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,
Pi 0
 ij  0
Pj

αij – relative volatility,

Pi0 – vapor pressure of pure liquid i
 VLE Curve and BP/DP Curves
1
T
Saturated Vapor

Saturated Liquid

0 0
xA 1 xA 1

Mixture of A and B
 Homogeneous Azeotropes
For non-ideal mixtures, the yP  x P
1 1 1 1
S

activity coefficients are yP  x P

2 2 2 2
S

different from unity:

P  x  P  (1  x )  P
1 1 1
s

1 2 2
s

If   1 the mixture has a minimum-boiling

i minimum azeotrope

Phase diagrams for Isopropyl ether – Isopropyl Alcohol

 Homogeneous Azeotropes
For non-ideal mixtures, the yP  x P
1 1 1 1
S

activity coefficients are yP  x P

2 2 2 2
S

different from unity:

P  x  P  (1  x )  P
1 1 1
s

1 2 2
s

If   1 the mixture has a maximum-boiling

i maximum azeotrope

Phase diagrams for Acetone – Chloroform

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

 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

x
 L'  i dxi
ln '   
 L0  xio yi  xi

Liquid Charge
Heat

L’, xi – remaining liquid and mole fraction at any subsequent time

L’0, xi0 – initial liquid amount and mole fraction

 Rayleigh Distillation (Contd)
• For binary mixture when ij is constant
y i / xi
 ij 
yj / xj

 ij .xi
yi 
1  ( ij  1).xi

 L'  1  xi (1  xi 0 )   1  xi 0 
ln '  ln 
   1 x (1  x )   ln 
 1 x 
 L0  ij  i0 i   i 
 Batch Evaporation
Qc

Accum 1 Accum 2

Qr
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
Qc

1 L D

••
Accum 1 Accum n

Qr
 Column Configurations
Inverted BD

Qc
F

F Qr
Qr

Accum 1 Accum n
 Column Configurations
Middle Vessel BD
Qc
Qc

Accum 1 Accum n
F

F
Qr

Qr

Accum n+1 Accum m

 Dual Column Configuration
• Side stream from the 260

main column fed to a

Q2

second column
262

• Can be used for 2 266 270 217

mixtures with 3 or more

216

components Side
3 Column
Main 218

• Take advantage of the Column

219 222

build up of medium 1
220 B

volatile component in Q3 214

the column 232 223

224

• Eliminate slop cut

228
C

230 240
• Reduce cycle time, Q1

energy consumption
 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 Qc

 Condenser composition
1 L D
 Accumulator composition, amount ••

Accum 1 Accum n
 Reboiler composition, amount
N

Qr
 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 Qc

V1 – vapor rate
leaving plate 1
V
1 L D

L / V – Internal reflux ratio

Vj, yj Lj-1, xj-1
L / D – Reflux ratio

Mj, xj
N
Plate j

Lj , x j
Vj+1, yj+1
Qr
 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
 Benzene–toluene
 Benzene–toluene–ortho-xylene
 Acetone–chloroform
 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

V1  L0 (1  1 / R)
 Column Model
• Mass balance equations on plate j
dM j
 V j 1  L j 1  V j  L j
dt
d
( M j xi , j )  V j 1 . y i , j 1  L j 1 .xi , j 1  V j . y i , j  L j .xi , j
dt
• Constant volume holdup • Constant molar holdup

M j  G j . j M j  Aj
• VLE on each plate • Constraint
y i , j  K i , j .xi , j yi
i, j 1
 Column Model (Contd)
• Enthalpy balance equations on plate j
d
( M j H Lj )  V j 1.H JV1  L j 1.H Lj1  V j .H Vj  L j .H Lj
dt

• Physical properties

K ij  K ij ( x j , y j , T j , P )
H  H ( x j , T j , P)
L
j
L
j

H  H ( y j , T j , P)
V
j
V
j

 j   j ( x j , y j , T j , P)
 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

 Benzene–Toluene 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
Benzene–Toluene–O-Xylene

20 plates
Acetone–Chloroform
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
Components
Model Cut Sequence
Simulator
Developer For each cut:
• Starting and stopping criteria
• Reflux ratio
Verified Model

Operator Simulator DCS

Feed Amount Column

Feed Composition
 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