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SEQUENCING OF AZEOTROPIC

DISTILLATION COLUMNS

Ref: Seider, Seader and Lewin (2004), Section 7.5


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Introduction
Separation sequences are complicated by the
presence of azeotropes, often involving mixtures of
oxygenated organic compounds:
Alcohols
Ketones
Ethers
Acids
Water

In these cases, distillation boundaries limit the


product compositions of a column to lie within a
bounded region

Prevent the removal of certain species in high


concentrations

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Instructional Objectives
When you have finished studying this unit, you should:
Be able to sketch the residue curves on a tertiary
phase diagram
Be able to define the range of possible product
compositions using distillation, given the feed
composition and the tertiary phase diagram
Be able to define the PFD for a heterogeneous
azeotropic distillation system
Be able to define the PFD for a pressure swing
distillation system

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Homogeneous Azeotropes
At equilibrium:
_ V

_ L

f f

y P x f
V

yP xP
yP xP

1 1

2 2

P x P x P x P (1 x )P
s

1 1

2 2

1 1

P (P P ) x
s

At fixed temperature
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Homogeneous Azeotropes (Contd)

Example Phase diagrams


for benzene-toluene
mixture at 90 oC

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Homogeneous Azeotropes (Contd)


For non-ideal mixtures, the
activity coefficients are
different from unity:

yP x P
yP x P

1 1

2 2

P x P (1 x ) P
s

1 1

2 2

If 1 the mixture has a minimum-boiling


azeotrope
minimum
i

Example Phase diagrams for Isopropyl ether-Isopropyl alcohol

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Homogeneous Azeotropes (Contd)


For non-ideal mixtures, the
activity coefficients are
different from unity:

yP x P
yP x P

1 1

2 2

P x P (1 x ) P
s

1 1

2 2

If 1 the mixture has a maximum-boiling


azeotrope
maximum
i

Example Phase diagrams for Acetone-Chloroform

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Heterogeneous Azeotropes
For a minimum-boiling azeotrope with large deviation
from Raoults law
), phase splitting may
i ( 1, usually 7
occur and a minimum-boiling heterogeneous azeotrope
forms, having a vapor phase in equilibrium with two liquid
phases.

Homogeneous Azeotrope
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Heterogeneous Azeotrope
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Residue Curves

Distillation still

Mass balance on species j:


Lx ( L ) y (L L )( x x ), j 1,K , C 1
j

As L 0:
Lx y dL Lx Ldx x dL dLdx , j 1,K , C 1
j

Rearranging:

dx

dL / L

x y x (1 K {T, P, x, y })
j

dx

dt
9

x y
j

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Residue Curves (Contd)


dx

dt

x y
j

Residue curves for


zeotropic system

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Residue curves for


Azeotropic system
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Liquid Compositions at Total Reflux


Species balance on top n-1 trays:
L x Dx V y
n 1

n 1

Approximation for liquid phase:


dx
x x
dh
n

n 1

Substituting:
dx
V
D
x
y
x
dh
L
L
n

n 1

n 1

At total reflux, D = 0 and Vn = Ln-1


Stripping section of
distillation column

dx
x y
dh
n

The residue curves approximates the distillation curves at total reflux


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Distillation Curves
An exact representation of the distillation curve
(operating line) at total reflux can be calculated based on:
1- Between two adjacent stages: x n y n 1

n 0, 1,

2- On each stage: x n and y n lie at the ends of the equilibrium tie lines

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Comparison of Residue and Distillation Curves

When the residue curve is linear (as for binary mixtures), the
distillation and residue curves are coincide. Their differences
are pronounced in the regions with extensive curvature.
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Sketching Residue Curves (Exercise)


dx

dt

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x y
j

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Product Composition Regions


for Zeotropic Systems

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Product Composition Regions


for Azeotropic Systems

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Heterogeneous Azeotropic Distillation


Example: Dehydration of Ethanol

Try toluene
as an
entrainer

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D1
M2
M1
S1
S2

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D2

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Pressure-swing Distillation

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Pressure-swing Distillation (Contd)


Example: Dehydration of Tetrahydrofuran (THF)
T-x-y diagrams for THF and
water

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Azeotropic Distillation - Summary


On completing this unit, you should:
Be able to sketch the residue curves on a tertiary
phase diagram
Be able to define the range of possible product
compositions using distillation, given the feed
composition and the tertiary phase diagram
Be able to define the PFD for a heterogeneous
azeotropic distillation system
Be able to define the PFD for a pressure swing
distillation system
Next week: HEN Synthesis
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