1

Distillation
A separation technique based on differences in boiling point
which results in differences in vapor pressure. It is covered by
chapter 11 in the text book.
Pages to be covered in the text 599-621
Partial pressure (P
A
) of component A is the pressure that A would exert at the same
temperature, if present in the same volumetric concentration as in the mixture.
Daltons law: Total pressure is equal to the sum of the partial pressures
=
i
P P
Raults law and Henrys law: Relates partial pressure to the liquid phase concentration
Raults law for high values of x
i
, and Henrys law for low values
i i i
x P P
o
=
i i
Hx P =
Raults: Henrys:
Partial pressures, and Daltons,
Raults and Henrys laws
Binary system: equilibrium
Relative volatility:
2
1
2
2
1
1
12
K
K
x
y
x
y
=
Where:
( )
( )
1 1
1 1
2
2
1
1
2
1
12
1
1
y x
x y
x
y
x
y
K
K

= = =
1
2 1
= + x x 1
2 1
= + y y and
( ) 1 1
12 1
1 12
1
+

=
x
x
y
( )
1 12 12
1
1
1 y
y
x

=

2
Vapor liquid equilibrium (VLE):
Binary system
Different types types of VLE
Distillatiom
F
n
, z
i,n
V
n
, y
i,n
L
n
, x
i,n
Stage n
V
n
, y
i,n
L
n
, x
i,n
L
n+1
, x
i,n+1
V
n-1
, y
i,n-1
Q
n
Column
Reboiler
Total-
condensor
F, x
F
W, x
W
D, x
D
rectifier
l
stripper
L
D
L
R =
Reflux
ratio
3
Column: Binary
Balances over the
whole column
Reboiler
Total-
condenser
F, x
F
W, x
W
D, x
D
L
Total balance: W D F + =
W D F
Wx Dx Fx + =
condenser W D
reboiler
F
Q Wh Dh
Q
Fh + + = +
Energy balance:
Component balance:
Equilibrium stage:
Binary
stage n
V
n
, y
n
V
n+1
, y
n+1
L
n
, x
n
L
n-1
, x
n-1
Total balance:
n n n n
V L V L + = +
+ 1 1
Energy balance:
Component balance: n n n n n n n n
y V x L y V x L + = +
+ + 1 1 1 1
n n n n n n n n
H V h L H V h L + = +
+ + 1 1 1 1
Equilibrium relation: ) (
n n
x f y =
Equilibrium stage:
Binary
steg n
V
n
, y
n
V
n+1
, y
n+1
L
n
, x
n
L
n-1
, x
n-1
It is assumed that there is constant molar overflow
Total balance:
V L V L + = +
Energy balance:
Component balance:
n n n n
Vy Lx Vy Lx + = +
+ 1 1
n n n n
VH Lh VH Lh + = +
+ 1 1
Equilibrium relation : ) (
n n
x f y =
4
Binary distillation: How many stages
are necessary for separation?
Reboiler
Total-
condenser
F, x
F
W, x
W
D, x
D
L
1. - Sorels method
algebraic
2. - McCabe-Thieles method
graphical
McCabe-Thieles mehtod
Constant molar overflow
upper operating line (system A)
F, x
F
W, x
W
D, x
D
y
m+1
x
m
y
n+1
x
n
A
B
y
L
V
x
D
V
x
n n D +
= +
1
R
L
D
=
V L D = +
L R D =
( ) V R D = + 1
y
R
R
x
R
x
n n D +
=
+
+
+
1
1
1
1
McCabe-Thieles mehtod
Constant molar overflow
Draw in the upper operating line
in the equilibrium diagram
y
R
R
x
x
R
n n
D
+
=
+
+
+
1
1 1
x
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
x
D
upper operating line
y
n+1
=x
D x x
n D
=
y
R
R
x x
n D D +
=
+
+
=
1
1
1
x
n
= 0
y
x
R
n
D
+
=
+
1
1
5
McCabe-Thieles metod
Lgg in driftlinjerna
(komponentbalanserna)
i jmviktskurvan
x x
m W
=
Undre driftlinjen
y
L
V
x
W
V
x
m m W +
=
1
x
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
x
D
upper operating line
x
W
lower operating line
V L W =
y
L W
V
x
m W +
=

1
y x
m W +
=
1
McCabe-Thieles mehtod: Stages
McCabe-Thieles method
Feed conditions
a Subcooled liquid
b Saturated liquid
c Mixture of liquid
and vapor
d Saturated vapor
e Superheated
vapor
ion vasporizat of Enthalpy
feed the of mole one vaporize to Enthalpy
q


=
6
q line
For a two phase feed (assumed in equilibrium)
F h
F
= L
F
h
L
+ V
F
h
v
where,
h
F
= specific enthalpy of feed
h
L
= specific enthalpy of saturated liquid
h
v
= specific enthalpy of saturated vapor
Generalize by defining q:
q = Enthalpy change req
d
to vaporize 1 mole of feed/
molar enthalpy of vaporization
= (h
v
- h
F
) / (h
v
- h
L
)
q > 1 Sub-cooled Liquid
q = 1 Saturated Liquid h
L
0 < q < 1 2-phase feed
q = 0 Saturated Vapor h
v
q<0 Superheated Vapor
Increasing
Specific
Enthalpy
McCabe-Thieles method
Feed condition on q-line
a Subcooled liquid
b Saturated liquid
c Mixture of liquid
and vapor
d Saturated vapor
e Superheated
vapor
Reflux ratio
7
Total reflux
Minimum reflux
Optimum reflux ratio is usually
1.2-1.5 times minimum
8
Merill R. Fenske, 1932
In the design of any (distillation) column it is important
to know at least two things. One is the minimum
number of plates required for the separation if no
product, or practically no product, is withdrawn from
the column. This is the condition of total reflux. The
other point is the minimum reflux that can be used to
accomplish the desired separation. While this case
requires the minimum expenditure of heat, it
necessitates a column of infinite height. Obviously, all
other cases of practical operation lie in between these
two conditions.
Multi-component distillation
The availability of large electronic computers
has made possible the rigorous solution of
the equilibirum-stage model for
multicomponent, multi-stage distillation
column to an exactness limited only by the
accuracy of the phase-equilibrium and
enthalpy data utilized.
Buford D. Smith, 1973
Binary vs. Multicomponent
distillation
Binary:
Unique equilibrium curve under constant pressure
Feed and distillate compositions for one
component known => bottoms product may be
choosen, D and W calculated by MB
Multicomponent:
Equilibrium depends on all components
Not same freedom of choice.
Complete composition of top and bottom product
cannot be fixed => trial&error calculations
9
Multi-component distillation
Component
1
2
3
4
5
.
.
.
LK (Light Key) primary goes overhead
HK (Heavy Key) primarily goes to bottoms
t ex
t e
x
HHK (Heavy Heavy Keys) main component in botten
LLK (Light Light Keys) main component in heads
Separation is between LK and HK
Ex: methanol, ethanol, n-propanol, water & n-butanol. Split between ethanol och water.
Minimum reflux ratio
Binary: R
m
gives pinch at F
Multicomp: Two pinches, one in stripping and
one in rectifying section
i. If no components lighter than LK;
stripping pinch near feed plate
ii. If no components heavier
than HK; rectifying pinch
near feed plate
F
W
D
M
N
y
LK
x
LK
Multi-component distillation
Short-cut method
Gillilands correlation (Stages vs Reflux)
Erbar-Maddox correlation (L/V vs. N
min
/N)
Fenskes equation (N
min
)
Underwoods method (R
min
)
Colburns method (R
min
)
10
Gillilands correlation
Gilliland found a graphical correlation between N
and R as a function of N
min
and R
min
:
5668 0
1
75 0 75 0
1
.
min min
R
R R
. .
N
N N

=
+

Underwoods method
q
x
i r , i
F , i r , i
=

1 + =

Min
i r , i
D , i r , i
R
x

And r is a reference component

is a root between
LK
and
HK
Distillation: Rigorous methods
F
n
, z
i,n
V
n
, y
i,n
L
n
, x
i,n
stage n
V
n
, y
i,n
L
n
, x
i,n
L
n+1
, x
i,n+1
V
n-1
, y
i,n-1
Q
n
11
Distillation: all equations
Material balance:
( ) ( )
n i n n n i n n n i n n i n n i n
x L L y V V y V x L z F
,
'
,
'
1 , 1 1 , 1 ,
+ + + = + +
+ +
Equilibrium:
n i
n i
n i
x
y
K
,
,
,
=
Summation:
1
, , ,
= = =

i
n i
i
n i
i
n i
z y x
Energy balance:
( ) ( )
n n n n n n n n n n n f n n
h L L H V V H V h L H F Q
' '
1 1 1 1 ,
+ + + = + + +
+ +
M
E
S
H
Design vs. Rating problems
Design: Feed variables, pressure, and a
reflux flow are specified. Specify separation
variables (recovery of key-components) and
number of stages is calculated.
Rating: Number of stages, feed and
product location are specified. Separation
variables are calculated.
Multi-component distillation
Rigorous methods
Earlier methods:
Lewis-Mathesons method (design)
Thiele-Geddes method (rating)
Current method:
Inside-out algorithm
The method solves the MESH-equations
for each tray
12
"Inside-out" algorithm
There is an inner and outer calculation loop for each tray.
In the inner loop there are calculations with
the MESH-equations. These are done using
simplified expression for equilibrium realtions
,etc..
In the outer loop these values are corrected
for the more rigourous expressions.
Example of simplified expressions
T
B
A K
K K
r
r r i i
=
=
ln
,
Equilibrium:
Enthalpy:
*) (
*
T T D C H
H H H
i i i i
i i i
=
+ =
Different flowsheeting programs
ASPEN
ChemCAD
Hysys - Hysim
Pro II
Massball
Gems - Wingems - Mops
13
Method
Condenser
Pressure
R/R
min
LK & HK
"Recovery":
Condenser
Pressure
Number of
trays
Feed tray
14
Specification of top and bottom of column
Distillation
and reflux
rates
Temperature
in top and
bottom
Number of interations is usually 20.