054402 Design and Analysis II

LECTURE 5: SEQUENCING OF
AZEOTROPIC DISTILLATION COLUMNS

Daniel R. Lewin
Department of Chemical Engineering
Technion, Haifa, Israel
Ref: Seider, Seader and Lewin (1999), Section 5.6

1 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Steps in Process Design and Retrofit

Assess Primitive
Problem

Detailed Process Plant-wide

Synthesis - Development Controllability
Algorithmic of Base-case Assessment
Methods

SECTION B
Detailed Design,
Equipment sizing, Cap.
Cost Estimation,
Profitability Analysis,
Optimization

2 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Section B: Algorithmic Methods

3 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 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

4 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 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

5 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Basics: The Lever Rule

6 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Basics: 3-Phase Diagrams

0.2 TBA

0.65 DTBP

0.2 DTBP

0.15 H2O

7 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Basics: 3-Phase Diagrams (Cont’d)

0.2 TBA

0.2 DTBP

0.6 H2O

8 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Homogeneous Azeotropes
At equilibrium:
_ V _ L

f  f
j j

y P  x f
j
V
j j j j
L

yP  xP
1 1 1
s

yP  xP
2 2 2
s

P  x P  x P  x P  (1  x )P
1 1
s

2 2
s

1 1
s

1 2
s

 P  (P  P )x
2
s

1
s

2
s

At fixed temperature

9 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Homogeneous Azeotropes (Cont’d)

Example – Phase diagrams

for benzene-toluene
mixture at 90 oC

10 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Homogeneous Azeotropes (Cont’d)
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 azeotrope

i

Example – Phase diagrams for Isopropyl ether-Isopropyl alcohol

11 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Homogeneous Azeotropes (Cont’d)
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 azeotrope

i

Example – Phase diagrams for Acetone-Chloroform

12 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Heterogeneous Azeotropes

For a minimum-boiling azeotrope with large deviation from

Raoult’s law (   1 ), phase splitting may occur and a
i

minimum-boiling heterogeneous azeotrope forms, having a

vapor phase in equilibrium with two liquid phases.

Homogeneous Azeotrope Heterogeneous Azeotrope

13 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Residue Curves

Distillation still

Mass balance on species j:

Lx  ( L) y  (L  L)( x  x ), j  1, , C  1
j j j j

As L  0:
Lx  y dL  Lx  Ldx  x dL  dLdx , j  1, ,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

14 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Residue Curves (Cont’d)
dx

j
 x y
dt
j j

Residue curves for

zeotropic system
Residue curves for
Azeotropic system

15 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 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

Approximation for liquid phase:

dx
 x x n

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
n
 x y
dh
n n

16 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Sketching Residue Curves (Exercise)
dx
j
  x y
dt
j j

17 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Product Composition Regions
for Zeotropic Systems

18 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Product Composition Regions
for Azeotropic Systems

19 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Heterogeneous Azeotropic Distillation

Example: Dehydration of Ethanol

Try toluene
as an
entrainer

20 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 D1
M2

M1
S1
S2
D2

21 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Pressure-swing Distillation

22 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 Pressure-swing Distillation (Cont’d)

Example: Dehydration of Tetrahydrofuran (THF)

T-x-y diagrams for THF and water

23 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5

 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

24 DESIGN AND ANALYSIS II - (c) Daniel R. Lewin Azeotropic Distillation - 5