henrys constant not necessarily equal
to P A . This law is applicable for low values of xA or at dilute concentrations of A.

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Laboratory Instruction Manual

Theoretical Background

Distillation/66

By combining these laws, the values of yA can be calculated for different values of xA.
Specifically, for mixtures of components A and B (binary) the partial pressures are:
P A P A x A Py A and PB PB x B Py B

Rearranging variables,

and

P
P x
yA A A A
P
P
PB PB x B
yB

P
P

[9a,b]

[10a,b]

Since y A y B 1 and x A x B 1 then

PA x A PB 1 x A

1
P
P

[11]

Simplifying and rearranging variables to solve for x A :

xA

P PB
P A PB

[12]

Relative Volatility
Another method of finding the relationship between the composition of the vapor and the
liquid in equilibrium is through relative volatility. The volatility of a material is defined to be
the ratio of its partial pressure to the mole fraction in the liquid:
Volatility A

The relative volatility is:

PA
PB
and Volatility B
xA
xB

Volatility A P A x A

Volatility B PB x B

[13a,b]

[14]

Applying Daltons law in Equation [14], simplifying and then rearranging variables gives:
yA
x
A
yB
xB

[15]

Substituting y B 1 y A and x B 1 x A into Equation [15] yields:

y 1 x A
x A
yA
A
or y A
and x A
1 1 x A
1 y A
x A 1 y A

[16a,b,c]

Equation [16] enables the composition of the vapor to be calculated for any desired value of
x if the relative volatility is known. To achieve separation, must not equal 1. Considering
the more volatile component, as increases above unity, y increases and the separation
becomes easier. If such equation is used to construct the equilibrium curve, an average value
of must be taken over the whole column. This is valid if the relative volatilities at the top
and bottom of the column differ by less than 15%. Otherwise, the equilibrium curve must be
constructed incrementally by calculating at several points along the column.

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Theoretical Background

Distillation/67

Guide Questions for further reading:

1.

What is the mechanism involved in fractional distillation? How is it carried out? What
are its advantages over differential distillation?

2.

How is equilibrium reached in flash distillation?

3.

How can separation be achieved at azeotropic points and at low relative volatilities?
What are azeotropic and extractive distillation? 8, 12

4.

How is distillation for multicomponent mixtures carried out? What are the equilibrium
correlations applicable? 3, 8

5.

What is the purpose of steam in steam distillation? 8

6.

What methods/measures can be employed to enrich the distillate with the more volatile
component?

7.

How are the stages in an enriching column (i.e. plate or packed towers) determined?

____________________________________________________________Chemical Engineering Department

University of San Carlos