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Cape Peninsula University of Technology

Department of Chemical Engineering
Chemical Engineering Technology 3B

DISTILLATION

1. Introduction

• Distillation is used in oil refining, wine & spirit

manufacture, the extraction of volatile oils from
plant matter, synthetic alcohol manufacture and air
separation.
• Here, we will gain insight into part of the design
process and the functioning of distillation columns.
• It is used to separate liquid or vapour mixtures into
fractions that are richer in the more volatile
components and those that are not.
• It may be assumed that all the components of all
solutions are volatile.
• Separations depend upon the distribution of a
particular component between a vapour and a liquid
phase.
• The phases differ by the amount of heat they
contain. This heat is, however, easily removed or
added by vaporisation or condensation.
• A distillation column provides a large number of
separate stages of vaporisation and condensation.
• A distillation column forms part of a distillation unit.
o It may have a heat exchanger that heats the feed
to the column, condensers, reboilers, pumps and
associated piping.
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o Distillation units usually operate in association

with several other distinct units.
o Distillation columns are compact and the use of
ground space is at a minimised. Typical sizes
are:
Diameter: 0,3 to 10 m
Height: 3 to 75 m

• Designers have to:

o Achieve desired product quality
o Minimise cost
o Provide constant purity of product with variation
in feed composition.

• When finding the number and size of trays

consider:
o Physical and chemical properties
of the fluid
o Fluid dynamics

2. Vapour Liquid Equilibrium

• An understanding of the equilibria existing between

the vapour and liquid phases of the mixtures is
essential.
• We will focus on binary mixtures of A and B. Where
A is for example benzene and B is toluene.
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• Assume that A is the more volatile component

(MVC)
o The vapour pressure of pure A at any
temperature is higher than that of B.
o The vapour pressure-temperature
relationship for each pure component of
the mixture is its vapour-liquid equilibrium.

• The additional variable of concentration must be

considered for binary mixtures.

• Mole fractions are the most convenient to use.

o y will represent the mole fraction of the
MVC in the vapour phase
o x will represent the mole fraction of the
MVC in the liquid phase.

• Complete graphical representation of the equilibria

requires a three-dimensional diagram. Constant
pressure and constant temperature diagrams can
then be extracted from this three dimensional
diagram. For distillation purposes it is easier to plot
y against x.

Revision of concepts:

2.1. Partial Pressures

PA = The pressure that would be exerted by
component A of a gas mixture if at the same
temperature and volume of the mixture.
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2.2. Dalton's Laws

PTOTAL = ΣinPi
PA = yAPTOTAL

2.3. Henry's Law

PA = HxA (H is Henry's Law constant.)

Henry’s Law holds for dilute solutions only.

2.4. Raoult's Law

PA = PAoxA
PAo = Vapour pressure of pure A at the same
temperature of the vapour mixture.
Raoult's Law applies for:
1. For high values of xA
2. Mixtures of organic isomers and some
hydrocarbons

If Raoult's Law is obeyed, the vapour pressure of a

mixture can be obtained graphically from knowledge of
the two pure component vapour pressures.

PA = PAoxA and PA = PyA

yA = PAoxA/P and yB = PBoxB/P

but yA + yB = 1 and xB = 1 - xA

therefore
PAoxA/P + PBo(1 - xA)/P = 1 and
xA = (P - PBo)/(PAo - PBo)

• Antoine equations are used to represent vapour

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pressure data: ln Pxo = A - B/(C + T).

• Dew point pressure of a binary mixture from

1
P=
Raoult's Law: y A / PoA + yB / PBo

• Bubble point pressure of a binary mixture from

Raoult's Law:

P = PBo + (PoA - PBo ) x A

3. The Fractionating Column

• The column consists of a cylindrical structure
divided into sections by a series of perforated trays
(Fig. 1.).
• The liquid reflux flows across each tray, over a weir
and downcomer to the tray below.
• Vapour rising from the top tray passes to a
condenser and then to some form of reflux divider
where part is withdrawn as product and the
remainder returned to the top tray as reflux.
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Notation

• V denotes the total molar flowrate of a vapour

stream (Fig. 2)
• L denotes the total molar flowrate of a liquid stream
• y is the mole fraction of the MVC in the vapour
phase
• x is the mole fraction of the MVC in the liquid phase
• The subscripts of V, L, y and x denote the plate
from which the stream comes.
• W, rich in the less volatile component (LVC) is
drawn off from the reboiler.
• Vapour from the top plate is condensed to give a
product stream D and a reflux stream R.
• The feed is introduced on some intermediate plate
where the liquid has approximately the same
concentration as the feed.
• The part of the column above the feed plate is
known as the rectifying section.
• The part of the column below the feed plate is
known as the stripping section.
• On an ideal plate the vapour rising from it will be in
equilibrium with the liquid leaving the plate.
However, a smaller degree of enrichment will occur
In practice.
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Fig.1 Schematic layout of a distillation column.

Fig.2. Schematic representation of the flows in a distillation column.

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NB The vapour rising from a plate and the reflux flowing

to it are not in equilibrium. i.e. Streams passing
one another in a distillation column are not in
equilibrium.

• On each plate the system tends to equilibrium

because:
1. Some LVC condenses from the rising vapour
into the liquid, thus increasing the
concentration of the more volatile component in
the vapour.
2. Some MVC is vaporised from the liquid on a
plate, thus decreasing the concentration of the
MVC in the liquid.

3.1. Principle of Equimolar Counterdiffusion

The number of moles passing from the vapour to liquid
stream and liquid to vapour stream on a particular ideal
plate will be approximately the same.

3.2. Number of Plates Required in a Distillation Column

1. Heat and material flows over the plate,
condenser and reboiler must be established.
2. Thermodynamic data is required to establish
how much mass transfer is needed to establish
equilibrium between the streams clearing each
plate.
3. Column diameter is dictated by the desired
flowrates and to operate within the available
pressure drop while ensuring proper mixing.
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• Four streams are involved in heat and mass

transfer on a particular plate:
Ln Ln-1 Vn Vn+1
• The plate brings Vn and Ln to equilibrium.
o Vn has a composition of yn and Ln has a
composition of xn.
• For plate n:
o Some MVC is vaporised from Ln+1, decreasing
its concentration to xn
o LVC is condensed from Vn-1 increasing the
vapour concentration to yn.
o The heat to vaporise the MVC from the liquid is
supplied by partial condensation of vapour Vn-1.

Summary:

MVC passes from the liquid going down to the

vapour going up.
LVC passes from the vapour going up to the liquid
going down.

4. McCabe-Thiele (M&T) Method

• Simplifying assumptions:
1. Constant molar heat of vaporisation of all
mixtures (Principle of equimolar
counterdiffusion).
2. No heat losses.
3. No heat on mixing.

• This leads to: Vn = Vn+1 (Vm = Vm+1)

Ln = Ln+1 (Lm = Lm+1)
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• Using these assumptions the following equations

are obtained:

(1) yn = (Ln/Vn)xn+1 + (D/Vn)xd

(2) ym = (Lm/Vm)xm+1 - (W/V)xw

• These equations represent straight lines and may

be drawn on the same diagram as an equilibrium
curve to give a simple graphical solution for the
number of stages required for a particular
distillation.

• Now let us examine the above equations more

closely. Consider the equation of the top operating
line (TOL), eq. (1):
o Put xn = xd (Remember that: Ln + D = Vn)
yn = (Ln/Vn)xd + (D/Vn)xd
= xd
i.e. yn = xd

The top operating line (TOL) therefore passes

through the point yn = xd.

• What is the y intercept of this line?

o xn+1 = 0
o yn = 0 + (D/Vn)xd
= (D/Vn)xd

The TOL therefore passes through the two easily

determined points: (xd, xd) and (0, Dxd/Vn)
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The second point is also (0, xd/(R+1))

• Consider the equation of the bottom operating

line (BOL), eq. (2):

Put xm+1 = xw
ym = (Lm/Vm)xw - (W/V)xw
i.e. ym = xw (Vm = Lm -
W)

The BOL therefore passes through (xw, xw) and

has a slope of Lm/Vm.

• When the two operating lines have been drawn on

the equilibrium curve (EC), the number of stages
required may be found by drawing steps between
these lines and the EC.

• Note that the assumption of constant molal overflow

is not too limiting since in very few systems do the
molar heats of vaporisation differ by more than
10%.

4.1. Enrichment in still and condenser

• Some enrichment of the vapour in MVC takes place

in the still or reboiler.
• Some enrichment of the liquid in the LVC takes
place in the condenser. Therefore:

Reboiler + Condenser = 1 ideal plate

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4.2. The Intersection of the Operating Lines

• Let us now consider the intersection point (xq, yq), of

the two operating lines (OL):

1 Vnyq = Lnxq + Dxd

2 Vmyq = Lmxq - Wxw
2-1 yq(Vm - Vn) = (Lm - Ln)xq - (Dxd + Wxw) (eq.
A)

• We now find expressions for:

o (Vm-Vn), (Lm - Ln) and (Dxd + Wxw).

• Do a mole balance over the feed plate:

o F + Ln + Vm = Lm + Vn or
o Vm - Vn = Lm - Ln – F (eq. 1)

• For the feed plate:

Hf = enthalpy per mole feed
Hfs = enthalpy of one mole of feed at its boiling point

• The heat required to bring

the feed to its boiling point
= F(Hfs - Hf)

• The moles of vapour that condensed to the liquid

phase to provide this heat = F(Hfs - Hf)/λ
(λ is the molar heat of vaporisation of the vapour)

• This condensed vapour increases the liquid flow in

the stripping section of the column.
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• Mole liquid balance under the feed plate:

Lm = Ln + F + F(Hfs - Hf)/λ
or Lm - Ln = F[(λ + Hfs - Hf)/λ]

• Let q = (heat to be added or removed from one

mole of feed to convert it to a saturated
vapour)/(molar latent heat of feed)

• Then Lm - Ln = qF (eq. 2)

• eq. 2 may be substituted into eq.1:

o Vm - Vn = qF - F (eq. 3)

• Overall mole balance around the entire column:

o Dxd + Wxw = Fxf (eq. 4)

• Substitute equations 2, 3 and 4 into equation A

(difference equation):
o F(q - 1)yq = qFxq - Fxf or
o yq = [q/(q-1)]xq - xf/(q-1)
o This function is linear and represents the
equation of the q-line.
o If: xq = xf then yq = xf

i.e. The q-line passes through the point (xf, xf).

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• In summary:
o The locus of intersection points of the two
operating lines is a linear function with a slope
of q/(q-1) that passes through (xf, xf).

o The intersection on the x-axis is found as

follows: If yq = 0
then xq = xf/q

• The condition of the feed or q influences the slope

of the q-line, q/(q-1).
Slope of q-line
Cold liquid feed q>1
Feed at bubble point q=1
Feed partly vapour 0< q<1
Saturated vapour feed q=0
Superheated vapour feed q < 0

o For a cold liquid:

o For a superheated vapour:

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4.3. Reflux Ratio, R

• By definition: R = Ln/D
• Use this definition in the equation for the TOL:
yn = (Ln/Vn)xn+1 + (D/Vn)xd
then yn = [R/(R+1)]xn+1 + xd/(R+1)

• Note that from the last equation, that any change in

R modifies the slope of the TOL and alters the
number of ideal plates required.

• If R is known, the TOL can be obtained by

connecting the following two points:

(xd, xd) and (0, xd/(R+1))

i.e. Ln and Vn do not have to be calculated

to find the number of theoretical
plates.

• Note the special case of total reflux:

o Here D = 0
o TOL slope = maximum
o The number of theoretical plates required is at
a minimum.
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• As R decreases:
o the slope of the TOL decreases and more
stages are required to enrich the feed from xf to
xd.
o at some stage the number of plates becomes
infinite. This would correspond to the minimum
reflux ratio, Rm.

This work was extracted from:

COULSON, J.M. and RICHARDSON, J.F.: Chemical

Engineering, vol. 2, 3rd edn.
(Pergamon Press)

TREYBAL, R.E.: Mass Transfer Operations, 3rd edn.

(McGraw-Hill International Editions)