Batch Distillation

Pharmaceutical API Process

Development and Design
Module Structure
Vapor Liquid Equilibrium Curves
Rayleigh Distillation
Column Configurations
Column Operation
Simulation
Design of Batch Columns


Distillation
Used for separating a mixture of two or
more liquids
Takes advantage of the differences in
volatilities (vapor pressure)
For a binary mixture,

0
0
j
i
ij
P
P
= o

ij
relative volatility,
P
i
0
vapor pressure of pure liquid i

VLE Curve and BP/DP Curves
y
x
A
0
1
1
0
1
T
Saturated Vapor
Saturated Liquid
Mixture of A and B
x
A
Homogeneous Azeotropes
For non-ideal mixtures, the
activity coefficients are
different from unity:
S
1 1 1 1
yP x P =
S
2 2 2 2
y P x P =
s s
1 1 1 1 2 2
P x P 1 x P ( ) = +
If the mixture has a minimum-boiling azeotrope
i
1 >
Phase diagrams for Isopropyl ether Isopropyl Alcohol
Homogeneous Azeotropes
For non-ideal mixtures, the
activity coefficients are
different from unity:
S
1 1 1 1
yP x P =
S
2 2 2 2
y P x P =
s s
1 1 1 1 2 2
P x P 1 x P ( ) = +
Phase diagrams for Acetone Chloroform
If the mixture has a maximum-boiling azeotrope
i
1 <
Heterogeneous Azeotropes
For a minimum-boiling azeotrope with large deviation from
Raoults law ( ), phase splitting may occur and a
minimum-boiling heterogeneous azeotrope forms, having a
vapor phase in equilibrium with two liquid phases.
i
1 >>
Homogeneous Azeotrope
Heterogeneous Azeotrope
Thermo Properties Calculations
Important properties of pure components,
mixtures
Vapor liquid equilibria
Y-X diagrams, T-X, T-Y diagrams
Existence of multiple liquid phases
Commercial packages
Part of process simulators
Activity++, PPDS etc
Helps you identify distillation boundaries
Rayleigh Distillation
Vapor
Liquid Charge
Heat
}

=
|
|
.
|

\
|
i
io
x
x
i i
i
x y
dx
L
L
'
0
'
ln
L, x
i
remaining liquid and mole fraction at any subsequent time
L
0
, x
i0
initial liquid amount and mole fraction
Rayleigh Distillation (Contd)
For binary mixture when o
ij
is constant

|
|
.
|

\
|

+
(

=
|
|
.
|

\
|
i
i
i i
i i
ij
x
x
x x
x x
L
L
1
1
ln
) 1 (
) 1 (
ln
1
1
ln
0
0
0
'
0
'
o
j j
i i
ij
x y
x y
/
/
= o
i ij
i ij
i
x
x
y
). 1 ( 1
.
+
=
o
o
Batch Evaporation
Q
c
Q
r
Accum 1 Accum 2
Batch Evaporation Example
Batch Distillation
Preferred method for separation when
Feed quantities are small
Feed composition varies widely
Product purity specification change with time
High purity streams are required
Product tracking is important
Feed has solids
Batch Distillation Advantages
Advantages
Flexible
Accurate implementation of recipe specific to a
given mixture
Several components separated using one column
Requires least amount of capital
Conventional Batch Distillation
Column
Q
c
Q
r
1
N
L D
Accum 1 Accum n

Column Configurations
Q
c
Q
r
Q
r
F
F
Inverted BD
Accum 1 Accum n
Column Configurations
Q
c
Q
r
Q
r
Q
c
F
F
Middle Vessel BD
Accum 1 Accum n
Accum n+1 Accum m
Dual Column Configuration
Side stream from the
main column fed to a
second column
Can be used for
mixtures with 3 or more
components
Take advantage of the
build up of medium
volatile component in
the column
Eliminate slop cut
Reduce cycle time,
energy consumption
Q1
C
Q2
A
262
260
270
232
228
240 230
B
Q3
2
1
3
266
216
217
218
219
Side
Column
Main
Column
223
224
220
222
214
Column Operation
Start-up period
Vapor boilup rate policy
Constant vapor boilup rate
Constant condenser vapor load
Constant distillate rate
Constant reboiler duty
Product period: Reflux ratio policy
Shutdown period
Column Operation
Operate under total reflux until the column reaches
steady state (L / V = 1, R = )
Change reflux ratio to the desired value
Collect distillate in accumulator
End the cut when certain criteria are satisfied
Duration
Condenser composition
Accumulator composition, amount
Reboiler composition, amount
Q
c
Q
r
1
N
L D
Accum 1 Accum n

Effect of Reflux Ratio
Increasing reflux ratio
Improves separation
Increases cycle time
Increases energy consumption
Profile optimization
Trade-off between cycle time and value of
recovered material
Maximize profit
Staged Separation
V
1
vapor rate
leaving plate 1
Q
c
Q
r
1
N
L D
L / V Internal reflux ratio
L / D Reflux ratio
Plate j
V
j
, y
j
V
j+1
, y
j+1
L
j-1
, x
j-1
L
j
, x
j
M
j
, x
j
V
Packed Columns
HETP Height equivalent to one
theoretical plate
Characteristic of packing
Number of plates = packed bed
height/HETP
Simulation of Batch Distillation
Simulation of startup period
Simulation of product period
Column model
Examples
Benzenetoluene
Benzenetolueneortho-xylene
Acetonechloroform



Simulation of Start-up Period
Dynamics of column during start-up are very
difficult to model
Rigorous model of tray hydraulics
Rigorous model of heating column internals
Typical simulation of start-up period
Run column under total reflux until column
reaches steady state
At the beginning, assume that liquid compositions
on plates and in the condenser are same as feed
composition
Simulation of Product Period
Total condenser without sub-cooling
Perfect mixing of liquid and vapor on plates
Negligible heat losses
Condenser material balance
) / 1 1 (
0 1
R L V + =
Column Model
Mass balance equations on plate j
j j
A M =
j j j j
j
L V L V
dt
dM
+ =
+ 1 1
j i j j i j j i j j i j j i j
x L y V x L y V x M
dt
d
, , 1 , 1 1 , 1 ,
. . . . ) ( + =
+ +
Constant volume holdup
j j j
G M . =
VLE on each plate
j i j i j i
x K y
, , ,
. =
Constant molar holdup
Constraint
1
,
=

i
j i
y
Column Model (Contd)
Enthalpy balance equations on plate j
L
j j
V
j j
L
j j
V
J j
L
j j
H L H V H L H V H M
dt
d
. . . . ) (
1 1 1 1
+ =
+ +
Physical properties
) , , , (
) , , (
) , , (
) , , , (
P T y x
P T y H H
P T x H H
P T y x K K
j j j j j
j j
V
j
V
j
j j
L
j
L
j
j j j ij ij
=
=
=
=
Solution of Dynamic Model
Vapor boilup rate from plate 1 is constant
Quasi steady-state approximation
During a small time interval, plate temperature, K values,
vapor and liquid flowrates remain constant
Solve the set of ODEs numerically up to the next
update interval
After each update interval, recompute
bubble point, K values, plate enthalpies
Vapor compositions
Reboiler composition from mass balance
Liquid and vapor flowrates from enthalpy derivatives
BenzeneToluene Distillation
Equimolar mixture of Benzene and Toluene
8000 liters charge
Vapor boilup rate 20 kmol/hr
Number of plates = 20
Plate holdup 4 liters
Condenser holdup 180 liters
Recover 99% mole fr Benzene and Toluene
Simulated using BDIST-SimOpt
Uses Activity++ physical properties package
BenzeneTolueneO-Xylene
20 plates
AcetoneChloroform
Azeotropic system
Use of Simulation in Batch
Distillation
Synthesis of operating recipe and rapid
characterization of batch distillations
Accurate determination of operating and
design parameters of a batch column
Use in column operation to determine cut
amounts and switching policy for each
batch
Role of Simulation in Column
Operation
Simulator
Verified Model
Simulator
Model
Developer
Operator
Feed Amount
Feed Composition
DCS
Column
Components
Cut Sequence
For each cut:
Starting and stopping criteria
Reflux ratio
Problems Related to Batch
Distillation
Design of a batch column
Operating policy determination for
individual column batches
Design and operation issues are
interdependent
Design of Batch Columns
Main design parameters
Number of stages
Vapor boilup rate
Diameter
Still capacity (batch size)
Reboiler and condenser size heat transfer areas
Single separation duty
Multiple separation duties