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 50C 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 57.8C,
methanol (2), which boils at 64.7C and n-hexane (3),
which boils at 68.7C.

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