85

Fractional Distillation using

Enthalpy-Concentration Method

molal flow rates need not to be constant
using enthalpy as well as material balances
When the operating lines are plotted with the
equilibrium curve on the x-y diagram, the McCabe-
Thiele step-by-step construction can be used to compute
the number of ideal plates. However, unless L
n
and L
m

are constant, the operating lines are curved and can be
plotted only if the change with concentration in these
internal streams is known. Enthalpy balances are
required in the general case to determine the position of
a curved operating line.

The enthalpy-concentration diagram requires the
following data at a constant pressure:
(1) heat capacity of the liquid as a function of
temperature, composition, and pressure.
(2) heat of solution as a function of temperature and
composition.
(3) latent heats of vaporization as a function of
composition and pressure or temperature.
(4) boiling point as a function of pressure, composition
and temperature.

The diagram at a given constant pressure is based on
arbitrary reference states of liquid and temperature,
which is usually taken as the boiling point of the lower-
boiling component A.
86

The saturated liquid enthalpy is
( ) ( )
sol b PLB A b PLA A x
H T T C x T T C x H A + + =
0 0
) 1 (

(1)
T
b
= boiling temperature of mixture at x
A

T
0
= reference temperature
C
PLA
= liquid heat capacity of A
C
PLB
= liquid heat capacity of B
AH
sol
= heat of mixing, usually ignored

The saturated vapor enthalpy is
( ) | | ( ) | |
0 0
) 1 ( T T C H y T T C H y H
d PVB VB A d PVA VA A y
+ A + + A =
(2)
T
d
= dew temperature of mixture at y
A

T
0
= reference temperature
C
PVA
= vapor heat capacity of A
C
PVB
= vapor heat capacity of B
AH
VA
= latent heat of A at the reference
temperature T
0
& calculated from that
at the normal boiling temperature T
bA
.

( ) ( )
0 0
T T C H T T C H
bA PVA VAb bA PLA VA
A + = A (3)
( ) ( )
0 0
T T C H T T C H
bB PVB VBb bB PLB VB
A + = A (4)

That is, the liquid is first changed from temperature T
0
to
T
b
and then evaporated at T
b
, the vapor temperature is finally
changed back from T
b
to T
0
.


87

Example D6. Enthalpy-concentration plot for
benzene-toluene

Prepare an
enthalpy-
concentration plot
for benzene-
toluene at 1 atm
pressure.
Equilibrium and
physical property
data are given.




T (K)
Vapor pressure (kPa) Mole fraction of
benzene at 101.325 kPa
Benzene Toluene x
A
y
A

353.3 101.32 - 1.000 1.000
358.2 116.9 46.0 0.780 0.900
363.2 135.5 54.0 0.581 0.777
368.2 155.7 63.3 0.411 0.632
373.2 179.2 74.3 0.258 0.456
378.2 204.2 86.0 0.130 0.261
383.8 240.0 101.32 0 0

Component Boiling
point
(
o
C)
Heat capacity
(kJ/kmol K)
Latent heat of
vaporization
(kJ/kmol)
Liquid Vapor
Benzene (A) 80.1 138.2 96.3 30820
Toluene (B) 110.6 167.5 138.2 33330
88

Solution.
We choose a reference temperature of T
0
=80.1
o
C so that
the liquid enthalpy of pure benzene (x
A
=1) at the boiling
point is zero.

For the first point, we select pure toluene (x
A
=0). For
liquid toluene at the boiling point of 110.6
o
C,
( ) ( )
kmol kJ
H T T C x T T C x H
sol b PLB A b PLA A x
/ 5109 ) 1 . 80 6 . 110 )( 5 . 167 )( 0 1 ( 0
) 1 (
0 0
= + =
A + + =

For the saturated vapor enthalpy of pure toluene, we first
need to calculate H
VB
at T
0
=80.1
o
C:
( ) ( )
kJ/kmol 34224
) 1 . 80 6 . 110 ( 2 . 138 33330 ) 1 . 80 6 . 110 ( 5 . 167
0 0
=
+ =
A + = A T T C H T T C H
bB PVB VBb bB PLB VB

Hence, at x
A
= 0,
( ) | | ( ) | |
0 0
) 1 ( T T C H y T T C H y H
d PVB VB A d PVA VA A y
+ A + + A =
= 0 + (1-0)[34224+138.2(110.6-80.1)]
=38439 kJ/kmol

For pure benzene, x
A
= y
A
= 1, T = T
0
=80.1
o
C, H
x
= 0,
( ) | | ( ) | |
0 0
) 1 ( T T C H y T T C H y H
d PVB VB A d PVA VA A y
+ A + + A =
=1[30820+96.3(80.1-80.1)] + 0 = 30820 kJ/kmol
Selecting x
A
= 0.5, the boiling point T
b
= 92
o
C and the
dew point for y
A
= 0.5 is T
d
= 98.8
o
C from the T-x-y plot.
( ) ( )
0 0
) 1 ( T T C x T T C x H
b PLB A b PLA A x
+ =

= 0.5(138.2)(92-80.1)+(1-0.5)(167.5)(92-80.1)
= 1820 kJ/kmol
( ) | | ( ) | |
0 0
) 1 ( T T C H y T T C H y H
d PVB VB A d PVA VA A y
+ A + + A =
= 0.5[30820+96.3(98.8-80.1)]
+(1-0.5)[34224+138.2(98.8-80.1)]
= 34176 kJ/kmol
89

By the similar procedure,
at x
A
= 0.3 and y
A
= 0.3,
H
x
= 2920 kJ/kmol and H
y
= 36268 kJ/kmol
at x
A
= 0.8 and y
A
= 0.8,
H
x
= 562 kJ/kmol and H
y
= 32380 kJ/kmol
Enthalpy-concentration data for benzene-toluene mixture at 1 atm.
Saturated Liquid Saturated Vapor
Mole
fraction, x
A

Enthalpy, H
x
,
(kJ/kmol)
Mole
fraction, y
A

Enthalpy, H
y
,
(kJ/kmol)
0 5109 0 38439
0.30 2920 0.30 36268
0.50 1820 0.50 34716
0.80 562 0.80 32380
1.00 0 1.00 30820


Enthalpy-concentration plot for benzene-toluene mixture at 1 atm.
The tie line represents the enthalpies and composition of
the liquid and vapor phases in equilibrium.
90

Distillation in Enriching Section of Tower
Material balances
V L D
n n +
= +
1
(5)
V y L x Dx
n n n n D + +
= +
1 1
(6)
By rearranging Eq. (6) we obtain the operating line
y
L
V
x
Dx
V
n
n
n
n
D
n
+
+ +
= +
1
1 1
(7)
L
n
and V
n+1
may vary throughout the tower so Eq. (7)
will not be a straight line on an xy plot.

Making an enthalpy balance,
V H L H DH q
n y n n xn xD c + +
= + +
1 1 ,
(8)
where q
c
is the condenser duty, kJ/h.
An enthalpy balance for the condenser only gives
q V H LH DH
c y xD xD
=
1 1
(9)
91

Substitute Eq. (9) into Eq. (8) we have
( )
xD y xn n
xD y xn n n y n
LH H V H D V
LH H V H L H V
+ =
+ =
+
+ +
1 1 1
1 1 1 , 1

(10)
Eqs. (7) & (10) are the final working equations for the
enriching section.

In order to plot the operating line Eq. (7), the terms V
n+1

and L
n
must be determined from Eq. (10). If the reflux
ratio is set, V
1
and L are know. The values of H
y1
and
H
xD
can be determined by Eqs. (1) & (2) or from an
enthalpy-concentration plot. If a value of x
n
is selected,
it is a trial-and-error solution to obtain H
y,n+1
since y
n+1

is unknown. The steps to follow are given below.
1. Select a value of x
n
. Assume V
n+1
= V
1
= L+D, then
L
n
= V
n+1
- D.
2. Use Eq. (7) to calculate the approximate value of y
n+1
.
3. Using this y
n+1
to obtain H
y,n+1
and x
n
to obtain H
xn
.
Substitute these values into Eq. (10) and solve for the
new V
n+1
. Obtain new L
n
from Eq. (5)
4. Substitute the above values into Eq. (7) to get the new
y
n+1
.
5. If the newly calculated y
n+1
= the assumed value,
repeat steps 3-4. Usually one iteration is enough.
Assume another x
n
and repeat steps 2-5.
6. Plot the curved operating line for the enriching section.



92

Distillation in Stripping Section of Tower

Material balances
L V B
m m
= +
+1
(11)
L x V y Bx
m m m m B
= +
+ + 1 1
(12)
so that the operating line is
y
L
V
x
Bx
V
m
m
m
m
B
m
+
+ +
=
1
1 1
(13)

Making an enthalpy balance,
( )
r xB xm m m y m
q BH H B V H V + + =
+ + + 1 1 , 1
(14)
where q
r
is the reboiler duty, kJ/h.

An enthalpy balance for the whole distiller gives
q DH BH q FH
r xD xB c F
= + + (15)
The final working equations are Eqs. (13) and (15).

Using a method similar to that of the enriching section to
solve the equations.

C
P
(kJ/(kmol K) H
vb

(kJ/kmol) Component T
b
(
o
C) Liquid Vapor
Benzene 80.1 138.2 96.3 30820
Toluene 110.6 167.5 138.2 33330
93

Example D7. Distillation Using Enthalpy-
Concentration Method

A liquid mixture of benzene-toluene is to be distilled in a
fractionating tower at 101.3 kPa pressure. The feed of
100 kmol/h is liquid, containing 45 mol % benzene and
55 mol % toluene, and enters at 54.4
o
C. A distillate
containing 95 mol % benzene and 5 mol % toluene and a
bottoms containing 10 mol % benzene and 90 mol %
toluene are to be obtained. The reflux ratio is 1.755. The
average heat capacity of the feed is 159 kJ/(kmol K) and
the average latent heat is 32099 kJ/kmol. Use enthalpy
balances to calculate the flow rates of the liquid and
vapor at various points in the tower and plot the curved
operating lines. Determine the number of theoretical
stages needed.

Solution:
F = 100 kg mol/h, x
F
= 0.45, x
D
= 0.95, x
B
= 0.10,
R = 1.5R
m
= 1.5(1.17) = 1.755,
D = 41.2 kg mol/h, B = 58.8 kmol/h
The feed enters at 54.5
o
C so q = 1.195.
The flows at the top of the tower are calculated as
follows.
R = L/D = 1.755; L = 1.755D = 1.755(41.2) = 72.3;
V
1
= L+D = 72.3+41.2 = 113.5

The latent heats of vaporization of benzene and toluene
at the reference temperature of 80.1
o
C are
AH
VA
= AH
VAb
= 30820 kJ/kmol
94

( ) ( )
0 0
T T C H T T C H
bB PVB VBb bB PLB VB
A + = A
= 167.5(110.6-80.1) + 33330 - 138.2(110.6-80.1)
= 34224 kJ/kmol

The saturation temperature (dew point) at the top of the
tower for y
1
= x
D
= 0.95 is 82.3
o
C.
H
y1
= 0.95[30820+96.3(82.3-80.1)]
+(1-0.95)[34224+138.2(82.3-80.1)] = 31206 kJ/kmol

The boiling point of the distillate D is obtained as
81.1
o
C.
H
xD
= 0.95(138.2)(81.1-80.1)
+ (1-0.95)(167.5)(81.1-80.1) = 139 kJ/kmol

Step 1: select x
n
= 0.55 and guess y
n+1
from Eq. (7)
y
L
V
x
Dx
V
n
n
n
n
D
n
+
+ +
= + = + =
1
1 1
72 3
113 5
0 55
41 2
113 5
0 95 0 695
.
.
( . )
.
.
( . ) .


Step 2: using the Figure in Example D6 for x
n
= 0.55
obtain H
xn
= 1590 and for y
n+1
= 0.695, H
y,n+1
= 33240.
Substituting into Eq. (10)
V
n+1
(33240) = (V
n+1
- 41.2)1590
+113.5(31206) - 72.3(139)
V
n+1
=109.5
Using Eq. (5),
109.5=L
n
+41.2 or L
n
=68.3

Step 3: substituting into Eq. (7),
y
n+
= + =
1
68 3
109 5
0 55
41 2
109 5
0 95 0 700
.
.
( . )
.
.
( . ) .
95

This calculated value is close enough to the approximate
value of 0.695 so that no further trials are needed.

Select other values of x
n
and calculate the responding
y
n+1
, plot the curved operating line in the enriching
section.

The condenser duty is obtained from Eq. (9)
q V H LH DH
kJ h
c y xD xD
=
= =
1 1
113 5 31206 72 3 139 41 2 139 3526100 . ( ) . ( ) . ( ) /

For x
B
= 0.10, H
xB
= 4350 from the Figure in page 89.
The feed is at 54.5
o
C, using Eq. (1), we have
H
F
= 0.45(138.2)(54.5-80.1)
+ (1-0.45)(167.5)(54.5-80.1) = -3929 kJ/kg mol
Using Eq. (15),
q
r
= 41.2(139) + 58.8(4350) + 3526100 - 100(-3929)
= 4180500 kJ/h

Making a material balance below the bottom tray and
around the reboiler we have
L B V
N b
= + (16)
Enthalpy balance
( )
r xB xN b yb b
q BH H B V H V + + = (17)
From the equilibrium diagram we find that for x
B
= 0.10,
y
B
= 0.207, which is the vapor composition leaving the
reboiler.

For the equimolal overflow in the stripping section,
L L qF
m n
= + = + = 72 3 1 195 100 191 8 . . ( ) . (18)
V V q F
m n + +
= = =
1 1
1 113 5 1 1 195 100 133 0 ( ) . ( . ) .
96


Selecting y
m+1
= y
B
= 0.207 and using Eq. (13), an
approximate value of x
m
= x
N
is obtained.
y
L
V
x
Bx
V
m
m
m
m
B
m
+
+ +
=
1
1 1

0 207
191 8
133 0
58 8
133 0
0 10 .
.
.
.
.
( . ) = x
N

Solving x
N
=0.174. From the Figure in example D6 for
x
N
=0.174, H
xN
=3800, and for y
B
= 0.207, H
yb
=37000.

Substituting into Eq. (17),
( ) 4180500 ) 4350 ( 8 . 58 3800 8 . 58 ) 37000 ( + + =
b b
V V
Solving V
b
= 125.0. Using Eq. (16) we get L
N
= 183.8.

Substituting into Eq. (13) and solving for x
N
.
0 207
183 8
125 0
58 8
125 0
0 10 .
.
.
.
.
( . ) = x
N

x
N
= 0.173
This value is quite close to the approximate value of
0.174.

Assuming other values of y
m+1
and solving for x
m
using
the same procedure, the curved operating line for the
stripping section can be constructed.

The number of theoretical stages is determined to be
10.4, compared with 9.9 steps using the constant flow
method.
97


Solid line: enthalpy-concentration method
Dashed line: constant molal overflow
The solid line is slightly above the dashed line.

98

Ponchon and Savarit method

Rectifying section
We rearrange Eq. (8) as
'
1 , 1
DQ q DH H L H V
c xD xn n n y n
= + =
+ +
(16)

where
D
q DH
Q
c xD
+
= '
The left hand side is the net rate flow of heat upwards
through the enriching section, while the right hand side
is constant. This means that the net rate of flow of heat
is constant and independent of the tray number in the
rectifying section.

Using Eq. (5) to eliminate V
n+1
in Eq. (6), we have
( )
D n n n n
Dx x L y D L = +
+1

( ) ( )
1 1 + +
=
n D n n n
y x D x y L
(17)

Hence,
( )
( )
ratio reflux internal
1
1
=

=
+
+
n n
n D n
x y
y x
D
L
(18)

99

This can be explained by the lever rule. A vapor of V
n+1

of composition y
n+1
is separated into a distillate D of x
D
,
and a liquid L
n
of x
n
. (V
n+1
, y
n+1
) is at the fulcrum of a
beam, balanced by the distillate (D, x
D
) and liquid (L
n
,
x
n
). In order for the beam to be balance, the moments
about the fulcrum must be equal. Hence, we have Eq.
(17).
A similar analysis for Eq. (16) gives
( ) '
1 ,
DQ H L H D L
xn n n y n
= +
+


( ) ( )
1 , 1 ,
'
+ +
=
n y xn n y n
H Q D H H L

or

( )
( )
ratio reflux internal
'
1 ,
1 ,
=

=
+
+
xn n y
n y
n
H H
H Q
D
L
(19)
Again this obeys the lever rule.

Combining Eqs. (18) & (19), we have
( )
( )
( )
( )
xn n y
n y
n n
n D n
H H
H Q
x y
y x
D
L

=
+
+
+
+
1 ,
1 ,
1
1
'
(20)
On the H-x-y diagram, this is a straight line through the
points (H
y,n+1
, y
n+1
) at V
n+1
, (H
x,n
, x
n
) at L
n
, and (Q, x
D
)
at
D
as linked above and shown in the figure below.
D

is termed the difference point.
100



Since the heat and mass balances apply to any tray, then
at the top plate, n = 0, we have
( )
( )
( )
( )
xD y
y
xD y
y
D
D
H H
H Q
H H
H Q
x y
y x
D
L
R

= =
1 ,
1 ,
1 ,
1 ,
1
1 0
length line
' length line '

The line length
xD y
H H
1 ,
is the latent heat of
vaporization at a distillate composition x
D
. If the reflux
ratio is specified, then the length of Q H
y,1
can be
calculated, and hence Q determined.


101

Equilibrium data are used to determine the liquid and
vapor compositions leaving the first theoretical plate.
The graphical solution of Ponchon and Savarit is
continued using the equilibrium data and the H-x-y
diagram until the reboiler composition is reached. In the
following case, a total of 4 theoretical plates is shown, 3
in the column and 1 for the reboiler having an enthalpy
H
R
and composition x
R
.




102

Stripping section
The same analytical techniques used in the rectifying
section can be applied to the stripping section and the
entire column.


We rearrange Eq. (14 ) as
' '
1 , 1
BQ q BH H V H L
r xB m y m xm m
= =
+ +

where Q = H
xB
q
r
/B, by eliminating B (B=L
m
V
m+1
),
( )
( )
( )
( ) "
"
,
1 ,
1
1
Q H
Q H
x x
x y
V
L
m x
m y
m B
B m
m
m

=
+
+
+
(21)

On the H-x-y diagram, this is a straight line passing
throught (H
y,m+1
, y
m+1
) at V
m+1
, (H
x,m
, x
m
) at L
m
, and (Q,
x
B
) at
B
as shown in the figure above.
B
is also termed
the difference point. B is W in the figure.


Eq. (21) applies to every plate in the stripping section.
On the H-x-y diagram, this is a line from V
Z+1
(vapor
leaving the reboiler and entering the bottom tray Z of the
103

tower) to
B
, intersects the saturated liquid enthalpy
curve at L
Z
, the liquid leaving the bottom plate. Vapor
V
Z
leaving the bottom plate is in equilibrium with the
liquid L
Z
and is located on the tie line Z.

The number of theoretical plates in the stripping section
can be determined from the H-x-y diagram by
alternatively constructing lines to
B
and tie lines. Each
tie line is a theoretical plate.


The complete column






104

The overall mass balance is
F = D + W
The more volatile component mass balance is
Fx
F
= Dx
D
+ Wx
W
The heat balance is
FH
F
= Q
C
+ DH
yD
+ WH
xW
Q
R
= DQ+WQ
Eliminating F yields
( )
( )
( )
( )
F
F
F D
W F
H Q
Q H
x x
x x
W
D

=
'
"

This is a straight line on the H-x-y diagram passing
through (Q, x
D
) at
D
, (H
F
, x
F
) at F, and (Q, x
W
) at
W

and is shown in the above figure for a case of liquid feed
below its boiling point (cold liquid).

The procedure to determine the number of theoretical
plates is summarized below.
1. Locate the feed enthalpy and composition
2. Locate x
D
and x
W

3. Locate
D
by computation of Q or for a specific
reflux ratio as R = L
0
/D
4. The line
D
, F is extended to x = x
W
and thus locates

W
whose coordinates can be used to calculate Q
R
.
5. The number of theoretical plates is then determined
by application of the straight line relationship on the
H-x-y diagram and the equilibrium data of the y-x
diagram.


105

Example D8. Distillation Using Ponchon Savarit
Method

Re-calculate the number of theoretical stages required
for example D7 using Ponchon Savarit method.

x
F
= 0.45, H
F
= -3929 kJ/kg mol
x
D
= 0.95, x
B
= 0.10
kJ/kmol 85724
2 . 41
3526100 ) 139 ( 2 . 41
' =
+
=
+
=
D
q DH
Q
c xD

Q = H
xB
q
r
/B =435 -4180500/58.8 = -66747 kJ/kmol
or in the H-x-y diagram, draw the line from
D
(x
D
=0.95,
Q=85724) through (x
F
=0.45, H
F
=-3929) to intersect
x
B
=0.10 gives Q = -66747 kJ/kmol from
B
.

The number of theoretical plates is then determined by
application of the straight line relationship on the H-x-y
diagram and the equilibrium data of the y-x diagram.
10.4 plates, or 9.4 plates plus 1 reboiler are needed. The
feed is at plate 6.


106


107