DISTILLATION

Its a physical process for separating a liquid mixture into two or more of its components
by partial vaporization and condensation.

The Basic Principle: the vapor formed has a different composition

from the remaining liquid.

But, when, the vapor and liquid have the same composition
=> the liquid mixture is k/as an azeotrope or azeotropic mixture.

Thus, distillation is modeled on an equilibrium basis and an approach to equilibrium is

used in determining equilibrium stages.

However, true equilibrium may not be reached and a newer approach so called rate
based operations taken into account and thus an efficiency term.

Rate based operations Mass transfer limitations Efficiency

VAPOR LIQUID EQUILIBRIA:

It concerns with the relations between vapor and liquid compositions over a range of
temperature and pressure.

Functionally, the mol fractions yi of component i in the vapor phase depends on as,

yi = f ( T, P, x1, x2, , xn) ...................1

Dependence on composition alone can be approximated by,

yi = Ki xi
...2

Where, Ki = Vaporization Equilibrium Ratio (VER) and f (T,P, x)

Equation 2 can be viewed as per Raoults law

Pi o
yi xi Pi o
i.e.
P
=> Ki ideal
P
A number of correlations for VER have been developed for hydrocarbon systems.

Approximate forms:

iL Pi o (At low pressure i.e. at ambient

Modified Raoults Law: Ki
P or pressure below 5atm)

Hi (From low pressure to moderate and at

Henrys Law: Ki
P supercritical temp.)

Rigorous Form:

iLiL Pi o .(All mixture from ambient to

Activity Coefficient: K i V
i P critical temperatue)

Or

f iV f i L
Activity Coefficient Deducted from experimental data of VLE

Or approximate values can be calculated from:

Structural Group Contribution Method => UNIFAC method

For more than two components the favored methods are

NRTL and Wilson

For solubility parameter method: UNIQUAC

Understanding Non-ideality of solutions:

In most distillation systems, the predominant nonideality occurs in the

liquid phase because of molecular interactions

When chemically dissimilar components are mixed together (for

example, oil molecules and water molecules), there can be repulsion
or attraction between dissimilar molecules.

If the molecules repel each other, they exert a higher partial pressure
than if they were ideal. In this case the activity coefficients are
greater than unity (called a positive deviation from Raoults law).

If the molecules attract each other, they exert a lower partial pressure
than if they were ideal. Activity coefficients are less than unity
(negative deviations).
At next.
The problem of interest are finding the conditions for onset of vaporization,

the bubble point, for the onset of condensation, the dewpoint and the composition

And the relative amount of vapor and liquid phases at equilibrium under specified

Conditions.
 VAPOR LIQUID EUILIBRIUM DATA:

Temp., C yA xA AB
64.5 1 1
66 0.958 0.900
69.3 0.870 0.700
73.1 0.779 0.500
78 0.665 0.300
84.4 0.517 0.150
89.3 0.365 0.080
93.5 0.230 0.040
100 0.000 0.000

VLE Data for Methanol (A) Water (B) System at P = 101.3 kPa

These results are conveniently presented in graphic form using several types
of phase diagram. Such T-xy, P-xy and x-y.
T-xy

x-y
Bubble-Point Temperuture Calculations:

1. Guess a temperature T.
2. Calculate vapor pressures of all components at T.
3. Calculate:
Nc
PTCal T xi Pi o T
i 1

4. Check to see if is sufficiently close to PT.

5. If not, reguess T and go back to step 2. If PCal.T is less than P, increase

T. If PCal.T is greater than PT, decrease T.

One of the most widely used correlations of saturated vapour pressure is that proposed
by ANTOINE.

The another equation is RIEDEL.

Alternative method can be,

In an n component mixture, select the rth component as the reference component.

Then, the relative volatility of the ith component with respect to rth is given as,

yi yi
yr xi Ki
ir
xi yr Kr
xr xr

n n
K i K r ir y i K r ir xi y
i 1
i K r ir xi
i 1

K xi 1
i i 1
 Or Ki can be directly obtained from DePriester Chart for ith component
At a given temperature and pressure.

n
Then, K x
i 1
i i 1

Similarly for Dew Point Calculation,

n
yi

i 1 K i
1

1. Guess a temperature T.
2. Calculate vapor pressures of all components at T.
3. Calculate:
yi PT T
xi
Pi o
n

x
i 1
i 1
Ex. 1: The constants in the Antoine equation,are:
For benzene: k1 = 6.90565 k2 = 1211.033 k3 = 220.79
For toluene: k1 = 6.95334 k2 = 1343.943 k3 = 219.377

where, P is in mm Hg, T is in C and log10 is used instead of loge.

Determine the bubble point of 0.5 mole fraction benzene and 0.5 mole
fraction of toluene.
Schematic of Continuous
fractionating column
 On each tray the system tends to reach equilibrium:
1. Some of the less volatile component condenses from the rising vapour into the
liquid thus increasing the concentration of the more volatile component (MVC) in
the vapour. (Absorption => M.T. from Vapor to Liquid)

2. Some of the MVC is vaporised from the liquid on the tray thus decreasing the
concentration of the MVC in the liquid. (Desorption => from Liquid to Vapor)

The number of molecules passing in each direction from vapour to liquid and in reverse
is approximately the same.

The above blue text can be only possible, when the two components have
equal and approximately constant molar Heat of vaporization.

Therefore, the flows of liquid and vapour in each part of the column will
not vary from tray to tray and will REMAIN CONSTANT, in such case.

Conditions of varying molar overflow can also arise from unequal molar latent
heats of the components that means when the system tends to..
 Designing Distillation Column

Graphical Equilibrium Stage method for Binary Mixture Distillation

1. Equilibrium Curve/Line: Obtained from VLE Data.

2. Operating Line: Obtained from Material Balance Over a Column.

3. q- line: Obtained from Heat Balance across feed plate.

Material Balance:

Across nth plate

Vn1 Ln1 Vn Ln

llly across (n-1)th plate

.
material balance above plate n, indicated
by the loop I

Vn = Ln+1 +D 1
for the more volatile component gives:

ynVn = Ln+1xn+1 + Dxd .2

Ln 1 D
yn xn 1 xd
Vn Vn
as we know,
L1 = L2 = L3 = Ln+1 = const. = Ln

Ln D
yn xn 1 xd 3
Vn Vn
is called as Top Operating Line or Rectifying Section Line
taking a material balance,
from the bottom to above plate m,
as indicated by the loop II

Lm+1 = Vm +W

ymVm = Lm+1 xm+1 Wxw

As we know, Lm = Lm+1

Thus,

Lm W
ym xm 1 xw
Vm Vm
is called as Bottom Operating Line
or Stripping Section Line
Overall Material Balance:
F=D+W

For MVC => F. zf = D.xd + W.xw

 1

TOL

BOL

0 1
x
The intersection of the operating lines and Feed Stage Condition:

If the two operating lines intersect at a point with coordinates (xq, yq ), the
from equations of TOL and BOL,

Vn yq Ln xq Dxd .I

Vm yq Lm xq Wxw II

Then, (II-I) =>

yq Vm Vn xq Lm Ln Dxd Wxw

Now, material balance over feed plate gives,

Vn Ln
F Ln Vm Vn Lm
F

=> Vm Vn Lm Ln F
Vm Lm
Contd
Vm Vn Lm Ln F

To obtain a relation between Ln and Lm , it is necessary to make an enthalpy

balance over the feed plate, and to consider what happens when the feed enters
the column?

If the feed is all in the form of liquid at its boiling point,

then the reflux Lm overflowing to the plate below will be Ln + F.

If the feed is a liquid at a temperature Tf , that is less than the boiling point,
then some vapour rising from the plate below will condense to provide
sufficient heat to bring the feed liquor to the boiling point.

These different cases can be understood graphically :

V< V
L

L>L+F V (A) Sub cooled liquid feed

 V= V V = V+VF
L
L

F
VF
F

L= L+F V
L=LF+F V
(B) Saturated liquid feed (C) Partially vaporized feed

V=V+F V > V+F

L
L

F
F

L < L V
L=L V

(D) Saturated vapor feed (E) Superheated-vapor feed

Now,
If, Hf is the enthalpy per mole of feed
and
Hfs is the enthalpy of one mole of feed at its boiling point
Then,
the heat to be supplied to bring feed to the boiling point is,
F H fs H f
Therefore,
the number of moles of vapour to be condensed to provide this heat is
F H fs H f

Where, is the molar latent heat of the vapour.

Thus, liquid flow below feed plate will be,

F H fs H f
Lm Ln F

 F H fs H f
Contd..
Lm Ln F

H fs H f
Lm Ln F

If, q is defined as,
heat to vaporize 1 mol of feed
q
molar latent heat of feed

H fs H f
q

Lm Ln Fq
Vm Vn Fq F

Therefore, from above all equations,

F q 1 yq Fqxq Fx f
 q 1
yq xq x f
q 1 q 1

This equation is commonly known as the equation of the q-line

Thus, from above the equation,

q
slope of q-line
q 1
The importance of the reflux ratio:

The ratio of the top overflow to the quantity of product is called the reflux ratio.
It is denoted by R.

Ln
i.e. R
D
This enables the equation of the operating line to be expressed in another way as,
Ln D
TOL => yn xn1 xd
Ln D Ln D

R xd
yn xn 1
R 1 R 1
Any change in the reflux ratio R will therefore modify the slope of the operating line.

Thus, This will affect the number of equilibrium stages required for a given separation.
 Mole fraction in vapor y

xd
R 1

Mole fraction in liquid x

Mole fraction in vapor y

Mole fraction in liquid x

 Mole fraction in vapor y

q - line

xd
Rmin 1

Mole fraction in liquid x

Determination of Minimum Reflux Ratio:

1. Graphical Method

2. Analytical Method:
Underwoods Equation for minimum Reflux Ratio.

a) Feed is saturated liquid (Boiling Liquid)

1 xd 1 xd
Rm
1 x f 1 x f

b) Feed is saturated vapor (Vapor feed)

1 . xd 1 xd
Rm 1
1 y f 1 y f
For any feed condition (for any value of q)

Rm z f qxd xd q 1 z f Rm 1

Rm 1 z f q1 xd Rm 11 z f q 11 xd
Determine the minimum reflux ratio for the binary distillation at standard atmospheric
presssure when,
i) Feed is saturated liquid
ii) Feed is at room temperature (say at 30oC)

Make use of the following data:

Feed = 100 kmol/h
Feed mixture: benzene toluene
Mole fraction of benzene in feed = 0.4
Mole fraction of benzene in distillate required = 0.09
Mole fraction of benzene in residue required = 0.02
Average relative volatility = 2.25

The constants in the Antoine equation,are:

For benzene: k1 = 6.90565 k2 = 1211.033 k3 = 220.79
For toluene: k1 = 6.95334 k2 = 1343.943 k3 = 219.377

Component Cp( kJ/kmoloC) (kJ/kmol)

Benzene 147 29391
Toluene 173 34667
Optimum Reflux Ratio

Total Cost (C)

Steam Cost (B)

Costs

Capital Cost (A)

Optimum Reflux Ratio (Ropt)

Rm Reflux Ratio

There is no simple relation between Rm and the optimum value, although practical values are generally 1.21.5
times the minimum.
Determination of Theoretical Stages

Methods valid for Binary Mixture Distillation:

Short Cut Method: Fenskes Equation, Smokers equation, Kremser Equation etc.

Detailed Method: McCabe Thiele, Lewis Sorel, Ponchon-Savarit etc.

McCabe Thiele Method:

Assumptions:
1. The two components have equal and constant molar enthalpies
of vaporization.

2. Component sensible-enthalpy changes and heat of mixing are negligible.

3. The column is well insulated so that heat loss is negligible.

4. Constant molar vapor and liquid flow.

McCabe Thiele Method:
Limitations:
1. The method should not be employed when relative volatility is less than 1.3
or greater than 5
That means 1.3 < <5

Stepwise procedure for applying McCabe-Thiele method is as follows:

1. Draw the vapor liquid equilibrium curve from the VLE data available at the operating
pressure of distillation column.
Or VLE data can be obtained by using following correlation, when relative volatility at
operating temp. and pressure is known.
x
y
1 1x
2. Make a material balance over the column to determine the top and bottom compositions,
xd and xw from the data given.

3. Mark the point, xd, zf, and xw on 45o diagonal line.

Low product concentrations:
When concentrations of the more volatile component of either product is very low the steps on
the McCabe-Thiele diagram become very small and difficult to plot.

If the operating and equilibrium lines are straight, and they usually can be taken as such when
the concentrations are small.

The number of stages required can be calculated using the equations given by Robinson and
Gilliland,

For the stripping section:

K s xr

1 1

log s xw 1
K s 1

s
Ns 1
K
log s
s
Where,

Ns number of ideal stages required from xw to some reference point xr in stripping section.
 Ks = equilibrium constant (VER) for the more volatile component in stripping section.

s = slope of the bottom operating line.

xw = mol fraction of the more volatile component in the bottom product.

xr = mol fraction of more volatile component at the reference point.

For the rectifying section:

1 R
xr
R K
R
xd
log
1 K R

NR 1
R
log
KR
Where,

NR number of ideal stages required some reference point xr to xd in rectifying section.

 KR = equilibrium constant (VER) for the less volatile component in rectifying section.

R = slope of the top operating line.

xd = mol fraction of the less volatile component in the distillate.

xr = mol fraction of less volatile component at the reference point.

Note: at low concentrations K =

Value of N for Different values of R/Rm

R/Rm 2 2.5 3 3.5 4

N 16 15 14 14 13.5

On increasing the value of R/Rm above 2, decrease in value of N is very marginal.

Hence, R = 2 Rm is considered to be nearer to the optimum value.
Use of Open Steam:
While distilling an aqueous solution, if non aqueous component is more volatile then water is
removed as residue product.

It is usually cheaper than the separate reboiler system as it avoids fixed cost and cleaning cost
of reboiler.

But, for the same value of reflux ratio and the given extent of separation, use of open steam
requires more number of equilibrium stages.

O.M.B.
F+S=D+W

MVC M.B.
F zf = D xd+ W xw

In this case the striping line starts at from (x = xw, y=0) point and has a slope Lm/S

If superheated steam is used as open steam, then S can be calculated as,

H s H sat
S S s 1

PONCHON SAVARIT METHOD:

For a non-ideal system, where the molar latent heat is no longer constant and where
there is a substantial heat of mixing, the calculations become much more tedious.

For binary mixtures of this kind a graphical model has been developed by RUHEMANN,
PONCHON, and SAVARIT, based on the use of an enthalpy-composition chart.

It is necessary to construct an enthalpy-composition diagram for particular binary

system over a temperature range covering the two-phase vapor-liquid region at the
pressure of the distillation.
The following data are needed:

1. Heat capacity as a function of temperature, composition and pressure.

2. Heat of mixing and dilution as a function of temperature and composition.

3. Latent heats of vaporization as a function of composition and pressure or

temperature.

4. Bubble-point temperature as a function of composition and pressure.

Enthalpy of liquid:
n
hm hi (1)
i

In regular / ideal mixtures:

hi x i hio (2)

For gaseous / vapor mixtures at normal T and P:

n n
Hm hi y i i (3)
i i
Enthalpy-composition diagram
The equations used to calculate enthalpy of liquid and
vapor are:

hmix x A hA xB hB Hsol (3)

hmix x A CP ,A T Tref xB CP ,B T Tref Hsol (4)

Hmix hmix mix (5)

mix x A A xB B (6)
EXAMPLE 2
Devise an enthalpy-concentration diagram for the
heptane-ethyl benzene system at 760 mm Hg, using the
pure liquid at 0C as the reference state and assuming
zero heat of mixing.

SOLUTION

heptane ethyl benzene

TB (C) 136.2 98.5
CP (cal/mole K) 51.9 43.4
(cal/mole) 7575 8600
 t, C xH yH H EB
136.2 0.000 0.000 -- 1.00
129.5 0.080 0.233 1.23 1.00
122.9 0.185 0.428 1.19 1.02
119.7 0.251 0.514 1.14 1.03
116.0 0.335 0.608 1.12 1.05
110.8 0.487 0.729 1.06 1.09
106.2 0.651 0.834 1.03 1.15
103.0 0.788 0.904 1.00 1.22
100.2 0.914 0.963 1.00 1.27
98.5 1.000 1.000 1.00 --
t = 136.2C
xH = 0.0 xEB = 1.0

h xH CP ,H t tref xEB CP ,EB t tref Hsol

= 0 + 1.0 (43.4) (136.2 0) + 0 = 5,911 cal/mole

mix = xH H + xEB EB = 0 + 1.0 (8,600) = 8,600

H = h + mix = 5,911 + 8,600 = 14,511 cal/mole

t = 129.5C
xH = 0.08 xEB = 0.92

h xH CP ,H t tref xEB CP ,EB t tref Hsol

= 0.08 (51.9) (129.5) + 0.92 (43.4) (136.2)

= 5,708 cal/mole
mix = xH H + xEB EB = 0.08 (7,575) + 0.92 (8,600) = 8,518

H = h + mix = 5,708 + 8,518 = 14,226 cal/mole

The computations are continued until the last point

where xH = 1.0 and xEB = 0.0
t, C xH h H
(cal/mole) (cal/mole)
136.2 0.000 5,911 14,511
129.5 0.080 5,708 14,226
122.9 0.185 5,527 13,937
119.7 0.251 5,450 13,793
116.0 0.335 5,365 13,621
110.8 0.487 5,267 13,368
106.2 0.651 5,197 13,129
103.0 0.788 5,160 12,952
100.2 0.914 5,127 12,790
98.5 1.000 5,112 12,687
 20,000
18,000
Vapor
16,000 Saturated vapor
14,000
12,000
H

10,000 2 Phase
8,000
6,000
4,000
Liquid Saturated liquid
2,000
0
0 0.2 0.4 0.6 0.8 1
x
Stepwise procedure to determine the number of theoretical trays
by Ponchon Savarit :

Step 1: Draw the equilibrium curve and the enthalpy concentration diagram for
the mixture to be separated.

Step 2: Calculate the compositions of the feed, distillate and bottom products.
Locate these compositions on the enthalpy-concentration diagram.

Step 3: Estimate the reflux rate for the separation and locate the rectifying section
difference point as R Point y1 is the intersection point of line joining point xD and
R and HV-y curve.

Step 4: Locate the stripping section difference point s. The point s is to be located
at a point where the line from R through xF intersects the xB composition coordinate.

Step 5: Step off the trays graphically for the rectifying section. Then the point of
composition x1 of liquid of top tray is to be determined from the equilibrium relation
with y1 of vapor which is leaving the tray and locate it to the HL-x curve. Then the
composition y2 is to be located at the point where the line of points R and x1
intersects HV-y curve. This procedure is to be continued until the feed plate is reached.
Step 6: Similarly follow the same rule for stripping section. In the stripping section, the
vapor composition yB leaving the reboiler is to be estimated from the equilibrium
relation. Then join the yB and S to find the xN. The vapor composition yN is to be
determined by extending a tie line to saturated vapor curve HV-y. The procedure is to
be continued until the feed tray is attained.

Determination of the reflux rate:

The reflux rate can be calculated from the energy balance around the condenser,

L QC' HV 1

D HV 1 H D
The Smoker equation:

An analytical equation that can be used to determine the number of stages when the relative
volatility is constant.
It can be used for any problem for which the relative volatilities in the rectifying and
stripping sections can be taken as constant.

Smoker shows that the number of stages required is given by the equation:

Where,

N = is the number of stages required to effect the separation represented by the concentration
change from x0* to xn*.

Where, x* = (x - k) ; and x0* > xn*.

k = is the value of the x-ordinate at the point where the extended operating lines intersect the
vapour-liquid equilibrium curve
Contd

s = slope of the operating line between xn* and xo*

= relative volatility, assumed constant over xn* to xo* .

A straight operating line can be represented by the equation;

y = sx +b .. 1

Eliminating y from equations 1 and 2 gives a quadratic in x

 .. 3

For any particular distillation problem equation (3) will have only one real root k,
between 0 and 1

.. 4

Rectifying Section:
Stripping section:

Note : If the feed stream is not at its bubble point, zf is replaced by the value of x at the intersection of operating lines.

Ex.5. A column is to be designed to separate a mixture of ethylbenzene and styrene. The feed will
contain 0.5 mol fraction styrene, and a styrene purity of 99.5 per cent is required, with a recovery
of 85 per cent. Estimate the number of equilibrium stages required at a reflux ratio of 8. Maximum
column bottom pressure 0.20 bar.

Given: