DISTILLATION

UNIT-1
Distillation is a unit operation in which vaporization of a liquid mixture yields a vapor phase
containing more than one component and it is desired to recover one or more of them in
nearly pure state.
Separation by distillation primarily depends on the difference in volatilities of the
components to be separated. The basic requirement of the distillation is that the
composition of the vapor should be different from that of the liquid with which it is in
equilibrium.
Although distillation appears to be similar to evaporation, these two operations are
basically different. For instance in evaporation vapor contains only one component while
in distillation the same contains at least two components. In evaporation, a volatile
component is separated from a nonvolatile one while in distillation all the components are
volatile but their volatilities are different.
The concentration of glycerin from dilute aqueous solution provides an excellent
example of the difference between these two operations. During concentration of glycerin
from dilute solution, up to 80 % glycerin, a single component, namely water is present in
the vapor phase and the operation is therefore evaporation. Beyond 80% glycerin, the
operation is distillation since both water and glycerin appear in the vapor phase
Since separation of the components of a liquid mixtures by distillation largely depends on
vapor liquid equilibrium. I.e. distribution of the components between the liquid and the
vapor streams at equilibrium.
Parts of Distillation column

Figure 1.1 Schematic of a typical distillation Column

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There are five most important part of distillation column which are as follows
1 A column having trays or a packing and suitable internals
2 The feed preheater A reboiler
3 A condenser for the overhead vapor
4 Reflux drum
5 Reboiler (for partial vaporization of the bottom liquid)
The hot bottom product may be used to preheat the feed for energy economy
F: Feed (liquid, vapor or a mixture of liquid and vapor)
D: Distillate or top product (It is rich in the more volatile)
W: Bottom product (It is rich in the less volatile)
Process description
 The feed enters at a suitable point of the water. The reboiler normally heated by
steam, partially vaporizes the liquid received from the bottom of the column.
 The vapor flows up through the trays or through the packing in the column leaves
at the top and enters into an overhead condenser.
 A part of the condensate is withdrawn as the top product and the rest is fed back
into the column as reflux which flows down the tray or the packing.
 An intimate contact between the down flowing liquid and up flowing vapor occurs
on the trays.
 Exchange of mass takes place between the liquid and the vapor phases.
 The more volatile components move from the liquid to the vapor phase and the
less volatile move in the reverse direction from the vapor to the liquid phase.
 As a result the concentration of the more volatiles gradually increase in the vapor
as it goes up and the concentrations of the less volatiles increase in the liquid
phase as it flows down the column.
 In this way a higher degree of separation of the more volatiles from the less
volatiles is achieved.
 The top product drawn from the condenser is rich in the more volatiles. The bottom
product has a high concentration of the less volatiles and only a small amount of
the more volatiles.
 The more the number of trays and the more the reflux ratio, the better is the
separation.

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Table 1.1 A few examples of separation of liquid mixtures by distillation
Feed components Industry/Plant Product
Crude petroleum Refinery Various petroleum
products
Ethylene oxide/water Petrochemical Ethylene oxide
Ethanol/water Distillery Ethanol
Aceticacid/acetic anhydride Acetic anhydride plant Acetic anhydride
Air Air separation Plant Nitrogen,Oxygen,Argon
Aniline/Nitrobenzene Aniline plant Aniline

Vapor liquid equilibrium

The number of molecules of a liquid becoming vapor will be equal to the number of
molecules condensing into liquid in a closed container. The rate of evaporation of the
liquid water is equal to the rate of condensation of water vapor. The liquid phase is in
equilibrium with its own vapor phase.
Vapor liquid equilibrium data is useful for determining how liquid mixture s will separate
because the liquids have different boiling points, one liquid will boil into a vapor and rise
in the column while the other will stay as a liquid and drain through the unit.
Bubble point temperature
The bubble point is the point at which the first drop of a liquid mixture begins to vaporize.
Dew point temperature
The dew point is the point at which the first drop of a gaseous mixture begins to condense.
Boiling point Temperature
The temperature at which the pressure exerted by the surroundings upon a liquid is
equaled by the pressure exerted by the vapor of the liquid. Under this condition, addition
of heat results in the transformation of the liquid into its vapor without raising the
temperature. The normal boiling point is the temperature at which the vapor pressure is
equal to the standard sea level atmospheric pressure. At sea level water boils at 100 0C.At
higher altitude the temperature of the boiling point is lower because at higher altitude, air
pressure is lower. When atmospheric pressure is lower, such as at a higher altitude, it
takes less energy to bring water to the boiling point. Less energy means less heat, which
means water will boil at a lower temperature at a higher altitude.

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Vapor liquid Equilibrium at constant pressure (T-x-y diagram)

Figure 1.2 Boiling point diagram at constant Pressure

The figure shows the vapor liquid equilibrium diagram (T-x-y) for a binary mixture of
compounds A and B. A being more volatile. In this diagram commonly known as the
boiling point diagram, mole fraction of A and B are plotted along the abscissa and
temperature is plotted along the ordinate. The lower curve joining the two boiling points
is obtained by plotting the boiling temperature against the liquid composition(x) and is
known as the bubble point curve. The upper curve obtained by plotting temperature
against the equilibrium vapor composition (y) is the dew point curve. The region above
the dew point curve consists of only vapor while the region below the bubble point curve
consists of only liquid. The region enclosed by these two curves is a two phase region.
Liquid and vapor mixtures at equilibrium being at the same temperature and pressure
throughout. The tie lines are horizontal. CE is a tie line joining the equilibrium mixtures at
C and E.There are infinite numbers of such tie lines. The point C on the lower curve is a
saturated liquid while the point E on the upper curve is a saturated vapor .A point such
as D represents a two phase mixture, the relative amount of the two may be determined
by the inverse arm rule as below
Moles of C/Moles of E = DE/CD

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 Figure 1.3 Vapor liquid Equilibrium Curve
Let us consider a solution at L in a closed container which can be kept at a constant
pressure with the help of a piston. If the solution assumed to be entirely liquid at the
beginning is heated, the first bubble of vapor forms at C having the composition E richer
in the more volatile component. Hence the lower curve has been termed the bubble point
curve .The last drop vaporizes at K from K to O the vapor is being super-heated.
It may be noted that the mixture has been vaporized over a range of temperature between
the bubble point and dew point curves and not at a definite temperature.. If the mixture at
O is cooled the entire process is reversed. Condensation starts at K on the upper curve
which is therefore termed the dew point curve.
Boiling point diagrams as such are not used in distillation calculations. But equilibrium
distribution (x vs y) curves as shown in figure are generally used for the purpose.
Equilibrium curves may be may be drawn from boiling point diagrams by drawing several
tie lines between the bubble pont curve and dew point curve of the boiling point diagram
and noting the values of x and y which are equilibrium values

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Vapor liquid Equilibrium at constant temperature (P-x-y diagram)

Figure 1.4 Vapor Liquid Equilibrium at constant temperature

The bubble point curve and the dew point curve extend from the vapor pressure of pure
B to that of pure A, but interchange their positions. As before there are infinite number of
horizontal tie lines such as MN which join an equilibrium vapor composition as at N to its
corresponding liquid composition at M. A solution in a closed container at P is entirely
liquid and if the pressure is reduced at constant temperature., the first bubble is found at
Q, complete vaporization occur at R and further reduction in pressure results in super-
heated vapor at S.
Raoult's Law
Raoult's Law states that, for an ideal solution, the equilibrium partial pressure of a
component at a fixed temperature T equals the product of its vapour pressure
(when it is pure) and its mole fraction in the liquid:
According to this law
P’A = PA xA
And for binary system
P’B = PB xB = PB (1-xA) because we know that xA + xB = 1
For ideal gas mixture, the total pressure is the sum of the partial pressures
Therefor we can write
Total Pressure P = P’A + P’B

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P = PA xA + PB xB
P = PA xA + PB (1-xA )
Where P is the total pressure
PA and PB are the vapor pressure of component A and B
P’A and P’B are the partial pressure of component A and B.
Characteristics of Ideal Solution
 The average intermolecular forces of attraction and repulsion in the solution are
unchanged on mixing the pure liquids
 The volume of the solution varies linearly with composition
 There is neither absorption nor evolution of heat in mixing the liquids
 The total vapour pressure of the solution varies linearly with composition (in mole
Relative Volatility
In order to separate a binary mixture using distillation process, there must be a differences
in volatilities of the components. The greater the difference, the easier it is to do so. A
measure for this is termed the relative volatility.
We define volatility of component-i as: partial pressure of component-i divide by mole
fraction component-i in liquid
For a binary mixture of A and B, therefore:
Volatility of A = P’A / xA
Volatility of B = P’B / xB
where P is the partial pressure of the component and x is the liquid mole fraction.
Relative volatility is the ratio of volatility of A (MVC) over volatility of B (LVC):
αAB = Relative volatility of A/ Relative volatility of B = (P’A / xA)/( P’B / xB)
αAB = (P’A xB) / ( P’B xA) ---1
From Raoults law we can write P’A = PA xA and P’B = PB xB
Substitute the above value of partial pressure in the equation of relative volatility
Then αAB = PA xA xB / PB xB XA
αAB = PA / PB
Therefore relative volatility of two substances forming an ideal solution is the ratio of their
vapor pressure.

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We know that P’A = PyA and P’B = PyB
We substitute this value in equation 1 and we get
αAB = PyAxB / PyBxA =( yA/yB )/( xA/ xB)---2
The relative volatility is the ratio of concentration ratio of A to B in the vapor phase to that
in the liquid phase
αAB = ( yA/yB )/( xA/ xB)
From equation no 2 we can write
αAB = yAxB / yBxA ------3
we know that xB = 1-xA and yB = 1 – yA because we know that yA + yB = 1
We substitute the above value in equation no 3
αAB = yA (1-xA) / (1-yA) xA
After simplifying we get
yA = αAB xA/ [1 +( αAB – 1) xA]
Dropping subscript we get
y= α x/ [1 +( α – 1) x]
When α = 1.0, no separation is possible: both component-A and component-B are
equally volatile. They will vapourise together when heated. Solving the above equation
for α = 1..0, we obtain: y = x.
The larger the value of a above 1.0, the greater the degree of separability, i.e. the easier
the separation. Recall that when a system has reached equilibrium, no further
separation can take place - the net transfer rate from vapour to liquid is exactly balanced
by the transfer rate from liquid to vapour. Therefore, separation by distillation is only
feasible within the region bounded by the equilibrium curve and the 45 o diagonal line.
From the equilibrium curve, we see that the greater the distance between the
equilibrium curve and the diagonal line (where y = x), the greater the difference in liquid
and vapour compositions and therefore the easier the separation by distillation. This is
shown in the Figure below:

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The Figure below showed several equilibrium curves with different values of the relative
volatility. Note that the greater the value of a, the greater is the separation area.

Positive and Negative deviations from ideal behavior

Deviation from ideal behavior can be classified as positive or negative, depending on
whether the total pressure exerted by the solution is greater or less than , that predicted
by Raoults law
Recall that for an ideal solution, the total pressure varies linearly with liquid molfraction
that is a straight line relationship. The greater the departure from a straight line, the
greater is the deviation from the ideal behavior. The non-ideal behavior is best
demonstrated using constant temperature phase diagrams.
When the total pressure of a system at equilibrium is less than the ideal value the system
is said to deviate negatively from Raoul’s law. In this case the activity coefficients for both
A and B are less than 1 and the P vs x lines are located below the straight lines provided

9
by Raoul’s law. The partial pressure of each component are smaller than ideal and the
total pressure curve PT vs. x is located below the straight line for ideal solution.
A mixture whose total pressure is greater than that computed for ideality is said to show
positive deviations from Raoults law. Most mixtures fall into this category.
In this case the activity coefficients are greater than 1 and the P vs x line are located
above the straight lines provided by Raoults law. The partial pressures of each
component are larger than ideal and the total pressure curve P T vs x is located above the
straight line for ideal solution.
Causes of non-ideal behavior
Molecules that are dissimilar enough from each other will exert repulsive forces. For
example, polar water molecules are strongly repulsed by organic hydrocarbon molecules.
The repulsive forces result in activity coefficients greater than unity, since the molecules
tend to leave the liquid phase.
A greater partial pressure will be exerted, leading to a positive deviation from ideality. On
the other hand if the molecules of the components attract each other strongly. The activity
coefficients will be less than unity (but still greater than zero) and less molecules will leave
the liquid phase. The mixture will exert lower partial pressure and producing a negative
deviation from ideality.
Azeotrope Mixture
Azeotrope is a special class of liquid mixture that boils at a constant temperature at a
certain composition. At this condition, it behaves as if it was one component with one
constant boiling point.
A boiling liquid mixture at the azeotropic composition produces a vapour of exactly the
same composition, and the liquid does not change its composition as it evaporates.
Two types of azeotropes are known: minimum-boiling and maximum-boiling (less
common). One of the best known minimum-boiling azeotrope is the ethanol-water
system which at 1 atm occurs at 89.4 mole percent ethanol and 78.2 oC. Other examples
are:
Minimum-boiling azeotropes
Example
A mixture of ethanol 95.63% and water 4.37%(by weight) ethanol boils at 78.4 0C water
boils at 100OC , but the azeotrope boils 78.20C , which is lower than either of its
constituents. Actually 78.20C is the minimum temperature at which any ethanol/water
solution can boil at atmospheric pressure.
carbon-disulfide - acetone (61.0 mole% CS2, 39.25 oC, 1 atm)
benzene - water (29.6 mole% H2O, 69.25 oC, 1 atm)

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Maximum-boiling azeotropes
Example
HCl at a concentration of 20.2% and 79.8% water (by weight). HCl boils at 84 0 C and
water at 1000C, but the azeotrope boils at 110 0C, which is higher than either of its
constituents. The maximum temperature at which any HCl acid solution can boils is
1100C.
hydrochloric acid - water (11.1 mole% HCl, 110 oC, 1 atm)
acetone - chloroform (65.5 mole% chloroform, 64.5 oC, 1 atm)
Minimum-boiling azeotrope
When the positive deviations from ideality are sufficiently large, the mixture is said to
form a minimum-boiling azeotrope. The Figures below show the constant temperature
phase diagram (left) and constant pressure phase diagram plus equilibrium curve (right)
for a minimum-boiling azeotropic mixture of carbon disulfide (CS 2) and acetone. The
characteristic of such mixture is that the total pressure goes through
a maximum (constant temperature phase diagram), and therefore
the temperature goes through a minimum (constant pressure phase diagram), shown
as point L.

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 At point L, the concentration in the vapour phase is the same as the concentration in the
liquid phase ( y = x ), and a = 1.0. This concentration is known as the azeotropic
composition (0.61 mole fraction CS2). At this point, the mixture boils at a constant
temperature (39.25 oC under 1 atm) and without change in composition. On the
equilibrium diagram, it can be seen that at this point, the equilibrium curve crossed the
45o diagonal.
Maximum-boiling azeotrope
It occurs when the negative deviations are very large, and the total pressure curve in
this case passes through a minimum, giving rise to a maximum in the temperature (i.e.
boiling point). The Figures below show the constant temperature phase diagram (left) and
constant pressure phase diagram plus equilibrium curve (right) for a maximum-boiling
azeotrope mixture of acetone and chloroform.

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The azeotropic composition is 0.345 mole fraction acetone. Point L in the Figures is now
a minimum on the constant temperature phase diagram, and a maximum (64.5 oC, under
1 atm) on the constant pressure phase diagram. These azeotropes are less common than
the minimum type.

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Separation of Azeotropic Mixtures
Azeotropic mixtures cannot be easily separated by ordinary distillation methods. For
example, in the case of ethanol-water, one cannot recover more than 89.4 mole% ethanol
using ordinary distillation, as the mixture becomes azeotropic at this point. Other
separation techniques (such as azeotropic distillation) must be used.
SIMPLE (DIFFERENTIAL) DISTILLATION
We will consider a binary mixture of A (more volatile) and B (less volatile). The set-up is
as shown in the Figure below. The system consist of a batch of liquid (fixed quantity)
inside a kettle (or still) fitted with heating element or steam jacket, and a condenser to
condense the vapour produced. The condensed vapour is known as the distillate. The
distillate is collected in a condensate receiver. The liquid remaining in the still is known
as the residual.

A
simple material balance for the process is shown in the Figure below.

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In this process, subsequent collection of distillates (see Figure) will yield a lower
concentration of the MVC.

The concentration changes can be analysed using the phase diagram, and detailed
mathematical calculations carried out using the Rayleigh Equation.(it shows that how the
concentration and quantity are related)
The separation can be extended to several more stages by re-heating the distillate
collected, and collecting the new distillate, as shown in the Figure.

The distillate product from the second stage will be purer in A compared to the first stage,
but the quantity of distillate collected in the second stage is lower than that of the first
stage. As more stages are added, purer distillate product can be obtained, but the quantity
collected will be lower than the previous stage.
The Rayleigh Equation
The Rayleigh Equation is useful in the analysis of simple distillation, as it shows how the
concentration and quantity are related.

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As the process is unsteady state in nature, the derivation is based on a differential
approach to changes in concentration with time. The equation to be derived (known as
the Rayleigh Equation) shows the relationship between total moles remaining in the
still and the mole fraction of the more volatile component in the still.
[Similar equation can be obtained for the relationship between the total moles of distillate
and the mole fraction of the more volatile component in the condensate receiver]
Material Balance for the still: see the Figure below
L1 = initial moles of liquid originally in still
L2 = final moles of liquid remained in still
x1 = initial liquid composition in still (mole fraction of A)
x2 = final liquid composition in still (mole fraction A)
At any time t, the amount of liquid in the still is L, with mole fraction of A in the liquid being
x.
After a small differential time (t + dt) , a small amount of vapour dL is produced, and the
composition of A in the vapour is y (mole fraction). The vapour is assumed to be in
equilibrium with the residue liquid.The amount of liquid in the still is thus reduced from L
to (L - dL), while the liquid composition changed from x to (x - dx). See the Figure below:

Performing a material balance on A:

Initial amount in still = Amount left in still + Amount vaporized

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We have,
xL = (x - dx) (L - dL) + y dL
xL = xL - x dL - L dx + dx dL + y dL
Neglecting the term dx dL, the equation reduces to:
L dx = y dL - x dL
Re-arranging gives the following:

Integrating from L1 to L2, and from x1 to x2, we obtain the Rayleigh Equation:

If distillation starts with F moles of feed of concentration x F and continues till the
amount of liquid reduces to W moles (composition = x W) the above equation
integrated to give

In a more convenient form we can write above equation as

ln[ FxF / WxW] = α ln [F(1-xW) / W(1-xF)]
FLASH (EQUILIBRIUM) DISTILLATION
A single-stage continuous operation where a liquid mixture is partially vaporized:
the vapour produced and the residual liquid are in equilibrium, which are then separated
and removed. See the Figure below:
Principle of Flash Distillation (Equilibrium distillation)

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The separation using flash distillation is based upon the flash vaporization. In flash
vaporization hot liquid mixture when passes from high-pressure zone to low-
pressure zone suddenly get vaporized. Reduced pressure reduces the boiling point
which leads to the vaporization of the liquid. The energy for vaporization is taken
up from the liquid itself, which causes a decrease in temperature. The molecules in
the vapour phase with low boiling points get condensed while high boiling point
molecules remain as vapour. The vapour and condensed liquid fraction remain in
contact till saturation. The liquid falls at the bottom and is collected whereas
vapours are further allowed to condense.

We start with a binary mixture of the components A and B . If the flow rate , the
composition, and enthalpy of the feed , the condensed top product and bottom
product are denoted as ( F , xF ,HF, ) ,(D, xD HD ) and (B,xB, HB) respectively and Q is
the rate of supply of heat to the heat exchanger, we may write the following
material and energy balance equations for a steady state equilibrium vaporization
unit.

Total material balance F = D + B -----1

Component balance F xF = DxD+ BxB------2

Enthalpy balance F HF + Q = DHD + B HB ------3

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Application
(i) It is used in the petroleum industry for refining crude oil.
(ii) It is used in the desalination of ocean water by multi-stage flash distillation.
(iii) It can also be used for separation of heptane from octane.
Advantages:
(i) It is a continuous process.
(ii) The equipment is smaller than the multi-stage flash distillation.
(iii) The operating costs are low compared to multi-stage flash distillation.
Disadvantages:
(i) It is not effective in separating components of comparable volatility.
(ii) It is not suitable for two-component systems.
(iii) It is not an efficient distillation when nearly pure components are required, because
the condensed vapour and residual liquid contain both components to some extent.
Operating Line Equation for Flash Distillation

We again consider a binary mixture of A (MVC) and B (LVC). The feed is preheated before
entering the separator. As such, part of the feed may be vaporized. The heated mixture
then flows through a pressure-reducing valve to the separator. In the separator,
separation between the vapour and liquid takes place. How much of A is produced in the

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vapour (and remained in the liquid) depends on the condition of the feed, i.e. how much
of the feed is entering as vapour state, which in turn is controlled by the amount of heating.
In other words, the degree of vapourization affects the concentration (distribution) of A in
vapour phase and liquid phase.
There is thus a certain relationship between the degree of heating (vapourization) and
mole fraction of A in vapour and liquid (y and x). This relationship is known as
the Operating Line Equation.
We will consider the separation of a binary mixture of A (more volatile) and B (less
volatile).If no vapourization takes place, then the liquid leaving the separator will have
the same composition as the feed. If total vapourization occurs, the vapour will also
have the same composition as the feed. Clearly, for effective separation, there must be
some vapour-liquid mixture present. This means that there exists a certain relationship
between the extent of heating, and the concentration in the vapour and liquid streams.
Define f : molal fraction of the feed that is vaporized and withdrawn continuously
as vapour Therefore, for 1 mole of binary feed mixture, (1- f) is the molal fraction of the
feed that leaves continuously as liquid.
Let
yD = mole fraction of A in vapour leaving
xB = mole fraction of A in liquid leaving
xF = mole fraction of A in feed entering
As noted earlier, the distribution of A (and B) in the vapour and liquid phases (yD and xB)
depends on the amount of preheating that takes place. Based on the definition for f, the
greater the heating, the larger the value of f. If the feed is completely vapourised, then f
= 1.0 Thus, the value of f can varies from 0 (no vapourization) to 1 (total
vapourization).
To see how yD and xB changes when f change, we will use material balance to obtain a
so-called operating line equation, which relates the variables y D, xB and f.
From material balance for the more volatile component (A):
1. xF = f yD + (1 - f) xB
f yD = xF - (1 - f) xB
Re-arrange into the form y = f(x):

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From the above operating line equation, we see that for a given value of f, we will obtain
certain values for yD and xB respectively.
The fraction f depends on the enthalpy of the liquid feed, the enthalpies of the vapour and
liquid leaving the separator.
Dropping the subscript 'D' and 'B' gave the general operating line equation:

For a given feed condition, and hence the known value of f and xF, the above equation is
a straight line equation with slope -(1-f)/f and intercept xF / f. It gave the relationship
between two unknowns: x and y. We will again solve the equation graphically using
equilibrium curve.If we let x = xF, then thus, y = xF The operating line crosses the point
(xF, xF) for all values of f. This provides one point on the straight line. The other point can
be obtained from the intercept. With xF known, we can construct the operating line on the
equilibrium curve. Intersection between the operating line and the equilibrium
curve yield the values for yD and xB. This is shown in the Figure below.

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For a binary mixture with constant relative volatility, the intersection point can be
determined mathematically by simultaneously solving the operating line equation and
equilibrium curve equation, as given below
Analysis of Operating Line: Changes in Fraction Vapourised
Recall that the operating line equation for flash distillation is:

For a given feed composition, xF is fixed. When the fraction of feed vapourised is
changed, the mole fraction MVC in the vapour and liquid
products changes accordingly. The left Figure below shows how the mole fraction
changes on an equilibrium diagram, and the right Figure below shows the temperature
and mole fraction changes on a phase diagram.

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Vacuum Distillation
Vacuum distillation is distillation performed under reduced pressure, which allows the
purification of compounds not readily distilled at ambient pressures or simply to save time
or energy. This technique separates compounds based on differences in their boiling
points. This technique is used when the boiling point of the desired compound is difficult
to achieve or will cause the compound to decompose. Reduced pressures decrease the
boiling point of compounds.

This method of distillation is very much similar to conventional distillation except that it
operates at very low (near vacuum) pressure. This method of distillation allows the
mixture to boil at a lower temperature and thus avoids the thermal degradation
problem mentioned earlier.
Vacuum distillation has several advantages. Close boiling mixtures may require
many equilibrium stages to separate the key components.
One tool to reduce the number of stages needed is to utilize vacuum distillation.
Vacuum distillation can improve a separation by:
 Prevention of product degradation or polymer formation because of reduced
pressure leading to lower tower bottoms temperatures,
 Reduction of product degradation or polymer formation because of reduced mean
residence time especially in columns using packing rather than trays.
 Increasing capacity, yield, and purity.
Another advantage of vacuum distillation is the reduced capital cost, at the expense of
slightly more operating cost. Utilizing vacuum distillation can reduce the height and
diameter, and thus the capital cost of a distillation column.

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In addition, to handle the larger volume of vapours that result from distillation at reduced
pressure, a vacuum distillation column usually have fairly large diameter and tray
spacings.
Steam Distillation
Steam distillation are widely used in the manufacturing of essential oils, for instance
perfumes. This method uses a plant material that consists of essential oils. Mainly orange
oil is extracted on a large scale in industries using this method.
Process Description
1 Water is heated creating steam
2 The steam passes through the plant material pulling out the oil
3 The oil rises with the steam
4 The condenser cools the steam
5 The oil rises to the top of the water and is extracted in the separator
6 The left over floral water can also be used in beauty and home products.

Steam distillation refers to a process in which live steam is in direct contact with the
distilling system in either batch or continuous operation. The basis of steam distillation
rest on the fact that water forms immiscible mixtures with most organic substances,
and these mixtures will boil at a temperature below that of either water or the other
materials. This is a very desirable feature, especially if the organic compound has a high
boiling point at which it may be unstable or decompose.

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As long as liquid water is present, the high boiling component will vapourise at a
temperature well below its normal boiling point.
Steam is widely used because of its energy level, cheapness, and availability.
Steam distillation is commonly used in the following situations:
(1) To separate relatively small amounts of volatile impurity from a large amount of
material
(2) To separate appreciable quantities of higher-boiling materials
(3) To recover high-boiling materials from small amounts of impurity which have a higher
boiling point
(4) Where the material to be distilled is thermally unstable or reacts with other components
associated with it at the boiling temperature
(5) Where the material cannot be distilled by direct heating even under low pressure
because of the high boiling temperature
(6) Where direct-fired heaters cannot be used because of fire hazards
Application of steam distillation
Distillation with steam is used extensively to extract natural products from parts of
plants, e.g., in the production of Lemongrass oil, orange oil and Eucalyptus oil. In this case,
a lab-scale distillation apparatus may be used
What is Molecular distillation?
It is special liquid-liquid separation technology, which is quite different from fractional
distillation. In molecular distillation we make use of the difference of molecular mean free
path of different substances.
What is Molecular Mean Free Path?
As we understand molecular mean free path is the average path travelled by a molecule
between two strikes.
The Process
In molecular distillation the liquid to be distilled is made to flow in a very thin layer in
laminar flow on a heated surface. Due to heating, the liquid molecules go into vapor
phase. Because of difference in mean free paths the lighter molecules will travel farther.
A condensation surface is placed at an appropriate distance. Lighter molecules having
longer mean free path are able to travel to the condensation surface where they condense
and are guided on a separate path and removed. Heavy particles in the meantime stay
close to the heated surface and are guided on a different path, separating the two. This
process is carried out in vacuum (pressure around .01 torr and below)

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Applications examples in Pharmaceutical:

 I t is used in the purification of substances low volatility as in separation of vitamin

A and vitamin E from fish lever oils.
 It is also used to enrich borage oil in γ-linolenic acid (GLA)
 It also to recover tocopherols from deodorizer distillate of soybean oil (DDSO
The difference between molecular distillation and ordinary distillation.

Ordinary
Category Molecular Distillation
Distillation

Principle boiling point molecular mean free path

Reversibility Reversible Irreversible

Separation ability weak Strong

System
boiling point well below the boiling point
temperature

Degree of vacuum low High

Heating time long Short

Scope of thermal sensitivity, high viscosity, high boiling

ordinary substance
application point materials

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