Chemical Engineering -

Separations 5
Lecture 6 – Separation of azeotropic
and close boiling mixtures

John Christy
 Types of difficult separation
• Azeotropes – vapour and liquid have same
composition so impossible to separate past
azeotrope in single column
• Close boiling mixtures – relative volatility
less than 1.1 leads to large number of stages
and high reflux ratio
• Mixtures with volatilities the wrong way
round, i.e. nearly all material must go
overhead, leading to high cost
 Means of improving separation
• Selectively modify relative volatility of
mixture so as to break azeotrope or increase
relative volatility of close-boilers.
• Achieve by:
– Changing pressure (often not practical)
– Adding mass separating agent (MSA)
• Use a ‘non-volatile’ solvent – Extractive Distillation
• Use an entrainer – the volatile entrainer usually is
chosen to form a heterogeneous ternary azeotrope –
Azeotropic Distillation
• For heterogeneous azeotrope, decant liquid
 Changing pressure

• Azeotrope composition may change with pressure

 Changing pressure

• Use higher P for initial separation, then use

azeotrope as feed to low pressure column
 Changing pressure

• By returning azeotropes into column operating at

different pressure, separation is possible
 Changing pressure

• If azeotrope composition varies only slightly with

pressure, then recycle flows are very large and
overhead flows are massive
• NB Azeotrope may disappear at high or low
enough P
 Heterogeneous Azeotropes

• If two liquid phases form, a decanter can be used to

separate D from C when azeotrope E is condensed
 Heterogeneous Azeotropes

x1 < ya < x2

• If z < x1, then obtain almost pure ‘lvc’ in bottoms

and heterogeneous azeotrope at top
 Heterogeneous Azeotropes

x1 < ya < x2

• If z > x2, then obtain almost pure ‘mvc’ in bottoms

and heterogeneous azeotrope at top
 Heterogeneous Azeotropes

x1 < ya < x2

eg butanol/water or phenol/water

• Combining
 Heterogeneous Azeotropes –
Pressure Effects

• Pressure alters difference in composition of two liquid

phases
 Heterogeneous non-Azeotrope

y
P2

P1

e.g.
mek/water

xL1 xz1 xL2 x

• Column 1 produces azeotrope distillate xz1 at P1 and x=0
bottoms
• Flash to P2 and decant xL2 to pump as feed to second column
at P1 whose distillate is xz1 and bottoms has x=1
 Use of Mass Separating Agents
• Can be used for close boiling mixtures,
homogeneous azeotropes and in order to
reverse volatilities
• If a relatively volatile MSA is used, it will be
chosen so that it forms an azeotrope (usually
min boiling) with either or both of the
original components (Azeotropic Distillation)
• If a non-volatile solvent is used, it will be
chosen to dissolve one component
preferentially, allowing other component to
leave in distillate (Extractive Distillation
 Azeotropic distillation
• Add substance that forms minimum boiling
azeotrope with one or both components.
• Take azeotrope off top and separate by
decanting or by solvent extraction
• May get binary or ternary azeotrope, either
homogeneous or heterogeneous
 Azeotropic distillation - examples
• Azeotropes
– Benzene/cyclohexane (74°C) use acetone to form
azeotrope with cyclohexane (53.1°C) and water
wash to recover acetone
– Ethanol/water – add benzene to form heterogeneous
ternary azeotrope (decant)
• Close Boilers
– Toluene/methylcyclohexane – add methanol to form
azeotrope with mch. Gives methanol/toluene in
bottoms (water wash)
– Butene/butadiene – add ammonia at 16bar – butenes
form heterogeneous azeotropes with ammonia
Azeotropic distillation - examples
• Reverse volatilities
– Paraffins/aromatics
• add methanol to take paraffins overhead. Water wash
then distill
• Add nitromethane to take paraffins overhead. Cool
and decant
Azeotropic distillation - examples

• Form heterogeneous ternary azeotrope with

benzene to separate ethanol/water
Azeotropic distillation - examples

• Form heterogeneous binary azeotrope of butene

with ammonia to separate butene/butadiene
 Azeotropic distillation - examples

• Form binary azeotrope of one component with

acetone to separate benzene/cyclohexane, then
use water to extract acetone from cyclohexane