Batch Distillation

http://essentialspirits.com/history.htm
Early distillation of alcohol
Alembic still for distillation of brandy
History
Simple batch distillation Multistage batch distillation
Major types of batch distillation
Reasons to use batch distillation
1. Small capacity (e.g., specialty chemicals)
2. Intermittent need
3. Test run for a new product
4. Up-stream operations are batch (e.g., alcoholic spirits)
5. Feed inappropriate for continuous distillation (suspended
solids)
6. Feed varies widely in composition

Simple batch distillation
no rectification ( = no column)
Characteristics:

- no column; a single equilibrium stage
(= the still pot)
- single charge (F) to still pot at time = 0
- vapor is withdrawn continuously
- composition of liquid in still pot (x
W
)
changes continuously
- composition of liquid distillate (x
D
)
changes continuously

time t: W, x
W
V, y

D, x
D
time 0: F, x
F
still pot with heater
Rayleigh equation
TMB: F = W
final
+ D
total

time t: W, x
W
y = x
D
V, y

D, x
D
time 0: F, x
F
still pot, with heater
CMB: Fx
F
= W
final
x
W,final
+ D
total
x
D,avg

Specify F, x
F
and x
W,final
or x
D,avg

Leaves 3 unknowns:
W
final
, D
total
and x
W,final
or x
D,avg

Need one more equation:
dCMB: - x
D
dW = - d(Wx
W
)
(vapor withdrawn)

=

(change in still

pot
composition)
chain rule: - x
D
dW = - Wdx
W
- x
W
dW

dW
W
F
W
final

dx
W
x
D
x
W
x
F
x
W,final

Rayleigh equation
where x
D
= f(x
W
)


K
y
D
x
W

x
D
x
W
WAIT! K is not constant;
K = K(T)
Integration of the Rayleigh equation

dW
W
F
W
final

dx
W
x
D
x
W
x
F
x
W,final

dx
W
x
D
x
W
x
W,final
x
F

x
D,avg

Fx
F
W
final
x
W,final
F W
final
y
D
x
D

x
W
1+( 1)x
W
Constant relative volatility:
area
dx
W
x
D
x
W
x
W,final
x
F

Simpsons rule:
area f (x)
x
2
x
1
6
x
1
x
2

f x
1
( )
+ 4f
x
1
+ x
2
2

+f x
2
( )

1
/
(
x
D

x
D
)

x = x
W
Numerical integration:
ln
W
final
F

1
1
ln
x
W,final
1 x
F
( )
x
F
1 x
W,final
( )

+ln
1 x
F
1 x
W,final

W
final
Fe
Area
Specify F, x
F
, and either W
final
or x
W,final
.
D
total
F W
final
x
W,final


x
F
Solvent switching
using simple batch distillation
Goal: replace one solvent by another, in order to facilitate crystallization of a
non-volatile product, or for a subsequent reaction step.
The Hard Way:
1. Boil off most of original solvent in a batch still.
2. Add second solvent.
3. Perform second batch distillation to remove residual original solvent.
The Easy Way: Constant-level batch distillation
Add second solvent continuously as first solvent vaporizes, keeping W
constant; more energy efficient and uses less solvent.
dTMB: dV = dS
(vapor withdrawn)

=

(new solvent added)
dCMB: 0 - ydV = - x
D
dS = Wdx
W

(W constant)

dS
W
0
S

dx
W
x
D
x
W,final
x
F

S
W

ln
x
F
x
W,final

+
1

x
F
x
W,final
( )
Batch steam distillation
W, x
W
V, y

D, x
D
= 1

H
2
O(l)

s
t
i
l
l

p
o
t
,


n
o

h
e
a
t
e
r

steam
Used for thermally fragile organics (e.g., essential
oils in perfume industry), and for slurries/sludges
containing organics.

H
2
O(l)
(to waste)
How much steam is required?
n
H2O
n
org

y
H2O
y
org

P
H2O
P
org

P
total
P
org
*
x
W
P
org
*
x
W
Steam also needed to heat and
vaporize the material in the still pot.
Also, constant vapor composition.
Raoults Law: P
total
= P*
W
x
W
+ P*
H2O
Both H
2
O and organic vaporize well below their
single-component boiling points.
Fix P
total
, then T cannot vary!
constant T < T
bp
(H
2
O)
D.o.F. = 2 components 3 phases + 2 = 1
If W, D are immiscible with water, we have
a heterogeneous azeotrope.
A single charge (F) added to still pot at
time = 0. Steam is added continuously.
Batch distillation with rectification
TMB: V
j+1
= L
j
+ D
CMB: V
j+1
y
j+1
= L
j
x
j
+ Dx
D

both are time-dependent
either D or x
D
(or both) change over the
course of the distillation

time t: W, x
W
y
1
= x
0
= x
D
V
1
, y
1
D, x
D
time 0: F, x
F
still pot, with heater
stage N+1
L
0
, x
0
L
N
, x
N
V
N+1
, x
N+1
stage 1

y
1
K / x
W
stage N

V
j+1
, y
j+1
L
j
, x
j
stage j

CMO: V
j+1
= V
j
and L
j
= L
j-1


operating line equation:
y = (L/V) x + (1 - (L/V)) x
D

y = x = x
D
slope = L/V

actually a family of operating lines, since
L/V or x
D
(or both) change over the course
of the distillation

therefore the operating line moves on
the M-T diagram

Choice of operating methods
Constant reflux ratio (variable x
D
)
Constant distillate composition (variable R)
x
D
x
D

distillation must end
when (or before) x
D,avg
= x
F
distillation must end
when (or before) R = (L/V = 1)

Easy to monitor and control.
Harder to monitor and control (need to detect
x
D
on-stream and adjust R accordingly).
Can solve graphically, if we assume no liquid holdup on the column.
Multistage batch distillation with constant R
1. For an arbitrary set of x
D
values,
draw a series of parallel operating
lines, each with slope R/(R+1)

2. Step off N stages on each
operating line to find its
corresponding x
W
3. Perform numerical
integration:
plot 1/(x
D
-x
W
) vs x
W

limits: x
F
, x
W,final
4. Calculate W
final
using Rayleigh
equation



1

2

For N = 2 (incl.
reboiler)


Given F, x
F
, x
W,final
, R and N,
find D
total
, x
D,avg

x
D,4
x
D,1
x
D,2
x
D,3
5. Solve mass balances for
D
total
and x
D,avg
If x
D,avg
is specified instead of x
W,final
: guess x
W,final
, calculate x
D,avg
, iterate.

x
W,1


1

2

x
W,2


1

2

x
W,3


1

2

x
W,4
Operating time at constant R (D)


t
batch
t
operating
+t
down
t
operating

D
total
D

F W
final
V L

F W
final
V(1 L / V)


1 L/ V
1
R+1
t
operating

(R+1)
V
F W
final
( )


D
max

V
max
R+1
V = V
max
when vapor velocity u = u
flood
u
flood
depends on column diameter
typically, operate at D = 0.75 D
max
depends on vapor flow rate (V),
which depends on boilup rate
shut down, cleaning and
recharging still pot, restart
if the boilup rate is constant, then V is constant, and D will be constant
D
V
R+1
condenser TMB:
Calculating column diameter
We want to use the smallest diameter that will not cause the column to flood.


u
flood
C
sb,flood

20






0.2

L

V

V
where is surface tension,
L
and
V
are liquid and vapor densities, respectively.

C
sb,flood
is the capacity factor, depends on flow parameter FP and tray spacing;
obtain from graphical correlation.


diameter (feet )
4V MW
v
( )

V
u
op
(3600)
where is the fraction of the column cross-sectional area available for vapor flow
(i.e., column cross-sectional area minus downcomer area).
Multistage batch distillation with constant x
D
1. Draw trial op. lines and step
off N stages to end at x
F


This is trial-and-error, except for
N = 2, or N = (R
min
)

3. Find x
W,min
using (L/V) = 1.
Rayleigh equation not needed!
Verify x
W,final
> x
W,min
.

N = 2 (incl. reboiler)


x
D
4. Solve mass balance for W
final

and D
total
.

Given F, x
F
, x
D
(maybe) x
w,final
and N,
find R
initial
, R
min
, x
W,min N = , R = R
min

x
F

x
W.min

Operating time with constant x
D


dW
dt
F
x
D
x
F
x
D
x
w
( )
2
dx
w
dt

dW
dt

dD
dt
V L V(1 L/ V)
t
operating
F
x
D
x
F
V
dx
W
(1 L / V) x
D
x
w
( )
2
x
W,final
x
F

1. Draw a series of arbitrary operating lines, each with a different slope L/V

2. Step off N stages on each operating line to find its corresponding x
W
3. Perform numerical integration (plot graph, use Simpsons rule)

4. Calculate t
operating


W F
x
D
x
F
x
D
x
W
mass balance:
area
dx
W
(1 L / V) x
D
x
w
( )
2
x
W,final
x
F

x = x
W
Numerical integration:
x
W,final


x
F
1
(1 L / V) x
D
x
w
( )
2
Optimal control
usually, we can assume vapor holdup is negligible
liquid holdup causes x
w
to be lower than it would be in the absence of holdup
causes the degree of separation to decrease

To assess the effect on batch distillation:
measure the amount of holdup at total reflux
perform computational simulation
Effect of liquid holdup on the column
use optimal, time-dependent reflux ratio (not constant R, not constant x
D
)
more energy-efficient
useful for difficult separations