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Separation Trains

Azeotropes
Chapt. 8
What is an Azeotrope?
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
Prevents the removal of certain species in high
concentrations
Binary x

Distillation IPA-IPE

IPA/IPE
x

Mininum-boiling or
Maximum-boiling
Azeotropes

x
Can multi-component Distillations
have Azeotropes?

Yes!
Azeotrope Conditions
Conditions on the Activity Coefficient
PT x1 1L P1s (1 x1 ) 2L P2s
Lj 1, j 1,2...C , Positive Deviations from Raoult' s Law
Lj 1, j 1,2...C , Negative Deviations from Raoult' s Law

Minimum Boiling, jL> 1


Maximum Boiling, jL< 1
xj=yj, j=,1,2,C
Raoults Law

Pi xi Psat
Homogeneous Azeotropes (Contd)
yP x P S

For non-ideal mixtures, the 1 1 1 1

activity coefficients are yP x P


2 2 2 2
S

different from unity: P x P (1 x ) P


s s

1 1 1 1 2 2

If 1 the mixture has a minimum-boiling


i minimum azeotrope

Example Phase diagrams for Isopropyl ether-Isopropyl alcohol


Homogeneous Azeotropes (Contd)
yP x P S

For non-ideal mixtures, the 1 1 1 1

activity coefficients are yP x P


2 2 2 2
S

different from unity: P x P (1 x ) P


s s

1 1 1 1 2 2

If 1 the mixture has a maximum-boiling


i maximum azeotrope

Example Phase diagrams for Acetone-Chloroform


Importance of Physical Property
Data Set
In all cases
Need sophisticated liquid phase model to
accurately predict the activity coefficient for the
liquid.
For High Pressure Cases Only
Also need sophisticated (non-ideal) gas phase
fugacity model
Two Types of Min. Boiling Azeotropes

Homogeneous Azeotrope Heterogeneous Azeotrope

Overlay with
Liquid/Liquid Separation which is sometimes best separation method
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
Concepts Needed
Phase Diagram for 3 phases
Lever Rule on Phase Diagram
Residue Curves
Basics: 3-Phase Diagrams

0.2 TBA

0.65 DTBP

0.2 DTBP

0.15 H2O

TBA = Tertiary-butyl alcohol


DTBP = Di-tertiary-butyl peroxide
Basics: 3-Phase Diagrams (Contd)

0.2 TBA

0.2 DTBP

0.6 H2O
Basics: The Lever Rule
Residue Curves

Distillation still

Mass balance on species j:


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

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

dx
Rearranging: j
x y x (1 K {T, P, x, y })
dL / L
j j j j

dx j
x y
dt
j j
Multi-component Azeotropes
Residue Curve Map
dxj /d = dxj /d ln(L) = xj yj
Integrate from various starting points

Arrows from low to High Temp


Path of the residue composition
Sketching Residue Curves (Exercise)
dx
j
x y
dt
j j
Distillation
XB, XF and YD form a
line for a Distillation
For Partial
Column
Condenser
Line can not cross
Feasible Region line

For Total
Condenser
Distillation Boundaries
Equilibrium Trays in Total Reflux

dx Vn D
xn yn y D xn y n , for D 0, L n -1 Vn
dh n 1 Ln 1 Ln 1
Distillation Lines
xn yn 1 , for all n 0,1,...
xn and yn lie on equilibrium tie lines
Tangent to Residue Curve
To Create Residue Maps
AspenPlus
After putting in the components and selecting
the physical property method
Choose
Tools/Analysis/Property/Residue
Residue Curves Liquid Compositions
at Total Reflux
Species balance on top n-1 trays:
L x Dx V y
n 1 n 1 D n n

Approximation for liquid phase:


dx
x xn

dh
n n 1

Substituting:
dx V D
x
n
y x n

dh L L
n n D

n 1 n 1

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


distillation column dx
x y
n

dh
n n
Nodes
Residue Curves (Contd)
dx

j
x y
dt
j j

Residue curves for


zeotropic system
Residue curves for
Azeotropic system
Defining Conditions for Multi-
component Azeotrope

t goes from 0 to 1, ideal to non-ideal to find Azeotrope


Product Composition Regions
for Zeotropic Systems
Product Composition Regions
for Azeotropic Systems
Heterogeneous Azeotropic Distillation

Example: Dehydration of Ethanol

Try toluene
as an
entrainer

What are the zones of exclusion?


Ethanol/Water
Distillation with
Toluene to Break
Azeotrope

M2
D1
Distillation Line
M1
S1 Tie Line
S2
Ethanol/Water
Distillation with
Benzene
To Break
Azeotrope
How To Break Azeotropes with
Entrainer
Separation Train Synthesis
Identify Azeotropes
Identify alternative separators
Some distillations are not Azeotropic and can be
accomplished relatively easily
Select Mass Separating Agent or Entrainer
Identify feasible distillate and bottoms product
compositions
Residue Curve Analysis
Pressure Swing to
Break Azeotrope
Temp. of
Azeotrope
vs. Pressure

Mole
Fraction
of
Azeotrope
Pressure-swing Distillation (Contd)

Example: Dehydration of Tetrahydrofuran (THF)

T-x-y diagrams for THF and


water
Other Multi-component Distillation
Problems
Multiple Steady States
Run same distillation column with same set
points but different computational starting point
Get Two or More Different Results
Top or bottom compositions
This is real in that the column will have two
different operating conditions!
Happens most often with multi component
distillation