INTRODUCTION

TO
PROCESS
SEPARATION UNIT

CHAPTER 7
 Objectives:

Students should be able to explain;

Types of distillation column
 Basic distillation equipment and operation
 Column internals
 Distillation principles
 Vapour liquid equilibrium (VLE)
 Distillation column design
 The factors that affect distillation column operation
 • INTRODUCTION

 In order to separate or remove one or more mixture of different

components from its original mixture, it must be contacted with another
phase.
 The two phases are brought into more or less intimate contact with each
other so that a solute or solutes can diffuse from one to the other.
 The two-phase pair can be gas-liquid, gas-solid, liquid-liquid or liquid-solid.
 The phase are then separated by simple physical methods.
• TYPES OF SEPARATION PROCESS

Liquid-liquid
Absorption Distillation Leaching
extraction

Membrane Crystallization Adsorption Ion exchange

 7.1 DISTILLATION PROCESS
 is the process of separating the components or substances from a liquid
mixture by using selective boiling and condensation. Distillation may
result in essentially complete separation, or it may be a partial separation
that increases the concentration of selected components in the mixture.
 A volatile vapour phase and liquid phase that vaporizes are involved. The
vapour phase is created from the liquid phase by vaporization at the
boiling point.
 less volatile, "heavy" or "high boiling point", components concentrate in
the liquid phase; the more volatile, "light“ or “low boiling point”,
components concentrate in the vapor.
 used for many commercial processes, such as production of gasoline,
distilled water, alcohol, and many other liquids
 • Types of distillation column
Batch Columns
– In batch operation, 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.
Continuous Columns
– continuous columns process a
continuous feed stream. No
interruptions occur unless there is
a problem with the column or
surrounding process units. They
are capable of handling high
throughputs and are the most
common of the two types.
 Types of Continuous Columns
*The type of column internals:
* The nature of the feed that they are #tray column - where trays of various designs are
processing: used to hold up the liquid to provide better contact
# binary column - feed contains only two between vapour and liquid, hence better separation.
components #packed column - where instead of trays, 'packings'
#multi-component column - feed contains are used to enhance contact between vapour and
more than two components liquid.

*Where the extra feed exits when it is used *The number of product
to help with the separation: streams they have
#extractive distillation - where the extra feed multi-product column -
appears in the bottom product stream column has more than
#azeotropic distillation - where the extra two product streams
feed appears at the top product stream
Comparison of simple distillation and
fractional distillation
 • Basic distillation equipment and
operation
Distillation columns are made up of several components, each of which is used
either to transfer heat energy or enhance mass transfer. 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.
 To hold the condensed vapor so that
liquid (reflux) can be recycled back to
To cool and condense the vapor leaving the column
the top of the column

Trays/plates Distillate D
and/or which is
packings which richer in the
are used to more
enhance
component volatile
separations component
of mole
fraction,
xD.

Bottoms B
-richer in the
less volatile
component,
where the mole
fraction of the
more volatile
component is,
xB provide the necessary vaporization for
the distillation process
 Basic Operation and Terminology
1. The liquid mixture that is to be processed is known as the
feed and this is introduced usually somewhere near the
middle of the column to a tray known as the feed tray.
The feed tray divides the column into a top (enriching or
rectification) section and a bottom (stripping) section. The
feed flows down the column where it is collected at the
bottom in the reboiler.

2. Heat is supplied to the reboiler to generate vapour. The source of heat

input can be any suitable fluid, although in most chemical plants this is
normally steam. In refineries, the heating source may be the output
streams of other columns.  The vapour raised in the reboiler is re-
introduced into the unit at the bottom of the column. The liquid removed
from the reboiler is known as the bottoms product or simply, bottoms.
3. The vapour moves up the column, and as it exits the
top of the unit, it is cooled by a condenser.
The condensed liquid is stored in a holding vessel known
as the reflux drum. Some of this liquid is recycled back
to the top of the column and this is called the reflux.

4. The condensed liquid that is removed from the system

is known as the distillate or top product. Thus, there are
internal flows of vapour and liquid within the column as
well as external flows of feeds and product streams, into
and out of the column.
 • Distillation
Column Internals
Trays and Plates
BUBBLE CAP TRAYS

o A bubble cap tray has riser or

chimney fitted over each hole, and a
cap that covers the riser. The cap is
mounted so that there is a space
between riser and cap to allow the
passage of vapour. Vapour rises
through the chimney and is directed
downward by the cap, finally
discharging through slots in the cap,
and finally bubbling through the
liquid on the tray.
o Sieve trays are simply metal plates with holes in
them. Vapour passes straight upward through
the liquid on the plate. The arrangement, number
and size of the holes are design parameters.

SIEVE TRAYS
 Liquid and Vapour Flows in
a Tray Column
o Each tray has 2 conduits, one on each side,
called DOWNCOMER. Liquid falls through
the downcomers by gravity from one tray
to the one below it.
o A WEIR on the tray ensures that there is
always some liquid (HOLDUP) on the tray
and is designed such that the holdup is at a
suitable height, e.g. such that the bubble
caps are covered by liquid.
o Being lighter, vapour flows up the column
and is forced to pass through the liquid,
via the openings on each tray. The area
Direction of vapour and liquid flow across a tray, and across allowed for the passage of vapour on each
a column.
tray is called the ACTIVE TRAY AREA.
 Column internals
 As the hotter vapour passes through the liquid on the tray
above, it transfers heat to the liquid. In doing so, some of the
vapour condenses adding to the liquid on the tray.
 The condensate, however, is richer in the less volatile
components than is in the vapour. Additionally, because of the
heat input from the vapour, the liquid on the tray boils,
generating more vapour.
 This vapour, which moves up to the next tray in the column, is
richer in the more volatile components. This continuous
contacting between vapour and liquid occurs on each tray in the
column and brings about the separation between low boiling
point components and those with higher boiling.
 Column internals –tray design
 A tray essentially acts as a mini-column, each accomplishing a
fraction of the separation task. From this, can deduce that the
more trays there are, the better the degree of separation and that
overall separation efficiency will depend significantly on the design
of the tray.
 Trays are designed to maximise vapour-liquid contact by
considering the liquid distribution and vapour distribution on the
tray. This is because better vapour-liquid contact means better
separation at each tray, translating to better column
performance.
 Less trays will be required to achieve the same degree of
separation. Attendant benefits include less energy usage and
lower construction costs. There is a clear trend to improve
separations by supplementing the use of trays by additions of
packings.
 Example
application of
distillation column
 7.1.1 Vapor-Liquid Equilibrium (VLE)

• describes the distribution of a chemical species between the vapour

phase and a liquid phase.

• Vapor-liquid equilibrium for a mixture of liquids is different from

that of pure liquid. In a 2-component (binary) mixture,
an equilibrium condition can exist between the vapour and the
liquid phase. It showed a typical equilibrium condition attained
under a certain pressure P and temperature T. The 2 components
that made up the mixture distribute themselves unequally in both
the vapour and liquid phases.
 Distillation columns are designed based on the
boiling point properties of the components in the
mixtures being separated.

 Thus the sizes, particularly the height, of

distillation columns are determined by the vapour
liquid equilibrium (VLE) data for the mixtures.
 Condition or state where the rate of evaporation (liquid changing to
vapor) equals the rate of condensation (vapor changing to liquid).

 VLE data can be determined experimentally using an equilibrium still.

 VLE data can be determined or approximated with the help of

certain theories such as Raoult's Law, Dalton's Law, and/or
Henry's Law.
 7.1. 2 Binary system-VLE Data
 There are several different types of plots for binary system:
1. Pxy diagram: x and y as functions of pressure at constant
temperature.
2. Txy diagram: x and y as functions of temperature at
constant pressure.
3. xy diagram: x versus y at constant pressure (temperature is
a parameter along the curve).

 Since most applications require data at constant pressure, Txy

and xy diagrams are the most commonly used.
 Boiling points diagram
The boiling point diagram shows how the equilibrium
compositions of the components in a liquid mixture vary with
temperature at a fixed pressure.

VLE data is obtained from Boiling points diagram

T
Tb(B) Vapor region
Dew point curve=sat vap line

T1 Superheated V
T2 Vapor-liquid
mixture region
T3
T4
Bubble point curve=sat liq line

Subcooled L Tb(A)

Liquid region
x1 x2 x3 y1 x4 y2 y3 y4

The dew-point is the temperature at which the saturated vapour starts to condense. xA
The bubble-point is the temperature at which the liquid starts to boil.
The region above the dew-point curve shows the equilibrium composition of the superheated vapour while
the region below the bubble-point curve shows the equilibrium composition of the subcooled liquid.
 XY diagram for binary system
xy Diagrams
 xy diagram for a binary system, relates the compositions
of the liquid and vapor phases in equilibrium with each
other.
 These diagrams be generated from Constant pressure-
boiling point diagram.
 The greater the distance between the equilibrium line
and the 45 degree line, the greater the difference
between the vapour composition yA and liquid xA.

 The VLE plot expresses the bubble-point and the dew-point of a binary mixture at constant
pressure. The curved line is called the equilibrium line and describes the compositions of the
liquid and vapour in equilibrium at some fixed pressure.

 This particular VLE plot shows a binary mixture that has a uniform vapour-liquid equilibrium
that is relatively easy to separate.
Txy Diagram (Phase Diagram)
 7.1.3 VLE Relationship
If experimental data are not available, estimation of VLE can still be
done. HOW?
 simplest method assumes ideal vapor and ideal liquid phases.

Raoult’s Law
Pyi  Pi xi
sat
pi  Pi xi
Where
pi= partial pressure of species i in the vapor

Pi = the vapor pressure of pure species

xi=mole fraction of species i in the liquid

27
 VLE at Low Pressures – Raoult’s Law
Calculations Using Raoult's Law

Bubble-point pressure problem -- T,x given -- P,y unknown.

The vapor pressures are found at the given temperature, which

allows direct calculation of the pressure and vapor mole fractions:
 Pyi  P   Pi xi
p A  pB  P
Where PA x A  PB (1  x A )  P
P = total pressure of component A in the vapor.
Pi xi
Pi = vapor pressure of species i yi 
xi =mole fraction of species i in the liquid
P
Calculations Using Raoult's Law
Dew-point pressure problem -- T,y given -- P,x
unknown.
No trial and error is needed, as P can be directly
calculated.

Pyi
xi  sat
Pi
x i 1

1
P
 y i / Pi sat 
 Example 1:
(Use of Raoult’s Law for boiling point Diagram)

Use Raoult's Law and calculate the vapour and liquid compositions in
equilibrium at 95Co (368.2 K) (in mole fractions, y and x) for the benzene-
toluene system using vapour pressure data measure at a pressure of 101.32
kPa as shown in Table 1 below :

Table 1:
ANSWER:

 from Table 1
For benzene P0A= 155.7 kPa Raoult’s Law
For toluene P0B= 63.3 kPa
pi=Pi o xi

Refer to equation Dalton Law:

Dalton’s Law
PAo x A  PBo (1  x A )  P ppAA  ppBB PP
155.7(xA) + 63.3 (1-xA)=101.32 kPa

Liquid composition; Vapor composition:

xA=0.411 and PAo x A
yA 
xB= 1-0.411=0.589 P

yA= (155.7 x 0.411)/101.32 = 0.632

yB= 1-0.632=0.368
 7.1.4 Relative Volatility of
Vapor-Liquid Systems
Relative volatility ( AB )
It is a measure of the differences in volatility between 2 components, and
hence their boiling points. It indicates how easy or difficult a particular
separation will be. yA / xA y A / xA
 AB  
y B / xB (1  y A ) /(1  x A )
Where αAB is the relative volatility of A with respect to B in the binary system.
PA0 x A PB0 x B
Raoult’s law: yA  yB 
P P
PA0
 AB  0
PB
 AB x A
yA  * when αAB is above 1.0, a separation
1  ( AB  1) x A is possible.
7.2 Preliminary Design of Distillation Column
o Perform stage-by-stage material balances in a
distillation column.
o Determine total number of stages needed for a
column.
o Determine the location of the feed stage.
o Understand minimum reflux ratio.
7.2.1 DISTILLATION WITH REFLUX AND McCABE-
THIELE METHOD

INTRODUCTION
o The vapour and liquid products from each stage (sieve plates or
trays) flow countercurrent to each other. The liquid in a stage
flows to the stage below and the vapour from a stage flows
upward to the stage above.
o In each stage a vapour stream V and a liquid stream L enter, are
mixed and equilibrated and a vapour and a liquid stream leave in
equilibrium.
Lin,xin Vout,yout At each stage of the column two
phases come in contact with each
other, mix, approach thermal and
composition equilibrium to the extent
Lout,xout Vin,yin
which depends on the efficiency of the
contact stage
Streams coming to the stage are not in equilibrium

Streams leaving the stage are in thermodynamic

equilibrium with each other
7.2.2 McCabe-Thiele method to calculate the
number of theoretical stages

– It is a mathematical graphical method for determining

the number of theoretical trays or stages needed for a
given separation of a binary mixture of A and B.
– The main assumption in this method is that there must
be an equimolar flow through the tower between the
feed inlet and the top tray and the feed inlet and the
bottom tray (L and V constant).
 Material balances for two
components systems
1. Total material balance on the entire
column
F=D+B

2. Component material balance on

component A

F xF= D xD+ BxB

B XB
Material Balances (top section)
On stage :
- Vapor and liquid
stream leave in
equilibrium (VLE
line)

Between stage :
- Vapor and liquid streams must satisfy the
material balance equation (operating line).
  Material balance around condenser: V  LD

 Overall material balance over the Fig 1.11: Vn 1  Ln  D

 Components material balance over the Fig 1.11:

Material balance equation for

rectifying operation line (ROP)
40
 Ln
R  slope
D
L R
R n 
Vn 1 R  1

41
 Operating Line: Rectifying (Upper)
y

R 1
yn 1  xn  xD slope=R/(R+1)
R 1 R 1

1
xD
R 1

x
xD

42
 Material Balances (bottom section- Stripping)

Vm 1  Lm  W

Vm 1 y m 1  Lm x m  WxW

Lm Wx w
y m 1  xm 
Vm 1 Vm 1
liquid flow to plate m+1 = Vapour flow from plate m+1 + Bottom product withdrawn

Overall components material balance over plate m+1:

Since equimolar flow is assumed ,the

slope is
Rearranging the equation : Lm
Vm 1
 Operating Line:
Stripping (Lower)

Intersection between
upper operating line and
q line
 Feed Line

The conditions of the vapor rate or the liquid rate may change
depending of the thermal condition of the feed.

It is related to the heat to vaporize one mole of feed divided by

molar latent heat (q)

 It is the locus of the intersection of the two operating lines

 Its intersection with the 450 line is y=x=xf where xf is the

overall composition of the feed.
 Feed Line Equation

– The point of intersection of the two operating lines lies

on the straight line of slope (q/q -1) and intercept (xF, yF)
q xF
yq  xq 
q 1 q 1

the heat needed to vaporize 1 mole of feed entering conditions

q
molar latent heat of vaporization of feed
 Feed line
behavior (q- Feed at saturated liquid Cold feed

x
line)

y=
y q=1 q>1

Feed partial vapor 0<q<1

Feed at saturated q=0 x=xf

vapour

Feed superheated q<0 q xF

yq  xq 
q 1 q 1
x

47
 THEORETICAL STAGES

– Starting at xD and stepping of the

plate xW or XB

– Since reboiler is considered a

theoretical step, the no of theoretical
trays in a tower is equal to the number
of the theoretical step, minus 1.

4 stages + reboiler
– No of trays = No of steps– 1(reboiler)
 Construction for the McCabe-Thiele Method
1. equilibrium 2. equilibrium
Step 1: Plot equilibrium curve and 45 degree line.
curve curve
45° line Step 2: Plot given compositions (xF, xB, and xD)
y y Step 3: Draw q-line from xF and yF
Step 4: Determine Rmin from intersection of the
rectifying section OL and the equilibrium curve.
45° line Step 5: Determine R from R/Rmin
Step 6: Draw OL for Rectifying section
Step 7: Draw OL for Stripping section
xB x=zF xD
x

5. and 6. 7.
3. 4.
equilibrium equilibrium equilibrium
equilibrium
curve curve curve
curve

y y y y

xB xD xB x=zF xD xB x=zF xD xB x=zF xD

x=zF

Rmin/(Rmin+1) R/(R+1)
 R 1 y
yn 1  xn  xD
R 1 R 1 y1

q xF
y x
q 1 1 q
zf
Lm Wx w
y m 1  xm 
Vm 1 Vm 1
1 yB
xD
R 1
xB xN zf xD
x
 Complete picture McCabe Thiele
Step 1: Plot equilibrium curve (VLE) data.
Step 2: Plot 45 degree line
Step 3: Plot given compositions
(XF, XB, and XD)
Step 4: Draw q-line from xF and yF y
Step 5: Draw OL for Rectifying section yD
Step 6 : Draw OL for Stripping section
Step 7: Start stepping off from the distillate
end until the intersection of the two operating
lines is passed.
Step 8: Continue stepping but use the
stripping operating line. yf
Step 9: Count the number of stages.
Step 10: Subtract one for the reboiler to give
the number of theoretical trays
yB

xB xf xD
x
 Reflux Ratio

– The analysis of fractionating columns is facilitated by the use of a

quantity called reflux ratio.
– Two ratios are used, one is the ratio of the reflux to the overhead
product and the other is the ratio of the reflux to the vapor.
– Both ratios refer to quantities in the rectifying section. The
equations for those ratios are

L V D L L
RD   and RV  
D D V LD
 Minimum Reflux Ratio Rm
• Reflux ratio, R that will require an infinite number of plate for the
given desired separation of xD and xB
• At any reflux less than total, the number of plates needed is larger
than at total reflux and increases continuously as the reflux ratio
decreased.
• This corresponds to the minimum amount of liquid return in the
tower, and hence the minimum reboiler duty and condenser cooling
capacity
If R is decreased, the slope of the (ROL)
operating line R/(R + 1) is decreased, and
the intersection of this line and the
stripping line with the q line moves farther
from the 450 line and closer to the
equilibrium line.

To achieve separation, the number of

steps required to give a fixed xD and xW
increases.

* Separation more difficult when driving

force of mass transfer is zero (operation at
equilibrium point)
 Minimum Reflux
Min Reflux happens when the two operating lines intersect on
equilibrium curve
1.0

0.9

0.8

0.7

0.6

Ya
0.5

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

XB Xa
XD
 Minimum Reflux
Don’t forget the q line. Min reflux occurs at intersection with
equilibrium curve because all three lines should intersect
1.0

0.9

0.8

0.7

0.6

Ya
0.5

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

XB Xa
XD
Calculation of Minimum Reflux Ratio, Rm
– Based on the previous figure, the slope of the line is
given by

R 1
yn 1  xn  xD
R 1 R 1

At this point: xn=x* and yn+1=y*

Rmin 1
y*  x* xD
Rmin  1 Rmin  1
xD  y *
Rmin 
y * x *
 y

Rmin 1
y*  x* xD
Rmin  1 Rmin  1
xD  y *
Rmin 
y * x * y*

x
xB x* xF xD
Feed –liquid at bubble point (saturated Feed –partially vapour( 0<q<1)
liquid feed) q=1

Feed –cold liquid (q>1) Feed –saturated vapor (q=0)

Minimum number of plates or Total
Reflux
– If no product is withdrawn from the still (D=0), the column is
said to operate under conditions of total reflux and, as seen
from equation , the top operating line has its maximum slope of
unity, and coincides with the line x=y.
R 1
Total reflux yn 1  xn  xD D=0
R 1 R 1
R=L/D=∞
F=0 L/V=1
If R=L/D= ∞ then R/(R+1)=1; also L=V
Ln  D  Vn1
yn 1  xn
Ln  Vn1
B=0
 Total Reflux
– All vapour is condensed and returned as liquid
– Minimum number of theoretical steps
– Can use Fenske equation to calculate Nmin

 xD
log .
 1  xB  

 1  x D  x B 
N min 
log  av
– (Ref. Transport Process and Separation Process
Principles, Geankoplis 4th ed. Page:658)
– Sometimes a column is operated in total reflux at start
up
• The factors that affect distillation column
operation

The performance of a distillation column is determined by

many factors:
1. feed conditions
 state of feed
 composition of feed
 trace elements that can severely affect the VLE of
liquid mixtures
2. internal liquid and fluid flow conditions
3. state of trays (packings)
4. weather conditions