Introduction to multicomponent distillation

Most of the distillation processes deal with multicomponent mixtures

Multicomponent phase behaviour is much more complex than that
for the binary mixtures

Rigorous design requires computers

Short cut methods exist to outline the scope and limitations of a
particular process
Rigorous methods (Aspen)
Stage j
F
j
F
j
F
j j i j
T P h z F , , , ,
, j
Q
1 1
1 1 , 1
,
, , ,


j j
L
j j i j
T P
h x L
1 1
1 1 , 1
,
, , ,
+ +
+ + +
j j
V
j j i j
T P
h y V
j j
L
j j i j
T P
h x L
,
, , ,
,
j j
V
j j i j
T P
h y V
,
, , ,
,
j
U
j
W
(See my notes on the web)
Short-cut methods:

Fenske-Underwood-Gilliland
(+Kirkbride)
Introduction to multicomponent distillation
Multicomponent distillation in tray towers
Objective of any distillation process is
to recover pure products

In case of multicomponent mixtures we
may be interested in one, two
or more components

Unlike in binary distillation, fixing mole
fraction of one of the components in a
product does not fix the mole fraction of other
components

On the other hand fixing compositions of all
the components in the distillate and the bottoms
product, makes almost impossible to meet
specifications exactly
D
B
y
1
,y
2
,y
3
,y
4

Key components
In practice we usually choose two components
separation of which serves as an good indication
that a desired degree of separation is achieved

These two components are called key components

- light key
- heavy key


There are different strategies to select these key
components

Choosing two components that are next to each other
on the relative volatility: sharp separation
Distributed and undistributed components
Components that are present in both the distillate and
the bottoms product are called distributed components

- The key components are always distributed components

Components with negligible concentration (<10
-6
) in one
of the products are called undistributed
A B C D E G
key
components
heavy non-distributed components
(will end up in bottoms product)
light non-distributed components
(will end up in the overhead product)
Complete design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.

a) Design a distillation process
F, zf
condenser
boiler
n-pentane: 0.04
n-hexane:0.40
n-heptane: 0.50
n-octane: 0.06
100kmol/h
Complete design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.

- Design a distillation process
F, zf
condenser
boiler
n-pentane: 0.04
n-hexane:0.40
n-heptane: 0.50
n-octane: 0.06
100kmol/h
What is design of
a column?

- P (pressure)
- N (stages)
- R (reflux)
- D (diameter)
- auxilary
equipment
(condenser, boiler)
Complete short cut design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.
- Pressure consideration:

- what if you were not given P=1atm, how would you choose it?
- how do you validate that P=1atm is appropriate?
F, zf
condenser
boiler
- condenser uses cooling water
(20C). Let say the exit water
temperature is 30C.

- To maintain the temperature delta
at 10C, the dew point can not be
lower than 40C.

- Thus, the dew point of the distillate
has to be at least 40C.

- If not, will need higher pressure
Complete design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.

- Design a distillation process
F, zf
condenser
boiler
n-pentane: 0.04
n-hexane:0.40
n-heptane: 0.50
n-octane: 0.06
100kmol/h
LK
HK
HNK
LNK
Complete short cut design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.
x
F
F x
F
Moles in D x
D
Moles in B x
B
Ki
Pentane 0.04 4 3.62
Hexane 0.4 40 1.39
Heptane 0.5 50 0.56
Octane 0.06 6 0.23
100
- Material balance conisderations
LK
HK
HNK
LNK
Complete short cut design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.
x
F
F x
F
Moles in D x
D
Moles in B x
B
Ki
Pentane 0.04 4 3.62
Hexane 0.4 40 39.2 1.39
Heptane 0.5 50 0.5 0.56
Octane 0.06 6 0.23
100
- Material balance considerations
LK
HK
HNK
LNK
Complete short cut design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.
x
F
F x
F
Moles in D x
D
Moles in B x
B
Ki
Pentane 0.04 4 4 3.62
Hexane
LK
0.4 40 39.2 1.39
Heptane
HK
0.5 50 0.5 0.56
Octane 0.06 6 0 0.23
100
- Sharp split: components lighter than the Light Key (LK) will end up completely
in the overheads
- Material balance considerations
LK
HK
HNK
LNK
Complete short cut design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.
x
F
F x
F
Moles in D x
D
Moles in B x
B
Ki
Pentane 0.04 4 4 0.092 3.62
Hexane
LK
0.4 40 39.2 0.897 1.39
Heptane
HK
0.5 50 0.5 0.011 0.56
Octane 0.06 6 0 0 0.23
100 D=43.7
- Material balance considerations
LK
HK
HNK
LNK
Complete short cut design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.
x
F
F x
F
Moles in D x
D
Moles in B x
B
Ki
Pentane 0.04 4 4 0.092 3.62
Hexane
LK
0.4 40 39.2 0.897 0.8 1.39
Heptane
HK
0.5 50 0.5 0.011 49.5 0.56
Octane 0.06 6 0 0 0.23
100 D=43.7
- Material balance considerations
i
F
i i
Dy Fx Bx =
LK
HK
HNK
LNK
Complete short cut design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.
x
F
F x
F
Moles in D x
D
Moles in B x
B
Ki
Pentane 0.04 4 4 0.092 0 3.62
Hexane
LK
0.4 40 39.2 0.897 0.8 1.39
Heptane
HK
0.5 50 0.5 0.011 49.5 0.56
Octane 0.06 6 0 0 6 0.23
100 D=43.7 B=56.3
- Sharp split: components heavier than the Heavy Key (HK) will
end up completely in the bottoms
- Material balance considerations
LK
HK
HNK
LNK
Complete short cut design
A mixture of 4% n-pentane, 40% n-hexane, 50% n-heptane and 6%
n-octane is distilled at 1 atm. The goal is to recover 98%of hexane and
1% of heptane in the distillate. The feed is boiling liquid.
x
F
F x
F
Moles in D x
D
Moles in B x
B
Ki
Pentane 0.04 4 4 0.092 0 0 3.62
Hexane
LK
0.4 40 39.2 0.897 0.8 0.014 1.39
Heptane
HK
0.5 50 0.5 0.011 49.5 0.879 0.56
Octane 0.06 6 0 0 6 0.107 0.23
100 D=43.7 B=56.3
- Sharp split: components heavier than the Heavy Key (HK) will
end up completely in the bottoms
- Material balance considerations
LK
HK
HNK
LNK
Gilliland correlation: Number of ideal
plates at the operating reflux
|
|
.
|

\
|
+

=
+

1 1
min
D
Dm D
R
R R
f
N
N N
Gilliland correlation: Number of ideal
plates at the operating reflux
|
|
.
|

\
|
+

=
+

1 1
min
D
Dm D
R
R R
f
N
N N
N
min

R
min

R=1.5R
min
N

Fenske equation for multicomponent
distillations
Assumption: relative volatilities of components remain constant
throughout the column
1
ln
ln
,
,
,
,
,
min

(

=
HK LK
HK D
HK B
LK B
LK D
x
x
x
x
N
o
LK light component
HK heavy component
) (
) (
) (
,
T K
T K
T
HK
LK
HK LK
= o
Fenske equation for multicomponent
distillations
) (
) (
) (
,
T K
T K
T
HK
LK
HK LK
= o
Choices for relative volatility:
D
B
T
1) Relative volatility at saturated feed condition
) (
,
, F
F
HK LK
T
HK LK
o o =
2) Geometric mean relative volatility
) ( ) (
, ,
, B
B
D
D
HK LK
T T
HK LK HK LK
o o o =
3
,
) ( ) ( ) (
, , ,
B
B
D
D
F
F
HK LK
T T T
HK LK HK LK HK LK
o o o o =
why geometric mean?
Non key component distribution from
the Fenske equation
(
(

=
+
HK B
HK D N
HK i
i B
i D
x
x
x
x
,
, 1
,
,
,
min
o
HK
i
HK i
K
K
=
,
o
(

+
(

=
+
+
HK B
HK D N
HK i
HK B
HK D N
HK i i F
i D
Bx
Dx
Bx
Dx
Fx
Dx
,
, 1
,
,
, 1
, ,
,
min
min
1 o
o
Convince yourself and
derive for
i B
Bx
,
Minimum reflux ratio analysis
At the minimum reflux ratio condition
there are invariant zones that occur
above and below the feed plate, where
the number of plates is infinite and the
liquid and vapour compositions do not
change from plate to plate


Unlike in binary distillations, in
multicomponent mixtures these zones
are not necessarily adjacent to the feed
plate location
y
x
z
f
z
f
x
B
x
D
y
1
y
B
x
N
Minimum reflux ratio analysis
At the minimum reflux ratio condition
there are invariant zones that occur
above and below the feed plate, where
the number of plates is infinite and the
liquid and vapour compositions do not
change from plate to plate


Unlike in binary distillations, in
multicomponent mixtures these zones
are not necessarily adjacent to the feed
plate location
y
x
z
f
z
f
x
B
x
D
y
1
y
B
x
N
Minimum reflux ratio analysis
F, zf
condenser
boiler
Invariant zones: presence of heavy and light non-distributed
components
Minimum reflux ratio analysis
F, zf
condenser
boiler
Invariant zones: only light non-distributed
components
Minimum reflux ratio analysis
F, zf
condenser
boiler
Invariant zones: only heavy non-distributed
components
Minimum reflux ratio analysis
F, zf
condenser
boiler
Invariant zones: no non-distributed
components
Minimum reflux ratio analysis:
Underwood equations

=
i
HK i
i F HK i
x
q
| o
o
,
, ,
) 1 (

= = +
i
HK i
i D HK i
m
x
D
V
R
| o
o
,
, ,
1
For a given q, and the feed composition
we are looking for A satisfies this equation
(usually is between
LK
and
HK
)
Once is found, we can calculate the
minimum reflux ratio
|
|
Minimum reflux ratio analysis:
Underwood equations

=
i
HK i
i F HK i
x
q
| o
o
,
, ,
) 1 (
Minimum reflux ratio analysis:
Underwood equations

=
i
HK i
i F HK i
x
| o
o
,
, ,
0
1.48
Minimum reflux ratio analysis:
Underwood equations

= = +
i
HK i
i D HK i
m
x
D
V
R
| o
o
,
, ,
1
Minimum reflux ratio analysis:
Underwood equations

= = +
i
HK i
i D HK i
m
x
D
V
R
| o
o
,
, ,
1
1.48
2.33
x
i
1 2 3 4 5 6 7 8 9 10
hexane LK
heptane HK
octane
pentane
Feed stage
Distribution of components in
multicomponent distillation process
Non-distributed
heavy non-key
component
Non-distributed
Light non-key
component
Kirkbride equation: Feed stage location
206 . 0
2
,
,
,
,
(
(

|
|
.
|

\
|
|
|
.
|

\
|
=
D
B
x
x
x
x
N
N
HK D
LK B
LK F
HK F
S
R
Complete short cut design:
Fenske-Underwood-Gilliland method
Given a multicomponent distillation problem:

a) Identify light and heavy key components

b) Guess splits of the non-key components and compositions
of the distillate and bottoms products

c) Calculate

d) Use Fenske equation to find Nmin


e) Use Underwood method to find R
Dm


f) Use Gilliland correlation to find actual number of ideal stages
given operating reflux

g) Use Kirkbride equation to locate the feed stage

HK LK ,
o
Stage efficiency analysis
In general the overall efficiency will depend:

1) Geometry and design of contact stages

2) Flow rates and patterns on the tray

3) Composition and properties of vapour and
liquid streams
Stage efficiency analysis
L
in
,x
in
L
out
,x
out
V
out
,y
out
V
in
,y
in
Local efficiency
1
*
1
+
+

'
=
n n
n n
mv
y y
y y
E
Actual separation
Separation that
would have been
achieved on an
ideal tray
What are the sources of inefficiencies?

For this we need to look at what actually happens
on the tray
Point efficiency
Stage efficiency analysis
Depending on the location on the tray
the point efficiency will vary
high concentration
gradients
low concentration
gradients
stagnation points
The overall plate efficiency can
be characterized by the Murphree
plate efficiency:
1
*
1
+
+

=
n n
n n
mV
y y
y y
E
When both the vapour and liquid
phases are perfectly mixed the plate
efficiency is equal to the point
efficiency
mv mV
E E =
Stage efficiency analysis
In general a number of
empirical correlations exist
that relate point and plate
efficiencies
c e
L
Pe
t D
Z
N
2
=
Peclet number
length of liquid
flow path
eddy diffusivity residence time of liquid
on the tray
Stage efficiency analysis: OConnell (1946)
(Sinnott)
Stage efficiency analysis: Van Winkle (1972)
(Sinnott)
Stage efficiency analysis


- AICHE method

- Fair-Chan
Chan, H., J.R. Fair, Prediction of Point Efficiencies for Sieve Trays, 1. Binary Systems,
Ind Eng. Chem. .Process Des. Dev., 23, 814-819 (1984)

Chan, H., J.R. Fair, , Prediction of Point Efficiencies for Sieve Trays, 1. Multi-component Systems,
Ind Eng. Chem. .Process Des. Dev., 23, 820-827 (1984)

(Sinnott)
Stage efficiency analysis
Finally the overall efficiency of the process defined as





actual
l theoretica
O
N
N
E =
If no access to the data: E0=0.5 (i.e. double the number of plates)
Column diameter, etc
Sinnott,


Jim Douglas, Conceptual design of chemical process
Column diameter, etc
Column diameter, etc