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Chapter 9

DISTILLATION- Part 2

Enshirah Da'na 1

DEVIATION FROM IDEALITY

Positive Deviation from Ideality
When the total pressure of a mixture is greater than that for ideal
mixtures computed using Raoult’s law, the mixture is said to exhibit
positive deviations from ideality.

Such mixtures are called minimum boiling

azeotropes.

At some composition the mixture shows

minimum boiling point (at constant pressure)
and maximum pressure (at constant
temperature).
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VLE of minimum boiling azeotrope at constant pressure.

Enshirah Da'na 3

Negative Deviations from Ideality

When the total pressure of a system is less than the ideal value as
computed using Raoult’s law, the system is said to deviate negatively.

Such systems are very rare and they are also called maximum boiling
azeotropes, at some composition the mixture shows maximum boiling
point.

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VLE of maximum boiling azeotrope at constant pressure.

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VLE of maximum boiling azeotrope at constant pressure.

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TYPES OF DISTILLATION COLUMNS

Batch Columns
The feed to the column is introduced
batchwise and the distillation is
carried.

When the desired quality is reached or

when the desired quantity is distilled
out, the operation is stopped and next
batch of feed is introduced.

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Continuous Columns
These columns have a continuous feed stream and are capable of
handling high throughputs.
These are further classified on the basis of:

• The nature of the feed they are further processing

Ø Binary columns—Feed has only two components
Ø Multicomponent column—Feed has more than two components

• The number of product streams they have

Ø Two product streams
Ø Multi product streams
Enshirah Da'na 9

• The use of additional components in distillation

Ø Extractive distillation—use of solvent

Ø Azeotropic distillation—use of entrainer

• The type of columns

Ø Tray columns—use of sieve plate columns/Bubble cap
trays/Valve trays for better vapour–liquid contacting
Ø Packed towers—use of packings in columns for better vapour—
liquid contacting.

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Enshirah Da'na 11

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STEAM DISTILLATION
Steam distillation can be a useful method of separating for:
v Systems with very high boiling points.

v Systems with substances that are unstable at high temperatures.

v Completely insoluble with each other.

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STEAM DISTILLATION
Some systems have very high boiling points and some of these substances
are unstable at high temperatures.
Especially when such systems are completely insoluble with each
other, steam distillation can be a useful method of separating
such mixtures.
For example, consider a mixture of hydrocarbon and water which are
immiscible.
The vapour pressure of either component cannot be influenced by the
presence of the other component and each exerts its own vapour
pressure at the prevailing temperature.
When the sum of the vapour pressures is equal to the total pressure, the
mixture boils. Enshirah Da'na 13

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With vapour pressure data of the individual components, one can also
estimate the temperature at which such distillations take place.
𝑷 𝑻 = 𝒑𝑨 + 𝒑𝑩
This distillation takes place at a temperature less than that of the
boiling point water.

This method suffers from poor efficiency in its operation, as large

quantity of water has to be evaporated.

Efficiency can be increased by:

Ø Operating at different total pressures in which case the ratio of
vapour pressure of the substances may be more favourable.
Ø Sparging the mixture with superheated steam or other insoluble gas.
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DIFFERENTIAL OR SIMPLE DISTILLATION

Feed F containing xF mole fraction of more volatile component fed into

a batch still.

L be the total moles present

in the still at any instant, t
and x be the mole fraction of
more volatile component.
dL be the moles distilled
out.

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The concentration of vapor in the leaving stream is y*.

The moles left behind in the still is (L – dL).
During this process the concentration of more volatile component left
behind in the still is (x – dx).

Total moles of more volatile

component present initially is Lx.

Total moles of more volatile

component in distillate is y*dL.

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Total moles of more volatile component in residue is (L – dL) (x – dx).

Making a component balance,

(Product of two very small quantities), Then:

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Integrating between limits:

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This equation is called Rayleigh’s equation.

The right-hand side cannot be integrated as y* is a function of x.

The right-hand side can be evaluated either graphically or

numerically with the help of x-y or VLE data.

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For systems where the relative volatility lies in a narrow range,

Hence, replacing y we get :

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Substituting the limits for x as xF and xW, we get

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EQUILIBRIUM OR FLASH DISTILLATION

Consider a feed at a flow rate of F (moles per hour), containing the more
volatile component with a composition of ZF and an enthalpy of HF (per
mole of feed) entering a preheater.

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Let the heat added in the preheater be Q.

The mixture then enters a flash chamber where a distillate leaves at a rate
of D (moles per hour) with a composition of yD and an enthalpy of HD (per
mole of distillate).
The bottoms (residue) leave at a rate of W, with a composition of xW and
an enthalpy of HW (per mole of residue).

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A total material balance, gives,

A component balance gives,

An enthalpy balance gives,

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From Eqs. (9.21) and (9.22), we get ,

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Similarly from Eqs. (9.21) and (9.23), we get

Dividing Eq. (9.25) by F, we get

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Let f be the fraction of feed vaporized and subsequently condensed

and removed.
(1 – f) is the fraction of feed left behind as residue.

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Eq. (9.30) is the operating line with a slope of [(f – 1)/f] and simplified
as,

The feed point is x = y = ZF

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Steps
Case I
When the equilibrium data and the either the distillate or the residue
and feed are available:

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· Draw the equilibrium curve

· Draw the diagonal (x = y)

· Locate feed point corresponding to xF on the diagonal (xF = yF = ZF)

· Draw the operating line with a slope of

[–W/D].

· The intersection of this line with

equilibrium curve gives xW and yD.

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Example 6
It is desired to separate a feed mixture containing 40% heptane and
60% ethyl benzene, such that 60% of the feed is distilled out. Estimate
the composition of the residue and distillate when the distillation
process is (i) equilibrium distillation, and (ii) differential distillation.
Equilibrium Data:

x, y: Mole fraction of heptane in liquid and vapor phase respectively.

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Solution
• Plot the equilibrium data and
draw the diagonal.

• Draw a line with a slope of –W/D =

– 0.4/0.6 = – 0.667 from a point on
the diagonal corresponding to xF =
0.4 and its intersection on the
equilibrium curve and read them as
xw and yD.

• xw = 0.24 and yD = 0.5

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• Compute 1/(y -x) and plot it against x :

• By trial and error, find the x which give the

area under the curve as 0.916 from xF = 0.4, xw
= 0.2.
• By making component balance, yD = 0.533.
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Case II
If the enthalpy–concentration data (HL vs x and HG vs y) and heat
added Q are available, then:
Ø Plot the enthalpy concentration data and
equilibrium curve below it.
Ø Locate the feed point corresponding to F(ZF,
HF + Q/F)

Ø Draw a tie line by trial and error, passing

through F.
Ø The points of intersection of this tie line with
enthalpy concentration curves gives the
enthalpy and concentration of both the
distillate and the residue. Enshirah Da'na 41

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MULTICOMPONENT SIMPLE DISTILLATION

Assume a multicomponent mixture fed to a still.
The distillate and the residue will be multicomponent mixtures.

For a three-component system wherein ∝ remains fairly constant.

Modified Rayleigh’s equation can be applied for material balance,

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Here, BPA < BPB < BPC, where BP is the boiling point.

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In a typical feed mixture, the values of F, xFA, xFB and xFC are known.

The unknown quantities will be W, D, xWA, xWB and xWC.

To solve, assume W.
By substituting in the first three equations, a relationship between
xWA, xWB and xWC is obtained.

Then it can be solved and checked for the validity of assumed value
of W using Eq. (9.35).

If not, a new value for W and repeat till Eq. (9.35) is satisfied.
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using the total material balance equation, D can be calculated and

then the mole fraction of each component in the distillate phase
(vapor phase) can be evaluated by making a component balance.

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Example 9

A liquid mixture of components A and B containing 30 mole percent A

is subjected to differential distillation. What percentage of the original
mixture must be distilled off in order to increase the concentration of A
in the residue to 65 mole percent? The relative volatility of B in respect
of A is 2.15.

Solution

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Therefore, if F = 100 kmol, W = 12.91 kmol. Hence, 87.09% of feed

has to be distilled.
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Example 10
Nitrobenzene (NB) has to be steam distilled. If the vaporization
efficiency is 85%, estimate the amount of nitrobenzene in the distillate if
100 kg of steam is present in distillate. The distillation takes place at a
total pressure of 760 mm Hg.
Vapor pressure data for nitrobenzene:

Vapor pressure of water:

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Solution
Boiling point of mixture = 99.0°C

At 99°C, vapor pressure of NB = 20 mm Hg

vapor pressure of water = 740 mm Hg

Vaporization 𝜼 = [(Actual NB/Actual water)]

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