TKS 35444

Perancangan Proses Teknik Kimia

(Chemical Process Design)
Lecture 11
SEQUENCING OF AZEOTROPIC DISTILLATION COLUMNS
Semester Genap 2018/2019 (Kelas A)
Prodi Sarjana Teknik Kimia Universitas Riau
INTRODUCTION
Separation sequences are complicated by the presence of
azeotropes, often involving mixtures of oxygenated organic
compounds:
 Alcohols
 Ketones
 Ethers
 Acids
 Water
INTRODUCTION
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
 x
Binary Distillation
IPA-IPE
IPA/IPE

Mininum-boiling Azeotropes

x
Binary Distillation
Aceton/Chloroform
Aceton/Chloroform

Maximum-boiling
Azeotropes
Can multi-component Distillations have
Azeotropes?

•Yes! Possibly Multiple!

γLi
•Raoult’s Law
Pi  xi Psat
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, γjL> 1

• Maximum Boiling, γjL< 1
• Giving Rise to
• xj=yj, j=,1,2,…C
Homogeneous Azeotropes
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

Homogeneous Azeotropes
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

Two Types of Min. Boiling Azeotropes

• Homogeneous Azeotrope • Heterogeneous Azeotrope

A B A B

Overlay with Liquid/Liquid Separation

which is sometimes best separation method (costs much less)
Basics: 3-Phase Diagrams

0.2 TBA

0.65 DTBP

0.2 DTBP

0.15 H2O

TBA = Tertiary-butyl alcohol, TBHP =Tertiary-butyl hydroperoxide

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

0.2 TBA

0.2 DTBP

0.6 H2O

TBA = Tertiary-butyl alcohol

DTBP = Di-tertiary-butyl peroxide
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 /dť = 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
dx
j
  x y
dt
j j
Distillation

• XB, XF and YD form a line

for a Distillation Column
• Line can not cross Feasible For Partial
Region line Condenser

For Total
Condenser
Distillation Boundaries
• Equilibrium Trays in Total Reflux

dx Vn D
 xn  yn  y D  xn  yn , 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
• In Properties Choose Residue Curves

• In Simulation Choose Distillation Search

Residue Curves  Liquid Compositions
at Total Reflux
Species balance on top n-1 trays:
L x
n 1 n 1
 Dx  V yD 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 dxn
 x y
dh
n n
Nodes
Residue Curves
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
Ethanol/Water Distillation
with Toluene to Break
Azeotrope

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
 Example: Dehydration of Tetrahydrofuran (THF)

T-x-y diagrams for THF and water

question