Introduction
Distillation is a method used to separate the components of liquid solution,
which depends upon the distribution of these various components between
a vapor and a liquid phase.
The vapor phase is created from the liquid phase by vaporization at the
boiling point.
p A PA x A
(1)
Where
pA is the partial pressure of component A in the vapor in Pa (atm)
PA is the vapor pressure of pure A in Pa (atm)
xA is the mole fraction of A in the liquid.
Composition in liquid: 1 x A xB
(2)
Composition in vapor: 1 y A y B
(3)
2
yA
p A PA x A
P
P
(4)
(5)
(6)
Where
pA, pB are the partial pressure of component A and B in the vapor in Pa (atm)
PA , PB are the vapor pressure of pure A and pure B in Pa (atm)
P is total pressure in Pa (atm)
xA is the mole fraction of A in the liquid.
5
Hence, xA= 0.411 and xB= 1 xA = 1 - 0.411 = 0.589. Substituting into eqn.
(6),
yA
p A PA x A 155.7(0.411)
0.632
P
P
101.32
7
The boiling point diagram can be calculated from the pure vapor-pressure
data in the table below and the following equations:
1
Minimum-boiling azeotrope
Maximum-boiling azeotrope
10
11
V2
Where
V1, V2 is a vapor
L0
L1
L0 V2 L1 V1 M
L0 x A0 V2 y A 2 L1 x A1 V1 y A1 Mx AM
12
V2
L0
L1
13
To solve equation above, the equilibrium relation between yA1 and xA1 in
figure below must be used.
First, we assume that xA1 = 0.20 and substitute into equation above to
solve for yA1.
110 (0.30) 100(0.40) 110 (0.2) 100 y A1
16
AB
yA / xA
y A / xA
y B / xB (1 y A )(1 x A )
P x
yA A A
P
AB
yA
yB
PB xB
P
PA
PB
AB x A
1 ( AB 1) x A
17
Exmpl Using data from table 1 calculate the relative volatility for the
benzene-toluene system at 85C (358.2K) and 105C (378.2K)
Solution: At 85C, substituting into equation below for a system following
Raults law,
AB
PA 116 .9
2.54
PB
46.0
Similarly at 105C,
204.2
2.38
86.0
The variation in is about 7%.
Answer
18
xA
Flash distillation is a single stage separation technique.
1. A liquid mixture is pumped through a heater to raise the temperature
and enthalpy of the mixture.
2. It then flows through a valve and the pressure is reduced, causing
the liquid to partially vaporize.
3. Once the mixture enters a big enough volume (the flash drum), the liquid and
vapor separate.
4. Because the vapor and liquid are in such close contact up until the flash occurs,
the product liquid and vapor phases approach equilibrium.
20
F V L
yA
Separator
xA
xF, yA and xA are mole fraction of component A in feed, vapor and liquid.
V
F V
xF ( ) y A ( ) x A
F
F F
x F f y A (1 f ) x A
Where
f = V/F = molal fraction of the feed that is vaporized and withdrawn continuously as vapor.
1-f = one as liquid
21
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
yA
F V L
Since f V / F ,
V fF 0.6(100) 60
L F V 100 60 40
22
V
F V
xF ( ) y A ( ) x A
F
F F
x F f y A (1 f ) x A
Substituting value of f =0.6 and xF =0.5 we get,
2nd
x=0
y-intercept= 0.834
yA
xA
3rd
xA =0.39
yA = 0.58
1st
xF =0.5
yF = 0.5
24
25
If a small amount of liquid dn is vaporized, the change in the moles of component A is ydn, or
dnA. Differentiating equation a gives
dn
dx
n
yx
26
x1
n1
dn
dx
ln
n0 n x0 y x n0
dn
dx
n
yx
yA
x
AB A
yB
xB
dn A dn dn A
n
AB A
dn B dn dn B
nB
dn A
dn
AB B
nA
nB
ln
Integrating
nA
n
AB ln B
n0 A
n0 B
nB n A
n0 B n0 A
1 / AB
27
Exmpl A batch of crude pentane contains 15 mole percent nbutane and 85 percent n-pentane. If a simple batch distillation at
atmospheric pressure is used to remove 90 percent of butane,
how much pentane will be removed? What will be the
composition of the remaining liquid?
Solution: The final liquid is nearly pure pentane, and its boiling point is
36C. The vapor pressure of butane at this temperature is 3.4 atm, giving a
relative volatility of 3.4. For the initial conditions, the boiling point is about
27C, and the relative volatility is 3.6. Therefore, an average value of 3.5 is
used for AB.
Basis: 1 mol feed
nOA 0.15
(batane) n A 0.015
nOB 0.85
nB n A
From equation: n
0B
n0 A
(pentane)
1 / AB
28
nB
1 / 3.5
0.1
0.518
0.85
nB 0.518(0.85) 0.440
Total mole of liquid left in still:
xA
0.015
0.033
0.455
29
Note that by steam distillation, as long as water is present, the highboiling component B vaporizes at a temperature well below its normal
boiling point without using a vacuum. The A and B are usually
condensed in condenser and the resulting two immiscible liquid
phases separated.
Disadvantage: large amounts of heat must be used to simultaneously
evaporate the water with high-boiling compound.
30
nB PB
n A PA
31
PA(water)
(mm Hg)
PB(ethylaniline)
(mm Hg)
353.8
80.6
48.5
1.33
369.2
96.0
87.7
2.67
372.3
99.15
98.3
3.04
386.4
113.2
163.3
5.33
32
Solution:
PA PB P
Temperature
K
PA
(water)
(kPa)
PB
(ethylaniline)
(kPa)
P=PA+PB
(kPa)
353.8
80.6
48.5
1.33
49.83
369.2
96.0
87.7
2.67
90.37
372.3
99.15
98.3
3.04
101.34
386.4
113.2
163.3
5.33
169.23
V2
V3
V2
Vn
Vn+1
L0
L1
L2
L1
Ln-1
Ln
Vn 1 Ln 1 Vn Ln
A component balance on A:
Vn 1 y n 1 Ln 1 x n 1 Vn y n Ln x n
34
36
Main assumption
1) Equimolar overflow through the tower between the feed inlet and the top tray and
the feed inlet and bottom tray.
2) Liquid and vapor streams enter a tray, are equilibrated, and leave.
37
Vn 1 Ln 1 Vn Ln
A component A balance:
Vn 1 y n 1 Ln 1 x n 1 Vn y n Ln x n
Where
Vn+1 is mol/h of vapor from tray n+1
Ln is mol/h liquid from tray n
yn+1 is mole fraction of A in Vn+1 and so on.
38
(1)
A component A balance:
Fx F Dx D Wx w (2)
Where
F is the entering feed (mol/h)
D is the distillate (mol/h)
W is the bottoms (mol/h)
39
Vn 1 Ln D
(3)
A balance on component A:
Vn 1 yn 1 Ln xn DxD
(4)
40
yn 1
Ln
Dx
xn D
Vn 1
Vn 1
(5)
y n 1
x
R
xn D
R 1
R 1
(6)
41
The theoretical stages are determined by starting at xD and stepping off the first
plate to x1. Then y2 is the composition of the vapor passing the liquid x1.
In a similar manner, the other theoretical trays are stepped off down the tower in
the enriching section to the feed tray.
42
Vm 1 Lm W
A component A balance:
Vm 1 ym 1 Lm xm Wxw (8)
(7)
43
ym 1
Lm
Dx
xm D
Vm 1
Vm 1
(9)
Vm 1 VN
= constant,
L Veqn. (2) is a straight line when plotted as y versus x,
m
with a slope of
m 1
The intercept at x = 0 is
y WxW / Vm 1
44
The theoretical stages for the stripping section are determined by starting at
xW, going up to yW , and then across to the operating line, etc.
45
Lm Ln qF
(10)
Vn Vm (1 q) F
(11)
Vn y Ln x Dx D
(12)
Vm y Lm x Wx w
(13)
(Vm Vn ) y ( Lm Ln ) x ( Dx D Wx w )
(14)
46
q 1
x
q
x F
q 1
q 1
c pL (Tb TF )
Cold-liquid feed
q 1
(15)
c pV (TF Td )
Superheated vapor
where
CpL, CpV = specific heats of liquid and vapor, respectively
TF = temperature of feed
Tb, Td = bubble point and dew point of feed respectively
= heat of vaporization
47
q = 0 (saturated vapor)
q = 1 (saturated liquid)
q > 1(subcooled liquid)
q < 0 (superheated vapor)
0 < q < 1 (mix of liquid and
vapor)
48
Slope = R/(R+1)
Slope = q/(1-q)
Slope = L/ V
Solution (a)
xF
40
78
40 60
78 92
0.440
xD
97
78
97 3
78 92
0.974
xB
2
78
2 98
78 92
0.0235
100
92
0.44(95 20)
1.37
89.7
x
q
x F
q 1
q 1
The slope of the feed line is -1.37/(1-1.37) = 3.70. When steps are drawn
for this case, as shown in Fig. below, it is found that a reboiler and 10
ideal plates are needed and that the feed should be introduced on the
sixth plate.
Vn 1 Ln D
(16)
Then Ln is very large, as is the vapor flow Vn. This means that the slope R/(R+1)
of the enriching operating line becomes 1.0 and the operating lines of both
sections of the column coincide with the 45 diagonol line, as shown in Fig below.
Minimum number of trays can be obtained by returning all the overhead
condensed vapor V1 from the top of the tower back to the tower as reflux, i.e., total
reflux. Also, the liquid in the bottoms is reboiled.
58
Nm
x D 1 xw
1 xD xw
log av
log
1/ 2
Rm
x y
D
Rm 1 xD x
60
61