Azeotropic Distillation

CHEN 4460 – Process Synthesis,

Simulation and Optimization

Dr. Mario Richard Eden

Department of Chemical Engineering
Auburn University

Lab Lecture No. 3 – Sequencing of Azeotropic Distillation Columns

October 2, 2012

Contains Material Developed by Dr. Daniel R. Lewin, Technion, Israel

 Introduction
• When two or more components differ in boiling by less
than approximately 50C and form a nonideal liquid
solution, the relative volatility may be below 1.10.

• Then ordinary distillation may be uneconomic, and if an

azeotrope forms even impossible.

• In that event, the following separation techniques, referred

as enhanced distillation by Stichlmair, Fair, and Bravo,
should be explored:
– Extractive distillation
– Salt distillation
– Pressure-swing distillation
– Homogeneous azeotropic distillation
– Heterogeneous azeotropic distillation
– Reactive distillation
 Example 1
• Given that methyl acetate (1), which boils at 57.8C,
methanol (2), which boils at 64.7C and n-hexane (3),
which boils at 68.7C.

A. Sketch any boundaries across which the residue curves

cannot traverse.

B. Sketch the residue curves for three feed compositions:

Mole Fractions
Component I II III
1 0.70 0.15 0.15
2 0.15 0.70 0.15
3 0.15 0.15 0.7
 Example 1
• Note the existence of four azeotropes, where
compositions are in mol %:

Azeotrope T oC
Methyl acetate (65%), methanol (35%) Binary 53.5

Methanol (51%), n-hexane (49%) Binary 50.0

Methyl acetate (60%), n-hexane (40%) Binary 51.8
Methyl acetate (31%), n-hexane (40%), methanol (29%) Ternary 49.0
 Example 1 – Solution
 Plot pure components on
vertices with Tb
B oC
(2) 64.7
 Plot all azeotropes on 0 1
diagram with Tb
 Plot the residue curves

(3)
connecting all azeotropes, 0.2 0.8

ne
azeotropes & vertices, and

xa

<<
He
finally vertices & vertices

Me
<<
with arrow heads pointing

tha
0.4 0.6

no
towards increasing boiling 50oC

l (2
)
point temperatures
0.6 0.4
o 53.5oC
49 C

0.8 0.2

1 0
C oC 0
(3) 68.7 0.2 0.4 o
0.6 51.8 C 0.8 A oC
1(1) 57.8
MA (1) >>
 Example 1 – Solution
 Plot pure components on
vertices with Tb
(2) 64.7oC
 Plot all azeotropes on 0 1
diagram with Tb
 Plot the residue curves

(3)
connecting all azeotropes, 0.2 0.8

ne
azeotropes & vertices, and

xa

<<
He
finally vertices & vertices

Me
<<
with arrow heads pointing

tha
0.4 0.6

no
towards increasing boiling 50oC

l (2
)
point temperatures
0.6 0.4
 Plot additional residue 49 Co 53.5oC

curves that “arch” towards

intermediate temperatures 0.8 0.2
on the way to the end point

1 0
(3) 68.7oC 0 0.2 0.4 o
0.6 51.8 C 0.8
o
1(1) 57.8 C
MA (1) >>
Feed I
 Example 1 – Solution
 Plot pure components on
vertices with Tb
(2) 64.7oC
 Plot all azeotropes on 0 1
diagram with Tb
 Plot the residue curves

(3)
connecting all azeotropes, 0.2 0.8

ne
azeotropes & vertices, and

xa

<<
He
finally vertices & vertices

Me
<<
with arrow heads pointing

tha
0.4 0.6

no
towards increasing boiling 50oC

l (2
)
point temperatures
0.6 0.4
 Plot additional residue 49 Co 53.5oC

curves that “arch” towards

intermediate temperatures 0.8 0.2
on the way to the end point

1 0
(3) 68.7oC 0 0.2 0.4 o
0.6 51.8 C 0.8
o
1(1) 57.8 C
MA (1) >>
Feed III Feed I
 Example 1 – Solution
 Plot pure components on
vertices with Tb
(2) 64.7oC
 Plot all azeotropes on 0 1
diagram with Tb Feed II
 Plot the residue curves

(3)
connecting all azeotropes, 0.2 0.8

ne
azeotropes & vertices, and

xa

<<
He
finally vertices & vertices

Me
<<
with arrow heads pointing

tha
0.4 0.6

no
towards increasing boiling 50oC

l (2
)
point temperatures
0.6 0.4
 Plot additional residue 49 Co 53.5oC

curves that “arch” towards

intermediate temperatures 0.8 0.2
on the way to the end point

1 0
(3) 68.7oC 0 0.2 0.4 o
0.6 51.8 C 0.8
o
1(1) 57.8 C
MA (1) >>
Feed III Feed I
 Example 1 – Solution
 Plot pure components on
vertices with Tb
 Plot all azeotropes on
diagram with Tb
 Plot the residue curves
connecting all azeotropes,
azeotropes & vertices, and
finally vertices & vertices
with arrow heads pointing
towards increasing boiling
point temperatures
 Plot additional residue
curves that “arch” towards
intermediate temperatures
on the way to the end point
 Example 2
• A stream consisting of a mixture of A, an organic
component, and water, B, which forms an azeotrope. A
separation process is to be designed to obtain pure
products A and B. The plant manager suggests that you
investigate the possibility of using component C as MSA.
Component Boiling Temperature (K)
A 360
B 400
C 370

F Azeotrope I Azeotrope II Azeotrope III Azeotrope IV

A 40% 50% 55% 30%
B 60% 55% 45% 45%
C 50% 45% 25%
Temp 350 K 360 K 330 K 315 K
 Example 2

• Indicate the location of the azeotropes on a

ternary diagram, as well as representative residue
curves.

• Suggest a process for the separation of A and B

into pure products and show its operating lines on
the ternary diagram.

• Draw a PFD for your process. Indicate flow rates

of all internal and external streams as multiples of
the flow rate of F.
 Example 2 – Solution

360 K

III, 330 K
I, 350 K

IV, 315 K

II, 360 K C
400 K 370 K
 Example 2 – Solution

S2
360 K D1 D2
M1 S1
F
B2 M2

B1 B2

III, 330 K D1
I, 350 K
M2
F
D2 S2
M1
S1 IV, 315 K

B1
II, 360 K C
400 K 370 K