UNIT OPERATION II

Reference Materials:
Coulson and Richardson – Chemical Engineering Vol
II, Particle Technology and Separation Processes, 2002
C. J. Geankoplis. Transport Processes and Unit
Operations, Prentice Hall, 1993
C. J. Kings. Separation Processes, McGraw Hill, 1980
R. E. Treybal, Mass transfer Operations, McGraw Hill,
1980
Equilibrium or Flash Distillation

2
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.
 Equilibrium or Flash Distillation
Total mass balance: F V L
(1)
yA

F yALx
Fx V Separator
Component A balance: A

heater
where
xA
F, V and L are flow rate of feed, vapor and liquid phases.
Figure 12
xF, yA and xA are mole fraction of component A in feed, vapor and liquid.
V FV
x F ( )yA ( ) xA xF fy A (
1 f) x A (2)
F FF
Where
f = V/F = molal fraction of the feed that is vaporized and withdrawn continuously as vapor.
1-f = molal fraction of the feed that is withdrawn continuously as liquid
 
( f  1) xF
yA  xA  (3) 4
f f
 Example 7
A mixture of 50% mole normal heptane and 50% normal
octane at 30ºC is continuously flash distilled at 1 standard
atmosphere so that 60 mol% of the feed is vaporized. What
will be the composition of the vapor and liquid products?
Table 5: VLE Data for n-heptane – n-octane binary system at 1atm
xA 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
yA 0.247 0.453 0.607 0.717 0.796 0.853 0.898 0.935 0.968

Solution: Given: xF = 0.5, f = 0.6

Find: xA, yA
Basis: F = 100 mol F  V L

Applying the mass balance yields:

f V / F
Since,
V 
fF0
.6
( )
100
60
5

LF
V 
100
60
40
 Material balance for more volatile component,

( f  1) xF
yA  xA 
f f

Substituting value of f =0.6 and xF =0.5 we get,

  0.6 −1 0.5
𝑦 𝐴= 𝑥 𝐴+
0.6 0.6

Assuming that xA = 0.5 and solving yA = 0.5.

Next, assuming that xA=0 and solving, yA = 0.83.
(These point are plotted on the graph.)
At the intersection of this line with the equilibrium curve,
yA = 0.58 and xA = 0.39. 6
 x=0
2nd
y-intercept= 0.834

yA

Figure 13
xA
3rd xA =0.39 xF =0.5
1st
yA = 0.58 yF = 0.5

7
 Continuous Distillation with reflux
• A typical schematic diagram of a multistage counter-
current binary distillation that is operated
continuously is shown in Fig. 14.
• The operation consists of a column containing:
– the equivalent number of theoretical stages
arranged in a two-section cascade;
– a condenser in which the overhead vapor leaving
the top stage is condensed to give a liquid distillate
product and liquid reflux that is returned to the top
stage;
– a reboiler in which liquid from the bottom stage is
vaporized to give a liquid bottom products and the
vapor boil off returned to the bottom stage;
– accumulator which is a horizontal (usually) pressure
vessel where the condensed vapor is collected;
– Heat exchanger where the hot bottoms stream is used to
heat up the feed stream before it enters the distillation
column.
– The feed enters the column at feed stage and contains
both the more volatile component and less volatile
component.
– The feed may be liquid, vapor or mixture of liquid and
vapor.
– The section above the feed where vapor is washed with
the reflux to remove or absorb the less volatile
component is called enriching or rectifying section.
– The section below the feed stage where liquid is stripped
of the more volatile component by the rising vapor is
called stripping section
Figure 14
Determination of Theoretical Number of Trays:
McCabe Thiele Method
McCabe-Thiele method uses the equilibrium curve
diagram to determine the number of theoretical stages
(trays) required to achieve a desired degree of
separation.

Using McCabe-Thiele method involves the plotting of

three straight lines on the equilibrium diagram. These
lines are the rectifying section operating line (ROL), the
feed line (also known as the q-line) and the stripping
section operating line (SOL)
The information required for the systematic
calculation are:
• the VLE data,
• feed condition (temperature, composition),
• distillate and bottom compositions;
• the reflux ratio.
The reflux ratio
• It is defined as the ratio of reflux liquid to the
distillate product.
• i.e. the ratio of the quantity of liquid returned to the
distillation column to the quantity of liquid
withdrawn as top product from the Column
• Mathematically written as: R = L / D
• The reflux ratio R is an important parameter in the
analysis. This is because the concentration of the
more volatile component in the distillate (in mole
fraction xD) can be changed by changing the value of
R.
• Total Reflux:
It is the operating condition where vapor and liquid are passing each other in the
column but no product is removed (i.e., D = 0 and R = L/D = ∞ ).
The slopes of the Operating Lines are then L/V = 1.0 and by material balance
between each plate y = x.
At total reflux, the number of theoretical plates required is a minimum. As the
reflux ratio is reduced (by taking off product), the number of plates required
increases.
• The Minimum Reflux Ratio (Rmin)
It is the lowest value of reflux at which separation can be achieved even with an
infinite number of plates.
It is possible to achieve a separation at any reflux ratio above the minimum reflux
ratio.
As the reflux ratio increases, the number of theoretical plates required
decreases.
• The Optimum Reflux Ratio (Ro)
It is that reflux at which the total cost of the distillation is a minimum, taking into
account the capital cost of the column (which depends on the number of
theoretical plates) and running cost, which depends on the minimum reflux ratio.
 McCabe-Thiele Method: assumptions of the method

• a. Constant Molal Overflow. The molar flow rates of the vapor

and liquid are nearly constant in each section of the column.
This also ensures the operating lines are straight lines.

• b. Heat Effects are negligible. For example, heat losses to and

from the column are small and neglected

• c. For every mole of vapor condensed, another mole of liquid is

vaporized.

• d. The liquid and vapor leaving the tray is in equilibrium with

the vapor and liquid entering the tray.
The steps to determine the number of theoretical stages using McCabe-Thiele Method

• Determination of required reflux ratio (R).

• Determination of the Rectifying section operating line (ROL).

• Determination of the feed condition (q).

• Determination of the feed section operating line (q-line).

• Determination of the stripping section operating line (SOL).

• Determination of number of theoretical stage.

 qD
D
L0 xD Overall mass balance:
Lm
m
Vm+1
F=D+B (1)
F

Lp
p

Vp1
qB
B
 A v1 ENVELOPE A:
Derivation of Rectifying Operation Line
qD
v1 D
L0 xD Vm+1 = Lm + D (2)
v2 L1
m
Vm+1
Vm+1 ym+1 = Lm xm + D xD (3)
Lm
Lm D
F
y m 1  xm  xD (4)
Vm1 Vm1

This is an equation of a straight line on a plot of vapor

composition versus liquid composition, where (Lm/Vm+1) is
the slope and (DxD/Vm+1) is the intercept which passes
through the point (xD, xD) and (xm, ym+1).
Since all L values are equal and all V values are equal (due
to constant molal overflow assumption:

 
Lm D
y m 1  xm  xD
Vm Vm (5)

Equation (4) is the operating line or material balance line

for the rectifying section.
Since:
Lm
R
D Lm Lm Lm D R
  
Vm Lm  D Lm D  1 R  1
Vm = Lm + D
D D 1 1
  
Vm Lm  D Lm D  1 R  1

In term of R, equation (4) can be written as:

 
R xD
y m 1  xm  (6)
R1 R1
 R
slope 
R1

xD
intercept 
R1

x xD
ENVELOPE B: Derivation of Stripping Operation Line

Vp1  Lp  B (7)

Lp
p Vp1 y p1  Lp xp  B x B (8)
Vp1
p+1
Lp B
VN1
y p1  xp  xB (9)
Vp1 Vp1
qB
LN
B
Since all L values are equal and all V values are equal (due to
constant molal overflow assumption:
 
y
L
 p x 
B
x
(10)
p1 p B
Vp Vp

Equation (9) is the operating line or material balance line for the
stripping section.
This is an equation of a straight line with slope L Vp p

and intercept  Bx B Vp passing through (x B, xB) and (xp, yp+1).

 This line can be drawn from point (xB, yB) to point or with slope
Lp Vp

The problem is, how to calculate Vp and Lp ?

Vp and Lp is calculated by material and enthalpy balance
relationship around the feed plate.
 Feed stage consideration
Definition of feed quality, q: It is the number of moles of saturated liquid formed on
the feed plate by the introduction of 1 mole of feed
´
 𝐹+ 𝐿 𝑚+ 𝑉 𝑝 =𝑉 𝑚+ ´𝐿 𝑝 (11)
Vm Lm
F  𝐹+ ( 𝑉
´ 𝑝 − 𝑉 𝑚 ) =( 𝐿
´ 𝑝 − 𝐿𝑚 )
Vp Lp
  𝑉´ 𝑝 − 𝑉 𝑚 𝐿´ 𝑝 − 𝐿𝑚
1+
𝐹
=
𝐹
(12)
 
Lp  Lm
q (13)
F

  𝑉´ 𝑝 − 𝑉 𝑚
putting (13) in (12), we have: 1+ =𝑞
𝐹

  ´ 𝑝− 𝑉 𝑚
 𝑉
𝐹
=𝑞 −1 (14)
Enthalpy balance on feed entrance
 
(15)
′ ′
h
  𝐿= h 𝐿 and 𝐻
  𝑉 =𝐻 𝑉

′ ′
F
  h 𝐹 + ( 𝑉´ 𝑝 −𝑉 𝑚 ) 𝐻 𝑉 =( ´𝐿 𝑝 − 𝐿𝑚)h 𝐿

  ( 𝑉´ 𝑝 −𝑉 𝑚 ) (𝐿
´ 𝑝 − 𝐿𝑚 )
h𝐹+ 𝐻𝑉 = h𝐿
𝐹 𝐹
h  𝐹 +(𝑞 −1)𝐻 𝑉 =𝑞 h 𝐿
h  𝐹 +𝑞 𝐻 𝑉 − 𝐻 𝑉 =𝑞 h 𝐿
 
  𝐻 𝑉 −h 𝐹
∴ 𝑞= (16)
𝐻 𝑉 − h𝐿
  𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 h𝑒𝑎𝑡 𝑛𝑒𝑐𝑒𝑠𝑠𝑎𝑟𝑦 𝑡𝑜 𝑣𝑎𝑝𝑜𝑢𝑟𝑖𝑧𝑒 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑡h𝑒 𝑓𝑒𝑒𝑑
∴ 𝑞=
𝑙𝑎𝑡𝑒𝑛𝑡 h𝑒𝑎𝑡 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛
Derivation of q-line: Component material balance of the feed stage

F xF   L p  Lm  xi  V p  Vm  yi (17)

xF 
 L p  Lm 
x 
V p  Vm 
yi
i
F F

xF  q xi   q  1 yi

  q xF (18)
yi  xi 
q1 q1
 Determination the feed condition (q):
The feed entering the distillation column may consists
of liquid, vapour or can be a mixture of both.

Some portion of the feed go as liquid stream to the

stripping and some portion go as vapour stream to
the rectifying sections.

The parameter q is the mole fraction of liquid in the

feed.

The limits of the q-value for various feed conditions

are shown in Table 7.
Eq. (18) is the equation of the q line having a slope of q/
(q – 1) and terminating at xF on the 45 line and at point
(xi, yi).

Table 7: q-value as per feed conditions

Feed condition Limit of q-value Slope of q-line

Saturated liquid feed (feed at bubble point) q=1 
Saturated vapor feed (feed at dew point) q=0 0
Cold liquid feed (below bubble point) q>1 +
Superheated vapor feed q<1 –
Partially vaporized feed (Two-phase feed) 0<q<1 –

where, q is the fraction of the feed that is liquid

When feed is partially vaporized:
Other than saturated liquid (q = 1) and saturated vapour (q = 0),
the feed condition is uncertain.
In those cases, the value of q must be calculated.
The q-value can be obtained from enthalpy balance around the
feed plate from the following form of equation:

(16)
where HF, HV and HL are enthalpies of feed, vapour and liquid
respectively which can be obtained from enthalpy-concentration
diagram for the mixture.
When feed is cold liquid or superheated vapor:
q can be alternatively defined as the heat required to convert 1
mole of feed from its entering condition to a saturated vapour;
divided by the molal latent heat of vaporization.
Based on this definition, one can calculate the q-value from the
following equations for the case whereby q > 1 (cold liquid feed)
and q < 0 (superheated vapour feed) as:

For cold liquid feed:

[19]
For superheated vapour feed:
[20]
Where;Tbp, Tdp = the temperature at bubble point dew point of the feed
respectively. TF = temperature of feed. CpL, CpV = specific heats of liquid and
vapor, respectively. λ = the latent heat of vaporization and is the temperature at
 q=1

q>1
0<q<1

q=0

xB xF xD
 q
slope 
q1
intercept
xD

R1

xB xF xD
 x1 , y 1

x2 , y 2
x1, y2

x3, y3
x2, y3

x4 , y 4 x3, y4

xB xF xD
 MINIMUM REFLUX

intercept
xD

R min  1

xB xF xD
TOTAL REFLUX

xB xF xD
EXAMPLE 8
A saturated liquid feed mixture which compose of 42
mole % heptane, 58 mole % ethyl benzene is to be
fractionated at 760 mmHg to produce distillate
containing 97 mole % heptane and a residue containing
99 mole % ethyl benzene. The VLE data for heptane-
ethyl benzene binary system at 760 mmHg are as
follows:

Table 8 VLE Data for heptane - ethyl benzene binary system at 760 mmHg
T(oC) 136.2 129.5 122.9 119.7 116.0 110.8 106.2 103.0 100.2 98.5
xH 0.000 0.080 0.185 0.251 0.335 0.487 0.651 0.788 0.914 1.000
yH 0.000 0.233 0.428 0.514 0.608 0.729 0.834 0.904 0.963 1.000
EXAMPLE 8
Determine:
a. the number of equilibrium stages needed for
saturated-liquid feed and reflux ratio R = 2.5 using
McCabe-Thiele graphical method
b. Rmin
c. minimum number of equilibrium stages at total
reflux.
SOLUTION
(a) The slope of the operating line in the rectifying section:
R 2.5
slope    0.715
R  1 2.5  1
 1.0

0.9
N = 11
0.8

0.7

0.6

0.5
y 0.4

0.3

0.2

0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x
 1
(b) 0.9

0.8

0.7

0.6
y

0.5

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
x

xD
Intercept =  0.45
R min  1

Rmin = 1.18
 1

(c) 0.9

0.8

0.7

0.6
y

0.5

0.4

0.3 N=8

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
x