Documente Academic
Documente Profesional
Documente Cultură
Azeotropes
S,S&L 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
Pi xi Psat
Homogeneous Azeotropes (Contd)
yP x P S
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
0.2 TBA
0.2 DTBP
0.6 H2O
Basics: The Lever Rule
Residue Curves
Distillation still
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
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 yn1 , 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 Vy
n 1 n 1 D n n
dh
n n 1
Substituting:
dx V D
x
n
y x n
dh L L
n n D
n 1 n 1
Try toluene
as an
entrainer
D1
M2 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
Some distillations are not Azeotropic and can be
accomplished relatively easily
Identify alternative separators
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)