Distillation

Prepared by: DEEDAR ALI QURESHI;

Assist by: PHAIXA ABBASI,
Former student of CHM KU.
References:
Outlines
of
Distillation

Outlines:
Definition of Distillation;
Theory of Distillation;
Types of Distillation;
Applications of Distillation;
Advantages of Distillation
over other techniques;
Modern trends of
Distillation.

DISTILLATION

Separation of mixtures of liquids into their components
- most important processes of the chemical industry
- a common method for this separation is distillation

Principle of Distillation
Distillation is based on the fact that the vapour
of a boiling mixture will be richer in the
components that have lower boiling points.
Therefore, when this vapour is cooled and
condensed, the condensate will contain more
volatile components. At the same time, the
original mixture will contain more of the less
volatile material.
Distillation is a process wherein a liquid or vapour mixture of two or more
substances is separated into its component fractions of desired purity, by
the application and removal of heat.

What is Distillation
Examples include:
separation of alcohol and water
liquid air into N
2
, O
2
and Air
crude petroleum into gasoline, kerosene, fuel oil and lubricating
stock

Differences in BPs of components (vapour pressure characteristics
of liquid mixtures) enables separation

Vapour pressure of a liquid ?
Equilibrium pressure exerted by molecules leaving and entering the
liquid surface.

Distillation occurs - due to differences in the relative volatility (ratio
of vps) of the components in the liquid mixture

Theory and basic principle of
Distillation
Its based upon Raoults law, Daltons law
and assume that vapor-liquid equilibrium are
attained.
Raoults law.
It states that the change in vapor pressure of a substance
can be determined by the product of the mole fraction of the
substance and the vapor pressure of the pure substance
Daltons law.
It states that the total pressure exerted by the mixture of non
reactive gases is equal to the sum of the partial pressure of
individual gas
Raoults Law
For a mixture of two miscible liquids (A and B), the total vapor pressure is the
sum of the individual vapor pressures:
P
total
= P
A
+ P
B
where
P
A
= N
A
liquid

x P
A
And P
B
= N
B
liquid
x P
B
where
P
A
is the vapor pressure of pure A and P
B
is the vapor pressure of pure B
and
N
A
liquid
is the mole fraction of A and N
B
liquid
is the mole fraction of B
where
N
A
liquid
= moles A/moles A + B and N
B
liquid
= moles B/moles A +B
9
4.1.2 Boiling-Point Diagrams and xy Plots
4.1 Vapor-Liquid Equilibrium Relations
Important points concerning vapour pressure are:
-energy input raises vapour pressure

-vapour pressure is related to boiling

-a liquid is said to boil when its vapour pressure equals the surrounding
pressure

-the ease with which a liquid boils depends on its volatility

-liquids with high vapour pressures (volatile liquids) will boil at lower
temperatures

-the vapour pressure and hence the boiling point of a liquid mixture
depends on the relative amounts of the components in the mixture
In distillation Vapor rich in more volatile components
original mixture - rich in less volatile material
columns are designed to achieve efficient separation

Most of the process engineers
- have a fair idea what distillation means

Some important aspects which are overlooked from the
manufacturing point of view are:
-distillation is the most common separation method
-it consumes enormous amounts of energy, both in terms of
cooling and heating requirements
-it can amount to more than 50% of plant operating costs
Possible ways to reduce operating costs of existing units include:

- improve their efficiency and operation
- via process optimisation and control

To achieve this improvement it is essential to have

- a thorough understanding of basic distillation principles
- familiarity with the design aspects of distillation systems
TYPES OF DISTILLATION COLUMNS
Batch Columns:
The feed to the column is introduced
batch-wise. That is, the column is
charged with a 'batch' and then the
distillation process is carried out.
When the desired task is achieved, a
next batch of feed is introduced.
(Batch is always unsteady-state, used
in organic chemistry lab)
Disadvantages:
large amounts of material
long residence times
Continuous Columns:
Continuous columns process a
continuous feed stream. No
interruptions occur unless there
is a problem with the column or
surrounding process unit.
Advantages:
More stages - improvement in
separation
Continuous columns can be further classified according to:
-the nature of the feed that they are processing

-binary column - feed contains only two components

-multi-component column - feed contains more than two
components

-the number of product streams they have

-multi-product column - column has more than two product
streams
-extractive distillation - where the extra feed appears in the
bottom product stream (solvent added near the top of the
column)
-azeotropic distillation - where the extra feed appears at the top
product stream
-(eg. Benzene added to alcohol/water mixture, with ternary mixture
boiling at 64.85C lower than binary bp 78C)
(Mixture that retains the same composition in the V state as in the L state when distilled)
-the type of column internals
-tray column - where trays of various designs are used to
hold up the liquid to provide better contact between vapour
and liquid, hence better separation
packed column - where instead of trays, 'packings' are used
to enhance contact between gas and liquid
-extractive distillation - where the extra feed appears in the
bottom product stream (solvent added near the top of the
column)
-azeotropic distillation - where the extra feed appears at the top
product stream
-(eg. Benzene added to alcohol/water mixture, with ternary mixture
boiling at 64.85C lower than binary bp 78C)
(Mixture that retains the same composition in the V state as in the L state when distilled)
-the type of column internals
-tray column - where trays of various designs are used to
hold up the liquid to provide better contact between vapour
and liquid, hence better separation
packed column - where instead of trays, 'packings' are used
to enhance contact between gas and liquid
FLASH DISTILLATION
In flashing operation a liquid is introduced into a
chamber at a pressure below that of the vapor
pressure of the feed liquid. A portion of the liquid
immediately vaporises or flashes, hence the name.
used on a large scale
in petroleum refining

not effective for separating
closely boiling mixtures
What is Flash Distillation?
FLASH DISTILLATION
F x
F
D x
D
B x
B
F = Feed flow rate

concentration = z
F

specific enthalpy h
F

D = distillate or top product (vapour)
flow rate

concentration = y*
D

specific enthalpy H
D

B = bottoms product (liquid) flow rate

concentration = x
B

specific enthalpy = h
B
Designer of a flash system needs to know

- P and T of the flash drum

- size of the flash drum

- the liquid and vapor compositions

- P, T and flow rate of the feed entering the drum or column

- how much the original feed has to be pressurised and heated


Pressures must be chosen such that at the feed pressure, the feed is below
its bp and remains liquid

At the pressure of the flash drum or column, the feed must be above its
boiling point and some of it vaporises
Balances:
Mass
F D B = +
Component
F z D y B x
F D B
= +
Enthalpy
F h Q D H B h
F D B
+ = +
Solving simultaneously gives:
=

=
+
|
\

|
.
|
+
|
\

|
.
|
B
D
y z
x z
H h
Q
F
h h
Q
F
D F
B F
D F
B F
On an x-y diagram, gives operating line
through (z
F
,z
F
), slope -B/D
x
y
-B/D
z
F
x
D
x
B
F x
F
D x
D
B x
B
F x
F
D x
D
x
F
T-x data (T - temperature in K and x mol fraction of hexane in
liquid):
399 378 367 357 350 344
0.0 0.2 0.4 0.6 0.8 1.0

T-y data (T - temperature in K and y mol fraction of hexane in
vapor):
399 393 387 378 367 344
0.0 0.2 0.4 0.6 0.8 1.0
Hexane-octane mixture containing 60 mol% hexane is flashed
at 1 atm. If one-fourth of the feed is vaporised what are the
compositions of the product streams? Extract equilibrium
compositions from the following T-xy data.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 0.2 0.4 0.6 0.8 1
x
y
Let f = D/F
F = D + B
Fx
F
= Dy
D
+ Bx
B
y
D
= {-(1-f)/f}x
B
+(1/f)x
F

Locate the intersection
of material balance line
with the equilibrium
curve and read liquid
and vapor compositions

x = 52%
y = 86%
Sections of Continuous Distillation
Columns
A typical distillation contains several
major components:
-a vertical shell where the separation of
liquid components is carried out
-column internals such as trays/plates
and/or packings which are used to
enhance component separations
-a reboiler to provide the necessary
vaporisation for the distillation process
-a condenser to cool and condense the
vapour leaving the top of the column
-a reflux drum to hold the condensed
vapour from the top of the column so that
liquid (reflux) can be recycled back to
the column
Fractional Distillation Set-up
The vertical shell houses the column
internals and together with the condenser
and reboiler, constitute a distillation
column.

Normally feed column near centre

Section above feed: enriching or
RECTIFYING section
removes less volatile components from vapour
(vapour is enriched in the volatile component)

Section below feed: STRIPPING section
the volatile component is stripped from liquid

Liquid coming down REFLUX

Top product DISTILLATE

Bottom product RESIDUE or
BOTTOMS.
Temperature - highest at the reboiler

Decreases progressively up the tower

Reaches a minimum (T) in the
condenser

Fractionator is quite literally a heat
engine
- separating feed mixture into
relatively pure products.

Heat addition to the system at a high
level and rejected at a lower level.
Fractional distillation
F x
F
D x
D
B x
B
V
1
L
0 n
Overall balances:
F D B
= +
Fz Dx Bx
F D B
= +
=


=


D
F
x x
x x
B
F
x x
x x
F B
D B
D F
D B
and
Net Flow Rates:
Rectifying Section:
Condenser:
D V L
=
1 0
Total D V L
n n
=
+
1
( = constant)
Conventions:
Number trays from the top down
(i.e. in direction of L-phase flow)
A bar over a flowrate, e.g. refers
to the stripping section
L
Component flow:
Dx Vy Lx V y L x
D n n n n
= =
+ + 1 1 0 0 1 1
= constant
Stripping section:
B L V L V
N N m m
= =
+ + 1 1
Bx L x V y L x V y
B N N N N m m m m
= =
+ + + + 1 1 1 1
= constant (mrefers to intermediate stage close to
feed point)
F x
F
D x
D
B x
B
V
1
L
0 n
F x
F
B x
B
D x
D
F x
F
D x
D
B x
B
V
1
L
0 n
Operating Lines:
Rectifying section:
1
0 0 1 1
1
1
+ +
+

+ =
n
n
n
n
n
V
x L y V
x
V
L
y
D
n
n
n
n
n
x
V
D
x
V
L
y
1 1
1
+ +
+
+ =
eliminating V
n+1
:
y
L
L D
x
D
L D
x
n
n
n
n
n
D +
=
+

+
1
F x
F
D x
D
B x
B
V
1
L
0 n
Stripping section:
y
L
V
x
V y L x
V
m
m
m
m
N N N N
m
+
+
+ +
+
= +

1
1
1 1
1
But
V y L x Bx
N N N N B + +
=
1 1

y
L
V
x
B
V
x
m
m
m
m
m
B +
+ +
=
1
1 1
eliminating V
m+1
:

y
L
L B
x
B
L B
x
m
m
m
m
m
B +
=

1
If L
n
or
L
m
vary

curved operating lines.

If enthalpy changes significant:

must use Ponchon-Savarit Method with

enthalpy/concentration (H-x) diagram.
If not significant:
called CONSTANT MOLAL OVERFLOW

use mole units

constant L
n
and
L
m

drop subscripts

ignore enthalpy changes

use McCabe-Thiele method based on

x-y diagram only
Inherent assumption in McCabe-
Thiele method -

distillation column is at the same
pressure

One can use constant pressure x-y
diagram.

Actually P decreases from bottom
to top.

Why??

A driving force is necessary for
the vapor to flow upward.
x
y
x
D
x
B
L/(L+D)
L/(L-B)
OPERATINGLINES:
D n n
x
D L
D
x
D L
L
y
+
+
+
=
+1
(rectifying)
y
L
L B
x
B
L B
x
m m B +
=

1
(stripping)
Onx-y diagram:
rectifying: through(x
D
,x
D
), slope
L
L D +
stripping: through(x
B
,x
B
), slope
L
L B
Adequate design problemdefinition:
Design a fractionator column to produce a desired separation for known F,
z
f
, x
B
&x
D
.
Material balance

yields B and D
Reflux quantity needed for the design
Relux ratio - is a common way of expressing the reflux amount
Reflux ratio

R
L
D
V D
D
D
= =

so
y
R
R
x
x
R
n
D
D
n
D
D
+
=
+
+
+
1
1 1

line with a y-intercept of x

D
/(R
D
+1) passing through (x
D
,x
D
) with
slope=R
D
/R
D
+1
OPERATINGLINES:
D n n
x
D L
D
x
D L
L
y
+
+
+
=
+1
(rectifying)
y
L
L B
x
B
L B
x
m m B +
=

1
(stripping)
Onx-ydiagram:
rectifying: through(xD,xD), slope
L
L D +
stripping: through(xB,xB), slope
L
L B
x
y
x
D
R/(R+1)
x /(R+1)
D
Total Condenser
D x
D
V
1
L
0
Total condensers - Simpler and cheaper
In a total condenser, all of the vapor leaving
the top of the column is condensed.
Consequently, the composition of the vapor
leaving the top tray y
1
is the same as that of
the liquid distillate product and reflux, x
D
.
Partial Condenser
In a partial condenser, the vapor is only partially liquified. The compositions of
these three streams (V
1
, D, and R) are different. Normally, D (composition y
D
)
is in equilibrium with R (composition x
D
).
A partial condenser functions as an equilibrium separation stage, so columns
with a partial condenser effectively have an extra ideal stage (extra condensing
and control equipment required)
Reboilers
Most reboilers are partial reboilers
meaning that they only vaporize part
of the liquid in the column base.
Vapor leaving the reboiler is in
equilibrium with the liquid leaving
as bottom product
Reboiler acts as an ideal plate.


y
N+1
is in equilibrium with x
B

x
y
x
B
y
N+1
B
m
m
m
m
m
x
B L
B
x
B L
L
y

=
+1
Determination of number of stages
Rectifying
section
y
L
L D
x
D
L D
x
n
n
n
n
n
D +
=
+
+
+
1
Stripping
section
y
L
L B
x
B
L B
x
m
m
m
m
m
B +
=

1
McCabe-Thiele: insignificant enthalpy changes
constant flows
=> constant molal overflow conditions
Ponchon-Savarit:
enthalpy changes or heat loss important
requires use of H-x diagram
Reflux ratio:
R
L
D
V D
D
D
= =

Upper operating line

two points i.e. (x

D
,x
D
) and
y-intercept.
Lower operating line

same manner

line will pass through the

point (x
B
, x
B
)

second point by
considering feed condition
Construction of stages
Feed Conditions
Saturated liquid
Vapor liquid mixture
Saturated vapor
Sub-cooled liquid ??

Superheated vapor??
FEED LINE:
q = fraction of the feed that is liquid at column
conditions
The feed stream increases
liquid by q.F and vapour by (1-q).F
Consequently,
( )
L L qF V V q F = + = + and 1
This can be rewritten as
( )
L L qF V V q F = = and 1
Operating Lines are:
B D
Bx x L y V and Dx Lx Vy = + =
Subtracting gives:
( ) ( )
yV V L L x Dx Bx
D B
= + +
Substituting for
L L
and
V V
gives:
( )
y q F qFx Dx Bx
D B
1 = + +
But
Dx Bx Fx
D B F
+ =

Feed Line is given by

y
q
q
x
x
q
F
=

+
1 1
passes through (x
F
,x
F
); slope

q
q 1
passes through intersection of rectifying and
stripping operating lines
Feed Plate Location
q = moles of liquid in stripping section that result from each mole of feed (or
fraction of the feed that is liquid at column conditions)
Slope of q-line is located graphically

q-line is the locus of intersection of upper
and lower operating lines
for saturated vapour:
( )
q
c T T
P b F
L
= +

where c
PL
liquid specific heat
T
b
bubble point
T
F
feed temperature

enthalpy change on completely

vaporizing 1 mole of saturated liquid
feed to saturated vapour.
for superheated vapour:
( )
q
c T T
P F d
V
=

where c
PV
vapour specific heat
T
d
dew point.
Steps for the complete column:

Locate x
D
, x
F
, and x
B

Locate the feed line: slope = -q/(1-q)

Determine the y-intercept for the rectifying
line, x
D
/(R
D
+1)

Draw in rectifying line

Draw in stripping line

Calculate the number of stages from x
0
downwards.
Get the number of stages (N)
Get the location of the feed stage (n
F
)
Important note: Remove one stage for reboiler
and one for partial condenser, if used
EXAMPLE
Feedtoa columnis 1000kg-mol/hr. The feedcompositionis
0.5; the topproduct compositionis 0.9; the bottoms composition
is 0.05. The equilibriumcurve is givenby

y x *=
For saturatedliquidfeedanda refluxratioof 2, determine the
number of stages requiredandthe positionof the feedstage.
x
y
z
F
x
D
x
B
Start at the top of the tower
with known distillate
composition, x
D
.

Proceed horizontally to the
left to find y
1
= y
D
on the
equilibrium curve.

Now drop vertically
downward to read off x
1
.

The point at which x
1

intersects the operating line
gives y
2
(by material
balance)

Repeated application of
this procedure gives number
of stages required to attain
the given separation.
Sub-cooled
liquid
Sat liquid
Vapr/liq mixture
Saturated vapor
Superheated
vapor
Feed condition
Stage construction
Y-intercept
x
d
/R+1
(x
d
, y
d
)
(x
f
, y
f
)
(x
b
, y
b
)
Sat vapour
1
6
5
2
4
3
Total reflux
(x
d
, y
d
)
(x
f
, y
f
)
(x
b
, y
b
)
Minimum number of stages
As R
D
changes, N changes
Rectifying slope = R
D
/(R
D
+1) (always < 1)
As R increases, slope increases
At R = , V=L, slope = 1
TOTAL REFLUX (returning all condensed
overhead to the column)
maximum separation in every stage
Minimum N
BUT
No product, bottoms flows
NO feed flow
L = V, L/V = 1, D = 0
L
b
= V
b
, L
b
/V
b
= 1, B = 0 (45 line)

Reflux ratio
R
L
D
V D
D
D
= =

y
R
R
x
x
R
n
D
D
n
D
D
+
=
+
+
+
1
1 1

Minimumreflux
R
min
< R<
R
min
corresponds to minimumslope of rectifying line
Generally occurs when:

feed line and operating lines intersect at the
equilibriumline
infinite number of stages
For constant o, Fenske equation can also be used
x
y
As the reflux ratio is further reduced,
the intersection of the operating lines
move along the feed line toward the
equilibrium curve, the area on the
diagram available shrinks, and the
number of steps increases.
When either one or both of
the operating lines touch
equilibrium curve, the
number of steps necessary
to cross the point of
contact becomes infinite.
Can also occur if operating line is tangent to equilibrium line:
x
y
Invariant zone or pinch
zone where there is no
change
in either L or V
concentrations
from plate to plate
Optimumreflux
Represents an economic compromise between
the investment cost of a tall tower at lowRand
high operating cost at high R.
The costs of heating and cooling will increase
with reflux.
Optimumreflux ratio is usually 1.1 - 1.5 R
min
Total costs will be operating costs plus capital
costs
C
o
s
t

(Heating and cooling costs)
(Fixed costs)
~ 1.1 to 1.5 R
min
R
min
R
min
requires infinite plates, fixed costs will be infinite, operating costs
lower
With R no of plates decrease, Column Dia increases due to large quantities
of L and V, Duties larger
Constant Molal Overflow
This occurs if & only if:
The molar heats of vaporisation of the binary
components are identical
Sensible heat distributions are negligible
Heats of mixing are negligible
With these criteria, internal energy balances around each
plate in the tower become trivial & molar flow rates of V
and L will be constant in any section of the tower. For this
case, we can use the graphical procedure of McCabe-Thiele
method to calculate no. of stages.
For many binary systems, this criteria is not valid and constant
molal overflow is a bad assumption.

Use of McCabe-Thiele analysis leads to underspecifying the
equipment (a situation to be definitely avoided)

So what are the alternatives???

Tedious trial and error procedure to solve coupled mass and energy
balances
OR
Ponchon analysis (this does not assume the liquid and vapor flow
rates are constant in each section of the tower)
The only assumption made with Ponchon method is that there are
no heat losses through the column walls.
Ponchon graphical methods
What is a Ponchon diagram?
Ponchon diagram is an enthalpy-concentration
chart
- used in solving energy balance problems as the
enthalpies can be read directly from the chart.
- charts are used to analyse binary distillation
processes
- suitable for systems which exhibits a large heat
of solution
- no significant heat losses from the column
What is a Ponchon
method???
It is a combination of
xy data with H-xy
charts to obtain
graphical solution of
coupled mass and
energy balances.

How charts are prepared??
heat capacity data (of pure and mixtures of liquids or
vapours)sat. L and V enthalpies
T-xy data for the system(bp, dp, equilibriumcomp)

Application distillation, crystallization or
extraction
F x
F
D x
D
B x
B
FLASH CALCULATIONS
Balances:
Mass
FDB = +
Component B D F
x B y D x F + =
Enthalpy B D F
H B H D H F + =
If F, x
F
andH
F
areknown, calculateD, B, x
B
, y
D
?
How to deal with continuous binary distillation columns?
We begin Ponchon analysis by writing balance equations around
the column (similar to flash columns) assuming no heat loss
through the column walls:

FH
F
+ q
rb
= B H
B
+ D H
D
+ q
cd
(11)
where q
rb
& q
cd
refer to the duty of the reboiler and condenser,
respectively, in BTU/h.
Since the column reflux ratio, r = L
0
/D is set, the condenser duty
may be found using

q
cd
= (L
0
+ D)
D
= D (1+r)
D
(12)
where
D
is the latent heat of vaporization of the distillate product.
Points d and l
1
must lie on the same
straight line as the point y
2
, H
v2
. Since we
know the location of points d and l
1
, we
can draw a line connecting these points.
StreamV
2
is sat. vapor and the intersection
of dl
1
with the saturated vapor line at point
v
2
must represent the enthalpy and
composition of streamV
2
.
Repeat the entire process to calculate L
2
and V
3
. A tie line is
drawn from the point v
2
to the saturated liquid line. Point l
2
,
thus determined specifies stream L
2
.From point l
2
a line is
constructed to point d.

By reasoning analogous to that following Equation 18, stream
V
3
is represented by the intersection of line l
2
d with the
saturated vapor line at point v
3
.

The process is continued for each plate in the rectifying
section of the column and the number of plates determined by
the number of tie lines, which were constructed.
When a tie line crosses line bfd, the feed point is determined. A new
set of material and energy balances is then used to find the no. of plates in
the stripping section. The no. of plates in the stripping section of the
column (plates below the feed point) is determined in much the same
manner as in rectifying section.
An energy balance is written around the second plate in the stripping
section and the reboiler as
L
4
H
L4
= V
5
H
v5
+ B (H
B
q
B
/B) (19)
b
By repeating this process until a tie line
intersects the saturated liquid line at or
below x
B
, we complete the Ponchon
analysis.

No. stages is determined by counting the
no. of tie lines that were constructed.

For example in the Figure we have a total
of equilibrium stages, 3 in the rectifying
section, one feed plate and 3 plates in the
stripping section.

The bottom stage in the stripping section
corresponds to the column reboiler.
b
The graphical analysis we have followed is equivalent to performing a
series of equilibrium calculations alternating with mass and enthalpy
balances.

Tie lines correspond to equilibrium calculations

Lines drawn from the saturated liquid locus to points d and b
represent the solution of coupled material and energy
balances
- Determine difference point (A) for enriching section
- Determine difference point for stripping section vt the
intersection point of x
A
z
f
line and the vertical line x
B
= x
A bar
.
- Stages may be stepped off from either end with use of the
appropriate delta point.
- Stages stepped off from the top of the column downward, by
alternate use of the equilibrium data and the delta point.
- Stepping off of stages is continued using (x
A
, h
A
) until z
f
is
reached.
- Then construction switches to the delta point for the stripping
section.
- The calculation is completed when the liquid composition equals
or exceeds the bottoms composition x
B
.
Calculation of feed line slope
Two-phase feed where 80% of the feed is vaporised
under column conditions

A superheated vapor where 1 mole of liquid will
vaporise on the feed stage for each 9 moles of feed
input

A liquid feed subcooled by 35F. Average liquid heat
capacity is 30 Btu/lb-mole.F and =15000 Btu/lb-
mole.

A mixture of ethanol and water containing 40mol%
ethanol. Feed is at 40C. Pressure is 1 kg/cm
2
. h
F
=
20 kCal/kg, H =395 kCal/kg, h = 65 kCal/kg