Documente Academic
Documente Profesional
Documente Cultură
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
. ;,-,
L Raoult's law :
Fig. 1.3 : Effect of increased pressure : vapour-liquid equilibrium
= 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)
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)
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
Mass Transfer - II 1. 7 Distillation
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)
Vapour
Coolant
out
Condenser
Coolant
Still/kettle in
(Jacketed)
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)).
Mass Transfer - II 1. 10 Distillation
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)
Mass Transfer - II 1. 11 Distillation
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,
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
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
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
Mass Transfer - II 1. 14 Distillation
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.
Mass Transfer - II 1. 15 Distillation
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
Mass Transfer - II 1.16 Distillation
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
Equation (1.54) is known as the material balance line or operating line of the
rectifying section.
V', y'
i----1 -
------ -.
Reboiler
Similarly,
Material balance of more volatile component (A) :
Lm Xm = Vm+l Ym+l + W xw ... (1.56)
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
Mass Transfer - II 1.20 Distillation
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
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 ·
Intercept { .
+
X-+- .0
i 21-----1
31-----1
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
Operating line
i
>,
Xo (rectification-section)
I
Xo- y
Rm = I - x I
y
Xn- XF I
... (1.82)
= XF- X
I (as y = XF)
1".0
t
>,
O x-
x --+
0,0
I
y' I
I
i
y
I
I
I
I
Xo
X--+ 1.0
0,0
Operating costs
i
Cost Fixed costs
I
I
I
:/Opt imum reflux ratio
Rm
R (Reflux ratio) -+
Feed
Bottoms
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
Mass Transfer - II 1. 78 Distillation
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
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,
Mass Transfer - II 1.80 Distillation
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
Mass Transfer - II 1.82 Distillation
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 .
. +-+
.+
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
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
Mass Transfer - II 1.84 Distillation
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
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-.
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.
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
Mass Transfer - II 1.88 Distillation
0.2
r--
(!)
"l
0 0.1
. . . . . - - - - - - 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-
Mass Transfer - II 1.90 Distillation
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
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
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
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-
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
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