Module IV

Mass Transfer
 Distillation
• Separation of a liquid mixture of miscible and
volatile substances into individual components or
group of components by vaporization.
• Example:
1. Separation of ethanol and water into its
components.
2. Crude petroleum into gasoline, kerosene, fuel
oil.
•Lighter products, such as butane and other liquid petroleum
gases (LPG), gasoline blending components, and naphtha, are
recovered at the lowest temperatures.
•Mid-range products include jet fuel, kerosene, and distillates(such
as home heating oil and diesel fuel).
•The heaviest products such as residual fuel oil are recovered at
temperatures sometimes over 1,000 degrees Farenheit.
 y  / (1  y  )
 ab 
x / (1  x)
Fractionation - Another term for distillation, or fractional distillation.
Feed - The liquid and/or gas feed into the distillation column. The tray below the inlet nozzle is
called the feed tray.
Heavy Component - The component with the lower relative volatility, for simple hydrocarbon
this is the component with the higher molecular weight. Found in higher concentration in the
bottom product of the column.
Light Component - The component with the higher relative volatility, for simple hydrocarbon
this is the component with the lower molecular weight. Found in higher concentration at the
top of the column.
Stripping section - The trays between the bottom of the column and the feed tray. In the
stripping section the aim is to concentrate the heavier component in the liquid phase.
Enriching/Rectifying section - The trays between the feed tray and the top of the column. In the
rectifying section the aim is to concentrate the lighter component in the vapour phase.
Top Product - The product which leaves the top of the column, also called distillate. This product
is usually passed through a heat exchanger and liquefied.
Bottom Product - The product which leaves through the bottom of the column.
Reflux - A portion of vapour from the top of the column which has been condensed to a liquid
and returned to the column as a liquid above the top tray.
Reboiler - A heat exchanger at the bottom of the column which boils some of the liquid leaving
the column. The vapour generated returns to the column at the bottom of the stripping section.
vapour-Liquid Equilibrium (VLE) Curve - A plot of the actual composition of the lighter
component in the vapour phase for a given composition in the liquid phase. Usually derived
from thermodynamic data.
• On abscissa: mol fraction x in liquid,
On ordinate: mol fraction y in vapor

Mol fraction in vapor y

and a reference line--diagonal line.
• It is seen that, for a binary mixture
with a normal y-x curve, the vapor is
always richer in the more volatile
component than the liquid from which
it is formed.

Mol fraction in liquid x

11
•A distillation column consists of a series of plates (or trays).
• In normal operation, there is a certain amount of liquid on each plate, and some
arrangement is made for ascending vapours to pass through the liquid and make contact
with it.
•The descending liquid flows down from the plate above through a downcomer, across
the next plate, and then over a weir and into another downcomer to the next lower plate
•Simple distillation is a procedure by which two liquids with different boiling points can
be separated.
•Simple distillation can be used effectively to separate liquids that have at least fifty
degrees difference in their boiling points.
 Steam Distillation:

•Steam distillation is a special type of distillation for temperature

sensitive materials like natural aromatic compounds.
•This technique is used for separating substances which are immiscible with water,
volatile in steam & having high vapour pressure at the boiling temperature of
water.
•Steam or water is added to the distillation apparatus, lowering the boiling points
of the compounds.
•Steam distillation is analogous to simple distillation, the main difference being
that steam (or water) is used in the distilling flask along with the material to
be distilled.
• So this method can be used for purifying liquids with very high boiling points.
•e.g. Aniline.
•If water is used as one of the immiscible liquids the method is called steam
distillation. It is also used for purifying liquids which decompose at their normal
boiling points.
•e.g. Glycerol
•Steam distillation is used for separating organic compounds from plant parts. e.g.
Lemon grass oil, Eucalyptus oil etc.
 • Azeotrope
• Constant boiling point mixture is a mixture of two or more liquids whose
proportions cannot be altered or changed by simple distillation.
• This happens because when an azeotrope is boiled, the vapour has the same
proportions of constituents as the unboiled mixture.
• Each azeotrope has a characteristic boiling point.
• The boiling point of an azeotrope is either less than the boiling point temperatures
of any of its constituents (a positive azeotrope), or greater than the boiling point of
any of its constituents (a negative azeotrope).
4 Methods of two-Component Mixture Distillation

• For distillation purposes it is more convenient to plot

y against x at a constant pressure, since the majority
of industrial distillation take place at substantially
constant pressure.

20
 3 Material Balances in Plate Columns

1. Overall material balances for two-component system

• How many top and bottom
products can be obtained for a
given feeds and required quality? D, xD
• The material balance for a total
F, xf
F  D B
column gives (9.22a)

• The material balance on the B, xB

more volatile
Fx F component
Dx D  BxABis (9.22 b )

21
 D x  xB
• Thus:  F ( 9 . 22 c )
F xD  xB

• And B xD  xF
 (9.22d )
F xD  xB

• The quantities of top and bottom products D, B depend the feed

rate F and the concentration of xf, and the required product
qualities of xD, and xB.

22
 2. Operating lines

• The relationship of concentrations of the vapor and liquid leaving an

ideal plate abides by the equilibrium curve. Since a stream of feed is
introduced at feed plate, the continuity of material flow in the
rectifying section is different from that in the stripping section.

• Thus the situations of rectifying section and stripping section must

be considered separately.

23
1) Material balance in Rectifying section
• A material balance above
V1
plate n in rectifying section L
Gives:
Vn 1  Ln  D (9.23) D, xD
n
• Expressing this balance on the Vn+1, yn+1 Ln , xn
n+1
more volatile component:
F, xf
Vn 1 yn 1  Ln xn  Dx D (9.24) m
Vm+1,ym+1 Lm , xm
• Thus: m+1
Ln D
yn 1  xn  xD (9.25) B, xB
Vn1 Vn 1

Fig.9.8
• Eliminating Vn+1 by Eq.(9.23) gives

Ln D
yn 1  xn  xD (9.26)
Ln  D Ln  D

Eq.(9.26) is called the equation of the operating line in the rectifying section.

25
2) Material balance in stripping section

Lm  Vm 1  B
Lm xm  Vm 1 ym 1  BxB
Vm 1 ym 1  Lm xm  BxB
(9.27)

26
• In a different form of Eq.(9.27a):

Lm B
y m 1  xm  xB (9.27 b )
Vm 1 Vm 1

• The equation gives the relation between the compositions of the vapor
rising to a plate and the liquid on the plate in the stripping section.
• It is called the equation of operating line for the stripping section of a
column.

27
 4 Number of plates
1 .Constant molar overflow

• If the molar heats of vaporization are approximately constant, the flows

of liquid and vapor in each part of the column will not vary from tray to
tray unless material enters or is withdrawn from the section

• This is the concept of constant molar overflow.

• So L0=L1=….Ln=L= constant &

• V= Vn+1=Vn=….= constant

28
 Method of McCabe and Thiele
• The simplifying assumptions of constant molar heat of vaporization,
of no heat losses, and of no heat of mixing, led to constant molar
vapor flow and constant molar liquid flow in any section of the column.
We have obtained the equations of the operating lines:
• Rectifying section
Ln D
yn 1  xn  xD (9.26)
Ln  D Ln  D
• Stripping section

Lm B
ym 1  xm  xB (9.27b)
Vm 1 Vm 1

29
• They are all straight lines. The operating line for rectifying section is a straight
line of a slope and La nintercept D xD
V n
Vn

• If xn=xD in equation (9.26), then

Ln D L D
yn1  xD  xD  n xD  xD (9.28)
Ln  D Ln  D Ln  D

• and it must pass through a definite point A(xD , xD) on the equilibrium diagram
x-y .
Dx D
• Further, if xn=0, then yn+1= Vn
Dx D
• this represents the another definite point B(0, ). V n

• The two definite points make the operating line easily drawn out AB, as shown
in fig.9.9
30
• Similarly, the equation of operating line for stripping section is also a
straight line of slope Lm Vmand if xm=xB , then

Lm B L B
ym1  xB  xB  m xB  xB
Vm Vm Vm
• and this represents the straight line has to pass through the point
C(xB,, xB).
• The operating line for stripping section is easy to be drawn out CG
with use of the slope Lm Vmand the point C(xB,, xB) as shown in fig.9.9.

31
 xD
S D
Mol fraction in vapor y
y

(xF, xF)

Intercept=
xD /R+1 B (xB , xB)
x xD
xF
Mol fraction in liquid x
Fig. 9.9 determination of number of plates

32
 3. Operating Lines(Feed Line)
• If the two operating lines intersect at a point with
coordinates(xq , yq), then
• The equation for this line of intersection can be derived as
following:

Vn yq  Ln xq  DxD (9.29)

Vm yq  Lm xq  BxB (9.30)

33
• Combining above two equations gives

(Vm  Vn ) yq  ( Lm  Ln ) xq  ( DxD  BxB ) (9.31)

• The relations (between Ln and Lm, Vn and Vm ) depend on

the thermal conditions of feed.

34
• The means of q is:

heat to vaporise one mole feed

q
molar latent heat of the feed

• Thus, q has the following numerical limits for the various

thermal conditions of the feed:
• 1) sub-cooled feed, q >1
• 2) saturated liquid, q=1
• 3) saturated vapor, q=0
• 4) feed partially vapor, 1>q>0
• 5) feed superheated vapor, q<0
35
• The equation is commonly known as the equation of the
q-line which represents a straight line, and on which all
intersections of the operating lines must fall.

q 1
yq  xq  xF (9.34)
q 1 q 1

36
• When the two operating lines have been drawn out, the number of
theoretical plates required can be determined by drawing steps
between the equilibrium curve and the operating line starting from
point D. The method is called McCabe-Thiele’s.

37
 y 1= xD A
G

Mol fraction in vapor y y

x2
x3
(xF, xF)
x4
B

C
xB x xD
xF
Mol fraction in liquid x

Fig. 9. 10 Determination Of Number O Plate by McCabe

38
39
• Summarizing the steps of determination of ideal plates
required by McCabe-thiele method for a given condition of
feed, requirement of separation and reflux L gives
• 1) plotting the equilibrium curve on x-y diagram based on
the data of equilibrium;
• 2)determining the four definite points of A(xD,xD), f(xF, xF),
C(xB,xB) and B(0,DxD/Vn )on the diagonal line or ordinate of
the x-y diagram;
• 3) drawing the operating line of rectifying section through
the points of A and B; drawing the q-line through the two
points of f(xF, xF) and slope q/(q-1); drawing the operating
lines of stripping section;

40
• 4) determining the number of ideal plates
required by step-by-step construction starting
either from A point or B point till the concentration
x on one plate being slight lower (or greater ) than
xB (xD); xD A
E
• 5) counting the number
y

Mol fraction in
of the steps, the ideal G
xq
plates required being

vapor y
B
xb
equal to that of the
steps. C
xB xF xD
Mol fraction in liquid x
Fig. 9.12 determination of location of
feed point
41