Distillation From Gavhane

Chapter ••• 0
DISTILLATION
Distillatio n is an unit operation in which constituent s of liquid mixture (solution) are
separated using thermal energy. Basically, the difference in vapour pressure of different
constituent s at the same temperatur e is responsible for such separation. This unit operation
is also termed as fractional distillation or fractionat ion. With this technique it is possible
to separate liquid mixture into its component s in almost pure form and this fact has made
distillation perhaps the most important of all mass transfer operations.
In distillation , the phases involved are liquid and vapour or gas (vapour phase is
created by supplying heat to liquid) and mass is transferred from both the phases to one
another, by vaporisatio n from liquid phase and by condensatio n from vapour phase. The
basic requiremen t for separation of component s by distillation is that the composition of
vapour be different from the composition of the liquid with which it is in equilibrium . The
vapour is always richer in the more volatile component than the liquid from which it is
formed. If the vapo_u r composition is same as the liquid composition, distillation technique
will not effect a separation.
Distillation is commonly encountere d in chemical and petroleum industries as a
means of separating the liquid mixture into its component parts. Separation of ethanol and
water mixture, production of absolute alcohol from 95% ethyl alcohol using benzene,
· separation of petroleum crude into gasoline, kerosene, fuel oil etc. are the typical examples
of distillation .
Evaporatio n is concerned with separation of solution containing non-volatil e solute
and volatile solvent whereas distillation is concerned with separation· of solutions where
all the component s are appreciably volatile. Thus, the separation of a brine into salt and
water is a evaporation whereas the separation of a mixture of alcohol and water into its
component s is a distillation .
Boiling Point :
For any given pressure, a pure liquid when heated will boil or vaporise at a certain
single temperatur e known as boiling point of the liquid. Boiling point of a liquid increases
with increase in pressure and vice versa. Boiling points at a given pressure vary greatly
for different liquids. For example, boiling point of water is 373 K (100° C), that of toluene is
383.6 K (110.6° C) and that of methanol is 337.7 K (64.7° C) at one atmospher e
(101.325 kPa).
In the binary mixture (two component system), the component with lower boiling point
or component with higher vapour pressure at a given temperatur e, is termed as more
volatile or lighter and the component with higher boiling point or with lower vapour
pressure at a given temperatur e is termed as less volatile or heavier.
Thus in case of binary mixture of methanol and water, methanol is more volatile
component and water is less volatile component. The whole mixture of methanol and water
will boil somewhere between 337.7 K (64.7° C) and 373 K (100° C) at atmospheri c pressure
(101.325 kPa).
(1 .1)
Mass Transfer - II 1. 5 Distillation
Majority of distillation operations are carried out at constant total pressure. For
distillation calculations, the equilibrium vapour-liquid composition can also be plotted as
shown in Fig. 1.2 wherein vapour phase composition (y) is plotted as ordinate and liquid
phase composition (x) is plotted as abscissa. Such a diagram is called as an equilibrium
diagram or distribution diagram. As the vapour is richer in more volatile component than
the liquid, the equilibrium curve lies above the 45° diagonal line which is drawn for
·comparison.
1.0
l l
. ;,-,
0,0 x,y ---+ 1.0 x--+
L Raoult's law :
Fig. 1.3 : Effect of increased pressure : vapour-liquid equilibrium
It is commonly used for predicting vapour-liquid equilibrium for an ideal solution in

equilibrium with an ideal gas mixture from vapour-pressure data. It states that
equilibrium p_ci:rtial pressure of a constituent at a given temperature is equal to the product
of its vapour pressure in a pure state and its mole fraction in the liquid.phase.
Thus,- for a binary (two component) system, if PA is the equilibrium partial pressure of
A, pA0 is the vapour pressure of A in pure state and xA is the mole fraction of
.
A in the liquid
phase, then,
0
PA = PA XA ... (1.1)
0
and PB = pB. XB ... (1.2)
= p; (1 - xA), as XA +XB =1
where PB = equilibrium partial pressure of B
XB = mole fraction of B in liquid phase
0
PB = vapour pressure of pure B.
~ t o.n 's law:
It states that the total pressure exerted by a gas I vapour mixture is equal to the sum of the
partial pressures of the components present in it. Thus, it expresses the additive nature of
partial pressures.
Mathematically, for a binary system :
p = PA+ PB ... (1.3)
where P is the total press1:1re.
Mass Transfer - II 1.6 Distillation
For ideal gas or vapour, the partial pressure is related to the mole fraction of the
component in the gas or vapour phase by the relation :
Partial pressure = Mole fraction x Total pressure
Thus, for component A,
PA = YA. p ... (1.4)
where YA is the mole fraction of A in the vapour phase.
Knowing the vapour pressures of components A (more volatile) and B at various values
of temperatur es, x - y data can be generated for an ideal solution as follows :
PA = PA0 . XA ... (1.5)
PB = p~. (1-xA) ... (1.6)
PA = YA . p . . . (1. 7)
PB = YB . p ... (lf)
From Equations (1.5) and (1.7), we get
P~. XA = YA . p ... (1.9)
po
_A
YA = p . XA ... (1.10 a)
po
Similarly, __..!!
YB = p . XB ... (1.10 b)
But YB + YB = 1 and xB = 1- xA
YA+YB = 1 ... (1.11)
Putting values of YA and YB from Equations (1.10) and (1.11), and of XB in terms of xA,
in Equation (1.11), we get,
0 0
PA PB
p . XA + p (1 - XA) = 1 . . . (1.12)
0 0 0
pA . XA + PB - PB . XA =p ... (1.13)
XA (p1- P~) = P-poB ... (1.14)
P - po
_ ___,B
.,_ . .. ( 1.15)
XA = o O
PA -pB
/ Knowi.ng xA, correspond ing equilibrium value of the vapour phase concentrati on (yA)
v :_obtained with the help of Equation (1.10 a).
Relative volatility :
.Volatility of A: It is defined as the ratio of the partial pressure of A to the mole fraction
of A in the liquid phase.
PA
Volatility of A = XA ... (1.16)
Similarly , Volatility of B PB
· . .. (1.17)
XB
Relative volatility is the ratio of the volatility of A (more volatile component) to that of
B . It is also known as volatility of A with respect to Band is denoted by a symbol aAB.
PAXB .. . (1.18)
a AB = XAPB
but Py A = PA and PyB =PB
YA XB .. . (1.19)
a AB = YB XA
YAI YB ... (1.20)
a AB =
XA I XB
Thus , relative volatility is the ratio of concentration ratio of A to B in the vapour phase
to that in the liquid phase.
YAXB
YB XA
We have, 1- yA ... (1.2 1)
1-xA ... (1.22)
YA (1 - XA) '
... (1.23)
(1 - YA) XA
CXAB (1 -yA) XA = YA (1 - XA)
aAB XA - a AB yA XA = yA-: y A XA
aAB XA YA + YAXA (aAB -1)
aAB XA = YA [1 + (aAB - 1) x~]
ClAB XA ... (1.24)
Dropping subscript, we get :

ax
y ... (1.25)
1 + (a - 1) x
y/(1 - y)
a = ... (1.26)
x/(1 - x)
From Equation (1.25), knowing a for a given binary system, .x - y data (equilibrium
data) can be generated by taking x = 0, 0.1 ...... to 1 and evaluating corresponding values of
y (equilibrium vapour phase composition).
For ideal system, the volatility is equal to the vapour pressure of the pure component.
Therefore, the relative volatility of two substances forming an ideal solution is the
ratio of their vapour pressures .
0
PA ... (1. 27)
Relative volatility = aAB = a 0
PB
Relative volatility is a measure of separability by distillation and when a = 1
separation by distillation is not possible. Separation by distillation is possible for relative
volatility values greater than one. Larger the value of relative volatility, easier is the
separation by distillation.
1.8 Distillation
THE METHODS OF DISTILLATION· BINARY SYSTEMS :
Basically, distillation is carried out in two ways :
1. The liquid mixture is heated to create vapour. The vapours formed are condensed
in a condenser and withdrawn as a product. As there is no reflux, the products of relatively
low purities are obtained.
2. The liquid mixture is heated to create vapour, vapours formed are condensed in the
condenser. Part of the condensed liqujd is returned· to the distillation system (as reflux)
and the remaining parf is withdrawn as a product. In this, liquid and v apour are brought
into intimate contact for a number of times and almost pure product can be achieved and
the operation is called rectification or fractionation'. The term rectification originated in
alcohol industry whereas the term fractionation is popular in petroleum industry.
Common methods used in distillation practice are :
1. Differential or simple distillation,
2 . Flash or equilibrium distillation,
3. Rectification or fractionation.
Out of these three methods, distillation with rectification or simply called rectification
is the most important. The first two methods are carried out without reflux and the third one
is carried out with reflux (- which is nothing but returning a part of the condensed liquid
b to the distillation system).
erential or Simple Distillation :
n this distillat~on tec~nique,. a kno_wn quantity. of liquid mi~ture is. cha~ged into a
Jacketed kettle or still. The Jacket is provided for heatmg the mass m the still with the help
of a heating media such as steam. The charge is boiled slowly, vapours formed are
withdrawn and fed to a condenser where they are liquified and collected in the receiver as
a distillate. In early stage of distillation, vapours leaving the still are richest in the more
volatile component and as the distillation proceeds the liquid in the still becomes lean with
Vapour
Coolant
out
Condenser
Coolant
Still/kettle in
(Jacketed)
'Condensate R 1R 2 - Di stillate receiver,
Fig. 1.4 : Simple distillation unit

r espect to more volatile component. The composi,tion of the less _volatile_compon_ent thereby
incr eases and hence the boiling point increases. The prod;ct (distillate) from such u n its
can be collected i"n several rec:eivers, called c?tst to give products of various purities over
the length of distillation period. The distillation 1s continued till the boiling point of liquid
r eaches a predetermi ned value and the content of the still is-finahy removed as residual
containing majority of less volatile component.
rial balance - binary mixtures :
s the composition of vapour issuing from distillation and that of the liquid remaining
in it changes during the course of operation, the mathemati cal approach should be
differentia l.
Let F be the kmol of liquid mixture (A + B) containing xF mole fraction of A which is
charged to distillation still. Let D be kmol of distillate and W be kmol of residual liquid in
still which are obtained at the end of operation. Let Ynavg and xw be the mole fraction of A
in distillate and bottom residual liq\}id.
Let L be the kmol of liquid in the still .at any time, during the course of distillation . and
let x be the mole fraction of A rin liquid. Let very small am~unt dD kmol of the distillate of
the composition y in equilibrium with-the liq°uid is vaporised. Then the composition and
quantity of liquid decreases from x to x - dx and L to L-dL respectively .
Then,
Overall material balance at any time is :
L = L-dL + dD ... (1.28)
dL = dD ... (1.29)
p Material balance of component A
e Lx '= (L - d.L) (x - dx) + y dD .. . (1.30)
.S Lx = Lx - Ldx - xdL + dLdx + ydD
·e dLdx being very small can be neglected .
.h 0 = - Ldx - xdL + ydD ... (1.31)
Put the value of dD as dL from Equation (1.29)
0 = - Ldx - xdL + ydL .. . (1.32)
Ldx = (y - x) dL ... (1.33)
dL dx ... (1.34)
L = y-x
Integrating the above equation between two extreme conditions :
L = F, x = Xp
and L = W, x = xw
F XF
J~= f xw
dx
y - x
.. . (1.35)
XF
ln WF = f dx
y-x
... (1.36)
Xw
(y is in equilibrium with x i.e. y is the vapour phase composition in equilibrium wit.h
liquid phase composition (x)).
Equation (1.36) is known as the Rayleigh equation. It is used to determine F , W, xF or
xw when three of these are known. RHS of Equation (1.36) i.e. integral on the RHS side is
evaluated graphically by plotting 1/(y - x) as an ordinate and x as the abscissa and
determining the area under the curve between x = xF and x = xw, The required data for
above procedure are taken from vapour-liquid equilibrium relationship.
Ifyo, avg. is a composition of composited distillate, then,
Material balance of component A is :
xF F = Yo, avg. D + xw W ... (1.37)
Though the simple or differential distillation as a method of separation is not effective,
many such units are used, especially where the components to be separated have widely
gjiferent boiling points and me~tod giving sharp separations are not necessary.
v'constant Relative Volatility:
During the course of distilla i n, although the temperature in distillation still/kettle
increases, the relative volatilit does not change much and so some average volatility a.
can be used, over the concentration range involved, which makes the direct integration of
RHS of Equation (1.36) possible and graphical integration can thus be avoided.
The relationship between the composition of vapour (y) and that of liquid (x), in
equilibrium, in terms of relative volatility is
y = a.x/1 + (a. - 1) x
So y from above Equation can be substituted in Equation (1.36).
XF
F
ln-
w =
f y dx- x
xw
XF
F
ln-
w =
xw
f a.x
dx
1 + (a. - 1) x
-x
XF
F f [1 + (a. - 1) x] dx
... (1.38)
ln W = a.x - x [1 + (a. - 1) x]
xw
1 + (a. - 1) x
Consider the term a.x _ x [l + (a. _ l) x] of RHS of Equation (1.38).
1 + (a. - 1) x 1 + a.x - x
a.x - x [1 + (a. - 1) x] = a.x - x - a.x 2 + x2
(1 - x) + a.x
= x (a. - 1) - x 2 (a. - 1)
(1 - x) + 'a.x
= (a. - 1) (x - x 2 )
(1 - x) + a.x
(a. - 1) x (1 - x)
1 [(1 -x) ax J
= a- 1 x (1 - x) + x (1- x)
= a~ 1 [~ + 1 ~ x]
Putting the above value ofRHS back into Equation (1.38), we get,
ln £._ = _ 1 [ xfp!dx + a fx~]

W a-1 x 1- x
Xw Xw
Integrating we get,
I ln ~ = ~ [ ln ~ - a ln ; =::JI .. (1.39)
Equation (1.39) relates F, W, xp and xw through a.
Equation (1.39) can be arranged in another useful form as :
Add and subtract ln [(1 - xwVCI - xp)] in bracket on RHS of Equation (1.39).
1nF- = -1- nXp
W a - 1 Xw
[1
- + l n 1 - Xw - l n 1 - Xw - a n
1 - Xp 1 - Xp
l 1 - Xp J
1 - xw
Combining and rearranging the terms in bracket,
1nF- = -1-
W a - 1
[i
n xp(l-xw) - 1n
Xw (1 - Xp)
1-xw +an
1 - Xp
1-xwJ
1 1 - Xp
ln £._ = _1_ [ln Xp(l - xw) + (a-1) ln 1-xwJ

1 - Xp
W a - 1 Xw (1 - Xp)
ln £._ = _ 1_ ln xp (1 - xw) 1 - xw ... (1.40)
1
W a - 1 · xw (1 - xp) + n 1 - _xp
This can be rearranged to another form as :
ln £._ - ln 1 - xw _1_ ln Xp (1 - xw)
W 1 - Xp a - 1 Xw (1 - Xp)
ln F (1 - xp) = _1_ ln xp (1- xw)
W(l-xw) a-1 xw(l-xp)
(a-l)ln F(l-xp) = ln xp (1 - xw)
W (1 - xw) Xw (1 - Xp)
~ ln F (1 - xp) - ln F (1 - xF) = lnxF(l-xw)
W (1 - xw) W (1 - xw) xw(l-xp)
aln F(l-xp) = ln xp (1 - xw) + ln F(l - xF)
W (1 - xw) xw(l - xp) W (1- xw)
aln F(l-xp) = ln xp(l - xw) . F(l - xF)
W (1 - xw) xw(l-xF) W(l-xw)
aln F(l-xp) = ln F xp
W (1 - xw) W Xw
ln F XF F(l-xF) ... (1.41)

=a 1n W (1 - xw)
Wxw
relates the number of moles of A remaining in the residue, W xw to that

Equation (1.41)
(1 - xw).
of B remaining, W
number of moles of A initially, let it be NoA.
F XF =
number of moles ofB initially, let it be NoB·
F (1 - XF) =
w xw = number of moles of A remaining, let it be NA
(after distillation is over)
WO - xw) = number of moles of B remaining, let it be NB.
ln NoA = a ln NoB
NA NB
NoA
NA = (%~Br
(~r
NoB =
NA
NoA
NB ( NA )1/a
NoB = NoA · · · (1. 42 )
/oo
ifferential Condensation :
In this case, vapour feed is slowly conden~ed and condensate is drawn in equilibrium
with vapour residue. Let F be the moles of vapour of composition YF and D be the moles of
vaporous residue of composition YD then the treatment similar to that described above yields
YD
ln WF = f y~
- x
... (1.43)
YF
Flash or Equilibrium distillation :
Flash distillation is normally carried out in continuous manner. In this method , a
liquid mixture is partially vaporised, vapour and liquid are allowed to attain equilibrium
and finally withdrawn separately.
.-------+ Vapour
'f' mole,
y
P.R.V.
i - - - Separator
Feed
I mole
XF
~ - - • Liquid
( 1 - f) mole, x
Fig. 1.5 : Flash/Equilibr ium distillation

Mass Transfer - II 1-. 13 Distillation
Feed is heated in a tubular heat exchanger. The hot liquid mixture is then fed to a
separator via pressure reducing valve whereby pressure is reduced and vapour is formed at
the expense of liquid adiabatically. The liquid is withdrawn from bottom of the separator
and the equilibrium vapour leaves t he separator from top which is then liquified in a
condenser. Flash distillation is commonly used in petroleum industry; handling
multicompone nt system in the pipe stills .
Consider one mole of liquid mixture, having xF mole fraction of more volatile
component, is fed to flash distillation unit. Let f be the fraction of feed that is vaporised and
is of composition y. Then (1 - D will be the moles of residual liquid obtained. Let x be the
mole fraction of more volatile component in liquid.
Then, material balance of more volatile component gives :
XF = f · y + (1 - D x .. . (1.44)
fy = - (1- f)x +xF ... (1.45)
(1 - f) XF
y = - -f - x+y ... (1.46)
Equation (1.46) is a material balance/opera ting line for flash distillation with slope
equal to - (1 - D/f and intercept equal to xF/f.
The point of intersection of operating line and diagonal (x = y) is,
(1 - f) X XF
y = f +y
x = y
( 1 - f) x XF
x +-
f f
xf = - x+xf+ XF
x = XF
and y = xF
For f = 1, feed totally vaporised (feed 100 mole per cent vaporised)
( 1 - f)
Slope =- - f - =0
and hence operating line is parallel to x-axis through point (xF, xF) on diagonal.
For f =0, - no feed is vaporised.
Slope = oo and operating line will be parallel to y-axis through point (xF, xF) on
diagonal.
The operating line for various values of f on equilibrium diagram is as shown in
Fig. 1.6.
l
y
I
I
I
I
I
I
I
~ X =XF
0,0 x ~
Fig. 1.6 : Plotting the material balance line (operating line) for flash distillation on
equilibrium diagram
x-.
Fig. 1.7 : Determinat ion of x and y for a given f
Fig. 1.7 shows method of obtaining equilibrium compositio ns of vapour (y ) and
1
liquid (x 1) for a given f.
Continuou s Rectificati on - Binary Systems :
Rectificatio n is commonly encountere d in industrial practice as it is possible to get
almost pure product by this method.
The enrichment of the ·vapour stream as it passes through the column in contact with
reflux is termed as rectification .
In this separation method, part of the condensed liquid is returned back as a reflux and
maximum enrichmen t of more volatile component in vapour is obtained by successive
partial vaporisatio n and condensatio n by multistage contact of vapour and liquid. This is
~ved in a single unit called as fractionatin g column.
J r 8~tionati ng Column :
Fractionati ng column or fractionato r consists of Ci) cylindrical shell divided into '
sections by a series of perforated trays, (ii) reboiler and (iii) condenser. The liquid
mixture to be separated is introduced in the cylindrical column more or less centrally. The
column itself is divided into two sections - rectifying and stripping section. The section
;:ibove the feed plate or tray is called the rectifying section, wherein vapour is washed to
remove the less volatile component with the liquid returned to the column from top (known
as reflux). The rectifying section is also called the enriching section as the feed is
enriched in this section, owing to which the top product/dis tillate is richer in the more
volatile component than the feed . The portion below the feed plate including feed plate is
called the stripping section wherein liquid is stripped off more volatile component by
rising vapour. Perforated trays are nothing but gas-liquid contacting devices on which
gas/vapour and liquid streams are brought into intimate contact for mass transfer to
occur.
The vapours are generated in the reboiler (generally steam heated) and are fed to the
bottom of the column. The liquid removed from the fractionato r rich in less volatile
component is called bottoms or bottom product. The vapour issuing from the top of column is
fed to the condenser where latent heat is removed with the help of circulating coolant
through the condenser. A part of condensed liquid is returned to the column (reflux) and
part is withdrawn as a top product or distillate which is rich in more volatile component.
As we move up the column, vapour becomes richer and richer in more volatile component
and as we move down the column, liquid becomes richer and richer in less volatile
component. As the liquid is at its bubble point and vapour is at its dew point, temperatur e is
maximum at bottom and minimum at top.
Accumulator
...:::,
0
0..
I
~
Cooler
i : - - - - (D )
Distillate
XO
Plate
Feed (F)
XF
Column
Vapour
Reboiler
(Wl
Bottom product , xw
Fig. 1.8 : Fractionating column
~cation on ideal plate:
Refer to the Fig. 1.9 wherein the plates are numbered serially from top down. Consider
nth plate from top in the cascade. The plate n- 1 is immediately above the plate n and plate
n + 1 is immediately below the plate n . On every plate, the two different fluid streams not at
equilibrium are brought into intimate contact, mass transfer takes place, phases are
separated, and finally two fluid streams leave the plate in equilibrium with each other.
Thus, the plate under consideration will receive the liquid Ln-l moles/h of composition
Xn- l and the vapour Vn+i moles/h of composition Yn+l from plates n-1 and n+l
respectively. The liquid Ln moles/h of composition Xn and vapour V n moles/h of
composition Yn leave this plate for plates n+l and n -1 respectively in equilibrium with
each other.
When vapour from plate n+l is brought into intimate contact on plate under
consideration with liquid from plate n-1 and (the diffusing substances distribute
themselves between the phases) their compositions tend to change to attain equilibrium
values. During the interchange process, some of the more volatile component is vaporised
from liquid Ln+l• decreasing the liquid concentration from Xn-l to xn; and some of the less
volatile component is condensed from the vapour Vn+l• increasing the vapour
concent ration from Yn+ 1 to Yn· In the column, as liquid is at its bubble point and vapour
is at
its dew point, the heat to vaporise more volatile compon ent from liquid is supplied
by the
heat released in the condens ation of less volatile compon ent from vapour. Thus
the net
effect is that the more volatile compon ent is transfer red to the vapour rising up
from the
liquid running down the column, while the less volatile compon ent is transfer red
to the
liquid running down from the vapour rising up the column. Liquid and vapour
phase
composi tion increase s along column height with respect to more volatile compon
ent and
therefor e tempera ture decrease s. The tempera ture of plate n is less than that of
the plate
n + 1 and greater than that of the platen - 1.
r Vn·I /
n - 2
Yn.1
Xn - 2
Platen - 1
'
Ln- I
xn-1 vn
·~. r
Yn
Platen
Ln
xn
Vn+ I
Yn + I
Platen+ 1 0,0 A C D
Ln+I B I. 0
x, y---+
Xn+ I V n+2
A = xn ' c = xii . I
D = Yn + I • B = Yn
Fig. 1.9 : Materia l balance over ideal plate Fig. 1.10 : Boiling point diagram showing
rectifica tion on an ideal plate
Conside r that the column is fed with F moles/ti me of liquid mixture (feed) with xF
mole
fraction of more volatile compone nt. Let D moles/ti me of composition xn are withdra
wn as
a distillat e and W moles/ti me of composition xw are withdra wn as a bottom product.
Overall materia l balance :
Feed = distillat e+ bottom product
F = D+W ... (1.4 7)
Materia l balance of more volatile compon ent (A) over fraction afur :
A in feed =
A in distillat e+ A in bottom product.
xF F xn D + xw W = ... (1.48)
With the help of Equatio ns (1.47), and (1.48), it is possible to calculat e D and
W
knowing F, XF, xn and xw.
1. 17 Distillation
Mass Transfer - II
get,
· Elim inatin g W from Equa tions (1.47) and (1.48), we
... (1.49 a)
D/F = (xF - xw )/Cxn - xw)
Elim inatin g D gives
... (1.49 b)
W /F = Cxn - xF)/Cxn - xw)
column then:,
Let L be the moles/time of liquid retur ned to the top of
Reflu x ratio = R =~
This reflux ratio is also know n as exter nal reflux ratio.
If Vis the (moles/t1me) molal flow rate of vapou
r leavi ng the top of colum n then, the
ratio LIV is know n as intern al reflux ratio.
v
Condenser
Platen
l i
Ln yn+ I
xn Yn+ I
Fig. 1.11 : Recti fying sectio n inclu ding conde nser

~ a l balan ce aroun d cond enser :
/ V = L+D
... (1.50)
L = V- D
and D = V -L
Over all mate rial balan ce over Fig.1 .11 is:
distil late withd rawn
Vapo ur flow to plate n = liquid flow from plate n +
... (1.51)
Vn+1 = Lu+ D
Similarly, mate rial balan ce of more volat ile comp onen t (A) is:
... (1.52)
Vn+iYn+l = Lu Xn + D Xn
Ln x +Dxn --
Yn+1 = - -
Vn+l n Vn+l
Ln Dxn ... (1.53)
Yn+1 = Vn+1 Xn +~ n+l
From Equa tion (1.51),
Vn+1 = Lu +D
There fore Equa tion (1.53) becomes :
Ln Dxn ... (1.54)
Yn+1 = Ln + D Xn + Ln +D
Equation (1.54) is known as the material balance line or operating line of the
rectifying section.
V', y'
i----1 -
------ -.
Reboiler
.___ _L',_x' _ _ __...___ __. W, xw
Fig. 1.12 : Stripping section including reboiler

Overall material balance over Fig. 1.12 :
Liquid flow to plate m + 1 = Vapour flow from plate m + 1
+ Bottom product withdrawn /
Lm = Vm+l + W ... (1.55)
Similarly,
Material balance of more volatile component (A) :
Lm Xm = Vm+l Ym+l + W xw ... (1.56)
Rearrangin g the Equation (1.56),

Wx.w
Ym+ 1 = -Lm-1 Xm
- --
Vm+1
... (1.57)
Vm+
We know from the Equation (1.55), that Vm+l = Lm - W
Lm Wxw ... (1.58)
Ym+ 1 = Lm - W Xm - Lm· - W
The Equation (1.58) is known as the material balance line or operating line of the
stripping section.
Analysis of fractionati ng columns :
The theoretical/ ideal stages/plat es required for a given degree of separation can be
obtained by :
1. McCabe - Thiele method.
2. Lewis - Sorel method.
y. '
Ponchon - Savarit method.
y ~~abe-Th iele Method:
It is a graphical procedure of obtaining theoretical plates.
Assumption s underlying the method are :
1. Constant molal heat of vaporisatio n.
2. No heat losses.
3. No heat of mixing.
Consider any plate n in the rectifying section.

Ln--1
i '"
Fig. 1.13
A heat balance across plate n is
Ln-1 HLn -l + Vn+l Hvn+l = Ln H 4i + Vn Hvn + heat losses+ heat of mixing
Heat losses are negligible for good insulation.
Heat of mixing is zero for ideal system.
Ln-1 HLn-1 + Vn+l Hvn+l = Ln H4i + Vn Hvn
HL and Hv - enthalpies of liquid and vapour per mol.
If the molar heat of vaporisatio n is constant (independe nt of the composition ) then
one mof ofvapour Vn+i on condensing releases, sufficient heat to liberate one mol of vapour
V0 . It follows that Vn = Vn+l· Therefore, the molar flow of vapour up the column is
constant. As the temperatur e change from one plate to the next is small, HL n can be taken
equal to HLn-f
Ln-1 HL n- 1 + Vn+1 Hvn+l = Vr1+1 Hvn+1 + Ln HL -n- 1
Ln-1 = Ln
So the moles of liquid reflux in this section are also const ant.
Therefore, Ln and Vn+l are constant in the rectifying section and Vm+ 1 and Lm are
constant in-the stripping section.
i.e. molar flow rates of vapour and liquid are constant in each section of the column.
Ln = Ln-i = L, Lm = Lm+i = L'
Vn = Vn+i=V, Vm+i =Vm = V'
[The above cited assumption s lead to a concept of constant molal vapour flow and
constant molal liquid flow in any section of the column. In other words, for one mole of
vapour condensed, one mole of liquid is vaporised. Thus Vn = Vn+ i, Ln = Ln+ 1 ... etc.]
The subscripts n, n + 1, m, m + 1 .. . etc. may be dropped and the operating lines then
plotted on equilibrium diagram are straight.
The operating line of the rectifying section becomes :
(r
L Dxn ... (1.59)
y = L + D x+ L + D
L
As R = D , above equation becomes :
R xn ... (1.60)
y = R+l x+R+l
Point of intersection of the operating line for the rectifying section and the 45° diagonat
(x = y) obtained as,
R XD
y =
R+l x+R + 1
Putting y x
R XD
x R+lx+R+l
(R + 1) x = Rx+ xD
x XD
and y = xD
Thus, the operating line of the rectifying section is to be drawn on equilibrium
diagram through the point with the coordinates (xD, xD) on the 45° diagonal and with the
slope equal to R/(R + 1) or intercept on y-axis equal to xD/(R + 1). / ,.,
The equation of the operating line of the stripping section becomes :
L' W xw
y = L'-Wx - L' - W
.. . (1.61 )
The point of intersection of the operating line of the stripping section and the 45°
diagonal is obtained as follows
L' W Xw
y = L' - W x -
L' - W
Diagonal y x
L' W Xw
x = L' - W x - L' -
w
L'·x - W·x = L'·x -W xw
x = Xw
and y = xw
Thus, the operating line of the stripping section is to be drawn through the point having
L'
coordin es Cxw, xw) on the diagonal and with the slope equal to L, _ w·
wise procedure for obtaining theoretical plafus :
1. By material balances, evaluate t h e terms D, W, L etc.
2. Draw the equilibrium curve and diagonal with the help of x - y data given.
If relative volatility is given, gen erate the x - y data.
3. Draw the operating line of the rectifying section through the point P (xD, xD) on the
diagonal and with the intercept equal to xD/(R + 1) or DxD/(L + D) or slope equal to
R/(R + 1).
4. Draw the operating line of the stripping section through the point M Cxw, xw) on the
diagonal and with the slope equal to L, ~ ' W .
5. Starting from (xD, xD) on diagonal, draw a horizontal line to meet the equilibrium
curve at point 'a'. Drop a vertical from point 'a' to meet the operating line at point 1.
1.21 Distillation
Mass Transfer - II
i
y
Line - 1 - Rectification Section ·
Line - 2 - Stripping Section
Intercept { .
+
X-+- .0
Fig. 1.14 : Determin ation of theoretica l plates by McCabe - Thiele Method

6. Proceed in this way, that is construct ing the triangles (represen ting the stages)
between equilibriu m curve and operating line of rectifying section, till we are
. above the point of intersecti on of two operating lines. Once we cross this point of
intersecti on, construct the triangles between equilibriu m curve and the operating
line of the stripping section i.e. dropping the verticals on the operating line of the
stripping section.
7. Proceed in the same manner till we reach exactly or cover the point M (xw, xw}.
8 , Count the number of triangles between x0 and .xw. Each triangle on x - y diagram
represent s a theoretica l plate.
9. If number of triangles are 'n', then 'n' represent s the theoretica l number of plates
including reboiler and n - 1 represent s the number of theoretica l plates in a
lumn to achieve the desired degree of separation .
ns of McCabe- Thiele Method:
1. It is not used when relative volatility is less than 1.3 or greater than 5.
2. It is not used when more than 25 .theoretica l stages/pla tes are required, and
3 . It is not used when operating reflux ratio is less than 1.1 times the minimum reflux
ratio.
2. Lewis- Sorel Method of Determin ation of Number of Theoretic al Stage&'P lates:
The equation of operating line of the rectifying section is :
Ln Dx0 .. . (1.62)
Yn+ 1 = Ln + D Xn + Ln + D
The equation of the operating line of the stripping section is :

Lm Wxw ... (1.63)
Ym+i = Lm- W Xm-Lm -W
1. From the data cited in problem, evaluate the terms - D, W, L etc.
1.27 Distillation
Mass Transfer - II
ositio n YD [Refe r Fig. 1.19 (b)J whic h is
Vapo ur leavi ng the parti al cond enser has a comp
reflu x.
in equil ibriu m with xe, comp ositio n of liqui d
cond enser is :
Oper ating line for rectif ying secti on with total
Yn+l = (R/R + 1) Xn + xD/R + 1
al cond enser is :
Oper ating line for rectif ying secti on with parti
Yn+l = (R/R + 1) Xn + YDIR + 1
only diffe rence is xD is repla ced by YD.

YD) on the diago nal wher e YD is t he
This oper ating line passe s throu gh point (yD,
state ).
comp ositio n of distil late with draw n (in vapo ur
enser is repre sente d by trian gle aba'.
As YD is in equil ibriu m with xe, the parti al cond
ating line ends at point a' with coord inate s
As far as the colum n is conc erned , the oper
in the colum n.
{xe, y 1) and trian gle a'b'c' repre sents the top plate
t the same proce dure of cons truct ion of
In case of parti al cond enser , we have to adop
cond enser [only diffe rence is xD is to be
stage s as that descr ibed previ ously for total
and coun t the numb er of stage s betw een YD
repla ced by YD - (com posit ion of vapo ur produ ct))
coun ted start ing from YD to xw will inclu de
and xw. Tota l numb er of theor etica l plate s
actin g as one theor etica l stage ).
reboi ler as well as parti al cond enser (each of them
YD and xw = n + 2.
Num ber of theor etica l plate s coun ted betw een
n = n = n + 2 - 2.
Num ber of theor etica l plate s requi red in colum
l plate s betw een y 0 - xw (i.e . inclu ding
For exam ple, supp ose we coun ted 10 theor etica
parti al cond enser and reboi ler) then
Num ber of theor etica l plate s = (n + 2) - 2
requ ired (in the colum n)
10 - 2=8
equiv alent to one theor etica l plate .)
(as the reboi ler and parti al cond enser are both
flux Rati o:
1 . Infin ite reflu x ratio or total reflu x ratio
, R., :
know the mm1 mum numb er of plate s
The total reflu x opera tion is of inter est to
s requi red) and is not a pract ical meth od of
requi red (it sets lowe r limit on numb er of plate
opera tion as at total reflu x the produ ct rate is zero.
n in Fig. 1.21. In this case, enou gh
A colum n oper ating unde r total reflu x is show
and colum n is opera ted unde r total reflu x.
mate rial is charg ed to -a distil latio n assem bly
issui ng from top are cond ensed and all
Duri ng the oper ation~ of the colum n, vapo urs
reflu x. Also all liqui d going to the reboi ler
conde nsed strea m is fed back to the colum n as
r the cond ition of tot al reflu x F = 0, D = 0
is vapo rised and is fed to the colum n. Thus, unde
colum n. The slope (LN) of both the opera ting
and W = 0, there fore V n+ 1 = Lri throu ghou t the
ting lines coinc ide with the diago nal and
lines beco mes unity and henc e both the opera
are then requi red for the desir ed degre e of
minim um numb er of stage s (theo retic al plate s)
spon ds to maxi mum reboi ler heat supp ly
epara tion (x 0 - xw). Total reflu x opera tion corre
.
and cond enser cooli ng capac ity for the separ ation
i 21-----1
31-----1
/ . . . Fig. 1.21 : Operation under total reflux

v ~· Minimum Reflux Ratio, Rm :
At total reflux, the operating lines of both sections coincide with the diagonal and to ·
effect desired separatio n, number of stages (theoretic al plates) required are minimum . As
the reflux ratio is reduced, the operating lines move towards the equilibriu m curve along
the feed line and the number of stages increase. Ultimatel y, further reduction in the reflux
ratio results into condition wherein the top operating line touches the equilibriu m curve as
shown in Fig. 1.22. The point of intersecti on of the operating lines lies on the equilibriu m
curve and at this point step becomes very close together, so that a zone of nearly constant
compositi on is formed near the feed plate. Infinite number of plates are then required.
This represent s a condition of minimum reflux. Thus, a minimum reflux ratio is that
reflux ratio at which an infinite number of plates are required for the desired -separation.
At minimum reflux ratio, the requirem ent of heat supply to the reboiler and that of coolant
supply to the condense r are minimum .
1.0
r
~ . , - -· (XD.·~D)
.I
I
I Line - I
I
I operating
I
y I line for Rm
. I
I
I
I
I. I
I I
I I
I I
(xw,Xw) I x = XF I
I . . I I
x--+ LO
Fig; l ~ : Minimum Reffux ratio

1.29 Distillation
ransfer - II
Calcula tion of minimu m reflux ratjo ffim) :

C
For liquid at its bubble point, the feed line is vertical (parallel to y-axis) and the point
lies on the equilibr ium curve and has the co-ordin ates (xF, YF).
the
Draw the equilibri um curve and diagonal and draw the feed line, a vertical through
ium
point P (xF , xF) on diagonal . Point of intersec tion of the feed line with the equilibr
curve is also a point of intersec tion of the operatin g lines at minimu m reflux.
1.0
Operating line
i
>,
Xo (rectification-section)
. 0,0 _ _x_--+ 1.0

Fig. 1.23 : Method of obtainin g Rm (saturat ed liquid feed)
Slope of the operatin g line AC is given as :
Rm xo - YF ... (1.79)
Rm+ 1 = Xo - XF
Rm (xo- xF) = (Rm+ 1) (xo-YF)
Rm Xn- Rm XF = Rm Xo - Rm YF + xo - YF
Rm (yF - XF) = xo-YF
xo - YF ... . (1.80)
Rm=
YF - XF
Similarl y for feed as a saturate d vapour, the feed line is horizont al.
Slope of the line AC is given as : I
Rm Xo - y ... (1.81)
Rm+ 1
= Xo- X
I
I
Xo- y
Rm = I - x I
y
Xn- XF I
... (1.82)
= XF- X
I (as y = XF)
1".0
t
>,
O x-
Fig. 1.24 : Rm for saturate d vapour

-~ --=·-
For feed as a cold. liquid : i.e. for 'q' values greater than one :
I
Xn- y
Rm = , , ... (1.83)
y - x
x --+
0,0
Fig. 1~25: 'Rm' for cold liquid

For 'q' values less than one and greater than zero :
Rm :xn- y'
Slope = R 1 = 1
m + xn- x
I
Xn- y
Rm= I I ... (1.84)
y - x
I
y' I
I
i
y
I
I
I
I
Xo
X--+ 1.0
0,0
Fig. 1.26: 'Rm' for feed-partially vapour

3. Optimum Reflux Ratio :
Any reflux ratio between infinite reflux ratio requiring minimum number of plates
and minimum reflux ratio requiring infinite number of plates is a workable system
which requires finite stages for desired degree of separation. At minimum reflux ratio as
infinite number of plates are required, fixed cost is also infinite while cost of heat supply to
reboiler and condenser coolant is minimum. As the reflux ratio is increased, the number
of plates decreases and the fixed cost decreases at first, passes through a minimum and
then increases as with higher reflux ratio the diameter of the column and sizes of reboiler
and condenser increase. The operating cost increases continuously as the reflux ratio is
increased as it is directly proportional to (R + 1). At total reflux, though the number of plates
1. 31 Distillation
Mass Transfer - II
conde nser coola nt is maxi mum and
are minim um, the cost of heat suppl y to reboi ler and
er of stage s for distil lation

Fig. 1.27 : Relat ion betwe en reflux ratio and numb
d. The total cost which is sum of fixed
also large capac ity reboi ler and conde nser are neede
and then incre ases with reflux ratio.
cost and opera ting cost also decre ases to a minim um
sum of the fixed cost and opera ting cost
The optim um reflux ratio occurs at a point wher e the
that reflux ratio at which the sum of
is minim um. The optim um reflux ratio is defin ed as
rough appro ximat ion, the optim um
the fixed cost and opera ting cost is minim um. As a
reflu x ratio.
reflu x ratio is usual ly 1.1 to 1.5 tunes the minim um
Operating costs
i
Cost Fixed costs
I
I
I
:/Opt imum reflux ratio
Rm
R (Reflux ratio) -+
__ Fig. 1.28 : Optim um reflux ratio for distil lation

Fens ke· Unde rwoo d Equa tions :
ratio, requi ring infini te numb er
Mini mum Reflu x Ratio (Rm) : The minim um reflux
ve volati lity is taken as const ant over
of plates , can be obtai ned analy ticall y when the relati
us obtai n the requi red relati onshi p
the conce ntrati on range conce rned (xn - xw). So let
with which we can calcu late Rm .
down ward throu ghou t its lengt h,
For the norm al equil ibrium curve which is concave
reflux , passe s throu gh the point of
the opera ting line of rectif ying sectio n, at minim um
.
inters ection of the q-line and the equil ibrium curve
dropp ing the subsc ripts is :
The equat ion of opera ting line for rectif ying sectio n
R xn .. · (I.BS)
y = R + 1 x +R + 1
Mass Tran~fer - II 1.75 Distillation
Fig. 1.61 : Downcomer - weir seal plot

Entrainment :
As gas/vapour bubbles through the pool of liquid on a plate, a large amount of turbulence
1s set up and the liquid particles can be entrained by the rising gas. Carry over of liquid
particles by rising gas from a plate below to the plate above is known as entrainment and is
much more pronounced at high gas flow rates . Entrainment reduces the concentration
change per plate and hence, decreases the plate efficiency. Tray spacing, vapour flow rate,
depth of liquid on tray are the factors on which rnount of entrainment depends.
PACKED COLUMNS FOR DISTILLATIO NV
For distillation operation, packed columns are especially useful whenever we have to
~arry out operation at low pressure (vacuum distillation) and whenever we are dealing
with heat sensitive materials. Packed columns are cheaper than plate for column diameter
less than 600 mm. A packed column consists of a ,cylindrical shell filled with some sort of
packings (rings or saddles) which offer large interfacial area for mass transfer. A
~ommon arrangement of the packed column for distillation operation is shown in Fig .
•.62, wherein the vapour flows upward and the refluxed liquid flows downward giving
ontinuous contact.
The ability of a given packing to effect the desired mass transfer between gas and
a quid phases (i.e. to effect the desired degree of separation) is usually expressed in an
empirical form, as the height equivalent to one theoretical plate (HETP). In case of plate
.olumns wherein a process of enrichment is stage wise, vapour leaving the plate is richer
"th respect to more volatile component than vapour entering the plate by one equilibrium
Etage. In packed columns, the same enrichment of vapour will occur in a certain height of
. acking which is termed as height equivalent to one theoretical plate or height equivalent to
.:. theoretical plate. Thus, in packed columns, one equilibrium step is represented by a
ertain height of a packed bed and the required height of packinf for the desired degree of
~eparation is given by : HETP x number of ideal plates required . HETP is defined as the
:..eight of packing (packed bed) giving the enrichment of vapour same as that can be
·btained by one theoretical plate (in stage-wise operation).
1. 76 Distillation
Mass Transfer - II
Feed
Bottoms
Fig. 1.62 : Packed colum n for contin uous distilla tion

on such as
The HETP can be estima ted with the help of an empiri cal equati
~k k3 ... (1.160)
HETP = k1 · u-2 · Dt · Zll3 · a · µJpL
functio n of type and size of
where k1, k 2 and k 3 are empiri cal consta nts for packin g and are
packin g. ·
G Superf acial gas mass velocit y
Dt Tower diame ter
Z Heigh t of packin g
a Relati ve volatil ity
µLand PL are viscos ity and densit y of liquid respec tively.
The HETP is an experi menta l quanti ty, charac teristic of each packin g and depend s on
tration .
the type and size of the packin g, flow rates of each fluid and concen
Method of Transfer Units:
uous counte rcurre nt
Fracti onatio n by means of a packed colum n involv es contin
nation by means of a plate column involves
contac t of the vapou r and liquid where as fractio
in the packed column there is a contin uous
stagew ise contac t of the vapou r and liquid. So
and in tl;te plate colum n there is a
chang e in the compo sition of the compo nents
compo nents (effect ed at each plate).
discon tinuou s change in the compo sition of
er unit and not the
The theore tical unit of separa tion in a packed column is- the transf
packin g conseq uently can be
theore tical plate (as it in a plate column). The efficiency of a
one transf er unit (heigh t 6f
measu red as the height of packin g to give a separa tion of
transf er unit).
1. 77
Distillation
Mass Transfer - II
d on the num ber of tran sfer unit s and the
The heig ht of a pack ed colu mn can be base by
a pack ed colu mn can easi ly be obta ined
heig ht of tran sfer unit . The heig ht of
by the heig ht of tran sfer unit .
mult iply ing the num ber of tran sfer unit s
tran sfer unit . ·
Z = Num ber of tran sfer unit s x heig ht of
Mor e
s~re of ease or diffi culty of sepa ratio n.
The num ber of tran sfer unit s is the mea if very high puri ty
s wou ld be requ ired . Hen ce,
diffi cult the sepa ratio n, the more such unit unit s will
sepa ratio n, a larg e num ber of tran sfer
prod ucts are desi red or for high degr ee of
be requ ired . ar
of the sepa ratio n effec tiven ess of a part icul
The heig ht of tran sfer unit is a mea sure surfa ce
d. If the rate of mas s tran sfer is high and
pack ing for the chem icals bein g proc esse smal l. For dete rmin ation
heig ht of tran sfer unit is
·area for mas s tran sfer is larg e then the coef ficie nts in unit s
a know ledg e of mas s tran sfer
of the heig ht of tran sfer unit , we requ ire
tion of phas es is expr esse d.
cons isten t with thos e in whic h the composi e
1.63 in whic h the com posi tion· of the mor
Con side r a pack ed colu mn as show n in Fig.
vola tile com pone nt incr ease s from Yb to
Yt·
To condenser
Reflux
Feed
Yti
Vapour Liquid
from reboiler to reboiler
on
Fig. 1.63 : Pack ed colu mn for disti llati
of a
l area , Z be the heig ht of pack ed secti on
Let A be the emp ty colu mn cros s-sec tiona (inte rfaci al area
ce per unit volu me of pack ing
colu mn, 'a' be the activ e inter ferc ial surfa
per unit volu me of pack ing).
ht dZ, thro ugh whic h two phas es pass
Con side r a diffe rent ial elem ent of heig s plac e.
chan ge in vapo ur com posi tion, dy, take
coun terc urre ntly , whe rein a diffe rent ial
liqui d com posi tion is dx.
At a sam e time , a diffe renti al chan ge in the
nce of the more vola tile com pone nt A over
For stea dy-s tate oper ation , mate rial bala mol ar
moi ar overflow i.e. negl ectin g char ige in
diffe rent ial heig ht dZ assu min g cons tant
flow rate in any part icul ar secti on is ... (1.161)
V dy = L dx
L is
g secti on of the colu mn in mole s/tim e _and
whe re V is the vapo ur flow rate in enri chin secti on.
e. V is cons tant in the enti re enri chin g
the mol ar· flow rate of liqu id in mole /tim nitu de depe ndin g upon
on but of diffe rent mag
It will be also cons tant in the strip ping secti
the feed cond ition s. of
catio n of mole s of A diffu sing i.e. rate
Each term of Equ atio n (1.161) is the indi is a state men t of
e or from the liqui d phas e and
addi tion or depl etion of A to the vapo ur phas to the total
sfer area in dZ. This mus t be equa l
, the rate of tran sfer of A acro ss the tran
e.
driv ing force divid ed by the total resis tanc
So the rate of change of a component A within the phase must be equal to the rate of
transfer to the phase.
Thus, for V-phase (vapour phase):
V dy = k 0 (yj - y)dS = Ko (/-y) dS ... (1.162)
where dS is the interfacial transfer area associated with the differential column height dZ.
dV = differential volume of packing in height dZ = AdZ
dS = differential interfacial ,area for mass transfer = aAdZ
in height dZ
V d;Y = ka <Yi -y) aA dZ = Ko (y* -y) aA dZ
V cfy = ka a (yi -y) A dZ = Ko a (y* - y) A dZ ... (1.163)
where (Yi - y) is the driving force over the gas film
(y* -y) is the overall driving force for the gas phase/vapour phase - (overall driving
force in terms of vapour composition).
Ko is the overaH gas phase mass transfer coefficient in mol/(time)·(unit driving force)
Ko · a is the volumetric overall mass transfer coefficient in mol/(volume) · (time)
(unit driving force).
In distillation operation, vapour and liquid compositions are expressed in terms of
molefraction, so units of Ko· a will be mol/(volume) · (time) · (molefraction).
Use of Ko · a requires the gas phase composition (y*) in equilibrium with the bulk
liquid composition and use of ka · a requires the gas phase composition (yi) at the interface.
It is possible only to measure the bulk composition and determination of interface
composition is ordinarily impossible.
Vdy = Koa(y*-y)AdZ ... (1.164)
(V/A) dy = Ko a (y* -y) dZ
dZ = Koay-y
V/A [-P-J
Integrating between limits,
z Yt
o
f dZ = f
Yb
VI~ ( *d~ )
Ko y y
The molar flow rates (V and L) are assumed to be constant in enriching section. The
overall mass transfer coefficient is a function of these phase flow rates. If the physical
properties do not vary appreciable, Ko is also a constant.
z Yt
f dZ = V/A
Koa
f~
y*-y
o Yb
z = Ko a V/A fYt *dy ... (1.165)

Yb y - y
In Equation (1.165), the integral term ·represents the integrated ratio of the change in
vapour composition to the available driving force (in terms of vapour composition) tending
1. 79 Distillation
Mass Transfer - II
on and Colb urn as the num ber of trans fer
to bring this abou t. This term is defin ed by Chilt
units (Nt), In our prese nt case, Nt is Ntoa·
Yt
dy ... (1.166)
Ntoa = f- *- -
Yb y - y
(i.e. numb er of trans fer units based on
N too is the num ber of overa ll gas trans fer units
gas phas e).
5) is calle d the heigh t of a trans fer
The quan tity outsi de the integ ral of Equa tion (1.16
unit (Ht), In prese nt case, Ht is Ht00 .
V/A ... (1.167)
Htoa = Ka a
Thus , Equa tion (1.165) can be writt en as ... (1.168)
Z = Htoa · Ntoa
term s of composition of more volat ile
A simil ar serie s of equa tions can be writt en in
ht can be evalu ated using chan ges in
comp onen t in liqui d phas e. The colum n heig
rate.
composition of A in ·liqui d phas e and corre spon ding ... (1.169)
dZ
Vdy = Kaa (y*- y)A dZ= Ldx =KL a(x- x*)A
... (1.170)
Ldx = KLa (x-x *)A dZ
of liqui d phas e composition.
wher e x - x * is the overa ll drivi ng force in term s
fer coeff icien t for liqui d phas e in
KL a is the over all volu metr ic mass trans
mol /( time) · (volume) · (unit drivi ng force).
icient in mol/(time) · (area ) · (unit
KL is the overa ll liqui d phas e mass trans fer coeff
drivi ng force).
So for liqui d phas e, we can write ,
NtoL = f~
Xt
x-x
... (1.171)
xii
fer units (num ber of trans fer units
N tOL is the num ber of overa ll liqui d phas e trans
base d on liqui d phas e).
LIA ... (1.172)
HtoL = -K La
HtoL is the heigh t of an overall liqui d trans fer unit.
while NtoL and Ntoa are dime nsion -
Htoa and HtoL are havin g dime nsion of lengt h
less .
Plate Effic iency :
Ponc hon- Sava rit meth od, we obtai n
By using eithe r the McCabe-Thiele meth od or the
s requ ired for achie ving the desir ed
the num ber of ideal /theo retic al/eq uilib rium stage
, the vapo ur leavi ng the plate is in
degr ee of sepa ratio·n. In case of an ideal stage
actua l pract ice, comp lete equil ibriu m is
equil ibriu m with the liqui d whic h leave s it. In
t conta ct time and incom plete mixi ng on
neve r reach ed on any plate . This is due to shor
is usua lly weak er in more volat ile
any plate . The vapo ur leavi ng an actua l plate
liqui d leavi ng it. Thus , · for achie ving
comp onen t than vapo ur in equil ibriu m with the
we requ ire more numb er plate s than ideal
desir ed degre e of sepa ratio n in actua l pract ice,
plates. To apply either of the methods to an actual case, it is necessary to convert the number
of ideal plates to actual plates. The factor that is used for converting ideal plates into actual
plate is the plate efficiency. The reboiler delivers vapour directly from the boiling liquid
and is thus considered as a perfect plate.
Types of plate efficiency :
( i) Overall efficiency/overall plate efficiency - pertains to the entire column.
(ii) Murphree efficiency - pertains to any single plate.
(iii) Murphree local/point efficiency- pertains to a specific location on a given plate.
Overall efficiency is the ratio of number of ideal plates required to produce a given
degree separation to the number of actual plates required to effect the same separation.
_ theoretical/ideal plates required
Ylo - actual plates required x 100
For example, if we need six theoretical plates to effect the desired separation and the
overall efficiency is 60% then the number of actual plates required are 6/0.60 = 10. The
overall efficiency may vary from 30 to 100 percent.
The Murphree plate efficiency:
It is the efficiency of any single plate based on vapour phase composition.
For the nth plate in the column, the Murphree efficiency is given by
Yn - Yn+l
YlM = *
Yn - Yn+1
where, Yn is the average composition of vapour leaving plate.
Yn+l is the average composition of vapour entering plate
y n* is the composition of vapour in equilibrium with liquid leaving plate.
It applies to a individual plate in a column and is defined as the actual change in
average vapour composition achieved by a given plate divided by the change in average
vapour composition if the vapour leaving the plate were in equilibrium with the liquid
leaving the plate . This efficiency is less convenient to use as it involves plate to plate
compositions rather than the terminal compositions .
Point/Local efficiency : It pertains to a particular place on the plate surface (applies to
single location on a given plate). It is defined by
Yl, = Yn,*local - Yn +1, local
Ylocal - Yn +1, local
where Yn, local is the composition of vapour leaving specific location on plate n
Yn+l, local is the composition of vapour entering platen at the same location.
y 1"'oca1 is the composition of vapour in equilibrium with the liquid at the same
location (i.e. in equilibrium with Xlocal) . v
To obtain satisfactory plate efficiencies, it is highly necessary that the plates must
operate properly. Adequate and intimate contact between vapour and liquid is essential.
Each of the unfavourable phenomena such as entrainment, excessive foaming, weeping,
short -circuiting and flooding lower the plate efficiency.
1.81 . Distillatiori
- Mass Transfer - II
ISOLVED EXAMPLES I
Ex. ·1.1 : A mixture containi ng benzene and toluene with 40% benzene and 60% toluene
and
is to be separate d .in _a fraction ating coiumn to give product containi ng 96% benzene
and one-thir d
bottom product contai~i ng 95% toluene. Feed is a mixture of two-thir d vapour
the
iiquid. Find out the number of theoreti cal stages required if reflux ratio of 1.5 times
minimu m is· used.
Data : Relative ;volatility aAB = 2.5.
Solutio n: Basis: Feed containi ng 40% benzene .and 60% toluene by weight.
Molecular weight of benzene (C 6 H 6 ) :::: 6 x 12 + 6 x 1 = 78
Molecul ar weig}:i.t of toluene (C 6 H 5CH 3 ) = 7 x 12 + 8 x 1 = 92
In 100 kg of feed there are 40 kg of benzene and 60 kg of toluene.
40n8 = 0.44 ~
Molefraction of benzen~ in feed = xF = 40/78 + 60/92
-DistiHate contains 96% benzene by weight.
96/78
Molefraction of benzene in distillate = Xo = -96 - - = 0.966
- - - -+- 41
178 92
Bottoni produtt contains 95% toluene and 5% benzene by weight.
. 5/78
Molefraction of benzene in bottom product = xw - 5178 + 95192 = 0.058
ex.AB = 2.5
Generat e x~y data with the help of equation :
ax
Y =
1 + (a - 1) x
Take x = 0, 0.1, 0.2 ... 1 and evaluate corresponding y values.
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x
y 0 0.22 . 0.385 0.52 0.625 0.714 0.79 0.85 0.91 0.96 1.0
Plot the equilibr ium curve.
Procedu re to determin e the minimum reflux ratio (Rm) :
q is the fraction of the feed that is liquid. Feed is two-thir d vapour and one-thir d liquid,
so 1 mole of feed results in 113rd mole of saturate d liquid in the strippin g section.
q = 1/3 = 0.333
or q = 1 - f, where f is fraction of feed that is vaporise d
= 1 :... 2/3 = 1 - 0.667 = 0.333
Slope of feed line = ·-=-9..
1-q
-0.333
= 1-0.333 =-0.5
Slope = tan e = ..:.. 0.5
e = - 26.56°
Intercep t on y-axis = XF/(1 - q)
= 0.44 I (1 ~ 0.333)
= 0.66
Draw the feed line th;ou gh the point Q (0.44, 0.44)
on the diago nal with slope equal to
- 0.5 (0 = - 26.56°) or with interc ept on y-axis equal
to 0.66 to cut the equil ibrium curve at
point P. Read y' and x' as the coord inates of point P.
From graph , y' = 0.51 and x' = 0.295.
Minim um reflux ratio for feed partia lly vapor ised is
given by
.
'
, - y,
Rm = Xo
y - x
0.966 - 0.51 = _
2 12
R =
0.51 - 0.295 m
Oper ating reflux ratio = R = 1.5 Rm = 1.5 x 2.12 =
3.18
Oper ating line of the rectif icatio n sectio n :
It has point (0.966, 0.966) on the diago nal and interc
ept on y-axis
. = x0 /(R +.1) = 0.966/(3.18 + 1) = 0.231
Draw this line throu gh M (0.966, 0.966) on the diago
nal with interc ept of 0.231 on y-axis.
Draw the opera ting line of the stripp ing sectio
n throu gh the point (xw, xw) =
N (0.058, 0.058) on the di,a gonal and passi ng throu gh
the point of inters ection of q-line i.e.
feed line and opera ting line of the rectif icatio n
sectio n. Do step- by-st ep const ructio n
betwe.en equil ibrium curve and opera ting lines starti
ng from the point M (0.966, 0.966) and
reach ing exact ly or cover ing the point N (0.058, 0.058
) and count the plates .
Numb er of theor etical plate s inclu ding reboi ler = n
= 11.
Numb er of theor etical plates requi red in the colum n .=
n - 1 = 11 - 1 = 10 ... Ans .
. +-+
.+
.. . .;, ~+ . .' ... ~ . . . M 0.966, 0.966) • : · ·r'! .

0.9 H
-++ .. t-t: . ~
3 •
..rt .
0.8 .. . + . +•· .
.4
··;.;. · · +e· · .t ·;:4· ·.t:t· · +
0.7 I 0.66 . : ·+l'." ·.·. ·•:;:, ,.,. · · · ·,.,tr:,
5 ·. ·tt:
t 0.6
.
~ ·q-line •
· r.+ · '+" .
. ·•
· .;. ·
·:··H
t-r-~-
<Y x
>- 0.5 +t+ -~Hi<
H-~ + ~+~ .
. tt .
•... Q R.S.O. line -
0.4
0.3
;p.2
:r,
x'
S.S.O. line
.1 •+.. ·d ·•+.
. :H- '!· . +
~.N(0.058, 0.058~ Xi= '0.4
. 0,0 0. 1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Fig. E 1.1 : Grap hical const ructio n of ideal stage s

1. 83 O istillation
Mass Transfer - II
Ex. 1.2 : A mixture of 35 mole % A and 65 mole % B is to be separated in distillation

column. The concentrati on of A in the distillate is 93 mole % and 96 mole % of all A is in
distillate. The feed is half vapour and reflux ratio is 4 : 1. The relative volatility (aAB) is
2.5. How many equilibrium stages are required in each section of column ? What could be
the minimum reflux ratio for such operation ?
Solution: Basis: 100 kmol of feed containing A and B.
F D+W
100 = D +W W = 100 - D
35 m
Xp = lOO = 0.35, Xo = lOO = 0.93
A in feed = 0.35 x 100 = 35 kmol

96 mole % of A is in distillate
A in distillate = 0.96 x 35 = 33.6 kmol
Distillate contains 93 mole % A.
A in distillate
Mole % A = distillate x 1OO
A in distillate
distillate (Mole % A/100 )
33.6
Amount of distillate = _
0 93
= 36.13 kmol
Bottom product = Feed - distillate
Bottom product = W 100 - 36.13 = 63.87 kmol
A in bottom product 35 - 33.6 = 1.4 kmol
1.4
Mole % A in bottom product = 63.87 x 100 = 2.2
Check:
Mole % B in bottom product 100 - 2.2 = 97.8
B in distillate Distillate - A in distillate
36.13 - 33.6 = 2.53 kmol
B in feed B in distillate + B in bottom product
0.65 x 100 =65 2.53 + 0.978 x 63.87 =64.995 "'65
D 36.13 kmol, W = 63.87 kmol, xp = 0.35, x0 = 0.93, xw = ~~ = 0.022, aAB = 2.5.
ax
y = 1 + (a - 1) x
Take x = 0, 0.1, 0.2 ... 1.0 and evaluate y and tabulate the data.
x O 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Y O 0.217 0.385 0.517 0.625 0.714 0.789 0.854 0.91 0.957 1.0
(i) Plot the equilibrium data and diagonal.
(ii) Plot -the q-line.
Feed is half vapour (given), so fee d is half liquid.
q fraction of feed that is liquid
q 0.5, (q = 0.5/1 = 0.5)
5 = _ 1.0
slope of q-line - q - o.
1 - q = 1 - 0.5
slope tan a = - 1.0 :. a = - 45°
Xp 0.35
Draw the q-line through the point Q (0.35, 0.35) on the diagonal and with a = - 45°
(measured from LHS).
(iii) Draw the operating line of the rectifying section through the point P having the
coordinates (0 .93, 0.93) on the diagonal and with intercept on y-axis equal to 0.186.
Intercept = xn/CR + 1), R = 4
= 0.93/(4 + 1) = 0.186
(iv) Draw the operating line for stripping section through the point M having the
coordinates (0.02, 0.02) on the "diagonal and passing through the intersectio n of
rectificatio n line and q-line.
(v) Construct the !;itages starting from xn (0.93) and covering xw (0.02).
While constructin g the triangles representin g stages/plat es, use the rectificatio n
section operating line upto xF = 0.35 and then use the operating line of the stripping section
upto xw = 0.02.
(vi) Count the theoretical stages :
Number of theoretical stages including reboiler = n = 10.
Number of theoretical plates required = n - 1 = 10 - 1 = 9 .. . Ans.
Number of theoretical plates in rectification section = 4 ... Ans.
Number of theoretical plates in stripping section = 5 ... Ans.
1.0
P 0.93, 0.93)
0.9
·' vis x·
0.8 .2
x
0.7
0.6 c - me R. S. Op. line
i
>, 0.5
....
4
a 45° y x
0.4
H '6 Q
0.3
7
S. S. Op. line
8
XF - 0.35
0,0 ~ 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
M (xw, xw)· x-.
Fig. E 1.2 : Graphical constructio n of ideal plates

1.85 Distillation
Mass Transfer - II
r condi tions speci fied below :
Ex. 1.3: A binar y distil lation colum n is opera ting unde
kmol/ h
Feed rate = 350 kmol/ h, overh ead produ ct rate = 150
produ ct = 0.97
Mole fracti on of more volati le comp onent in overh ead
Bottom produ ct = 0.02
Botto m produ ct rate = 200 kmol/ h
Reflu x ratio = 3.5
ractio n of more volat ile comp onent
In the stripp ing sectio n, it was found that the molef
ractio n in the liquid comin g to the same
in the vapou r leavin g a plate is 0.33 while its molef
deter mine whet her the feed is vapou r,
plate is 0.25. Assu ming const ant mola r overf low,
liquid or partia lly vapor ised.
Solu tion : Basis : 350 kmol/ h of feed to column.
D 150 kmol/h, xn = 0.97
W 200 kmol/ h, xw = 0.02
R = 3.5
In stripp ing sectio n, we have :
Lm
Ym+1 = Xm
Vm+1
Lm Vm+1 +W
Vm+1 = Lm- w
Lm W xw
Ym+1 = Lm - W Xm - Lm - W
L' W low
Ym+1 L, _ W Xm - L, _ W · xw, for const ant mola r overf
We have, - Ym+1 0.33 and Xm = 0.25

L' x 0.25 _ 200 x 0.02
0.33 200 ) (L' - 200)
(L' -
1
0.33 (L' - 200) 0.25 L - 4
L' 825 kmol /h
Vm+1 V', L' = V'+ W, for stripp ing sectio n
V' L' - W
V' 825 - 200 = 625 kmol/ h
F = 350 kmol /h
LID R :. L = RD
L 3.5 x 150 = 525 kmol/ h in rectif ying sectio n
F = 350 'I jv
jv'
d:t I
L'
Rectifyng
section
Stripping
section
Fig. E 1.3
Mass Transfer - 11 1.86 Distillation
L = 525 and L' = 825, so remain ing (825 - 525) liquid should come from feed.
L' = L + qF - in strippi ng section
825 = 525 + q (350)
q = 0.8572
Check :
L' = L + part of feed which is liquid.
Part of feed which is liquid = 1
L - L = 825 - 525 = 300 kmol/h
Also, part of feed which is liquid = qF =0.8572 (350) =300 kmol/h
Part of feed which is vapou r = (1 - q) F
= (1 - 0.8572) x 350 = 50 kmol/h
. ilso, part of feed which is vapou r = feed - part of feed that is liquid
= 350 - 300 = 50 kmol/h
= 50 kmol/h
In rectify ing section :
V = V' + part of fe~d that i_s vapou r
= 625 + 50 = 675 kmol/h ". (1)
In this section , we have,
V = L+D
= RD + D =(R + 1) D
= (3.5 + 1) x 150
= 675 kmol/h ". (2)
We get same results by (1) and .(2) .
As q is less than one (q = 0,8572), feed is partial ly vapori sed.
... Ans.
In feed, we have : liquid + vapour .
In feed mixtur e :
Feed in liquid form : 85. 72% and feed in vapou r form : 14.28%.
i.e. feed is (300/350 i.e.) 6f7th liquid and (50/350 i.e.) 117th vapour
. . .. Ans.
Ex. 1.4 : 100 kmol/h of a feed contai ning 40 mole % hexane and 60
mole % heptan e is to
be·dist illed in a column consis ting of a still pot and a plate and
a partia l conden ser. The
feed, a liquid mixtur e at its bubble point, is fed to a reboile r from
which a residu e is drawn
contin uously . The reflux is return ed to a plate. The distilla te
contai ns 80 mole % hexane .
The ratio of liquid reflux flow to distilla te is 2.
(i) Using McCab e-Thie le metho d, calcula te the distilla
te flow rate in moles/ h and the
bottom compo sition.
Equili brium data :
Molefr action hexan e in liquid, x 0 0.045 0.192 0.4 0.69 1
Molefr action hexan e in vapour , y 0 0.1775 0.538 0.78 0.932 1
(ii) If the relativ e volatil ity a = 6, do the calcula tion analyti cally.
1.87 Distillation
Mass Transfer - II
Solutio n : Basis : (i) 100 kmol/h offeed to the distillat ion unit.
Molefra ction of hexane in feed = xF = : = 0.4.

80
Molefra ction of hexane in distilla te produc t = Yo = xo = 100 = 0.80.
Molefra ction of hexane in bottom = xw =?

Liquid reflux = L _ 2 R _ 2
Distilla te D - ' -
We have,
V = L+D
= Lxn + D·~o
L D
Yn+1 = V Xn + V YD
L L LID 2 2
v L +D =LJD + 1 = 2 + 1 =3
1 1 1
DIV D/L + D =(UD + 1) =(2 + 1) =3
LID 2 if D = 1 then L = 2.
nt contact time
Partial conden ser is conside red to act as one theoret ical stage (if sufficie
d then vapour and liquid stream s will
betwee n vapour produc t and liquid reflux is provide
x
leave in equilib rium, y 0 is in equilib rium with 0 ).
Yo = 0.8
So mark the point Yo = x 0 = 0:8 on the y = x line i.e. diagona l.
Yo, the point
Conditi ons in the conden ser are fixed and as x 0 is in equilib rium with
0.8, on y = x line, with
(x 0 , Yo) is located . Draw the operati ng line through the point Yo = x 0 =
slope equal to LIV or interce pt equal to D · YolV.
· Slope of operati ng line = LIV = 213.
Interce pt of operati ng line on y-axis = D y 0 N = y0 /R + 1 = 0.8/2 + 1 =
0.267.
2
Slope = 3 =0.66667
tan e . = o.66667 :. e =.33.69"
to the line-
Draw .a line throug h y 0 = 0.8 on the diagona l malting an angle of 33.69°
through y 0 and paralle l to x-axis.
. OR mark interce pt =0.267 on y-axis and joint it with y 0 =0.8 on the
diagona l to get the
op~~ati ng line.
so includi ng .
Partial conden ser and re boiler each corresp onds to one theoret ical stage;
f three theoret ical
a plate there are totally three t.lieoretical stages (3 ideal plates) so step-of
rium curve and operati ng line and
stages · by constru cting the triangl es betwee n equilib
read xw corresp onding to the third stage.
From Fig. E 1.4 (a), xw = 0.135
... Ans; (i)
Compos ition of bottom product = xw = 0.135
0.2
r--
(!)
"l
0 0.1
0.1 0.6 0.7 0.8 0.9

x-
Fig. E 1.4 (a) : Deter mina tion of xw by const ructio

n of stage s
Over all mate rial balan ce :
F = W+D
Mate rial balan ce of hexan e (over all)
xFF W xw +Dy0
W = = 100 - D
F- D
0.40 x 100 = (100 - D) x 0.135 + D x 0.80
D 39.85 kmol /h
Disti llate flow rate = 39.85 kmol /h
... Ans. (i)
(ii) Deter mina tion of xw and D analy ticall
y for a = 6.0.
Given : a = 6
The x-y equil ibrium relati onshi p is given as
ax
Y = 1 + a (1 - x)
Rearr angin g it,we get,
y
x
y + a (1 - y)
1.89 Distillation
Mass Transfer - II
. . . . . - - - - - - D, Yo
Partial condenser
L, x0
Plate
V,Yw
Reboiler
" - - - - - W,xw
Fig. E 1.4 (b) : Reboil er, plate and partial conden ser
te) is in equilib rium
We have in a partia l conden ser, Yo (composition of vapou r distilla
with Xo (comp osition of reflux liquid).
We have Yo = 0.8
We will determ ine 0x (in equilib rium with y 0 ).
YD
Xo = Yo + a ( 1 - Yo)
0.80
= 0.80 + 6 (1 - 0.80)
= 0.40
Xo, Y1 is_()n operat ing line, so using Xo, we will determ ine Yi·
Materi al balanc e about partial conden ser :
VYn+i = LXn +DYD
V Yi = L Xo + D YD
L D
Yi =y Xo+ y YD
R 1
= R + 1 Xe, + R + 1 Yo
2 1
= 3 (0.40) + 3 (0.80)
= 0.533"
Xi is in equilib rium with Yi and is determ ined as follows :
Y1
Xi = Y1 + a {1 - Yi)
0.533
= 0,533 + 6 (1 - 0.533) .
=· 0.16
a -plate and conden ser
Using xi, we wilf determ ine Yw by doing materi al balanc e about
· togeth er.
V Yw = Lx1 +D YD-
L D
Yw =V X1 + V YD
2 1
= 3 (0.16) + 3 (0.80)
= 0.373
Xw is in equilibrium with Yw and is determined as follows :
Yw
Xw = Yw+ a (1-yw)
0.373
= 0.373 + 6 (1 - 0.373)
= 0.090
Composition of bottom = 0.090 ... Ans. (ii)
Overall material balance :
F= W+D
w = F- D = 100-D
Material balance of hexane over entire unit :
XFF = DyD + Wxw
xFF = D YD+ (100 -D) xw
0.40 x 100 = D (0.80) + (100 - D) x 0.09
D = 43.67 kmol/h
Molar flow rate of distillate = D = 43.67 kmol/h ... Ans. (ii)
Ex. 1.5: A liquid mixture of benzene-toluene is to be distilled in a tower at 101.3 kPa
pressure. The feed of 100 kmol/h is liquid and it contains 45 mole % benzene and 55 mole %
toluene and enters at 327.6 K (54.6 °C). A distillate containing 95 mole % benzene and
5 mole % toluene and bottoms containing 10 mole % benzene and 90 mole % toluene are to be
obtained. The reflux ratio is 4 : 1. The average heat capacity of the feed is 159 kJ/(kmol.K)
and the average latent heat is 32099 kJ/kmol. Calculate the kmol/h of distillate and bottom
product and the number ofplatesrequired.
Data: B.P. of benzene = 353 Kand B.P. of toluene= 383.8 K
x 1 0.78 0.581 0.411 0.258 0.130 0
y 1 0.90 0.777 0.632 0.450 0.261 0
Solution : Basis : 100 kmol/h of feed
F = 100 kmol/h
XF = 45/100 = 0.45
XD . = 95/100 = 0.95, Xw = 10/100 = 0.1
100 = D+W W= 100-D
and 0.45 x 100 = 0.95D+O.l W
45 = 0.95 D + 0.1 (100 - D)
1. 91 Distillation
Mass Transfer - II
D 41.2 kmol/h
W 100 - 41.2 = 58.8 kmo1/h
... Ans.
Molar flow rate of distillate = 41.2 kmo1/h
... Ans.
Molar flow rate of Residue/ Bottom product = 58.8 kmol/h
(ii ) Determi nation of number of theoreti cal plates required :
Feed is liquid and it enters at 327.6 K
Average Cp of feed = 159 kJ/(kmo l.K)
Boiling point of benzene = 353 K
Boiling point of toluene = 383.8 K
Molefrac tion of benzene in feed = xp = 0.45
Molefraction of toluene in feed = 1- 0.45 = 0.55
Mean boiling point of feed = T
n
T I, (mo lefractio n x boiling point)
i= 1
T 0.45 x 353 + 0.55 x 383.8 = 369.94 K

Average latent heat = Aavg. = 32099 kJ/kmol .
Temper ature offeed = Tr = 327.6 K
Heat to convert 1 mole of feed to saturate d vapour
q = Molar latent heat of vaporisa tion
Cp CT - Tr ) + Aavg
Aavg
159 (369.94 - 327.6) + 32099
q 32099
= 1.2097 "" 1.21
~ _ -1.21
Slope of q-line 1 - q - 1 - 1.21 = 5.762
Slope = tan a = 5.762
a = tan- 1 (5. 762) = 80.15°
( i ) Draw the equilibr ium curve and diagonal .
on the
(ii ) Draw the operatin g line of rectifyin g section through the point P (0.95, 0.95)
diagonal and with intercep t on y-axis = xn /CR + 1) = 0.95/(4 + 1) = 0.19.
(iii) Draw the q-line through the point (0.45 , 0.45) on the diagonal and with a= 80.15°.
having
(iv) Draw the operatin g line of the strippin g section through the point
tion of q-line
coordina tes (0.1, 0.1 ) on the diagonal and passing through the point of intersec
and top operatin g line.
for
(v) Constru ct the stages between equilibr ium curve and operatin g lines required
separati on xn - xw and count them.
Number of theoretic al plates includin g reboiler = n = 8
Number of theoretic al plates required = n - 1 = 8 - 1 = 7 ... Ans.
Feed plate : 5th from top . . .. Ans.
Mass Transfe r - II 1. 92 Distillation
0.8 0.9 1.0
Fig. E 1.5 : Construcion of ideal stages

Ex. 1.6 : The feed consists of methanol and water containing 80 mole % methanol and
20 mole % water. The overhead product is to contain 99 mole % methanol and the bottom
product contains 0.5 mole % methanol. The feed is cold and for each mole of feed, 0.2 moles
of vapour is condens·ed on the feed plate. The reflux ratio is 1.35 and the reflux is at its
bubble point.
Calculate :
(i) the minimum r eflux rat io
(ii) n umber of theoretical plates using t otal condenser and
(iii) number of theoretical plates using a reboiler and partial condenser operating with
reflux in equilibrium with a vapour going to the final condenser.
Data:
x 0 0.10 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
y 0 0.42 0.58 0.67 0.73 0.78 0.83 0.87 0.92 0.96 1
Solution : Basis 100 kmol offeed
F = 100 kmol
XF = 80/100 =0.8
1. 93 Distillat ion
Mass Transfe r - 11
Xo 99/100 = 0.99
xw 0.5/100 = 0.005
ng section for each mole
q is the numbe r of moles of satura ted liquid resulti ng in strippi
of feed .
total moles of satura ted
As for each mole of feed, 0.2 moles of vapou r is conden sed,
feed . The larger moles are
liquid resulti ng in strippi ng section are 1.2 moles per 1 mole of
resulti ng in strippi ng section as the feed is cold.
1 + 0.2 12
q = 1 = .
with the diagon al is
(i) Minim um reflux ratio : The point of interse ction of the q-line
(xF, XF with XF = 0.80).
-=-9..._
Slope of q-line 1-q
- 1.2
=6
1 - 1.2
tana.= 6 ... a 80.54°
the diagon al, draw the
Draw the equilib rium curve and diagon al. Throu gh xF = 0.8 on
at the point P.
q-line with angle a = 80.54° which will cut the equilib rium curve
value of Rm .
Join PQ (not shown in Fig. E 1.6 (a)) and slope of PQ will give the
The coordi nates of the point P are :
y' = 0.927 and x' = 0.82
For the cold feed , Rm is given as
I
Xo- y
I I
y - x
0.99 - 0.927 = 0 588 "" 0 59

0.927 - 0.82 . .
= Rm = 0.59 ... Ans. (i)

The minim um reflux ratio
(ii) Numb er of theore tical plates with total conden ser.
Xo = 0.99, Xw = 0.005
Locate point Q (0.99, 0.99) on the diagon al.

R = 1.35 (given )
Interc ept on y-axis of operat ing line (rectify ing section ) is :
Interce pt = x 0 /(R + 1) = 0.99/(1.35 + 1) = 0.42
) throug h the point
Draw the top operat ing line (opera ting line for rectific ation section
to 0.42.
Q (0.99, 0.99) on the diagon al and with int ercept on y-axis equal
Mass Transfer - II 1 . 94 Distillation
Locate the point (xw, xw, xw = 0.005 ) on the diagonal and through this draw the
operating line of the stripping section which passes through the point of intersection of
q-line and top operating line.
Construct the stages starting from x 0 and reaching exactly or covering xw (0.005).
Number of theoretical plates required including reboiler =n =9 ... Ans. (ii)
Number of theoretical plates required = n - 1 = 9 - 1 = 8 ... Ans. (i)
(iii) Number of theoretical plates - using partial condenser :
Method of constructing number of plates in cas.e of partial condenser (followed by final
condenser) is same as that given in (ii ). We have to start with point (x 0 , x 0 ) and so on.
So separate graphical procedure is not required , but the difference is :
Composition of the vapour leaving the partial condenser is y 0 which is same as xo,
Yo = xo.
The vapour leaving the partial condenser Yo is in equilibrium with liquid which is
refluxed to a column from it Cxc ) .
The operating line ends at point b and triangle abc represents the top plate in the
column. As vapour leaving the partial condenser y0 is in equilibrium with liquid reflux
(xc ), the partial condenser is equivalent to one theoretical plate/stage.
Number of theoretical plates using partial condenser including reboiler =n =:: 9.
Number of theoretical plates required in the column (using partial condenser)
=n - 2=9- 2= 7 .. :Ans. (iii)
(Xe, y')
Y1 y' = Yo
y' = Xo ....-----,~::;...,,,._-+-(xo, Yo)
Vapour Vapour
------L- (xc, Y1) Partial
condenser
Reflux Final
condenser
Xo
Yo= y'= Xo
Fig. E 1.6 (a) : Partial condenser

[Number of theoretical plates required in the column = n - 2, 2 = 1 + 1 : one for reboiler
and one for partial condenser as reboiler and partial condenser are each equivalent to one
theoretical stage. 2 is subtracted from n (total theoretical plates) to get theoretical plates in
the column .]
1.95 Distillation
Mass Transfer - II
a 80.54°
q - line
p 2
3 Xe
0.9 4
5
0.8 y vis x 0.8 0.8
0.7
6
0.6
t
>- 0.5
R.S.Op. line
y x
0.4
s.s:op. line
7
0.3
C\J
-.:!"
0
0.2 8
0.1
0,0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x-
Fig. E 1.6 (b) : Determinat ion of number of ideal plates

Ch ap ter ••• @
Q U ID -L IQ U ID EXTRACTION
/L 1
ans of a liq uid
rem ovi ng one com pon ent from a sol id or liq uid by me
Th e tec hni que s of ng or sol id ext rac tio n and
two cat ego rie s, the firs t one is cal led as lea chi
sol ven t fall int o tte r fro m its
rac tio n. Le ac hin g is use d to dis sol ve sol ubl e ma
the sec ond as liq uid ext sep ara te two mis cib le
ins olu ble sol id wh ere as liq uid ext rac tio n is use d to
mi xtu re wit h an thi s cha pte r, our
ven t wh ich pre fer ent iall y dis sol ves one of the m. In
liq uid s by the use of sol liq uid pha se wi th a
tric ted to liq uid ext rac tio n - the ext rac tio n of the
dis cus sio n is res
sol ven t. en sep ara tio n
s is not eas ily sep ara ble by dis till ati on i.e. wh
Wh en a mi xtu re of liq uid plo yed . Th e liq uid
e or ver y dif ficu lt, liq uid ext rac tio n is em
by dis till ati on is ine ffe ctiv , or (ii) wi th
sti tue nts hav ing ver y clo se boi lin g poi nts
mi xtu res : (i) wi th the con ble (i.e. it is
h boi lin g poi nts for the hea tin g me dia ava ila
con stit uen ts hav ing too hig , or (iii) wit h
per atu res eas ily wit h the hea tin g me dia ava ilab le)
dif ficu lt to att ain suc h tem n un der vac uum
ths tan d the tem per atu re of dis till atio n, eve
con stit uen t(s ) tha t can not wi en be sep ara ted
hea t sen siti ve, tha t get dec om pos ed) ma y oft
(i.e. wit h con stit uen t(s) -th at are re. As a res ult ,
ion , a sol ven t is add ed to the liq uid -liq uid mi xtu
by ext rac tio n. In thi s ope rat nts of dif fer ent
for me d, bo th con tai nin g var yin g am oti
two im mi sci ble lay ers are usi ng den sit y
lay ers are the n sep ara ted and rem ove d
com pon ent s. Th e iso lat ed by dis till atio n
of the sol ven t for reu se, ext rac tio n is followed oft en
dif fer enc e. Fo r rec ove ry
or eva por atio n. ref ers to an operation
n (liq uid ext rac tio n or sol ven t ext rac tio n)
Liq uid -liq uid ext rac tio tin g it wit h a sui tab le
liq uid mix tur e are sep ara ted by con tac
in wh ich the com pon ent s of a com pon ent s. In thi s
ich pre fer ent ial ly dis sol ves one or more
ins olu ble liq uid sol ven t, wh end s upo n the une qua l
of the com pon ent s of a sol uti on dep
ope rat ion , the sep ara tio n uid ext rac tio n, the
s bet we en the two imm isc ibl e liqu ids . In liq
dis trib uti on of the com pon ent d to effect sep ara tio n
res ent s one pha se and sol ven t to be use
feed sol uti on to be han dle d rep ses in con tac t are bot h
In thi s ope rat ion , the two imm isc ible pha
rep res ent s the sec ond pha se. ute (liq uid ) tak es pla ce
a liq uid -liq uid ope rat ion . Th e ma ss tra nsf er of sol
liq uid and so is
sol ven t pha se.
from the feed sol uti on to the sep ara tio n of con stit uen ts
liq uid -liq uid ext rac tio n are use d for
Bo th the dis till atio n and ati on as we ll as by liq uid -
er to ach iev e a sep ara tio n by dis till
of a liq uid mi xtu re. In ord n, it is nec ess ary to hav e
ary to hav e two pha ses . In dis till atio
liq uid ext rac tio n, it is nec ess duc e the vap our pha se.
pha se, and the hea t is use d to pro
a liq uid ph ase and a vap our ses and the sol ven t is use d
is nec ess ary to hav e two liq uid pha
In liq uid -liq uid ext rac tio n, it uid -liq uid ext rac tio n is
uid pha se. So the sol ven t use d in liq t in
to pro duc e ano the r liq -liq uid ext rac tio n and hea
to the hea t use d in dis till atio n. (Solve nt in liq uid
ana log ous
dis till ati on are ana log ous ). sep ara tio n of con stit uen ts
of liq uid
tio n bot h are use d for
Dis till ati on and ext rac l me tho ds .
re bas ed on rel ati ve me rits /de me rits of the ind ivi dua
mi xtu
(2· 1)
Mass Transfer - II 2.2 Liquid-Liquid Extraction
~ r e n c e between distillation and extraction:

Distillation Extraction
1. Distillation/fractionation is an operation 1. Extraction is an operation in which,
in which cons ti tuen ts of the liquid constituents of the liquid mixture are
mixture are separated by using thermal separated by using insoluble liquid
energy. solvent.
'
2. Distillation utilises the differences in 2. Extraction utilises the differences in
vapour pressures of the components to solubilities of the components to effect
effect separation. separation.
3. In distillation, relative volatility is used 3. In extraction, selectivity is used as a
as a measure of degree of separation. measure of degree of separation.
4. In distillation, a new phase is created by 4 . In extraction, a new insoluble liquid
addition of heat. phase is created by addition of solvent to
the original mixture.
5. In distillation, mixing and separation of 5. In extraction, phases are hard to mix and
phases is easy and rapid. harder to separate.
6. Distillation/fractionation gives almost 6 . Extraction does not give pure product and
pure products. needs further processing.
-
7. It does not offer more flexibility in choice 7. It does offer more flexibility in choice ofl
of operating conditions. operating conditions.
8. It requires thermal energy. 8. It requires mechanical energy for
mixing and separation.
9. It needs heating and cooling provisions. 9 . It does not need heating and cooling
provisions.
10. It is primary choice for separation of 10. It is secondary choice for separation of
components of liquid mixture. components of liquid mixture.
11. Extractive distillation is the extraction of 11. Liquid extraction is extraction of liquid
the vapour phase with solvent. phase with solvent.
Field of application of Liquid Extraction :
Whenever separation by both distillation and extraction is possible, the choice is
usually distillation, irrespective of heating and cooling requirements. In case of
extraction, a solvent should be recovered for reuse and hence extraction is usually followed
by distillation for recovery of solvent. This combined operation is more complicated and
more expensive than ordinary distillation. But whenever separation of components· of
liquid mixture is difficult by distillation, the extraction can be thought of as an alternate
process to it.
Thus, (i) whenever very large amount of latent heats are required (as in the case with
very dilute solutions where water must be vaporised, latent heats of organic liquids are
substantially lower than that of water), (ii) whenever we are dealing with liquid mixture
forming azeotrope I close boiling mixtures and (iii) whenever we are dealing with
substances that are thermally unstable/heat sensitive, separation by distillation is
Mass iransfer - II 2.10 Liquid-Liquid Extraction
G B G B
Wt. fraction B 1.0
(a) (b)
Fig. 2.7: Rectangular coordinates (For system with one pair partially miscible/soluble)
One of the important factors in selecting a solvent for extraction is the selectivity of the
solvent and is given by
YE* · (wt. fraction of A in R)
~ = xR •· (wt. fraction of A in E)
' .
The selectivity has same significance in extraction as relative volatility has in
distillation. So it is a measure of separation by extraction. When selectivity is equal to one,
separation by extraction is not possible. For all practical operations, the selectivity should
be greater than one. The selectivity in extraction and relative volatility in distillation are
analogous. Poor selectivity (near unity) means large solvent to feed ratios and so large
. ~ er of extraction stages will be required for good separation.
~ l~on of Solvent for Extraction: ,
Any particular liquid to be used as a solvent for extraction will not possess all the
properties considered desirable for extraction and hence compromise is usually necessary
of selecting thepest solvent out of various possible liquid solvents available.
While selecting a solvent for extraction, the qualities such as selectivity,
recoverability, distribution coefficient, density, etc. should be given consideration.
1 . Selectivity : The ratio of concentration ratio of solute to feed solvent in the extract
phase to that in the raffinate phase is called the selectivity or separation factor. It is the
measure of effectiveness of the solvent for separating the constituents of feed. Selectivity
should be greater than one for all useful extraction operations and if it is equal to one,
separation by extraction is not possible.
If B is the solvent, feed contains C and A, where C is the solute, and E and R are the
equilibrium phases then selectivity, ~ is given as -
~ _ [Wt. fraction of C/Wt. fraction of A]E
- [Wt. fraction of C/Wt. fraction of A]R
-
'W is analogous to 'a' in distillation.
Liquid-Liquid Extraction
2.11
Mass Transfer - II
by dis till atio n,
As the sol ven t mu st be rec ove red for reu se usu all y
2. Re co ve rab ilit y: ove ry, the
ope wit h the ext rac ted sol ute . Fo r low cos t of rec
it sho uld not for m an aze otr sho uld be sm all
be hig h. Th e lat ent hea t of vap ori sat ion of sol ven t
rel ativ e vol atil ity sho uld
atil ise d (va por ise d).
wh ene ver sol ven t is to be vol fficient are gen era lly
ffi cie nt : Hig her val ues of the dis trib uti on coe
3. Di str ibu tio n coe ges are req uir ed
s am oun t of sol ven t and les s num ber of ext rac tio n sta
des ira ble as the n les
for a giv en ext rac tio n dut y. rac ted sol ute . In ter nar y
abi lity of the sol ven t to dissolve the ext
4. Ca pa cit y : It is the an inf ini te am oun t of sol ute
tia lly mis cib le, sol ven t can dis sol ve
sys tem s wit h one pai r par ter nar y sys tem s wit h two
ult s in gen era lly low er sol ven t req uir em ent s tha n for
and thi s res
pai rs par tia lly mis cib le. ura ted liq uid pha ses sho uld be
lar ger for
enc e in den siti es of sat
5. De nsi ty: Th e dif fer
ses . .
phy sic al sep ara tio n of the pha uid sol ven t (feed
ve nt : Th e sol ven t ins olu ble in the ori gin al liq
6. Ins olu bil ity of sol ute to be ext rac ted
fer red and it sho uld hav e hig h sol ubi lity for the sol
sol ven t) sho uld be pre
ven t are req uir ed.
as the n sm all am oun ts of sol h for coa les cen ce of
sio n : Int erf aci al ten sio n sho uld be hig
7. Int erf ac ial ten n dis per sio n.
mo re rea dil y, as the sam e is of gre ate r im por tan ce tha
em uls ion s to occ ur s the oth er com pon ent s
sol ven t sho uld be sta ble che mic ally and ine rt tow ard
8. Th e con stru ctio n.
not be cor ros ive tow ard s the common ma ter ial s of
and sho uld
ap.
9. Th e sol ven t sho uld be che e.
non -to xic and non -fla mm abl
10. Th e sol ven t sho uld be pre ssu re for eas e in
hav e low vis cos ity, fre ezi ng poi nt, vap our
11. Th e sol ven t sho uld rat es and set tlin g of
rag e (low vis cos ity is des ire d for bet ter ma ss tra nsf er
han dli ng and sto
dis per sio ns) . usi ng : (1) sta gew ise
cti on op era tio ns ma y be car rie d out by
Liq uid -li qu id ex tra ren t or cou nte rcu rre nt)
ay be sin gle sta ge or mu ltis tag e-c ros scu rre nt, con cur
equ ipm ent (m .
nti nuo us con tac t equ ipm ent
and (2) dif fer ent ial con tac t/co
Sta gew ise Co nta ct: (i) con tac tin g
it is pre sum ed tha t eac h sta ge has the fac ilit ies of
In sta gew ise con tac t, ble liq uid s and
ext rac tin g sol ven t i.e. con tac tin g the ins olu
the fee d sol uti on and the tio n ope rat ion
duc t str eam s. Ea ch sta ge inv olv ed in the ext rac
(ii) of sep ara tin g the pro the ext rac t and
J
l or equ ilib riu m sta ge so tha t the pro duc t str eam s i.e.
.I
rep res ent s a the ore tica
I equ ilib riu m wit h eac h oth er.
raf fin ate lea ve the sta ge in
Sin gle Sta ge Op era tio n : bat chw ise or con tin uou s
sta ge ext rac tio n ope rat ion ma y be per for me d in
A sin gle
ma nn er.
e pa ir par tia lly mi sci ble :
(A) A ter na ry sys tem wi th on of feed sol uti on
d sol uti on (fo r bat ch) or ma ss per un it tim e
Le t F be the ma ss of fee t fra ctio n of C
nin g sol ute C and fee d sol ven t A wit h XF ma ss/ we igh
(for con tin uou s) con tai
is fed to a sin gle sta ge. e) of a sol ven t
con tac ted wi th ma ss 8 1 (or ma ss per un it tim
Th e fee d sol uti on is Ys = 0 and S 1 = B.
B wit h y we igh t fra ctio n of C. If sol ven t is pur e B,
con tain ing pri nci pal ly ext rac t E 1
equ ilib riu m raf fin ate R 1 and
8
i Aft er con tac tin g and pha

~ach one is me asu red in ma
se sep ara tio n, we
ss or ma ss per un it tim e.
get the

Distillation From Gavhane

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Distillation From Gavhane

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Chapter ••• 0

0,0 x,y ---+ 1.0 x--+

It is commonly used for predicting vapour-liquid equilibrium for an ideal solution in

PB = p~. (1-xA) ... (1.6)

XA (p1- P~) = P-poB ... (1.14)

Dropping subscript, we get :

'Condensate R 1R 2 - Di stillate receiver,

Fig. 1.4 : Simple distillation unit

ln £._ = _ 1 [ xfp!dx + a fx~]

ln £._ = _1_ [ln Xp(l - xw) + (a-1) ln 1-xwJ

ln F XF F(l-xF) ... (1.41)

relates the number of moles of A remaining in the residue, W xw to that

Fig. 1.5 : Flash/Equilibr ium distillation

Fig. 1.11 : Recti fying sectio n inclu ding conde nser

.___ _L',_x' _ _ __...___ __. W, xw

Fig. 1.12 : Stripping section including reboiler

Rearrangin g the Equation (1.56),

Consider any plate n in the rectifying section.

diagonal and with the slope equal to L, ~ ' W .

Line - 2 - Stripping Section

Fig. 1.14 : Determin ation of theoretica l plates by McCabe - Thiele Method

The equation of the operating line of the stripping section is :

only diffe rence is xD is repla ced by YD.

/ . . . Fig. 1.21 : Operation under total reflux

Fig; l ~ : Minimum Reffux ratio

Calcula tion of minimu m reflux ratjo ffim) :

. 0,0 _ _x_--+ 1.0

Fig. 1.24 : Rm for saturate d vapour

Fig. 1~25: 'Rm' for cold liquid

Fig. 1.26: 'Rm' for feed-partially vapour

er of stage s for distil lation

__ Fig. 1.28 : Optim um reflux ratio for distil lation

Fig. 1.61 : Downcomer - weir seal plot

Fig. 1.62 : Packed colum n for contin uous distilla tion

z = Ko a V/A fYt *dy ... (1.165)

.. . .;, ~+ . .' ... ~ . . . M 0.966, 0.966) • : · ·r'! .

Fig. E 1.1 : Grap hical const ructio n of ideal stage s

Ex. 1.2 : A mixture of 35 mole % A and 65 mole % B is to be separated in distillation

A in feed = 0.35 x 100 = 35 kmol

0.6 c - me R. S. Op. line

Fig. E 1.2 : Graphical constructio n of ideal plates

We have, - Ym+1 0.33 and Xm = 0.25

Molefra ction of hexane in feed = xF = : = 0.4.

Molefra ction of hexane in bottom = xw =?

0.1 0.6 0.7 0.8 0.9

Fig. E 1.4 (a) : Deter mina tion of xw by const ructio

T 0.45 x 353 + 0.55 x 383.8 = 369.94 K

0.8 0.9 1.0

Fig. E 1.5 : Construcion of ideal stages

0.99 - 0.927 = 0 588 "" 0 59

= Rm = 0.59 ... Ans. (i)

Locate point Q (0.99, 0.99) on the diagon al.

Fig. E 1.6 (a) : Partial condenser

Fig. E 1.6 (b) : Determinat ion of number of ideal plates

~ r e n c e between distillation and extraction:

i Aft er con tac tin g and pha

Potrebbero piacerti anche

.___ _L',_x' _ _ ..._ __. W, xw